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Mass changes during hydrothermal alteration, Silver Queen epithermal deposit, Owen Lake, central British.. Cheng, Xiaolin 1995-12-31

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MASS CHANGES DURING HYDROTJIERMAL ALTERATION SILVER QUEEN EPITHERMAL DEPOSIT, OWEN LAKE, CENTRAL BRITISH COLUMBIA by XIAOLIN CUENG B.Eng., The China University of Geosciences (Wuhan), 1982 M.Sc., The China University of Geosciences (Wuhan), 1985 A THESIS SUBMITFED IN PARTIAL FULFILLMENT OF TUE REQUIREMENTS FOR TUE DEGREE OF DOCTOR OF PHILOSOPHY in TIlE FACULTY OF GRADUATE STUDIES (Department of Geological Sciences) We accept this thesis as conforming  THE UNIVERSITY OF BRITISH COLUMBIA October 1995 © Xiaolin Cheng, 1995  In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission.  (Signature)  Department of óe.iic.cA  2 ’ 4 Sc v i  The University of British Columbia Vancouver, Canada  Date Oct-  DE-6 (2/88)  9  ,  ABSTRACT  A procedure for determining metasomatic norms is developed in this thesis to quantitatively and objectively estimate mineral abundances from lithogeochemical data, The norm calculations use the same principles as do other norms such as CIPW, but the different mineral phases present in alteration systems are used as the normative standard minerals. Another distinctive difference between a metasomatic and a conventional norm is that the calculation procedure proposed for a metasomatic norm does not proceed along such a fixed hierarchical path as in the case of an igneous norm. A particular useful approach to the application of the norm concept to metasomatic rocks is to constrain the calculated normative mineralogy by apriori knowledge of existing minerals (i.e. to approximate the mode as closely as possible). Where an immobile component can be recognized the metasomatic norms for protoliths and altered rocks, as well as the chemical constituents lost or gained, can be further recast into the absolute amounts of minerals and chemical constituents relative to a given mass of parent rock. Known errors within lithogeochemical data studied can be propagated to the final results of all norm calculations. As a result, a chemico mineralogical model for material exchange, including absolute losses and gains of chemical constituents, normative minerals in extensive units, as well as the corresponding propagated errors, is formulated in this work as follows: Mineral.ent rock ± error + Constituent gained from solution ± error =  iVlineralafted rock ± error + Constituent  lost from wall rock ±  error  (I)  Equation I is particularly useful because it is quantitative and easily applied: information that can be obtained from the equation includes the mineralogy of the initial and final rocks, absolute gains and losses of specific chemical constituents as well as the uncertainties on each estimate at a specified confidence level.  11  The methodology for this approach is a natural extension of the use of Pearce element ratio (PER) diagrams for the study of metasomatic rocks. The metasomatic norm recovers the same quantitative information as do Pearce element ratio diagrams. The common principles are (i) correction for closure, that provides true relative lithogeochemical and mineralogical variations between parent and daughter rocks, and (ii) an effort to explain chemical variability in terms of mineralogical variability. The strategy of a PER diagram is to test whether chemical changes in different rocks can be explained purely by the variation(s) of certain mineral(s), as demonstrated by disposition of the binary plotted points along predefined trends (slopes). Metasomatic norms are displayed more effectively as equations or profiles showing the spatial distributions of normative mineral assemblage, as well as the absolute losses and gains of chemical constituents based on comprehensive mass balance relationships. The approach described in the first part of this thesis is applied to a hydrothermal alteration study of the Silver Queen mine in central British Columbia. Hydrothermal alteration at the Silver Queen mine was derived from a multiple precursor system. However, local, individual alteration profiles exhibit the attributes of a single precursor system. Six types of hydrothermal alteration at Silver Queen mine have been described: viz. propylitization, sericitization, argillization, silicification, pyritization and carbonatization. In general, the wall rock alteration in the study area is composed of a widespread regional propylitic alteration with superimposed carbonatization. Regional alteration gives way, as the vein is approached, to an outer envelope of sericitic and argillic alteration + carbonatization and an inner envelope of silicification and pyritization +  sericitic or argillic alteration + carbonatization. Thus, the sequence of alteration  development is (i) widespread regional propylitic alteration, (ii) sericitic and argillic outer envelope, and (iii) silicification and pyritization inner envelope. Most of the hydrothermally altered samples in alteration envelopes at the Silver Queen mine have gained mass during hydrothermal alteration. In contrast, samples from 111  the profile of the northern segment of the No. 3 vein have lost mass. Other spatial variations of hydrothermal alteration from the southern segment to the northern segment of the No. 3 vein and from different levels (from 2600-foot level to 2880-foot level) have been recognized. In brief, the wall rock alteration is most intense in the alteration envelope at the central segment of the No. 3 vein and mildest at the northern segment of the No. 3 vein. The total mass change of each altered sample is largely the result of depletion of CaO 0 and CO 2 . 2 ,H K O ,2 2 0, and addition of Si0 2 and Na  iv  TABLE OF CONTENTS Abstract  II  Table of Contents  V  List of Tables  xlii  Acknowledgement  X  Chapter 1. Background and Objectives  1 1  1. 1. Introduction 1. 2. Current Quantitative Approaches to the Study of Hydrothermal Alteration  4 5  1.2.1 The Closure Effect 1.2.2 Comparison of Various Techniques Used to  7  Remove the Closure Effect 1.3. Two Requirements for Loss and Gain Calculation  10  1.4. Pearce Element Ratios (PER) and Their Application to Hydrothermal Alteration 1.5. Additional Problems  16 23  Chapter 2. Metasomatic Norms: A Method ofNorm Calculation Adapted to Hydrothermally Altered Rocks  26  2.1. Introduction  26  2.2. The Principle of Metasomatic Norms  28  2.3. A Set of Standard Normative Minerals for Metasomatic Systems  32  2.4. A Manual Procedure for Metasomatic Norm Calculation  33  2.5. A Quantitative Model of Metasomatic Systems  41  2,6. Case Histories: Application of Metasomatic Norms  43  2.6.1. Sigma Mine, Abitibi, Quebec  43  2.6.2. Erickson Gold Mine, Northern British Columbia  47  2.7. Conclusions  55 V  Chapter 3. Quality Control/Assessment of Lithogeochemical Data  57  3.1. Introduction  57  3.2. Strategies of Sampling and Sample Preparation  58  3.3. Quality Assessment of Analytical Measurements Based on a Small Set of Duplicates 3.4. Propagation of Errors in Lithogeochemical Calculations  64 71  Chapter 4. Geology of the Silver Queen mine, Owen Lake area, Central British Columbia  76  4.1. Introduction  76  4.2. Regional Geological Setting  77  4.3. Geology of the Study Area  80  4.4. Lithogeochemical Characters and Two Series of Igneous and Volcanic Rocks  92  4.5. Veins: Character and Correlation  96  4.6. Structures and the Interpretations  99  4.7. Summary  106  Chapter 5. Hydrothermal Alteration Associated with Epithermal, Base- and Precious-Metal Veins at Silver Queen Mine: Petrographic Variations  108  5.1. Introduction  108  5.2. Petrography of Hydrothermal Alteration Types  109  5.3. The Spatial Zonation of Hydrothermal Alteration  115  5.4. Paragenetic Sequence of Hydrothermal Alteration  125  5.5. Discussion and Conclusions  130  Chapter 6. A Quantitative Evaluation of Hydrothermal Alteration at Silver Queen Mine, Central British Columbia  133  6.1. Introduction  133  6.2. Sampling and Sample Preparation  134 vi  6.3. Errors inherent in Lithogeochemical Data  140  6.4. Lithogeochemical Data of Altered Rock and Determination of immobile components  142  6.5. Calculation of Absolute Losses and Gains of Chemical  Constituents and their Spatial Variations  144  6.6. Application of PER Diagram to the Interpretation of Hydrothermal Alteration 6.7, Application of Metasomatic Norm Methodology  149 158  6.8. Propagated Error Analysis and Confidence Level of the Quantitative Evaluations 6.9. A Comprehensive Model of Hydrothermal Alteration  167 169  Chapter 7. Conclusions and Recommendations  172  Bibliography  183  Appendix A. Megascopic Description of Altered Sample, Silver Queen Mine  196  Appendix B. Lithogeochemical Duplicate Analyses, Silver Queen Mine  201  Appendix C. Use of “Quattro Pro for DOS 5.0” to Calculate Metasomatic Norms  205  Appendix D. Diagrams of Alteration Evaluation, Silver Queen Mine  246  Appendix E. Tables of Alteration Evaluation, Silver Queen Mine  268  vii  LIST OF TABLES Table 1-1. A Summary of Quantitative Techniques Devised to Remove 8  the Closure Effect and Evaluate Mass Transfer Process Table 1-2. Eight Possible Cases of PER Diagram  13  Table 2-1. A List of Standard Normative Minerals for Metasomatic Volcanic Rocks Associated with Epithermal Ore Deposits  34  Table 2-2. Variations in Major Element Oxide Concentration (in wt%) in the Profile 2103 across Alteration Envelope Around Tension Vein, Sigma Mine, Quebec  44  Table 2-3. The Calculation Results of Metasomatic Norms (in wt%) in the Profile 2103 across Alteration envelope around Tension Vein, Sigma Mine, Quebec  44  Table 2-4. Summary of Characteristics of Alteration Zones of Enclosing Gold-Bearing Quartz Veins and the McDame Dolomite Vein, Total Erickson Mine  48  Table 2-5. Chemical Analyses of Jennie Vein Alteration Profile, Erickson Gold Mine  50  Table 2-6. Metasomatic Norms of Jennie Vein Alteration Profile, Erickson Gold Mine  50  Table 2-7. Metasomatic Norms Corrected for Closure and Absolute Losses and Gains of Components from Profile 80-88-JH across the Jennie Vein, Erickson Mine, Northern British Columbia  52  Table 3-1. The Classification ofMajor Variations of Lithogeochemical Data Generated by Different Processes  57  Table 4-1. Table of Formations, Owen Lake Area  83  Table 4-2. Lithgeochemical Data of Various Types of Rock at Owen Lake Area, Central British Columbia  94  Table 5-1. Estimated Modes of Alteration Minerals in Hydrothermally Altered Rock around the No. 3 Vein, Silver Queen Mine, Central British Columbia  120 viii  Table 5-2. Paragenetic Sequence of Mineral Assemblages, Silver Queen Mine  129  Table 6-1. Estimation of Optimal Sample Size by Using Binomial Function  136  Table 6-2. Estimated Optimal Fineness of Subsample by Using Binomial Function  138  Table 6-3. Error of Lithgeochemical Data Estimated by Using Sample Duplicates  141  Table 6-4. Error of Lithogeochemical Data Estimated by Using Measurement Duplicates  141  Table 6-7. Metasomatic Norms Corrected for Closure and Absolute Losses and Gains of Components (in Moles) around the No. 3 Vein, Silver Queen Mine, Owen Lake, Central British Columbia  160  Table 6-8. Metasomatic Norms Corrected for Closure and Absolute Losses and Gains of Components (in Grams) around the No. 3 Vein, Silver Queen Mine, Owen Lake, Central British Columbia  161  Table 6-9. Propagated Errors of Metasomatic Norms Corrected for Closure and Absolute Losses and Gains of Components in Grams at the 68% Confidence Level, the No. 3 Vein, Silver Queen Mine, Central British Columbia  168  ix  ACKNOWLEDGMENTS In the course of completing my thesis, several individuals and agencies have provided much appreciated assistance, without which the thesis would have been an impossibility. I am especially indebted to Dr. Alastair J. Sinclair for offering me the opportunity to work on the Owen Lake Project as a Ph. D. graduate student under his supervision, and for his constructive criticism, insights, and extraordinary patience that allowed me to complete this work. Dr. Gerry Carlson, Dr. Craig Leitch and Dr. Margaret Thomson provided much needed assistance in deciphering the geological story behind the Silver Queen preciousand base-metal vein deposit and greatly supplemented the evolution of this thesis with their own work. My thanks also go out to my coworkers Christopher T. S. Hood, Zophia Radlowski and Asger Bentzen for their suggestions, discussions and assistances. Pacific Houston Resources Inc. and New Nadina Explorations Ltd. are thanked for allowing access to the Silver Queen workings and for financial assistance in and out of the field. J. Hutter and W. W. Cummings provided helpful discussions on the mine area during my stay at Silver Queen mine. Dr. L. A. Groat and K. N. Nicholson are thanked for the advice and assistance with the X-ray diffraction operation; Dr. W.K. Fletcher and S. Horsky for the guidance on the XRF analytical measurement. I am also grateful to Dr. T. J. Barrett, Dr. T. H. Brown, Dr. R. L. Chase, Dr. G. M. Dipple, Dr. C.I. Godwin, Dr. J. K. Russell, Dr. C. R. Stanley and Dr. Mm Sun for providing instruction and discussion. This work was supported by Pacific Houston Resources Inc., New Nadina Explorations Ltd. and by a grant from the Natural Science and Engineering Research Council of Canada to Dr. A.J. Sinclair.  x  Chapter 1.  Background and Objectives  1.1. Introduction  Bates and Jackson (1987) define alteration as:  “  ...  any change in the mineralogical  composition of a rock brought about by physical or chemical means, especially, by the action of hydrothermal solutions .“It is one of the most important topics studied by . .  economic geologists because in many hydrothermal ore deposits the changes in composition, mineralogy and/or texture of wall rocks, etc., that enclose the ore deposit are more extensive and more obvious than the ore deposit itself. Hydrothermally altered wallrock is thus a “fossil” of a hydrothermal system; many parameters of the depositional environment of ore are interpretable from the assemblages of alteration minerals. Consequently, wall-rock hydrothermal alteration has been used widely as a guide during exploration of hydrothermal ore deposits and as a clue to the properties of the hydrothermal solution from which ores precipitated. However, hydrothermally altered wall rock can be the product of the reaction between wall rock and ore-bearing hydrothermal solution either before, during or after the precipitation of ore minerals from hydrothermal solutions. To understand the relation between ore and associated hydrothermally alteration is a challenging task. Uncertainties can lead to errors or complexities in using wallrock alteration as a guide to exploration of hydrothermal ore deposits if different types of alteration are confused. Appleyard and Guha (1991) review such practical uses of hydrothermal alteration and state: Wall-rock alteration was generally accorded little signficance as an exploration focus. Dunbar (1948), for example, noted with reference to the ores of the Porcupine district that moderate bleaching of the chloritic host rock was considered to be a condition favorable for ore occurrence but such evidence can only be utilized in a very general way. Conversely, he found strong bleaching to be a poor indicator of mineralization and wrote that it cannot be said that the ore 1  occurs where its effect (that of hydrothermal alteration) is most intense. Since those days, technical improvements have been at the heart of the advancement of the state of knowledge we have seen rather than the appearance ofnew paradigms. Lithogeochemistry, isotope geochemistry, fluid inclusion studies, statistical applications, and geochemical modeling are all areas where great advances in technique and important observations have been achieved. In recent years, research into hydrothermal alteration associated with preciousmetal ore deposits has accelerated appreciably with increasing interest in understanding water/rock interactions, mass losses and gains, the geometry of alteration zones relative to the associated mineral deposit, and assemblages of alteration minerals. This information leads to the development of comprehensive models of alteration systems and provides a basis for designing mineral exploration guidelines, particularly as they relate to the use of lithogeochemical data and their integration into deposit model definition as an exploration tool. The general aim of this thesis is to improve quantitative methods of evaluating hydrothermal alteration associated with precious- and base-metal vein deposit in volcanic sequences. This goal will be approached through a particular case study of alteration at the Silver Queen mine, central British Columbia. This study is preceded by a brief review of the current status of the study in the field of quantitative losses/gains to wallrock during hydrothermal alteration. The basic aims of many alteration studies involve such questions as: (1) What are the changes in mineralogical assemblage of the rock during the alteration process? (2) What variations in chemical compositions of the rock arise from the alteration process? (3) What are the sequences, distribution patterns and spatial extents of alteration?  2  (4) What are the conditions of formation of alteration minerals and the properties of hydrothermal solution? (5) What are the mechanisms of hydrothermal alteration? and  (6) What is the relationship between hydrothermal alteration and ore deposition? To answer such questions commonly involves two complementary approaches, mineralogical and lithogeochemical; both can be directed to the quantitative estimation. The basic tasks of these two approaches as applied to the evaluation of material exchange during hydrothermal alteration are: (i) determination of mineral assemblages of altered and parent rocks, and (ii) calculations of the losses and gains of chemical components as a result of hydrothermal alteration. The mineralogy of altered rocks has been particularly important as a means of classification, such mineral-dependent terms as phyllic, sericitic, argillic, propylitic, etc., are entrenched in the literature. One reason for this is that a mineral assemblage contains information both about the chemical composition and the formation environment of the rock. Such information contributes to answering question 1 to 3, above, and less significantly to questions 4 to 6. Unfortunately, fine grain size, absence of easily identifiable optical features, and mixtures of non-ideal structures of alteration products can obscure mineralogy and/or make mineral abundances impractical to estimate with confidence. Consequently, the use of a mineralogical approach to study and classification of hydrothermally altered rocks, while essential, is limited. A lithogeochemical approach to the study of altered rock complements and has some advantages over the mineralogical approach. The large samples commonly used for chemical analysis can be more representative than, say, small areas of a thin section; thus, more accurate and consistent quantitative data can be obtained. A lithogeochemical approach to the study of hydrothermal alteration commonly is directed toward quantifying the loss or gain of each component during the alteration process and thus provide an  3  objective and quantitative chemical classification scheme. Elliott-Meadows and Appleyard (1991) state: the outer limits of alteration can be detected more sensitively by their geochemical signatures than by their mineralogical expression, as can alteration zone boundaries. Lithogeochemical data provide information on the chemical compositions of rock. Rocks with similar chemical composition will have different mineral assemblages under different physical conditions. Therefore, a simple lithogeochemical analysis can provide definitive answers to question 2, and partial ones to question 3, 5 and 6, above, but can not give any answers to questions 1 and 4. Mineralogical- and lithogeochemical-based methodologies utilize different types of data. However, the two are related through the compositions and amounts of individual minerals. These two approaches are complementary; many researchers have integrated them in different ways (e.g. Gresens, 1967; Meyer and Hemley, 1967; Giggenbach, 1984; MacLean and Barrett, 1993; Barrett et al., 1993; Madeisky and Stanley, 1993). A review of the various approaches used to quantitatively evaluate hydrothermal alteration is given in the following sections.  1. 2. Current Quantitative Approaches to the Study of hydrothermal Alteration The quantitative evaluation of material exchange during hydrothermal alteration relies on lithogeochemical data. With the development of X-ray fluorescence (XRF), atomic absorption spectrometry (AA), inductively coupled plasma-atomic emission spectrometry (ICP) and other advanced analytical techniques, the availability of high quality, sensitive, precise, and inexpensive analyses for a long list of elements has come about. It is probably fair to say, however, that the use of these data in exploration has to date been largely limited to empirical procedures including: (i) the identification and 4  distribution of pathfinder elements (e.g., Descarreaux, 1973; Boyle, 1979; Fyon and Crocket, 1982; Davies et al., 1982; Kishida and Kerrich, 1987), and (ii) the application of a varieties of empirical indices, such as an alteration index (A.I. 0)/(Na K 0 2  +  0 2 K  +  CaO  +  =  100 x (MgO  +  MgO)) proposed by Ishikawa et al. (1976), and many others  + (Fe + 3 0 MgO+CaO+NaO), MgO)/(Fe ,2 /Na 3 0 2 A1 including 2 /(Fe Fe + 3 0 MgO), 0 0/(Na Na 0 , MgO/CaO, 2 0/Na 2 K +K ), 0 0/(Na K 0 2 0 0 2 K  +  0 2 CaO) and CaO/(Na  +  +  0/(Na + K 0 0 +CaO), 2 2 K  0 +CaO) (Hashiguchi and Usui, 1975; Spitz and 2 K  Darling, 1978; Saeki and Date, 1980). A thorough review of these indices has been made by Stanley and Madeisky (1993). Depletion or enrichment anomalies, especially of silica, alkalis, and some metals, have been regarded as favorable signs in conjunction with the more conventional positive anomalies. In some cases, however, where subjective interpretation procedures have been used, these depletion or enrichment anomalies have been misconstrued as to whether or not they are absolutely depleted/enriched or relatively diluted/concentrated by the enrichment/depletions of other components. For example, silica depletion anomalies have been confused with Al or Mg enrichment effects (Appleyard and Guha, 1991). This confusion of enrichment and/or depletion is a product of the closure effect of lithogeochemical data. 1.2.1. The Closure Effect  In attempting to deal quantitatively with the material exchange during alteration using lithogeochemical data, a common problem arises, the closure effect. In a multicomponents system closure refers to the fact that all components must total 100 2 is added, the relative abundance percent. Thus, if a single component is changed, say 5i0 of all other components decrease even though their absolute amounts are unchanged. This is the problem of the closure effect. Lithogeochemical analyses of altered rocks superficially can provide a distorted view of losses and gains of components. The matter 5  0 consisting can be evaluated quantitatively as follows. Assume an original, simple system S of three components X, Y and Z. 0 S  =  0 X  +  +  =  100(gram)  (1-1)  (upper case letters are used for weights) During an alteration process, components change by the absolute amounts dx, dY and dZ respectively. The total change of the system (in grams) will be: dS=dX+dY+dZ  (1-2)  +dZ are not accessible directly 0 +dX, 0 0 dY and Z Y + In practice, the values of X because chemical analytical data are conventionally presented as percentage, that is, s=x+y+z=100%  (1-3)  (lower case letters are used for percentages) where x, y and z, the concentrations of components can be further described in the following form: dS) +dX)I(S 0 100(X +  (1-4)  dS) +dY)I(S 0 100(Y +  (1-5)  z= 0 dS) +dZ)/(S 100(Z +  (1-6)  y  =  Equations 1-4 to 1-6 indicate that the difference in the concentration of a particular component between the unaltered parent and the altered product is affected not only by the absolute change of individual component (dx, dY or dZ), but also by the total absolute change of all components (dS). With regard to the impact of the closure effect on different constituents, Stanley and Madeisky (1993) indicate: Closure will most affect those constituents that occur in large concentrations in a system and which are added to or removedfrom the system in an incomplete way. Conversely, it will least affect those elements that have been added to or removed from the system in more complete ways. In essence, the larger the concentration of a constituent in a rock relative to the amount ofmaterial transfer that constituent 6  has undergone, the more closure will obscure our ability to understand the material transfers using the constituent concentrations. As a result, the closure effect should be removed before a meaningful interpretation of geochemical data proceeds.  1.2.2. Comparison of Various Techniques Used to Remove the Closure Effect The closure effect has long been recognized and researchers working in related fields have devised various techniques to deal with this problem. The earliest paper dealing with this issue has been traced back almost a hundred years. Geochemists working with weathered rock, calculated losses and gains of constituents by assuming the amount of alumina to have remained constant during the weathering process (e.g., Merrill, 1897; Golditch, 1938; Krauskopf, 1967). Later researchers in the field of metasomatic alteration and igneous fractionation developed their own techniques to remove the closure effect from lithogeochemical data (e.g., Gresens, 1967; Pearce, 1968; Winchester and Floyd, 1977; Floyd and Winchester, 1978; Finlow-Bates and Stumpfl, 1981; Grant, 1986; MacLean and Kranidiotis, 1987, MacLean and Barret, 1993). A summary of their principal contributions is presented in Table 1-1. The formulae of Table 1-1 are presented with standardized symbols to emphasize the degree of similarity of proposals by various authors. Among these techniques, Gresens’ equation (Gresens, 1967) and its modification (Grant, 1986) have been widely used by economic geologists to quantify the losses and gains of constituents during hydrothermal alteration processes (e.g., Babcock, 1973; Appleyard, 1980; Morton and Nebel, 1984; Robert and Brown, 1986; MacLean and Kranidiotis, 1987; Leitch and Day, 1990, Leitch and Lentz, 1994; Marquis et al., 1990; Sketchley and Sinclair, 1987, 1991; MacLean, 1990; Richards et al., 1991; Bernier and MacLean, 1989; Barrett and MacLean, 1991, Barrett el al., 1993).  7  Table 1-1. A Summary of Quantitative Techniques Devised to Remove the Closure Effect and Evaluate Mass Transfer Process Study  Year  Merrill, G. P.  1897  Application  Formula .  weathering  = (ZP) —  Zd  1967  Gresens, R. L.  dK =  dX  1968  Pearce, T.H.  —  1977 1978  Grant, 3. A.  1986  1993  MacLean, W. H.  Xd  Za  =  zp  .  metasomatism  x, Zp  Xd  —  Xa =  —  —  Za  p  z A1 3 and assumed to be 0 2 immobile  f can be assumed to be one or determined by assuming one component is immobile so f  —  Z,  Winchester et al. Floyd et al.  —  p  Notes  —  xp  P (x + ) D  —  = —  Za  -“  =PpXp/j.  igneous fractionation  x can be a combination of several components, Z is immobile.  metabasalt classification  Both z and x are immobile.  Metasomatic alteration  p / .D  Metasomatic alteration  z = immobile elements such as Zr, Ti, Al, Nb, Y.  = Za / Z,  Notes: where: P- mass of parent rock; D- mass of daughter or altered rock;  dX the mass gains or losses of component x from 100 grams parental -  rock; x.  weight or molar fraction of component x in parent rock;  -  Xd  weight or molar fraction of component x in daughter or altered rock;  -  z weight or molar fraction of immobile component z in parent rock; -  d 2  weight or molar fraction of immobile component z in daughter or  -  altered rock; p specific gravity of parent rock; -  Pd specific gravity of daughter or altered rock; and -  -  volume factor = vd / v.  8  Pearce element ratio (PER) diagrams, devised by Pearce (1968) for examining material exchange during the process of fractional crystallization, recently have been extended by Stanley and Madeisky (1994) to metasomatic rocks. PER diagrams have been used in the past to examine chemical variations caused by igneous differentiation (Russell and Stanley 1990). More recent applications are to hydrothermal alteration, in particular, that associated with volcanogenetic massive sulfide deposits (Stanley and Madeisky, 1993). In brief, this method converts the weight units of raw chemical analytical data into molar units, then uses a conserved/immobile element as a reference scale to remove the closure effect, and finally, utilizes various diagrams designed in the light of the stoichiometries of the relevant minerals, to test various causes of the lithogeochemical variations in terms of mineralogical variation(s). Gresen& equation and Pearce element ratio diagrams are superficially different but they are used to solve similar problems. Cheng and Sinclair (1991), and Stanley and Madeisky (1993) show that these two techniques, although having different starting points, are fundamentally similar in principle  —  that is, they both remove the closure effect  in order to decipher the true chemical variations during alteration. Even though an independent solution exists for Gresens’ equation where the volume factor is known and the specific gravities have been measured, in practice, the volume factor can not be estimated except through the use of either an immobile component or an assumption such as constant volume during the hydrothermal alteration process. The concept of immobile element is defined by Stanley and Madeisky (1993) as an element that is neither signficantly added nor removedfrom a rock during metasomatism because of its low solubility in aqueousfluids (the stabilities of aqeuous complexes that contain it are signflcantly lower than the stabilities of minerals that contain it).’ The procedure of removing the effect of closure by using an immobile component is illustrated as follows. Given that a component Z is immobile (i.e. dZ  =  0) then we have: 9  (1-7)  z = 100ZJ(S +&) 0  The use of this immobile component to remove the effect of closure involves using the immobile component as a divisor (standard reference) for other components as follows: x  xo  Z  Zo  100(Xo+dK)/(So+&) /(S 100Z + 0 dS)  X d 0 X 0 Z 1,  18  The final result dX/Z 0 in equation 1-8 can also be treated as the absolute change of 0 0 because 4, = z element x with the reference unit of conserved or immobile component z if the original system is assumed to be 100 gram. Rearranging equation 1-8 produces Grant’s version of Gresens’ equation: —X 0 dX=—x  (19)  In summary, these various techniques of dealing with closure are all based on the same fundamental principle, an immobile component that allows the calculation of the true variations in rock compositions caused by material exchange. Applications of these techniques rely on a knowledge of either the change in rock volume during hydrothermal alteration (e.g. Robert and Brown, 1986), or the recognition of immobile component(s) in the rocks (e.g. MacLean and Kranidiotis, 1987).  1. 3. Two Requirements for Loss and Gain Calculations Before applying these quantitative techniques for estimating losses and gains in a metasomatic system, two requirements must be met. First, the available analytical data must be shown to contain immobile components; second, a suite of samples for which loss/gain variations are to be evaluated, must be the alteration products of either: (i) a common parent rock characterized by chemical and mineralogical homogeneity (single precursor system), or (ii) a suite of rocks with determinable pre-alteration chemical composition (multiple precursor system).  10  In order to examine whether a set of lithogeochemical data meets the first requirement, Nicholls (1988) summarizes three ways of recognizing a conserved element for the study of igneous differentiation: (1) The petrologic behavior of the element can be used to select conserved elements. They are usually the incompatible elements. (2) The ratio of two conserved elements will be constant in a comagmatic suite. (3) An element ratio diagram that is not constructed with a set of conserved element in the denominator will have a trend with a near zero intercept. The geochemical behavior of elements is helpful to infer which elements might be conserved or immobile, particularly under certain circumstances where they are incompatible with the known mass transfer process. For example, the elements P, K and Ti are commonly thought to be incompatible with the main minerals that crystallize in a basaltic system, such as olivine, pyroxene and plagioclase (Pearce: 1968,1987; Nicholls, 1988; Russell, 1986; Russell and Nicholls, 1987; Russell and Stanley, 1989, 1990a, 1990b). For hydrothermal alteration the assumption of Zr, Ti and/or Al immobility has been used widely because of the relative insolubilities of these components in hydrothermal solutions. An objective method is needed to test these assumptions. In practice, ratios of immobile components remain constant regardless of the nature of alteration. This is an objective criterion for the recognition of immobile or conserved elements, and it can be easily proven as follows. Given that both dX and dZ equal to zero (i.e. both X and Z are immobile), then we have equation 1-4 divided by equation 1-6: x —  (S 1dS) 0 100X + /(S 100Z + 0 dS)  Zo  —  —  (1-10)  Thus, a bivariate plot of two immobile components from altered samples with a common parent will define a linear trend that extends through the origin. The concept of equation 1-10 for determining whether certain elements have been immobile in 11  metasomatism and hydrothermal alteration has been discussed and applied by Gresens (1967), Babcock (1973), Finlow-Bates and Stumpfl (1981), Grant (1986), Kranidiotis and MacLean (1987), MacLean (1988, 1990), Elliott-Meadows and Appleyard (1991), and MacLean and Barrett (1993). For example, Al, Ti, Zr, Nb, Yb and Lu commonly are shown to be immobile in hydrothermal alteration zones formed in homogeneous volcanic rock units (single precursor systems) at the Phelps Dodge deposit (MacLean and Kranidiotis, 1987), at Atik Lake (Bernier and MacLean, 1989), and at other mines in the Noranda district (Cattalani et al., 1989). Some problems arise with the application ofNicholls’ (1988) third criterion for immobility. First, let us see theoretically how many possible patterns can be present in a PER diagram based on simple ratios. The linear relation for any two points on x/z versus. y/z diagram can be described by the following equation: (1-11) the general form of the slope will be: m_-=z_11z2 2 d(x/z) dX/z—xdZ/z  zdY—ydZ zdX—xdZ  (1-12)  the general form of intercept will be: z  z  z  (zdX  —  xdZ)z  ydX-xdY zdX xdZ  (1-13)  —  If the slope and intercept of each individual pair of points in a data set are equal, then all points will plot as a straight line on a PER diagram. Otherwise, a data set may show a scattered distribution pattern to various extents on a PER diagram. Eight possible cases are summarized in Table 1-2. According to Table 1-2, we see that Nicholl’s third criterion for recognizing immobility is correct only under certain constrained conditions: (i) where elements in both  12  numerators are conserved (case 5), or (ii) dY << dz (case 4), then the intercept (dY/dz) will be close to zero. Other possibilities also exist for a trend going through the origin but with a conserved or immobile component as the denominator. For example, in case 2, where ydX xdY = 0, then its slope dX/dY = X/Y and its intercept is equal to zero. The -  Eight possible cases of PER diagram*  Table 1-2. case 1  dX <  >0  dY <  >0  slope  intercept  zdY ydZ zdX xdZ  ydX xdY zdX xdZ  =0  dY dX  ydX xdY zdX  <0  —ydZ zdX xdZ  ydX zdX xdZ  dZ <  >0  —  —  2  <  3  <>0  >0  <  >0  =0  -  4  =0  5  0  6  =0  7 8  *  <  >0  =0  <  <  -  —  distributed pattern infinite lines or randomly distributed  -  -  >0  <  >0  zdY ydZ -xdZ  dY dZ  0  <  >0  y/x  0  infinite lines through the origin  cc  a line// y/z axis  >0  0  -  {x/z  =  xdzo}  0  =0  0  =0  =0  undefined  {y/z  /z y } 0  undefined  a line II x/z axis a point  After Russell and Stanley, 1990  physical meaning of this example is that components x and y are highly correlated to each other (i.e. both of them may exist in the same mineral phase concerned and have very similar geochemical properties). When this mineral phase is removed from the current system, either depletion by crystal fractionation or by hydrothermal alteration, the contents of these components may change in the same proportion as their initial ratio. As a result, there is also a trend with a near zero intercept on the PER diagram. In addition, an 13  element ratio diagram that is not constructed with a set of conserved element in the denominator could be randomly distributed rather than having a well defined trend with a near zero intercept, as in cases 1, 3 and 4 according to Table 1-2. In summary, it is reasonable to infer some possible conserved or immobile components on the basis of understanding the behaviors of these components and the geological processes in which they are involved. Nevertheless, it is risky to accept such assumptions without objective tests. It is efficient and rational to demonstrate immobility in the available data set on the basis of the theorem that the ratios of conserved or immobile components remain constant. Moreover, a re-examination of all possible candidates for immobility is warranted to demonstrate that they are not mineralogically or geochemically compatible with each other during the hydrothermal alteration process. The concepts of mobile/immobile and compatible/incompatible are used frequently in the literature. These terms share many features in common, but it is necessary to clarify their specific implications in the context of hydrothermal alteration. The concepts of mobile/immobile are used to indicate whether or not a component has mass loss or gain during a hydrothermal alteration process. The terms incompatible and conserved have been used to describe certain elements not involved in a primary differentiation processes. Here the terms compatible/incompatible are used to describe whether or not the geochemical relationship among a particular group of components/elements are sufficiently correlated that they may have mass loss or gain in proportion to their initial ratio during a hydrothermal alteration process. Therefore, a pair of possible immobile components, determined from their constant ratio or highly correlated linear trend passing through the origin of the binary plot, also should be incompatible with each other. To emphasize the point, consider a pair of mobile components such as K and Rb which are also highly compatible with each other and which in a hydrothermal alteration system may display a highly correlated linear trend passing through the origin of the binary plot.  14  In reality, there is no perfectly constant ratio of a pair of immobile components. The reason for this is that apparent variability in ratios is a combination of geological variation, sampling and analytical error. Theoretically, the immobile component has not been involved in chemical transfer processes so the mass of the immobile component remains constant in a single precursor system. In reality, samples may not have been absolutely identical to each other before hydrothermal alteration in terms of immobile components, but if this inherent geological variation of a component is sufficiently small, this component can be treated as immobile. So immobility is a concept that depends on a high degree of homogeneity in the parent system prior to hydrothermal alteration. Analytical error is another major source of apparent variation of ratios of immobile constituents. Considering the influence of analytical error, Russell and Stanley (1 990a, 1990b) suggest that one could test for immobile/conserved components with a Pearce Element Ratio diagram accompanied by the propagated analytical error. If the dispersion or standard deviation of the ratio of two immobile or conserved candidates is less than or equal to the propagated analytical error, the dispersion can be interpreted to result entirely from analytical error. In such a case, the two candidates may be used as immobile or conserved components. This rule has been used in the study of basalt systems by Russell and Stanley (1989, 1990a, 1990b). The rule should be used cautiously. If the PER ratio is constructed with one of the components having a large geological variation and the other having poor analytical precision, then the latter component will contribute more to the final propagated error of the ratio, especially where it is used as the denominator of the ratio. As a result, mobility of the former component might be obscured and the plot might lead to the correct conclusion that both numerator and denominator are immobile. Therefore, ‘immobile’ components of relatively high analytical quality should be accepted in preference to those with poor analytical precision.  15  The second requirement for the removing of closure from lithogeochemical data can be met conventionally through the careful investigation of field and petrographic relationships in the study area. Rock derivatives altered to various degrees from a common homogeneous parent rock commonly are in close spatial proximity and may show gradational contacts between each other. Primary textural and structural features may remain identifiable in least-altered to more intensely altered derivatives. To examine these types of variations rigorously it is recommended that samples be collected systematically along alteration profiles from the strongly altered rock adjacent to or within a mineralized zone, to the least altered rock far from the ore deposit itself. Such sampling should be done after a careful field investigation of the profile. Even though the altered rocks are of main concern, careful attention should be paid to the least altered or unaltered rocks. They provide important information about the parent rocks that preceded hydrothermal alteration and give insight into the occurrence of single precursor or multiple precursor systems. For a multiple precursor system, the sequential relationships between different volcanic or intrusive events and their phase variations should be determined as clearly as possible. An efficient way of defining a single precursor system versus a multiple precursor system is to examine lithogeochemical plots, especially those constructed with immobile 3 (MacLean, 1990). A single precursor system will 0 2 components such as Zr, Ti and Al  present a trend that extends through the origin on the plot. The plot pattern for multiple precursor system will be more scattered but generally convergent toward the origin. If the numbers of least altered or unaltered samples collected and analyzed are sufficient, their plots may present a well defined trend either going through or cutting tangentially the region where the altered samples plot, as in the case of a sequence of volcanic precursors related through fractional crystallization from a common magma.  16  1. 4. Pearce Element Ratios (PER) and their Application to Hydrothermal Alteration  The PER approach to examining metasomatic systems has an advantage over other procedures in not only removing the closure effect of lithogeochemical data but also: (i) explaining the corrected chemical variations in terms of mineralogical variation(s), and (ii) testing for a multiprecursor system (Stanley and Madeisky, 1993). PER diagrams have been widely applied to the interpretation of igneous fractionation (Russell and Nicholls, 1987, Russell and Stanley, 1989, 1990a, 1990b). Commonly, igneous crystal fractionation can be interpreted by the addition or subtraction of one or a few minerals. Thus, a specific PER diagram can be designed to illustrate this crystal fractionation trend according to the known stoichiometries of the relevant mineral phases. For example, the compositional variations of a suite of samples which are subjected only to olivine fractionation must be related to the stoichiometry of olivine [(Fe, 4 SiO 2 Mg) ] , e.g., one mole Si gain or loss along with two moles of Fe and Mg; thus the appropriate combinations (e.g., axes coefficients) of numerator elements for the axes of PER diagram are SiI(conserved element) as x-axis and 0. 5(Fe+Mg)/(conserved element) as y-axis. Finally, the hypothesis of olivine fractionation can be tested according to whether the plots of data are consistent with the model trend that has a predesigned slope of one on the binary plot SiI(conserved element) versus O.5(Fe+Mg)/(conserved element). Recently, Madeisky and Stanley (1993) applied PER analysis to lithogeochemical data for altered rhyolites collected from the volcanic hosted massive sulfide (VHIvIS) deposit at Rio Tinto, Spain. Their work revealed that quartz, potassium-feldspar and plagioclase fractionation and crystal sorting contribute to geochemical variations of the unaltered rhyolite. The fractionation trend is clearly shown on a PER diagram constructed with Al/Zr as abscissa and (2Ca+Na+K)/Zr as ordinate. In addition, metasomatism (alkali depletion) disperses data on such a plot, toward the abscissa, away from the fractionation trend on the same PER diagram. Metasomatic additions and losses of elements have been 17  recognized up to 3 km from the centre of the mineralization system (Cerro Colorado open pit). Madeisky and Stanley (1993) also indicate that the rhyolite directly underlying the mineralization is a highly evolved melt and only the most evolved portions of this rhyolite are metasomatized, suggesting a genetic link between these highly evolved rhyolites and the associated VITIVIS mineralization. Recent advances in dealing with metasomatic system have not dealt quantitatively with mineral abundances of both parent and altered rocks. Nor have there been enough efforts to integrate mineralogical variations with chemical exchange in a quantitative way. A specific PER diagram can be used to test the hypotheses that chemical variations are due to variations of particular mineral(s), but the amount of these minerals have not been determined explicitly. The methodology of designing such a specific PER diagram for the purpose of testing an hypothesis is based on a simple matrix equation (Stanley and Russell, 1990; Stanley and Madeisky, 1993, 1994). CxA=P  (1-14)  where C is a phase composition matrix (with minerals down the side and elements across the top), A is an axes coefficient matrix (with elements down the side and axes across the top) and P is a phase displacement matrix (with minerals down the side and axes across the top). The phase composition matrix contains the formulas of minerals whose mass transfer effects are to be considered on the diagram. The axes coefficient matrix contains the coefficients for the linear combinations for each axis of the PER numerator. The phase displacement matrix depicts the displacement that mass transfer due to specific mineral losses or gains will have on each axis. A number of PER diagrams with known axes coefficients have been designed for specific petrological material transfer hypothesis (e.g., Russell and Stanley, 1990a; Stanley and Madeisky, 1994). They can be used to test real data sets for particular mineralogical variations as explanation of chemical variations. However, in attempting to design a 18  diagram, without knowing the PER numerator linear combination coefficients, a more difficult set of procedures must be followed. These rely on the fact that a number of constraints, both mineralogical and geometric on the PER diagram being designed, can be assigned. This information allows determination of the entries in the ‘phase displacement matrix’. Thus, with knowledge of the mineral formulae, the ‘axes coefficient matrix’ may be calculated using the approach of Stanley and Madeisky (1993). If C is a square and nonsingular matrix, the unique solution for A can be found by: A=C’xP  (1-15)  If C is a non-square matrix but CTxC is a non-singular matrix, the possible solution for A can be obtained through:  T xP T xC’xC A=(C  (1-16)  The following example is used to illustrate the procedure of designing a specific PER diagram, given a host rock of andesite in which feldspar and clinopyroxene are dominant. Propylitic, sericitic, argillic and silicic alterations and carbonatization are thought to be major causes of secondary lithogeochemical variations. Specifically, the replacement of primary feldspar (about 60%) by muscovite or kaolinite and quartz, and the replacement of primary mafic minerals (mainly augite and hornblende, about 5% and 3%, respectively) by epidote, chlorite and carbonates are the major contributors to lithogeochemical variations. Thus a composition matrix (C) could be composed of fourteen mineral phases (anorthite, albite, orthoclase, augite, hornblende, epidote, chamosite, clinochiore, calcite, siderite, magnesite, kaolinite, muscovite and quartz) and seven constituents (Si, Al, K, Na, Ca, Fe and Mg). This composition matrix C is then used as a simplified system to test the hypothesis. The displacement vectors of primary minerals such as anorthite, albite, K-feldspar and augite are defined to have slopes equal to one. The displacement vectors of alteration minerals are designed to have their slopes different from one, such as kaolinite and muscovite have slopes equal to 1/4 and 7/6, respectively, on this specific PER diagram. Then the x-axis and y-axis of this specific PER 19  diagram can be determined by using equations 1-15 and 1-16. The detailed procedure of this calculation is as follows.  0 2 2 0 1 0 0 0 3 1 0 0 0 1 3 1 1 0 0 0 0 2 0 0 1 0 0.5 0.5 Qtz 1 0 0 0 0 0 0 0 Kao22000 0 0 Mus 3 3 1 0 0 0 0 Ep 32020 1 An Ab Or Aug  x. xAL X  2 An 3 Ab 3 Or 2 2 Aug 1 0 Qtz 20.5Kao 3 35 Mus 3 4 Ep  YAK  YK  K  Ya  XNaYNa Xpe  YFe  XMgYMg  x  C  2 3  y  A  117 -  =P  Multiply the right side matrix (P) of equation 1-17 by the inverse matrix C to produce  X,  Ysz  XK  YAL YK  XCa  YCa  XNa  YNa  XAI  XFe  x Mg  6 YF .1Mg  A  =  0 0 0 1 0 —2 0 =  0 0 0 0 1 0 0  0.29 —0.36 0.36 0.14 —0.5 —0.43 —1  0 0 0 0 0 0 2  0.43 —0.29 —0.71 —0.29 —1 —0.14 —1  0.29 0.14 —0.14 —0.86 —1 0.57 0  xCT 4 (CTxC)  —0.29 0.36 0.64 —0.14 0.5 0.43 1  2 0 0 0 0 x 0 o”s 1 3 3:5 —1 x  P  =  =  1 0 0 0 0 0 0  0 0.25 2.75 1.5 (1-18) 2.75 0.5 0.5 x y  The results of this calculation show that this specific PER diagram has a SiI(immobile component) as its x-axis and [1/4A1+ 1 1/4(Na+K)+3/2Ca+ 1/2(Fe+Mg)j/(immobile component) as its y-axis. The physical implications of this PER diagram can be understood through the stoichiometries of relevant minerals. For example, the decrease or increase in molar units of augite can be decomposed into two vectors (i.e., a one mole decrease or increase of both Ca and Fe and/or Mg (along the y-axis) will cause a corresponding two mole decrease or increase of Si (along the x-axis) on this specific PER diagram because of . As a result, the plots of different samples Mg)Si ] 6 0 the stoichiometry of augite [Ca(Fe, 2 whose lithogeochemical variation is caused by the fractionation of augite only, will display  20  a trend with a slope of one on this particular PER diagram. The vector directions of other relevant mineral phases including hornblende, chlorite (chamosite and clinochlore) and carbonate (calcite, siderite, magnesite) then be projected on this PER diagram by using equation 1-14.  1 0 Fe—Cl 3 2 0 0 0 5 0 33 Mg—C13200005 0001000 Ca X_01.5 OOoOolOxX,,1_OOS Sd 00.5 0000001 Ma 7201022 Hb 00:5  -  ‘  C  x  A  =P  The expected mineralogical variation paths on this PER diagram are illustrated in Figure 1 for various hydrothermal products commonly associated with precious- and basemetal vein mineralization in volcanic sequences. A detailed description about this PER diagram is given as follows: (1) If all lithogeochemical variations are restricted by mineralogical variations of feldspar, augite and chlorite, then this set of lithogeochemical data will plot along a trend of slope equal to one and an intersection of zero. (2) Where quartz exists and has not been involved in mass change, the trend above will be shifted toward the right. (3) If the wall rock has suffered propylitic alteration (i.e. augite is replaced by chlorite, and primary feldspars are partially replaced by sericite through the addition of volatile components), the ‘loss’ of primary minerals can be pictured as moving 1 down along the trend of slope equal to one from the precursor composition (P) to a 2 and the ‘addition’ of alteration minerals can then be viewed as moving from P to a along the trend of slope equal to one (the replacement of primary mineral and  21  1.4-  1.6  1.8  +  ‘I  +  +  /  ,,  I  ,(  1  /  / /d /  1  +  / / / / ! / / / / / ,I //  .-  A  C  at  2  2 a  e  Si/TiO  Carb  error  -  -  Ab,O r,Chl  Ep  Kao Qtz  Alteration path  Legend  -  -  6  -  -  -  -  Figure 1-1. PER diagram specifically designed to discriminate primary fractionation and hydrothermal alteration types commonly associated with precious- and base-metal deposits in volcanic sequences. qtz. Qtz quartz, Carb carbonates, Kao kaolinite, An anorthite, Ab albite, Or, K-feldspar, Chi chlorite, Aug augite, Mus muscovite, Ep epidote. See texts for cetailed explanation.  0-  0.2-  0.4-  0.6-  0.8-  1-  ÷ 1.2-  c”1  +  3 c5  2  -  formations of alteration mineral happen in the meantime, but it is convenient to analyze a metasomatic process as two superimposed processes on this PER diagram). As a result, propylitically altered samples will plot roughly around their primary precursor’s position (P) on this diagram. (4) Where the wall rock has altered into a bleached alteration envelope around the epithermal precious- and base-metal vein, in general, all primary mafic minerals ). 1 and feldspar are completely replaced by alteration minerals (from P to b (5) If carbonates and pyritization are the dominante alteration products which  replace the primary minerals (i.e. intense carbonatization plus pyritization), samples will plot along a vertical trend shown on the left side of the primary fractionation trend of slope equal to one (from b to c). (6) If muscovite or sericite is the dominante alteration product (i.e. intense sericitization), samples will plot around a trend of slope equal to 7/6, which is close to the primary fractionation trend but slightly shifted toward the left (from b to d). (7) If kaolinite is the dominante alteration product (i.e. intense argillization), samples will plot toward a trend of slope equal to 1/4 (from b to e). (8) If quartz is the dominante alteration product (i.e. intense silicification), samples will plot around a trend parallel to x-axis (from b to f). In brief, some of the alteration types commonly associated with precious- and base-metal vein mineralization in volcanic sequences are expected to be discriminated in a preliminary fashion on the PER diagram of Figure 1 by the relative displacements of altered samples from the primary feldspar and augite fractionation trend (slope  =  1).  1. 6. Additional Problems Mineral assemblages commonly occurring in alteration envelopes or zones can be identified routinely with the aid of various conventional and advanced modern instruments. However, still lacking is an objective and efficient way to assess the 23  abundances of each alteration mineral with confidence. This arises because hydrothermally altered rock commonly is characterized by a very fine-grained nature and/or intimate intermixing of mineral species. The technique of point counting, useful for medium to coarse grained rocks (especially igneous and metamorphic rocks) is limited in applications to products of hydrothermal alteration. In addition, serious sampling problems commonly arise in using thin sections for quantitative modal analysis. The losses and gains of chemical components during the hydrothermal alteration process can be calculated with the aid of immobile components. This leads to an appreciation of possible reactions between primary minerals and altered minerals. However, the results of such calculations are not linked routinely in a quantitative way with the mineralogical changes that arise during hydrothermal alteration. To make such quantitative links immobile constituents must be identified and the precursor must be known; such needs are relatively difficult to provide in hydrothermally altered rocks that are products of open systems. PER diagrams are superior to other quantitative approaches for the evaluation of hydrothermal alteration by not only removing the closure of lithogeochemical data, but also by linking the lithogeochemical variations to the mineralogical variations. However, the PER diagram approach still has some limitations in a quantitative evaluation of hydrothermal alteration. As demonstrated above, the PER diagram can be used to test hypotheses that chemical variations are due to variations of particular mineral(s). But the amount of these minerals can not be determined explicitly when a complicated multivariable system is dealt with because the total displacement on a PER diagram commonly is the sum of the displacements of different minerals. The length and slope of a displacement vector on a PER diagram may be the combination of various displacement vectors (i.e., various types of alteration). Briefly, the ambiguity about the relationship between lithogeochemical variations and mineralogical variations may arise where too many variables are squeezed into a two dimensional space. It is one of the goals of this 24  thesis to develop the idea of linking the lithogeochemical variations to the mineralogical variations and overcoming this limitation of PER diagrams. The following study consists of two parts: (i) a theoretical documentation about a quantitative approach extended from the PER diagram to hydrothermal alteration systems; and (ii) a detailed, quantitative case history of the alteration system associated with the Silver Queen polymetallic epithermal vein deposit in central British Columbia.  25  Chapter 2.  Metasomatic Norms: A Method of Norm Calculation Adapted to Hydrothermal Altered Rocks  2.1. Introduction  Modeling a hydrothermal system quantitatively using either only mineralogical or only lithogeochemical data limits our knowledge of the system. We commonly limit our quantitative understanding of chemical losses and gains in a system if hydrothermal alteration minerals are the extent of our study. Conversely, if only chemical gains and losses are determined from lithogeochemical data (cf. Gresens, 1967) important mineralogical features are commonly minimized. Clearly, a procedure that takes account of both mineralogy and chemistry of altered rocks is desirable. lVlineralogy and chemistry of rocks are intimately linked through mineral abundances and the compositions of individual minerals. One way of combining mineralogical and lithogeochemical approaches to the study of altered rocks is to compute mineral abundances from the lithogeochemical data. It is easy to calculate an ideal mineral composition or norm. But it is not possible, in general, to calculate modal abundances without additional information because: (i) the minerals so-generated are idealized, or are end members of complex mineral families, and (ii) certain minerals or combinations of minerals are 2 SiO + Si0 2 Mg) chemically equivalent, for example, (Fe, 4  =  2(Fe, Mg)Si0 . However, 3  where sufficient mineralogical and chemical controls are available, the norm can be made to approximate closely or even coincide with a mode. A norm is a’  ...  theoretical mineral composition of a rock expressed in terms of  standard mineral molecules that have been determined by specific chemical analysis....’ (Margaret, et al., 1972). Norms are used to standardize rock description and classification and to provide insight into some aspects of genesis. The concept, applied widely to igneous rocks, has had limited application to other rock types. Applications to metasomatized rocks  26  are hindered by the wide range of chemical changes involved and the complexity of many mineral compositions and mineral assemblages. Various researchers have attempted to derive mineralogical information from lithogeochemical compositions for rocks other than igneous rocks. A particularly informative work by Brown and Skinner (1974) and Capitani and Brown (1987) use thermodynamic constraints and mass balance relations to calculate the weights of the minerals in the equilibrium mineral assemblages. Their results compare remarkably closely with modes. Davis and Ferry (1993) use mass balance relations to calculate the model protolith mineral abundances by assuming that a simple mineral assemblage (including calcite, dolomite/ankerite, quartz, albite, K-feldspar, muscovite and rutile (e.g., Rice, 1977; Ferry, 1985 a, 198 5b) suffers isochemical metamorphism. MacLean and Barrett (1993) recommend the Niggli-Barth cation normative calculation procedure (Barth, 1962) for metasomatic rocks for the purpose of approximating modes of altered rocks. The above techniques share the use of mass balance relations between bulk rock composition and mineral abundances. They differ in the method used to select a reasonable mineral assemblage with which to partition the lithogeochemical data. Brown and Skinner (1974) and Capitani and Brown (1987) determine the mineral assemblage based on whether or not the minerals are stable under specific thermodynamic circumstance. Barth (1962), Rice (1977), Ferry (1985a, 1985b), Davis and Ferry (1993), MacLean and Barrett (1993) and many others choose the mineral assemblage according to petrographic observation and/or their experience. An important difference between the ‘thermodynamic and ‘petrographic approaches, above, is in the interpretation of the residuals of constituents. Ideally, there should be a perfect match between the analyzed bulk rock composition and the corresponding estimated normative mineral abundances. In reality, such is not the case. Some norm calculations leave some chemical components unused (residuals), such residuals should be in the range of analytical error. In general, the smaller the residuals are, the better is the quality of mass balance. Brown and Skinner (1974), Capitani and Brown (1987) and 27  Davis and Ferry (1993) explain residuals as the mass losses or gains of corresponding constituents. The assumption of a stable equilibrium relation in a hydrothermal system is often questionable, whereas petrographic examination can provide the actual mineral assemblage. Normative approaches originally designed principally for igneous rocks are rigid in their application, and in general, do not accomodate important alteration minerals. In particular, volatile components are essential constituents of many metasomatic rocks but are not involved directly in determining normative minerals either by the CIPW norm or Niggli-Barth norm procedures. A different approach to the determination of norms of hydrothermally altered rocks by combining petrographic and lithogeochemical data warrants investigation.  2.2. The Principle of Metasomatic Norms  A possible approach to the application of the norm concept to metasomatic rocks is to constrain the calculated normative mineralogy by a priori knowledge of existing minerals (i.e., to approximate the mode as closely as possible). The methodology for this approach is a natural extension of the use ofPER (Pearce element ratio) diagrams for the study of metasomatic rocks (e.g., Stanley and Madeisky, 1993, 1994). Metasomatic norm calculation uses the same principles as the calculation of CIPW norms (e.g., Cross et al., 1903; Cox et al., 1979; Hughes, 1982; Philpotts, 1990). However, a wide range of possible mineral products is necessary for the determination of metasomatic norms that represent hydrothermal alteration systems. Moreover, the calculation of a metasomatic norm needs to take volatile components into account. Another distinctive difference between a metasomatic and a conventional igneous norm is that the calculation of a metasomatic norm can not proceed along as fixed a hierarchical path as is the case of an igneous norm. More flexibility is necessary because of the wide range in both rock and mineral compositions. In some cases, where constrained by known 28  mineralogy, the calculations must iterate back and forth using various abundance of normative minerals in order to eventually balance or best fit a calculated mineral assemblage with the fixed chemical composition of an altered rock (i.e., to make the chemical masses and the mineral masses balance). In addition, the calculation of a metasomatic norm must take into account possible incompatible mineral pairs in hydrothermal system, for example, kaolinite and feldspar are not stable in the presence of quartz. The mathematical relationship between lithogeochemical data and metasomatic norms is discussed by Cheng and Sinclair (1994) as follows: a rock mass, P, is comprised of the masses of a set of minerals (mj): (2-1)  For practical purposes, this equation can be extended in terms of the measurable items (in weight units) as follows: Px  =  i=1  for i= 1, 2,  ...,  q; and j1, 2,  ...,  1=1 j=1  (m x f,))  (2-2)  p.  where -q is the number of components analyzed; -p is the number of involved mineral phases; -wi is the weight fraction of component i of the rock sample (Zwi  1);  -mj is the weight percent of mineralj of the rock sample in grams;  -fij is the weight fraction of component i in mineral phase j; The relation between the weight fraction of component i in mineral phase j and corresponding molar amounts can be expressed as follows:  29  (2-3) for i  =  1, 2,  ...,  q, andj  =  1, 2,  ...,  p, where nij is the number of moles of component un  mineral phase j, a is the molar weight of component i, and bJ is the molar weight of mineral phasej. The reference weight P can be assigned any value, for example, 100 grams, and equation 2-2 can be converted into molar units as follows: ) x n) 1 a ((m/b /= (w ) 100 x 1  (2-4)  1=1 j=i  1=1  In equation 2-4 the weight fraction of each chemical constituent of the rock (Wi) is measurable through whole rock chemical analysis; a and b hold the constant molar weights for each chemical constituent i and each mineral phase j; f 1 and nij are either measurable through an analysis of mineral separates or referenced from the standard stoichiometry of corresponding minerals; mj, the remaining unknowns, are to be determined. Since 1/2a and 1/b can be converted into a diagonal matrix [l/aijlpxq and [l/b]pxq (for  ij, 1/aij 0 and 1/bij 0), the relationship can also be expressed in matrix form as: =  =  . 1/a . 1  0..  0  o :::: o o : o  flu  ...  fllj  ...  flip  flqi...flqj...flqp  11 1/b  }*;q  •.  0  •.  0  o :::: o o::o::i  rni (2-5) ,,  or AxW=NxBxM  (2-6)  30  1 = 0), W where A [l/ajjlpxq (for ij, lIa  =  [wjlq, B  =  [l/bijlpxq (for ij, 1/b = 0), N = [njjlpxq  and M = [m]. Generally, there is a larger number of unknowns than equations in the linear set of equations 2-5 or 2-6. The values q and p are related to the number of analytical items and the number of mineral phases considered, respectively. Usually, the composition of a rock sample is composed of only about a dozen major and minor components (q). In contrast, the mineral phases considered may be over twenty or more (p). Therefore, in general, matrix N is not square. Consequently, this set of linear equations cannot be solved s 3 explicitly. Some constraints are needed to reduce the number of independent variable m through either: (i) thermodynamic calculations (e.g., Brown and Skinner, 1974) to decide what are the stable mineral assemblages, or (ii) observation of the assemblage comprising the rock in question. It is essential that p is equal to or less than q in order that a unique solution is possible. In some cases the matrix might be singular or overdetermined. These problems may be caused by analytical errors and/or discrepancies between the compositions of real mineral phases of the rock sample and standard normative mineral phases used in matrix N. Thus, such set of linear equations needs to be solved using a fitting procedure, such as 2 (e.g. Wright and Doherty, 1970; Stout and Nicholls, minimizing the sum of squares, R 1977). The principle of the technique is to search for the solution which produces the least 2 (sum of squares of residual) is given by: , where R (R ) 2 value 2 R 2 =>(w/a->(m R  x))2  (2-7)  The least squares technique can provide either the best fit solution or the best fit approximations. In brief, the calculation of metasomatic norms as introduced here rests on the suppositions that lithogeo chemical data are of adequate quality, and that the principal  31  alteration minerals have been identified. Norms determined in the foregoing manner are objective and quantitative. They are representative of the processes being modeled and can closely approximate modes of the altered rocks under study if appropriate constraints are available.  2.3. A Set of Standard Normative Mineral Components for a Metasomatic System The metasomatic process of wall rock alteration, in most cases, can be described 0, C0 2 as the additions of volatile components (H , S, etc.) and ionic components (K, Si, 2 etc.) from hydrothermal fluid to wall rock and a corresponding depletion of some ionic components of the wallrock (Na, Ca, Mg etc., extracted from the wall rock and contributed to hydrothermal fluid). This process of chemical exchange can also be described partly in terms of mineral transformations. For example, anhydrous silicates such as olivine, pyroxene and feldspars, alter to (i) phyllosilicates such as chlorite, muscovite, kaolinite, chlorite, (ii) carbonates such as calcite, magnesite, siderite, rhodochrosite, dolomite, ankerite, etc., and, (iii) sulfides such as pyrite. Volatile components clearly are an essential part of a hydrothermal alteration system and cannot be omitted as in the case of C]PW normative calculations. The selection of a set of standard minerals for metasomatic norm calculation should be based on geological observations. Rock-forming minerals which account for most of the chemical components clearly have priority. In most cases for hydrothermally altered rock systems the major components are composed of: Si0 , Al 2 , Fe 3 0 2 , FeO, 3 0 2 MgO, CaO, Na 0, K 2 0, H 2 0 and CO 2 . The standard minerals for metasomatic norms 2 must include hydrous phases, carbonates and sulfides as well as anhydrous minerals. Ivlinerals found to be appropriate for metasomatic systems can be classed into nine categories: (1) anhydrous cafemic silicates such as olivine and pyroxene (Fe, Mg, Ca-silicates); (2) anhydrous calc-alkali aluminous silicate such as K-feldspar, albite and anorthite; 32  (3) hydrous caic-ferric aluminous silicate such as epidote; (4) hydrous mafic aluminous silicate such as chlorite; (5) hydrous alkaline aluminous silicate such as muscovite;  (6) hydrous aluminous silicate such as kaolinite; (7) carbonate such as calcite, magnesite, siderite; (8) sulfide such as pyrite; and (9) oxides such as quartz, magnetite and hematite. 5 (apatite), Ti0 0 2 2 The minor components contained in accessory minerals such as P (ilmenite or rutile), are less important to make the masses balance. The abundances of such accessory minerals generally do not exceed a few weight percent; however, in certain cases these normally minor minerals or trace minerals can be relatively abundant and can have strong impact on the norm calculation. For example, S can be dealt with as a minor component in most cases, but if a sample has more than a few weight percent of pyrite then S becomes an important component. A set of standard normative minerals based on the autho?s experience in treating metasomatism associated with precious- and base-metal deposits in volcanic sequences is listed in Table 2-1. This list is not exhaustive. It can be extended by the addition of new standard normative mineral(s) or substituted by other identified mineral species in order to meet specific requirements.  2.4. A Manual Procedure of Metasomatic Norm Calculation Practically, the calculation of metasomatic norms is completed using a computer, but it is essential to understand the conceptual nature of the calculations. A manual procedure has been developed patterned after the CIPW procedure. These calculations must balance the available components (analytical data for an altered rock) with the amounts of a particular group of minerals of known or assumed compositions. By using alteration minerals presented in the altered rock as members of the starting group of 33  Table 2-1. A List of standard normative mineral components for metasomatic volcanic rocks associated with epithermal ore deposits Normative mineral Fayalite Forsterite Ferrosilite Enstatite Wollastonite Rhodonite Orthoclase Albite Anorthite Epidote Chamosite Clinochlore Muscovite Paragonite Kaolinite Quartz Calcite Magnesite Siderite Rhodochrosite Pyrite Ilmenite Rutile Hematite Magnetite Apatite  Symbol  Formula  Fa Fo Fs En Wo Rn Or Ab An Ep Fe-Cl Mg-Cl Mu Pa Ka Qz Ca Ma Sd Rc Py Tm Ru He Mt Ap  SiO 2 Fe 4 4 S 2 Mg iO FeSiO3 3 MgSiO 3 CaSiO 3 MnSiO 8 O 3 KA1Si Og 3 NaAlSi Si CaA1 8 O 2 i 2 FeAl Ca S 2 1 O 3 (OH) 1 i 0 A 5 Fe S 2 1 O 3 (OH)g l i 0 A 5 Mg S 2 1 O 3 (OH)g i 0 S KA1 1 O 3 2 (OH) i 0 S NaA1 1 O 3 2 (OH) 4 Si (OH) A1 5 O 2 2 Si0 3 CaCO 3 MgCO 3 FeCO 3 MnCO 2 FeS 3 TiFeO 2 TiO 3 0 2 Fe 4 0 3 Fe ( 5 Ca ( 3 ) 4 OH) P0  Molecular weight 203.79 140.71 131.94 100.4 116.17 131.03 278.34 262.24 278.22 483.24 713.48 555.78 398.3 382.2 258.14 60.09 100.09 84.32 115.86 114.95 119.97 151.75 79.9 159.7 231.55 502.21  standard minerals, a metasomatic norm is expected to approximate the mode of the hydrothermally altered rock. The extent to which this end can be achieved depends on how close the true mineralogy is reflected in the norm and whether appropriate mineral compositions have been used in the calculations. In principle, the calculation scheme is designed to allot cations to various normative minerals and to add in as many anions as required. Hence, the difference in value between calculated cations and the corresponding analyzed cations is generally equal to zero. To illustrate the procedure of metasomatic norm calculation, equation 2-3 or 2-4 is expanded by using the standard normative minerals listed in Table 3-1 and a set of equations results as follows. wax3 map/bap  (2-8a)  w= a x2m,/b 5  (2-8b) 34  (2-9a)  WTj WMil  (2-9b)  ax(mm/b+mrc/brc)  WNa= aNax(maIjbabt  (2-9c)  mpa “bpa)  (2-9d)  WK= aKx(mo/bor+ mmu/bmu) mMgcl/bMgcl+ 5 mfo/bfo+ men/ben+ 2 WMg= aMgx(  mma/bmj  mep/bep+ mca/bca+ 2 mapfbap) 5 acax(mwo/bwo+ mjb+  WCa=  WFe+3  mma/bmj 2 x(mep/bep+ m hjbhe+ aFe+3 3  WFe+2  mFeC/bFeC1 5 mfa/bfa+ e’bfe+ 2 aFe+2x( +mSd/’bSd+  /b m/b) 3 m ,+ 13  (2-9e) (2-9f)  (2-9g)  (2-9h)  aflfb+ aMx(mO/bor+ m m mabfbab+ m 2 Fec1/bFec1 ep/bep+  1 w  mkaka) 2 mMgcl/bMgcl+ 2 + m 3 mu/bmu+ aThpa+  (2-1 Oa)  asix(mf.a/bfa+mf.o/bfo+mfe/bfe+mefl/befl+mwo/bwo +n+3mo/bof+3mab/bab+2mafl/bafl+3mep/bl, +3 3 .pa/bpa mMgc1/bMgcI+ mFec1/bFe.C1+ m m fl.u/bmu+  mkabka+mdb) 2 + 03 w =  x(m/b+m.a/bma+mJbsd+ml.Jbfc) 3 aco  (2-lOb) (2-11 a)  flIrcFeC1/bFe1 8 mMgcl/bMgcl + 8 WOH aoHY(meJbl,+  +2m/b+2mp/b+4Imjbka+map/bap) WTO1  =  Wet.j1s  (2-i ib) (2-lie)  where w represents the weight percent of the certain constituent indicated by subscript, a represents the molar weight value of the constituent denoted by subscript, m is the weight fraction of the mineral indicated by subscript, and b is the molar weight value of the mineral indicated by subscript. A general procedure to be followed in determining a metasomatic norm has been developed patterned after the procedure used in igneous norm calculation. Significant changes arise in the “metasomatic procedure mainly due to the necessity of accounting for volatile components. A detailed procedure for establishing a metasomatic norm follows. 35  1. Recast the oxide weight percentage values to cation amounts, obtained by dividing the weights percent of oxides by their respective molecular weight, multiplying by the , then 3 0 2 number of cations in the oxide formula. For example, if a sample has 12 wt% AJ  3 A1  =  (12.00x2)/(26.98x2+16x3)  =  0.2354  P0 A unique solution exists 4 ( 5 [Ca ( 3 OH)]. 2. Use all P (and necessary Ca) to make apatite ) for equation 2-8a because apatite is the only mineral in the set of standard normative minerals containing P. . There is a unique solution for (FeS ) 3. Use all S (and necessary Fe) to make pyrite 2 equation 2-8b because pyrite is the only sulfide considered in the current set of standard normative minerals. ) and temporarily 3 4. Use all Ti (and necessary Fe) to make provisional ilmenite (FeTiO assign the value  Of mrjtjle  equal zero (equation 2-9a).  ) and assign the value of mrhodocosjte 3 5. Use all Mn to make provisional rhodonite (MnSiO equal zero temporarily (equation 2-9b). ) and let the value 8 O 3 6. Use all Na to make provisional albite (NaA1S1  Of 1 pagomte  equal  zero temporarily (equation 2-9c). ) and the value of 8 O 3 7. All K is provisionally allotted to K-feldspar (KAISi  is set  to zero temporarily (equation 2-9d). 8. There are 3 independent variables in equation 2-9e. Use all Mg to make provisional , and leave the values of other Mg-bearing (MgSiO ) Mg-end member pyroxene, enstatite 3 minerals as zero temporarily. 9. There are five mineral phases in equation 2-9f the value of m  tite  has been calculated  previously with equation 2-8a. If the composition of plagioclase is known (i.e., the ratio of Ca:Na in plagioclase can be set) then an appropriate amount of Ca can be allotted Si by assigning all Na to albite. In other words, 2 (CaA1 ) 8 provisionally to anorthite O is dependent on malbite. Finally, use the remaining Ca to make provisional Ca end member of pyroxene, wollastonite (CaSiO ) and set the values of mepjdote and mcalcjte 3 36  to zero. 10. There are three mineral variables in equation 2-9g; the value of mepjdote has been set provisionally in equation 2-9f above. Use all Fe 3 and corresponding amount of ferrous FeO) and leave the values of mhematjteto be 3 O 2 iron to make provisional magnetite (Fe zero temporally. 11. The values of m.te and  mmagnetjte have  been determined by previous equations so there  2 to make provisional are four items unknown in equation 2-9h. Use the remaining Fe Fe-end member of pyroxene, ferrosilite (FeSiO ) and leave the values of the remaining 3 ferrous iron bearing minerals in equation 2-9h at zero. 12. Even though equation 2-lOa has 9 items, all of them but mkaolte have been determined by previous equations. As a result, the remaining excess Al is used to make provisional kaoliriite 4 S [A1 ( 5 O 2 ] OH) . i However, the rock may already have a deficit of A1 3 at this stage. In this eventuality the variable mkao1te in equation 2-1 Oa disappears and equation 2-lOa becomes a constraint for the previous equations. To eliminate a deficit of At 3 the 3 are used to substitute for independent variables of certain minerals containing less A1 some or all of the provisional minerals in previous equations. 13. All of the items but mqu in equation 2-lOb have been determined by previous ). Of 2 equations. As a result, any excess Si is used to make provisional quartz (5i0 course, Si 4 may already be in deficit at this step, in which case equation 2-lOb becomes a constraint for the previous equations. This deficiency can be accounted for by using as 4 relative to the provisional independent variables, certain minerals containing less Si minerals estimated in previous equations. For example, convert pyroxene Si to provisional olivine 4 [(Fe,Mg) ] 6 O 2 SiO to the extent necessary to rectify 2 [(Fe,Mg) ] the deficiency. 14. All items in equation 2-1 la have been determined by previous equations. Therefore, it is a constraint equation. If the sum of the provisional values on the right side of the equation is not equal to the measured value on the left side, adjustments are required to 37  make the mass of CO; 2 balance. Usually, the value on the left side is greater than that on right side of the equation at this step because the provisional allotments set the values of all carbonates to be zero. Therefore, more carbonate(s) should be allotted to balance the equation. 15. There are no unknown items in equation 2-1 lb. As a result, it is another constraint equation. If the sum of the provisional values on the right side of the equation is not equal to the measured value on the left side, adjustments are required to balance the equation. If the measured value on the left side is greater than that on the right side of the equation, the independent variables of minerals containing more hydroxyls are required and provisional amounts of anhydrous mineral must be reduced. Conversely, in other cases it may be necessary to reduce the amounts of hydroxyl-bearing minerals. 16. Equation 2-11 c is a general constraint related to the mass balance of 02. If the two sides of this equation are not balanced, the preceding allotments of standard mineral abundances are somewhere in error. To this point in the calculation, there are two equations with unique solutions (2-8a and 2-8b), eight equations having 14 independent variables in total (2-9a, 2-9b, 2-9c, 2-9d, 2-9e, 2-9f, 2-9g, 2-9h), two equations having single dependent variable (2-lOa and 2-lob), and three constraint equations (2-11 a, 2-1 lb and 2-11 c). There are more unknowns than available equations so far. More constraints are needed to achieve a satisfactory solution. 17. The first simplification for the calculation of a metasomatic norm is that olivine is not compatible with quartz. In other words, the following reactions move to the right until one of the components on the left side of the reactions is used up. SiO + Si0 2 Fe 4 2 Fa  2 SiO + Si0 2 Mg 4 Fo  3 2FeSiO  Qz  Qz  Fs  =  3 2MgSiO En  (2-l2a) (2-12b)  18. The second simplification is that kaolinite is not compatible with feldspar and  38  pyroxene under the condition that quartz exists. In other words, the following equilibria proceed to the right until either kaolinite or anhydrous silicates on the left side of the reactions are used up. 3 Si + Fe 2 2CaA1 8 4 + 2CaSiO 0 3 8 +O O 3 i + KA1Si 4 S A1 ( 5 O 2 OH) Mt An Or Ka Wo =  3 i + FeSiO 2 Si0 + 3 (OH) F 2Ca S 2 1 O eA1 i2 0 (OH) S KA1 1 O 3 + 2 Ep Mu Fs Qz  3 Si + Fe 2 2CaA1 8 4 + 2CaSiO 0 3 8 +O O 3 i + NaA1Si 4 S A1 ( 5 O 2 OH) Mt An Ka Ab Wo =  (2-1 2c)  (2-12d)  3 eAl i + FeSiO 2 2+3 (OH) F 2Ca S 2 1 O i Si0 0 (OH) S NaA1 1 O 3 + 2 Pa Fs Ep Qz  1 i Si 4/9CaA1 FeSiO 1/9Fe OH) S M ( 5 + + S + 8 O 2 + 4 0 3 Or Ka Mt Fs An  (2-1 2e)  i 3 Si =KA1 02 3 2 0 eAI 23/9SiO 2/9Ca + 10 F S M 5 (OH)+2/9Fe 1 O 3 + 8 (OH) Qz Fe- Cl Ep Mu i 0H) NaMSi FeSi0 h/9Fe 4/9M S ( 5 2 + + 8 22 + 4 0 3 Fs An Mt Ka Ab  (2-1 2f)  i 1 =NaA1 2 3 2 0 eA1 23/9SiO 2/9Ca 0 Si + F A 5 (OH)+2/9Fe S 1 O 3 + 8 (OH) Fe-Cl Ep Qz Pa 3 i MgSiO 4/9CaA1 1/9Fe KISi OH) M ( 5 + + 3 S + 8 O 2 + 4 0 Ka  An  Or  En  Mt  (2-1 2g)  32 =KA1 i 1 2 0 eAI 23/9SiO 2/9Ca 0 Si + F A 5 (OH)+2/9Mg S 1 O 3 + 8 (OH) Mu  Mg-Cl  Ep  Qz  + MgSiO 4 O 3 3 i 1/9Fe 4/9CaAl NaAlSi OH) A1 ( 5 + 4 + 3 S 2 + 8 O Ka  Ab  An  En  Mt  (2-1 2h)  i Si0 1 3 (OH) =NaA1 2 0 2 2/9Ca 23/9 eA1 0 Si + F A 5 (OH)+2/9Mg S 2 1 O 3 + 8 Pa  Ep  Mg-Cl  Qz  This simplification is supported by geological observation and thermodynamic relations. For example, according to the copper porphyry model, a phyllic or sericitic zone separates a potassic alteration zone from an argiffic alteration zone. On log (JQ/Hj versus 4 SiO activity-activity diagram, the stable region of K-feldspar is log(H )  39  separated from that of kaolinite by muscovite in the presence of quartz. 19. Some additional practical constraints can be set on a normative calculation. For example, the composition of plagioclase (k) is easily measured, thus, the relation between anorthite and albite can be expressed as follows: k  =  malbite /(mote+ma1bjte)  (2-13)  A similar relationship can be applied to the end members of other solid solution minerals. As a result, more constraints can be established. In addition, a set of constraints can be established limiting the values of calculated norms as never less than zero. In summary, there are 14 independent variables after initial allotments, three constraints related to the mass balance equations of OH-, C 0;2 and total, and eight constraints derived from two simplifications. In most cases, the bulk chemical composition of the rock studied can be explained by about a dozen minerals within this set of standard normative minerals. The final result is that a particular sample represents a system that is simpler than that initially assumed. In other words, a realistic system generally has substantially less than 14 independent variables. Therefore, a satisfactory solution can commonly be achieved by using the above approach. A complex system, such as a weakly altered rock in which significant amount of primary minerals coexist with secondary alteration minerals, may have even more independent variables. Therefore, additional constraints are needed. Modern analytical techniques can provide the required knowledge-based constraints. The general procedural scheme for metasomatic norm calculation has been introduced. The procedure, however, is grossly inefficient for manual calculation. Consequently, a computer-based procedure using Quattro Pro 5.0, a sophisticated and readily available spread sheet program, has been devised to process norm calculations. It can be easily converted to other spread sheet software (Appendix C). The procedure involves the use of a built-in module (the ‘Optimizer’) in the software. The general 40  0 W procedures of using Optimizer is to (i) decide the solution destination such as W -  mineral  =  0, (ii) choose the variables (standard minerals) to be included in the calculation, and  (iii) set up the constraints indicated at the end of the forgoing section. Then the Optimizer module can adjust the amounts of the variables and adhere to the constraints to provide a final best fit solution. Unlike other ‘black box’ types of software, this calculation model is transparent. Users can easily adjust and develop it according to their own purposes.  2.5. A Quantitative Model of Metasomatic Systems The central goal of this work is to develop the concept of metasomatic norms and to apply the technique. One important outcome is the likelihood that with appropriate petrographic constraints the norm and mode can be made to coincide. With the recognition of an immobile component and a set of lithogeochemical compositions that includes both least altered parent rock (Zr) and altered daughter rock (Zd), the metasomatic norms and chemical constituents of an altered rock (xd) can be fhrther recast into the absolute amounts of minerals and chemical constituents (x+dx) for a given mass of parent rock (xe) by using the following equation to remove the closure effect (e.g., Merrill, 1897; Gresens, 1967; Pearce, 1968; Grant, 1986; MacLean and Kranidioties, 1987; MacLean and Barrett, 1993; Cheng and Sinclair, 1991): z  (2-14)  XP+dXEXd  Consequently, the contribution of each mineral to the chemical variations of bulk rock, the absolute loss or gain of individual chemical constituents during hydrothermal alteration process can be stated explicitly as follows: Mineralent rock =  +  Constituent gained from solution  Minerala1tered rock +  Constituent  lost from wall rock  (2-15)  41  where all items have extensive units (e.g. grams). Such an equation is comprehensive, quantitative, and provides an easily understood chemico-mineralogical model; it illustrates and interprets a hydrothermal alteration system in terms of initial and final normative mineral assemblages (corrected for the closure) plus absolute losses and gains of chemical constituents. The model can be applied without the constraints of closed system and equilibrium assemblages. The value of such a model is that it provides useful, quantitative information about the hydrothermal system. If the altered rock is the product of a simple and unique hydrothermal alteration process, the model may reveal the properties ofhydrothermal solutions associated with metasomatic events. In reality, the reaction used may more likely represent the final result of a series of sequential and/or superimposed processes. That is, the model incorporated in the equation is an ‘end member’ model. Specifically, the model includes starting and ending rock mineralogies that may be evident in the field, as well as documenting gains and losses of specific chemical constituents. This model is quantitative in the same way as Pearce element ratio diagrams. The common principle is the correction for closure that provides true relative lithogeochemical and mineralogical variations between parent and daughter rocks. The normative approach is a useful supplement to PER analysis; the two procedures have much in common and contain much the same information presented in different ways. The sequence of developing a PER diagram is to: (1) remove the closure effect of lithogeochemical data to calculate the absolute chemical changes of elements by using an conserved or immobile element, and (2) interpret these absolute chemical variations in terms of specific mineral or mineral assemblage on a binary plot. In contrast, the technique of metasomatic norm is to: (1) allot the chemical analytical data of bulk rock into an assemblage of normative minerals (that in certain cases will approximate the mode), and 42  (2) remove the closure effect of the norms and use the difference between norms (modes) of parent and metasomatized rocks and elemental losses and gains to develop a combined chemico-mineralogical model of the metasomatic process. The strategy of a PER diagram is to test whether chemical changes between two rocks can be explained purely by changes in amounts of one or a few minerals as demonstrated by the distribution of points along predefined trends (slopes). Metasomatic norms are displayed more explicitly as equations (models) or profiles showing the spatial distributions of normative mineral assemblage as well as the absolute losses and gains of chemical constituents based on the comprehensive mass balance relationships.  2.6. Case Histories: Application of Metasomatic Norms 2.6.1. Sigma Mine, Abitibi, Quebec Mesothermal gold-quartz veins of the Sigma mine are enveloped by well defined, if narrow, walirock alteration zones (Robert and Brown, 1984, 1986). An outer cryptic alteration zone is succeeded by a visible alteration zone immediately adjacent to the vein. The semiquantitative mineral variations across the alteration envelope are illustrated in Figure 2-1. Unaltered rocks are composed of a greenschist mineral assemblage: albite chiorite-epidote-white mica-biotite-quartz with minor carbonate and accessory apatite, ilmenite, and pyrite. The cryptic alteration is characterized by the variable replacement of epidote by carbonate; the zone of visible alteration is marked by an abrupt outer transition (2-3 mm wide) parallel to vein margins, a carbonate-white mica outer subzone and a carbonate-albite inner subzone immediately adjacent to the vein. The salient mineralogical feature of visible alteration is the complete destruction of chlorite and biotite originally present in the parent volcanic rocks. A reassessment of the overall process of hydrothermal alteration at Sigma mine can be made by applying the technique of metasomatic norms using the lithogeochemical data presented in Table 2-2. The results of such a calculation (Table 2-3 and Figure 2-2) 43  wt%) in the profile Variations in major element oxide concentration (in Table 2-2. mine, Quebec 2103 across alteration envelope around tension veins, Sigma 2103-13a 2103-13b 2103-13c 2103-13d 2103-13e 2103-14 Sample_id cb-ab cb-ab cb-ab cb-mi ch-cb-mi u Alteration 33.79 40.75 49.59 50.04 59.19 61.28 Si02 9.22 10.52 13.04 11.73 16.33 15.66 A1203 1.62 1.27 1.33 2.23 0.7 0.66 Ti02 12.8 8.63 2.89 1.96 5.16 5.39 FeO 0.17 0.17 0.18 0.27 0.12 0.14 MnO 0.59 0.62 0.63 0.66 2.56 2.65 MgO 14.1 14.52 13.42 14.76 4.65 5.03 CaO 4.6 5.38 7.35 6.56 4.12 4.34 Na20 0.03 0.02 0.03 0.02 1.57 0.67 K20 0.78 0.65 0.49 0.54 0.23 0.23 P205 0 0 0 0.13 2.05 1.98 H20 10.63 10.76 9.67 10.43 2.94 2.1 C02 10.31 6.2 1.81 0.8 0.86 0.12 S 98.64 99.49 100.43 100.13 100.48 100.25 Total 2.98 2.84 2.74 2.71 2.74 2.74 Density -  Profile 2103 is in feldspar porphyry. arbonate-chlorite-white mica, Alteration facies: U=unaltered rock, CH-CB-MI=c bite CB-MI = carbonate-white mica, CB-AB=carbonate-al not detected Data source: Robert & Brown 1986. nd  =  profile The calculation results of metasomatic norms (in wt%) in the Table 2-3. c mine, Quebe Sigma veins, tension pe around envelo on 2103 across alterati 2103-13a 3b 2103-1 3c 2103-1 3d 2103-1 3e 2103-1 2103-14 Sample_id cb-ab cb-ab cb-ab eb-mi ch-cb-mi u Alteration 21.749 22.769 21.690 23.118 0.133 0.000 Calcite -0.000 -0.000 -0.000 0.000 18.323 20.367 Epidote 0.000 0.000 0.249 2.270 0.041 0.000 Ca.pyx* 4.401 4.497 2.489 0.000 0.000 0.000 Anorthite 1.078 0.000 0.000 -0.000 5.355 3.543 Mg-carb 0.008 0.000 0.000 0.300 0.000 2.637 Mg-chl 0.178 1.544 1.569 1.373 0.000 0.000 Mg-pyx 0.956 1.621 0.000 -0.000 1.611 0.730 Siderite 0.007 0.000 0.000 -0.000 0.939 3.524 Fe-chl 0.000 0.738 1.583 0.000 0.000 0.000 Fe-pyx 0.003 0.000 0.000 0.169 13.279 5.667 Muscovite 0.175 0.118 0.177 0.000 0.000 0.000 K-feldspar 0.003 0.000 0.016 2.775 1.254 3.973 Na-mica 38.924 45.526 62.185 53.607 34.003 33.999 Albite 1.375 0.582 0.000 2.246 0.000 0.000 Ilmenite 0.896 0.963 1.330 1.047 0.700 0.660 Rutile 0.009 0.000 0.000 0.198 0.300 -0.000 Kaolinite 4.901 6.175 3.856 9.618 21.980 24.126 Quartz 0.275 0.275 0.292 0.438 0.194 0.227 Mn-carb 1.840 1.533 1.156 1.274 0.543 0.543 Apatite 19.290 11.600 3.387 1.497 1.609 0.225 Pyrite 0.000 0.000 0.000 0.000 0.000 0.000 Hemtite 96.067 97.943 99.978 99.930 100.265 100.220 total *  pyx pyroxene; carb carbonate; chl chlorite. -  -  -  44  ()1  -  D  D <  o CD  0  CD  C CD  CDb  CD  SD  CD  C  C)) 00  CD  C  CD  0 C  -t  CD  .  -CD CD  0  CD  oo  cL.CD  -t  -t  CD  CD  CD  CD  -I  CD  0  wt%  CD  II  CD  CD  -  o  CD  (  C  -i  0  0  II  o  CDt  0  1  t  o-t  .  0  II  CD CD CD  II  C  I.  vol.%  agree qualitatively with the results reported by Robert and Brown (Figure 2-1), but a few quantitative differences arise. One is that the norm profile shows no significant difference between unaltered rock and cryptic alteration zone in contrast to the claim that rocks in the cryptic zone have a marked decrease in epidote (from about 10 % to zero) and carbonate increase (from 1 % to more than 10 %) relative to unaltered rock (Robert and Brown, 1984). Moreover, in all three alteration profiles for which chemical data are published by Robert and Brown (1986) it is clear that the CO 2 content of the cryptic zone is indistinguishable from the CO 2 content of unaltered rock (the contents of CO 2 in unaltered samples versus cryptic altered samples in profile 2103-10, profile 2103-13 and profile 2209-01 are 2.61 versus 2.74, 1.98 versus 2.05 and 0.89 versus 1.08, respectively); this is true for any reasonable level of analytical error. The second obvious difference between the profiles of published modes and the normative calculations reported here is the existence of abundant pyrite in an inner subzone of visible alteration zone. Even though Robert and Brown (1984) describe the existence of pyrite, they did not estimate its abundance. Up to 10.6 % of S has been measured, equivalent to about 10 wt.% pyrite or other sulfides. The third difference between the profile of norms and generalized modes is in the estimation of albite abundance. The reported modes indicate no change in the abundance of albite between the unaltered rock and the cryptic alteration zone (about 50 volume % in both) and an obvious increase in the amount of albite in the visible alteration zone (up to 55  %). In contrast, metasomatic norm calculations indicate the presence of about 35 wt. %  albite in both the unaltered and cryptic alteration zone, with a marked increase to about 60 wt. % in the outer subzone of the visible alteration zone and a decrease to about 40 % in the inner subzone immediately adjacent to the vein. The differences noted above emphasize how important quantitative changes can be overlooked where semiqualitative modes are reported. A more objective procedure,  46  illustrated here by the metasomatic norm calculation, clearly avoids ambiguity in measuring mineralogical changes.  2.6.2. Erickson Gold Mine, Northern British Columbia The Erickson gold-bearing deposits are quartz veins that cut Mesozoic basalts in the Cassiar area of northern British Columbia (Sketchley and Sinclair, 1991). These veins are surrounded by extensive alteration envelopes (Sketchley and Sinclair, 1987) that can be divided megascopically into 6 distinctive zones (Table 2-4). A semiquantitative cumulative volume percentage of the mode of each mineral is also estimated (Figure 2-3). Quantitative gains and losses during the alteration process have been calculated using 2 and A1 3 were immobile (Sketchley 0 2 Gresens equation and the assumption that Zr, Ti0 and Sinclair, 1987, 1991). The parent rock at the Erickson mine is noncarbonated basalt that has been regionally metamorphosed to the upper greenschist faces. Sketchley and Sinclair (1991) concluded that the major chemical changes that took place during the development of the carbonate alteration envelope are: (i) volatile components increase progressively from unaltered rock toward the vein, (ii) K 0 is added throughout an alteration envelope but is most pronounced near 2 the vein, (iii) Na 0 is depleted throughout an envelope, 2 (iv) Si0 2 is increased throughout an envelope, particularly where a quartz vein is present, (v) CaO is depleted in the outer part of an envelope and added to the inner part, and (vi) MgO and Fe 3 are depleted throughout an envelope except where quartz 0 2 veinlets are present ( depletion is greater near the vein than in the outer portion of an alteration halo). They further qualitatively interpreted these variations as follows: 47  variations in mineralogy as afunction ofhost-rock composition and losses and gains of components. Minerals noted in the carbonated basalt are ankerite, siderite, quartz, muscovite, kaolinite, titanium oxides, andpyrite. The presence of carbonates, hydrous aluminum silicates, andpyrite implies that the volatile (LOl) 0, and S. An increase in volatile content corresponds to a 2 include, at least, CU ,H 2 volume increase. Table 2-4. Summary of Characteristics of Alteration Zones of Enclosing Gold Bearing Ouartz Veins and the McDame Dolomite Vein, Total Erickson Mine Color Mineralogy Thickness Occurrence Zone B-Noncarbonated basalt 2C-outer carbonate 2B-intermediate carbonate  (m)  Host  Pale to dark green  p1, chl, act, epi, aug, calc(trace), ti-oxides, ±py±qtz±hem±mt  1  very common  pale green to buff and pale gray  10  very common  buff to pale gray  p1, chl, ank, sid, qtz, ser, ti-oxide, ±kao±dol±py±carbon±calc±epi± aug±act ank, sid, qtz, ser, ti-oxides±kao±dol ±py±carbon  <4  common  <  <  lB-outer carbon  <  1  uncommon  buff to pale gray with minor green mottling buff to black  lA-inner carbon  <  3  uncommon  black  2A-inner carbonate  ank, qtz, ser, py, ti-oxides±sid± carbon±arsenopy±pl ank, qtz, ser, py, ti-oxides, carbon± sid±arsenopy ank, qtz, ser, py, ti-oxides, carbon± sid±arsenopy  pl-plagioclase, chl-chlorite, act-actinolite, epi-epidote, aug-augite, calc-calcite, py-pyrite, qtz quartz, hem-hematite, mt-magnetite, ank-ankerite, sid-siderite, ser-sericite, kao-kaolinite, dol dolomite, arsenopy-arsenopyrite. Data source: Sketchley and Sinclair (1991) Note:  Even though the chemical data (Sketchley and Sinclair, 1991; listed in Table 2-5) 0 and C0 2 contain LOT rather than measurements of F1 , it is still possible to allot cation 2  to carbonates and hydrous minerals in such a way that the H 0 plus CO 2 2 comprising LOT can be balanced. Normative calculations of minerals comprising the alteration envelope at Erickson gold mine involve such a partitioning and results are in good agreement with estimated modes  (Table 2-6, and compare Figures 2-3 and 2-4). Zone B (unaltered basalt) 48  has a mineral assemblage consisting of primary minerals such as plagioclase, pyroxene, etc., with a significant amounts of epidote and minor amounts of carbonate, ilmenite and apatite, that is, a greensehist facies assemblage. Zone 2C is characterized by kaolinite and more quartz. Zone 2A is composed of abundant carbonates, sericite, quartz etc. The distribution pattern of chlorite, the main difference between the normative and modal (petrographic) estimates, may arise due to an underestimation of LOl (particularly ) since there is obvious difference between 100% and the reported analytical total 2 C0 (about 95%). More CO 2 than reported will reduce the abundances of chlorite and Kfeldspar and form more carbonate, sericite and quartz according to the following reaction. (Fe, (OH) A 5 Mg) S 2 1 O 3 8 0 1 i + KA1Si + 5C0 8 O 3 2 CM  =  Or  5(Fe, Mg)C0 3 + (OH) S KAIi 1 O 3 + 2 0 i2 3SiO + 3H 0 2 Fe-Mg carbonate Mu Qz  (2-16)  This reaction also indicates the importance of accurate measurements of H 0, CO 2 2 and S in order to reduce errors that are carried through the calculation of a metasomatic norm. Another possible cause for the difference between the two chlorite profiles may arise from the calculation of sericite abundance. In reality, sericite may not be pure muscovite; instead it may be a non-ideal mixture of, for example, muscovite, paragonite, phlogopite and biotite, etc. Several pairs of chemical constituents (e.g. Zr, Ti0 , A1 2 , total Fe 3 0 2 ) show a 3 0 2 linear trend through the origin of a binary plot (Figure 2-5); these pairs of components or elements are incompatible and they are interpreted as having been immobile during the alteration process. Metasomatic normative minerals can be divided by an immobile component/element, such as Zr, to correct for closure (as in the case of PER diagrams) and produce a quantitative model of mineralogical changes during alteration. Figure 2-6 shows the result of such calculation for a ‘typical’ Erickson alteration profile, by treating the percentage values of components of parent rock as the mass values in grams. It  49  U’ C  Metasomatic Norms of Jennie Vein Alteration Profile, Erickson Gold Mine Table 2-6. 80-88-JH- 80-88-JH- 80-88-311- 80-88-illSample_id 80-88-IN- 80-88-311- 80-88-ill- 80-88-ill- 80-88-illB B 2C 2C 2A 2A 2A 2A 2A Alteration 3.44 5.59 4.03 3.40 23.03 27.37 28.73 34.47 34.48 Carbonate 18.68 22.40 8.74 18.69 0.00 0.00 0.00 0.00 0.00 Epidote 17.00 18.37 4.91 0.78 12.42 18.94 19.12 21.63 21.03 Sericite 0.00 0.10 12.09 15.81 0.07 0.00 0.00 0.00 0.00 Kaolinite 0.00 0.22 29.78 27.52 25.52 19.81 18.72 12.99 13.49 Chlorite 35.87 31.77 0.23 0.00 0.00 0.00 0.00 0.00 0.00 Pyroxene 0.00 0.00 0.00 0.50 5.48 8.18 7.50 3.91 4.32 K-feldspar 12.51 3.77 0.09 0.05 0.00 0.00 0.00 0.00 0.00 Plagioclase 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Pyrite 6.46 10.81 32.63 25.09 25.17 20.39 20.14 22.35 22.08 Quartz 2.74 2.59 2.65 2.30 1.80 1.21 1.31 1.36 1.37 others 96.70 95.62 95.15 94.14 93.48 95.89 95.52 96.70 96.77 Total  Chemical Analyses of Jennie Vein Alteration Profile, Erickson Gold Mine Table 2-5. 80-88-.JH- 80-88-ill- 80-88-1H- 80-88-311Sample_id 80-88-311- 80-88-JH- 80-88-JH- 80-88-ill- 80-88-311B B 2C 2C 2A 2A 2A 2A 2A Alteration (wt %) 47.90 46.81 52.60 48.19 41.82 40.04 39.55 38.95 38.84 Si02 14.14 13.52 13.43 15.15 10.02 12.06 12.07 11.46 11.40 A1203 1.32 1.24 1.27 1.40 0.86 1.04 1.02 1.01 1.00 Ti02 11.33 10.87 10.38 10.61 8.97 8.97 8.93 8.46 8.69 Fe203 0.16 0.17 0.19 0.16 0.18 0.15 0.15 0.15 0.15 MnO 7.31 7.14 5.83 5.58 5.98 5.61 5.60 5.83 5.87 MgO 10.40 11.19 4.36 6.23 10.43 10.14 10.40 11.21 11.21 CaO 2.11 1.40 0.01 0.01 0.10 0.29 0.28 0.28 0.30 Na20 0.11 0.13 0.58 0.17 2.25 3.20 3.12 2.81 2.78 1(20 0.10 0.10 0.10 0.10 0.07 0.07 0.07 0.11 0.12 P205 2.96 4.14 7.44 7.60 13.70 15.22 15.22 17.28 17.28 LOT 96.70 95.62 95.15 94.14 93.48 95.89 95.52 96.70 96.77 Total 87.58 83.06 81.41 88.68 64.92 71.65 70.75 73.02 73.89 Zr ppm 570-587 Data Source: Sketchley, D.A. and Sinclair, A. J. 1991, Econ. Geol.vol. 86, pp.  : 70  .--.---  ---:fl  0  > a) -o  n  ...-.  ..  •--•---  -...  .‘-.-.-  0  / / — ‘ , / , ., / , , , / , . ‘. ‘. ‘. ‘. ‘. . .. ‘. ‘. . ‘. ‘. ‘‘... ////////‘ S. ‘. ‘‘S.. ‘. ‘ ‘. \ ‘. ‘. ‘.. ‘ .‘ . ‘. ‘. ‘. ‘ ‘ , ,,,,, ,,,,—,/—,,,,, .S. 5.5.5. ‘.S.S.S.S. S. \S.’. ‘. S. \‘.S.S.’ // / / ,/, , ,, ,/,. /,,, , .5.\S. 5.S.’.S .S.5.5. S.5.S.S.\5.S.5.5.’.5.’  -  ,  5.5.  -  .  -  ‘ttt’‘  ‘  S.5.5.S.5.5.5.’.5.5.5.5.  5.5.5.5.5.5.S.S.S.5.S.S.5.S.  40 ::::.: -‘--:-  2A  2A  2A  Y’’sericite  ZC 2C outer carbonate zone  I* kaolintie fl I  ,metabasalt epidote  pyroxene Ti-oxide  quartz  vein  Figure 2-3  ZA  2A  Inner carboante zone  chlorite  tY/’/i  plagioclase  throughout carbonate alteration Generalized distribution of mineral species white quartz veins and carbon veins. envelopes enclosing gold-bearing veins, (1991) Simplified from Sketchley and Sinclair  80 70  60 50 ‘ %- % S. S. S. S  40 -  30  : -  20 10 0  (2A Jennie Vein  LI I  2A  2A  lo1ate pyroxcne  2A  Inner Carbonate Zone epidote  V//j plagioclase  2A  2C  20  Outer carbonate Zone sericite K-feldspar  r  Metabasalt  kaolinite  I quartz  Jennie vein, Erickson gold mine, northern Figure 2-4. Metasomatic norms profile British Columbia  51  Table 2-7a.  gains of components Metasomatic norms corrected for closure and absolute losses and northern British Columbia from profile 80-88-JET across the Jennie vein, Erickson mine, 80—88-JH-4  80-88-JH-5  80-88-JH-6  80-88-JH-7  Sample_id 8O-88-JH-1 80-88-JH-la 80-88-JH-2 80-88-JH-2a 8O-88-JH-3 B B 2C 2C 2A 2A 2A 2A 2A Alteration mole 0.000 -0.000 0.040 0.03 1 0.249 0.219 0.228 0.237 0.234 Calcite 0.000 0.000 0.000 0.000 0.034 0.061 0.000 0.033 0.029 Mg-carb 0.000 0.000 0.000 0.000 0.025 0.052 0.108 0.126 0.128 Fe-carb 0.002 0.003 0.003 0.002 0.003 0.003 0.003 0.003 0.003 Mn-carb 0.022 0.037 0.031 0.027 0.033 0.022 0.034 0.028 0.029 Mg-chl 0.004 0.009 0.021 0.017 0.022 0.017 0.006 0.000 0.000 Fe-chi 0.000 0.000 0.013 0.002 0.038 0.047 0.049 0.055 0.052 Muscovite 0.007 0.001 0.000 0.000 0.004 0.011 0.011 0.011 0.011 Na-mica 0.000 0.000 0.050 0.06 1 0.000 0.000 -0.000 0.000 0.000 Kaolinite 0.127 0.225 0.584 0.412 0.565 0.415 0.415 0.446 0.435 quartz 0.050 0.053 0.019 0.038 0.000 0.000 -0.000 0.000 0.000 Epidote 0.002 0.003 0.000 0.002 0.027 0.036 0.033 0.017 0.018 K-spar 0.020 0.014 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Anorthite 0.061 0.047 0.000 0.000 0.000 0.000 0.000 -0.000 0.000 Aibite 0.031 0.044 0.001 0.000 0.000 0.000 0.000 0.000 0.000 Ca-pyx 0.035 0.000 0.000 0.000 0.000 0.000 0.000 -0.000 0.000 Mg-pyx 0.028 0.015 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Fe-pyx 0.017 0.016 0.017 0.009 0.015 0.000 0.002 0.001 0.001 ilmenite 0.000 0.000 0.000 0.008 0.000 0.016 0.014 0.014 0.013 rutile 0.000 0.000 0.001 0.000 0.000 0.000 0.000 0.001 0.001 apatite 0.408 0.468 0.781 0.610 1.016 0.900 0.902 0.970 0.954 total 0.000 -0.024 -0.145 0.005 -0.142 -0.017 -0.018 0.020 dSiO2* 0.031 0.000 -0.002 -0.006 -0.016 0.012 -0.012 -0.016 0.008 0.012 dAl+3 0.000 0.000 -0.001 -0.001 0.002 0.001 0.001 0.001 0.002 dTi±4 0.000 -0.002 0.002 0.011 -0.010 0.005 0.003 0.015 0.013 dFe+2 0.000 -0.000 -0.001 0.000 -0.001 -0.000 -0.000 -0.000 -0.000 dMn+2 0.000 -0.005 0.026 0.045 -0.019 0.011 0.009 0.008 0.009 dMg+2 0.000 -0.025 / 0.102 0.076 -0.065 -0.036 -0.044 -0.054 -0.05 1 dCa+2 0.000 0.020 0.068 0.068 0.064 0.057 0.057 0.057 0.057 dNa+ 0.000 -0.001 -0.011 -0.001 -0.062 -0.081 -0.080 -0.069 -0.068 dK+ 0.000 -0.000 -0.000 0.000 0.000 0.000 0.000 -0.000 -0.001 dP+5 0.000 -0.026 0.147 0.139 -0.072 -0.048 -0.065 -0.025 -0.015 Sum 0= 0.000 -0.076 -0.194 -0.182 -0.129 -0.077 -0.084 -0.041 -0.042 dH2O 0.000 -0.000 -0.041 -0.031 -0.309 -0.333 -0.336 -0.396 -0.390 dCO2 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 dS 0.000 -0.141 -0.054 0.111 -0.731 -0.531 -0.571 -0.477 -0.444 dTotal 0.000 -0.051 -0.341 -0.321 -0.057 -0.029 -0.019 -0.017 -0.026 dH2O’ 0.000 0.000 -0.334 -0.308 -0.166 -0.237 -0.206 -0.347 -0.360 dCO2’ 0.000 -0.05 1 0.000 0.000 0.000 0.000 0.000 0.000 0.000 dOH0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 dCO3= 0.000 -0.000 0.294 0.277 -0.143 -0.096 -0.129 -0.049 -0.030 dHCO3uent between the least altered and altered rocks * prefixe d stands for the absolute difference of corresponding constit  52  Metasoniatjc norms corrected for closure and absolute losses and gains of components from profile 80-88-Ill across the Jennie vein, Erickson mine, northern British Columbia  Table 2-7h. Sample_id Alteration gram Calcite Mg-carb Fe-carb Mn-carb Mg-chl Fe-chl Muscovite Na-mica Kaolinite quartz Epidote K-spar Anorthite Albite Ca-pyx Mg-pyx Fe-pyx ilmenite rutile apatite total dSiO2* dAl+3 dTi+4 dFe+2 dMn+2 dMg+2 dCa+2 dNa+ dK+ dP+5 dH2O dCO2 dS dTotal Residual dH2O’ dCO2’ dOlldCO3= dHCO3-  80-88-JH-1  8O-8-JH-1a 80-88-JH-2  80-88-JH-2a 80-88-JH-3  80-88-JH-4  8O-88-JH-5  2A  2A  2A  2A  2A  2C  2C  23.38 2.43 14.78 0.29 15.99 0.00 20.54 4.39 0.00 26.17 0.00 5.13 0.00 0.00 0.00 0.00 0.00 0.22 1.07 0.34 114.70 1.86 0.33 0.08 0.72 -0.01 0.21 -2.06 1.30 -2.64 -0.02 -0.75 -17.17 0.00 -18.39 -0.40 -0.48 -15.83 0.00 0.00 -1.86  23.69 2.81 14.56 0.29 15.58 0.00 21.80 4.14 0.00 26.81 0.00 4.69 0.00 -0.00 0.00 -0.00 0.00 0.22 1.10 0.31 115.98 1.18 0.21 0.07 0.83 -0.02 0.19 -2.18 1.32 -2.71 -0.01 -0.74 -17.42 0.00 -19.68 -0.40 -0.30 -15.25 0.00 0.00 -3.01  22.77 0.00 12.49 0.30 19.12 4.06 19.39 4.27 -0.00 24.93 -0.00 9.28 0.00 0.00 0.00 0.00 0.00 0.33 1.09 0.20 118.24 -1.06 -0.42 0.03 0.19 -0.02 0.23 -1.77 1.31 -3.11 0.01 -1.51 -14.77 0.00 -21.93 -0.40 -0.34 -9.08 0.00 0.00 -7.90  21.92 5.16 6.08 0.30 12.10 12.10 18.78 4.37 0.00 24.92 0.00 10.00 0.00 0.00 0.00 0.00 0.00 0.00 1.27 0.20 117.21 -1.04 -0.32 0.03 0.26 -0.02 0.27 -1.43 1.30 -3.16 0.01 -1.39 -14.66 0.00 -20.91 -0.40 -0.52 -10.42 0.00 0.00 -5.87  24.89 2.91 2.87 0.39 18.41 16.01 15.09 1.66 0.09 33.95 0.00 7.39 0.00 0.00 0.00 0.00 0.00 2.20 0.00 0.22 126.11 -8.52 0.33 0.10 -054 -0.06 -0.46 -2.62 1.47 -2.43 0.00 -2.32 -13.60 0.00 -29.81 -0.40 -1.03 -7.29 0.00 0.00 -8.75  3.10 0.00 0.00 0.26 15.20 11.98 0.71 0.06 15.62 24.78 18.45 0.49 0.01 0.04 0.00 0.00 0.00 1.38 0.66 0.23 92.97 0.31 -0.44 -0.04 0.60 0.00 1.09 3.04 1.56 -0.05 0.00 -3.28 -1.36 0.00 3.64 -0.09 -5.77 -13.56 0.00 0.00 16.91  4.01 0.00 0.00 0.33 17.29 14.74 5.28 0.00 13.01 35.11 9.40 0.00 0.01 0.09 0.25 0.00 0.00 2.59 0.00 0.25 102.36 -8.69 -0.16 -0.03 0.11 -0.03 0.63 4.08 1.56 -0.43 -0.00 -3.50 -1.79 0.00 -5.90 -0.24 -6.14 -14.72 0.00 0.00 17.93  80—88--IH-7  80-88-111-6  B  B  -0.00 0.00 0.00 0.29 20.76 6.26 0.00 0.38 0.11 13.52 25.48 0.81 3.98 12.23 10.24 0.00 4.04 2.48 0.00 0.25 100.82 -1.46 -0.06 0.01 -0.09 -0.01 -0.13 -1.00 0.47 -0.02 -0.00 -1.37 -0.01 0.00 -4.10 0.02 -0.91 0.00 -0.87 0.00 -0.02  /  53  0.00 0.00 0.00 0.26 12.31 2.76 0.00 254 0.10 7.62 24.16 0.65 5.68 16.12 7.28 7.09 7.40 2.51 0.00 0.24 96.71 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00  15  LI  C’]  Q I—  c ca  0  •  0  0. 0.  Zr ppm •  Ti02  *  A1203  C  Fe203  Figure 2-5. Immobile components scatter plot, Erickson gold mine, northerm British Columbia  2 0)  vein  inner carbonate zone  11111111 carbonate epidote  outer carbonate zone metabasalt pyroxene  I::  sericite  chlorite  kaolinite  plagioclase K-feldspar  quartz mDis  Figure 2-6. Metasomatic norm profile after closure effect removed, Erickson gold mine, northern British Columbia  54  provides a clear and quantitative appreciation of mineralogical differences between parent and daughter rock. The metasomatic norms corrected for closure can be integrated with the results of the absolute loss or gain of each chemical component to illustrate the total chemico/mineralogic effect of the hydrothermal alteration process in equation form (Table 2-7a and 2-7b). For example, the hydrothermal alteration of parent rock (sample 80-8 8JH-7) to altered rock (sample 80-88-JH- 1) at Erickson gold mine can be illustrated in a  simplified balanced equation as follows: 0.O02Carbonate 0.26 g  +  0.O5Epidote + 0.026CM 15.07 g 24.16 g  +  O.O94Pyroxene + O.081P1 + 0.O07Sericite 21.76 g 21.8 g 2.54 g  +  0.l27Qtz  7.63 g  3 + 0.0261120+ 0.36C0 5 + 0.03HC0 2 + 0.068K+ +2 p+ 2 +0.Ol7llmenite+ Apatite+ 0.05 1Ca 1.86 g 15.83 g 2.64 g 0.01 g 0.02 g 0.48 g 0.24 g 2.06 g 2.51 g  =  0.394Carbonate  40.87 g  +  0.O29Chlorite 15.99 g  +  0.O92Sericite + 0.018K-spar 5.13 g 24.92 g  +  0.435Qtz+0.Ol3Rutile  26.17 g  1.07 g  2 +0.0 12A1+ 0.OO2Ti +0.0 13Fe 2 +0.00 lllmenite+0.OolApatite+0.03 lSiO 0.33 g 0.08 g 1.86 g 0.72 g 0.34 g 0.22 g +0.009Mg +0.057Na 2 1.30 g 0.21 g  (2-17)  This equation explicitly indicates which minerals are destroyed, which minerals are formed and which components are gained and lost during the hydrothermal alteration process.  2.7. Conclusions A metasomatic norm, particularly if constrained to approximate a mode, provides a useful tool to quantify the combined mineralogical and lithogeochemical changes affected  during walirock alteration associated with hydrothermal mineral deposits. Advantages of both mineralogical and lithogeochemical approaches to the study of such systems are  inherent in the procedure, Where modes can be approximated by norms the normative procedure generally will provide results more efficiently and more optimally because of  55  the better representative of samples collected for lithogeochemical analysis relative to those generally used for modal analysis. Moreover, lithogeochemical analytical data generally are more objective and reproducible than are modal data. In summary, metasomatic norms: (i) lead to high quality estimates of mineral abundances, and thus, provide accurate mineral distribution profiles across alteration envelopes, (ii) provide an objective and quantitative basis for a mineralogical classification of hydrothermally altered rock, (iii) give an interpretation of lithogeochemical variations in terms of mineralogical variations which are more compatible with field observations than are interpretations quantifying lithogeochemical losses and gains only, (iv) with the recognition of an immobile component, can be recast into the absolute masses (not percentages) of minerals relative to a specified amount of the parent rock (e.g. about 100 grams), and (v) can be combined with the results of calculated absolute losses and gains of lithogeochemical constituents to form comprehensive mass balanced equations (model) for a hydrothermal alteration system no matter whether it is closed or open, or in equilibrium or disequilibrium.  56  Chapter 3  Quality Control/Assessment of Lithogeochemical Data  3.1. Introduction  In a quantitative evaluation of hydrothermal alteration, it is essential to know the quality of data so that conclusions can be derived with confidence. Thus, it is important to understand all sources of lithogeochemical variations and know how to separate the variation(s) generated by geological process(es) of interest from those generated artificially. The major causes for the variations of lithogeochemical data are listed in Table 3.1. Table 3.1.  The classification of variations of lithogeochemical data generated by different processes  Primary causes  Secondary causes  Artificial causes  Fractionation  metamorphism  sampling and sample preparation  Mixing  hydrothermal alteration  analytical measurement  Assimilation  weathering  closure effect  Ideally, variations generated by artificial processes should be eliminated. In practice, they can only be minimized through quality control, such as the estimation of the optimum sample size and the necessary fineness of the ground particle size. These variations should be evaluated by quality assessment in terms of precision, accuracy and detection limit. Among the artificial causes, closure effect has already been discussed in the foregoing chapter. Consequently, this chapter focuses on: (i) strategies of field sampling and sample preparation (i.e., estimation of an optimal sample size and the fineness of grain size of prepared subsample); (ii) determination of precision and detection limit by using a small set of duplicates, and (iii) the propagation of error through data evaluation procedures.  57  3.2. Strategies of sampling and sample preparation  Variation caused by improper strategies of sampling and sample preparation has been discussed thoroughly among analysts (Shaw, 1961; Wickman, 1962; Wilson, 1964; Kleeman, 1967; Maxwell, 1968; Ondrick and Suhr, 1969; Ingamells and Switzer, 1973; Ingamells, 1 974a, 1 974b, 1981; Potts, 1987) who generally agree that the error caused by sampling and sample preparation may be so large that the meaning of lithogeochemical data can be seriously distorted or obscurred. The object of lithogeochemical sampling and sample preparation is to use a small amount of sample or subsample to represent a much larger geological entity. However, silicate rocks, with few exceptions, contain two or more mineral species with various grain sizes; rock powders prepared from them are heterogeneous to some extent. Consequently, it is possible that artificial variations which could significantly obscure lithogeochemical variations could arise from improper procedures of sampling and sample preparation. The concepts of homogeneity and heterogeneity of certain elements in a sample or subsample are relative and depend on the following factors: (i) sample size, (ii) grain size of the mineral(s) containing the element of interest, and (iii) abundance(s) of the mineral(s) containing the element of interest. With the variation of one of these three factors the homogeneity or heterogeneity of the element of interest in different samples can change correspondingly. From the perspective of sampling and sample preparation, the abundance of the mineral(s) containing the element of interest is an objective constant or nearly so. However, the sample size is adjustable at the sampling stage and the particle sizes of sub samples are definable at the stage of sample preparation to make the sample or subsample more representative. Heterogeneity between the samples from the same site or subsamples from the same sample could be reduced to a minimum degree if the size (mass) of sample is large enough or the particle size of a subsample is fine enough. In general, the coarser the grain size of a 58  rock, the larger the sample size needed to be representative. The smaller the size (mass) of a subsample, the finer the sample must be ground in order to obtain the subsample. Regardless of the approaches of increasing the sample mass or grinding to a finer particle size prior to subsampling, the effects are the same (i.e., increasing the number of grains or particle (n) of the sample or subsample). To estimate the optimum mass for a sample or the necessary fineness of the particle size for subsampling, the concept of a ‘two-mineral mixture of uniform grain size’ is helpful (e.g., Wilson, 1964; Kleeman, 1967; Ingamells and Switzer, 1973; Ingamells, 1974a, 1974b; 1981). This concept can be described through the following simplifications: (i) a hypothetical mixture contains only two minerals, one is rich in the element of interest and the other is poor in the element of interest; (ii) all the particles in a sample are of uniform volume; (iii) each particle consists of one mineral species only; and (iv) the chemical composition of each mineral species has uniform composition throughout the bulk specimen. In reality, a sample or subsample may consist of more than two minerals and the distribution of the element of interest can be more complicated than in the simplified system above. However, the main concerns here are: (i) whether the element of interest is homogeneously distributed in the sample or subsample, and (ii) to what extent the homogeneity of the sample or subsample can be achieved. The distribution of the element of interest in a natural and complicated system is generally more homogeneous than in a simplified ‘two-mineral mixture of uniform size’ system. For example, to analyze a rock consisting of quartz, K-feldspar and plagioclase as phenocrysts by using ‘two-mineral mixture of uniform size’ model, plagioclase will be treated as the only mineral phase containing sodium and calcium, K-feldspar as the only mineral having potassium and quartz phenocryst as the main contributor to the 59  . As we know, plagioclase also can contain a minor amount of 2 heterogeneity of Si0 potassium, K-feldspar, similarly, can contain small amount of sodium and calcium too. Both feldspars contain significant amounts of silica. Therefore, the homogeneity of various elements as described in the simplified system is adequate in place of the more complicated real system. In brief, the simplified system is adequate for our discussion; use of real, more complicated systems may be more complicated than necessary in most cases and too complicated to deal with practically, in other cases. With regard to the simplification of uniform grain size, the mineral rich in the element of interest contributes to both the total concentration of the element of interest and the error in determining concentration. Therefore, the grain size of the mineral rich in the element of interest is usually used as the reference of uniform grain size. The rest of the grains containing a low content of the element of interest are treated as the matrix. In reality, the grain or particle size of a sample or subsample is not commonly uniform. The assumption of a uniform grain size is acceptable if we either: (i) imagine that a coarse grain of mineral containing a negligible content of the element of interest is the equivalent of a number of grains as fine as the mineral enriched in the element of interest, or (ii) treat a few finer grains of minerals containing a negligible content of the element of interest as the equivalent of a coarser grain of the mineral enriched in the element of interest. In brief the concept of uniform grain size always uses the grain size of the mineral rich in the element of interest as the reference. With the above simplifications, a binomial distribution function can be used to simulate the distribution of major and trace elements during sampling and subsampling processes because: (i) each sample or subsample consists of n identical grains; (ii) each grain results in one of two outcomes, the grain is rich in the element of interest or it is poor in the element of interest;  60  (iii) the probability of getting a grain rich in the element of interest on a single trial is equal to p and remains the same from grain to grain, and the probability of getting a grain poor in the element of interest is equal to q = (1  -  p);  (iv) the grains are independent; (v) the random variable of interest is x, the number of the grains rich in the element of interest among the n grains. For a binomial distribution we have P(x)=  n! pxqn_x x’(n—x)!  (3-1)  where n is the total number of equant grains; x is the number of equant grains rich in the element of interest; p is the volume percentage of the grain rich in the element of interest; (1 -p) is the volume percentage of the grains with negligible concentration of the element of interest. Thus, the expectation (p.) of the binomial distribution is ,u=np and its variance  (a2)  (3-2)  j o2  =np(l—p)=npq  (3-3)  and its coefficient of variation (Rg) is (34) Equation (3-4) given by Kleeman (1967) illustrates the relationship between the number of grains (n) of the sample or subsample and the coefficient of variation of the grain distribution (Rg) generated by sampling or stages of sample preparation. Engels and Ingamells (1970) improved Kleeman’s equation through converting the coefficient of variation (Rg) generated by sampling the non-representative grain distributions to the coefficient of variation generated by lithogeochemical inhomogeneity (RE). The reason for doing this is to take into account the minor contribution of the grains which are poor in the element of interest to the total concentration in the sample of the element of interest. 61  (3-5)  p+q=1  where p and q are the weight fractions of the minerals rich and poor in the element of interest, respectively. The relationship between the volume proportions and the weight proportions of the two minerals in the mixture is: qqd P  (3-6)  PWdL  where dH and dL are the densities of the minerals rich and poor in the element of interest respectively. (3-7)  E=Hp+Lq where E represents the concentration of the element of interest in sample; H is the  concentration of the element of interest in the grain population with p fraction; L is the concentration of the element of interest in the grain population with q fraction. From Kleeman’s equation R=./i  (3-8)  RL=lJi  (39)  where RH is the relative error due to sampling the mineral rich in the element of interest; RL is the relative error due to sampling the mineral poor in the element of interest. The total sampling error, EREi5 not a statistical addition of the two components LRL and  HRH because these are not independent: as p increases, q decreases and E  approaches H. The exact relation is: =(PWHRH 2 (ERE)  —  2 qLR)  (3-10)  The physical implication of equation (3-10) is that the distribution of the element of interest will become more and more homogeneous if the contributions from both populations of grains to the total concentration of the element of interest become closer and closer to each other; thus the error from sampling and sample preparation will become 62  less and less significant. Furthermore, substitution of equation (3-6) in (3-8) and (3-9), and then substituting (3-8) and (3-9) in (3-10), gives RE  =  I  fndHdL 1  x  Hdff  —  LdL  (3-il)  E  Next, the relationship between the weight of the sample or subsample (w) and the coefficient of variation is derived as follows: =  + wq dffv  =  w (PWdL + qd)  dLv  (312)  dHdLv  where v is the grain or particle volume in cubic millimeters; w is the weight in gram of a sample or a subsample. Substitution of equation (3-12) and (3-7) in equation (3-11) gives:  R(pWdL + qd)  (Hdff—LdL) 2 2 (Hp + Lq)  (3-13)  Rearranging equation (3-13) gives: =  wR(p,(,d +qdff)  (Hp,, +Lq) (HdH  —  2  2 LdL)  (3-14)  In equations (3-13) and (3-14) the value of RE can be predefined; the values of H, L, dH and dL are known when the ‘two minerals’ are determined, the values of p and q, can be reasonably estimated by examining the hand specimen. Consequently, equation (3-13) can be used to calculate the optimum weight of the sample after the value of v is estimated through examining the grain size of the mineral containing the element of interest. For the purpose of determining the necessary fineness of the subsample, equation (3-14) can be used after the subsample weight has been defined by the analytical measuring technique. Applications of equation 3-13 and 3-14 to Silver Queen lithogeochemical data are described in Chapter 6. It is helpful to understand the significances of equation 3-13 and 314 by following the calculation of a realistic example.  63  3.3. Quality assessment of analytical measurements based on a small set of duplicates  The discussion in the foregoing section has been aimed at the improvement in quality of lithogeochemical data at the stages of sampling and sample preparation. Next, it is important to focus on the quality assessment of lithogeochemical data at the stage of analytical measurement. A similar concept, quality control, has been commonly used by chemical analysts. However, the quality of lithogeochemical data in terms of analytical precision is not in all cases under the control of the geologist, but the quality of lithogeo chemical data can be assessed through the examination of different types of duplicates. All analytical measurements are subject to error. There are two types of errors: (1) random errors arising from the variations inherent to any sampling or measurement process, and (2) non-random errors causing systematic negative or positive deviations from the true result. Bias can be recognized through repeated measurement of standards and is not considered here. Errors are assessed in terms of either precision or accuracy. Precision is a measure of analytical repeatability. A precise analysis is one where a set of replicate analyses forms a tight cluster around the average. The degree of precision is normally measured by the standard deviation of the analyses or by the relative error (coefficient of variation). Accuracy is a measure of how close the analyzed data lie to the ‘true’ composition of the sample. One of the difficulties in silicate rock analysis is that the true composition, even in reference material, is in some cases poorly known (Potts, 1987). From a practical viewpoint adequate accuracy can be considered to have been achieved where different analytical methods give essentially identical results (Fletcher, 1981). Further discussion on this issue is beyond the scope of this thesis. Of practical concern is the issue of how to determine the precision by using a small set of duplicate analyses.  64  Thompson and Howarth (1976, 1978) demonstrate that errors in analytical determinations can vary significantly and systematically over a wide range of concentrations. Therefore, a single value of standard deviation calculated from a set of duplicates of one sample cannot properly describe the analytical precision of a particular set of geochemical data over a wide range of concentrations. Instead, quantification of the systematic relation of error to concentration is desirable. This approach leads to realistic error estimates in contrast to the usual assumption of either a constant absolute error (by using the standard deviation), or a constant relative error (by using the coefficient of variation). Thompson and Howarth (1976, 1978) approximate the variation of error as a standard deviation (Se) as a linear function of the concentration (C): +kC 0 S=S  (3-15)  The parameters S 0 (intercept) and k (slope) can be used to quantif,’ the precision (Pc) at the 95% confIdence level and at concentration C, by means of: P=2SJC  (3-16)  Substitution for S in equation (4-16) gives: =  /C + 2k) 0 (2S  (3-17)  In addition, the practical detection limit Cd (when P = 1.0) can also be estimated from equation (3-17) as follows: Cd  =  0 /(1-2k) 2S  (3-18)  Equation (3-18) indicates that the detection limit Cdis proportional to S 0 and k, but the value of k should not be equal to or larger than 0.5, otherwise the detection limit C will be infinite or negative and meaningless in the present context. To calculate the precision (Pa) of a particular component in a sample at a specific 0 and k. There are two concentration (C), it is necessary to know the values of S procedures utilizing duplicate analyses to estimate these values (Thompson and Howarth, 1976, 1978). Procedure 1 needs 50 or more duplicates which cover the whole range of concentration of interest in a relatively uniform pattern. These duplicates are further 65  divided into five or more groups (concentration ranges) with equal number of duplicates in each group; this is done easily with a data set ordered using average concentrations of + 1 [(X ) /2] X and the median of the pairs 2 + 1 [(X ) /2]. X The mean of the concentration 2  -X 1 (1X 1 2 ) for each group is then calculated. A linear regression of these values of 2 + 1 [(X ) /2] X and 2 -X 1 (1X 1 ) for each group is calculated or obtained graphically. The difference  regression parameters (intercept and slope) are multiplied by a coefficient (e.g. 1.048 at 50th percentile because median values rather than mean values as the y-coordinate) to give 0 (intercept) and k (slope) of the error model (cf. Fletcher, 1981). S Procedure 2 requires only 10 to 50 duplicates. This is normally the range of lithogeochemical duplicates for a study of hydrothermally altered rocks. Therefore, a detailed discussion will be given herewith. The basic idea of this procedure is to test the available duplicate data against an empirical standard of precision to see whether the analytical duplicates can be accepted at a specific precision. The empirical equations given by Thompson and Howarth, (1976, 1978) are listed below: 90 d  =  0 + kC) 2.326(S  (3-19)  99 d  =  0 + kC) 3.643(S  (3-20)  The equations above are derived from equation (3-15) and the specific constants (2.326 99 and and 3.643) represent specific percentiles of a one-sided normal distribution (i.e. d 90 represent the 99th and 90th percentiles respectively of the absolute difference 1 d -X 1X 2 ,X 1 )). These absolute difference are estimators of 2 between pairs of duplicate analyses (X the standard deviation (Se) at composition C where C  =  + 1 (X ) 2 /2. X Consider an example  2 + 1 (X /2 X as x-axis and 2 to illustrate this procedure. Figure 3-1 is constructed with ) -X 1X 1 0 3 duplicate data are plotted. Then assuming S 0 2 as y-axis; eighteen pairs of Al  =  0, two  percentile lines (90th 99th respectively) are drawn on this diagram according to equation 3 in this set of lithogeochemical data is better 0 2 3-17 to test whether the precision of Al  than 2 % (Pc  =  0.02). If the duplicate analytical data comply with the specification, on  90 line and 99 % of the points below the average 90% of the points will fall below the A 66  99 line. If in Figure 3-lA, the precision is worse than that tested, then the value of k A should be raised, a poorer precision will result. In this example, a satisfactory result is achieved by raising the value of precision to 4.2%. As a result, around 90% of the plotted points fall below the 90th percentile line and 99 % of the plotted points below the 99th percentile line in Figure 3-lB. For general geochemical purposes a control chart (for 10% precision, i.e. with percentile lines drawn for the specification S=0.05C on logarithmic axes) devised by Thompson and Howarth (1976,1978) has been widely used. Difficulties in the use of this control chart arise where the concentrations of some duplicates are close to the detection limit, that is, where the precision is near 100%. For example, an alteration profile cross cutting a propylitic alteration halo and a sericitic/argillic alteration envelope are usually 0 in propylitically altered rock, but an almost 2 characterized by a high concentration ofNa 0 occurs within the sericitic/argillic alteration envelope. Using 2 complete depletion ofNa O measurement tends to be largely 2 the control chart, above, the precision ofNa overestimated because only the k value of the linear equations 3-19 and 3-20 is adjustable to meet the plotting requirements imposed by the 99th and 90th percentile lines (i.e. there is no point above the 99th percentile line and there are less than or equal to 10% of points above the 90th percentile line). There is an obvious discrepancy between the calculated precision and the deviation represented by the duplicates of high concentration (Figure 32A). The cause of this problem is that the detection limit has not been taken into account. This problem may not appear where all duplicates have concentrations far removed from the detection limit. There is a substantial disparity between procedure 1 and 2. Procedure 1 defines error as a linear flinction of concentration, procedure 2 assumes a constant relative error. It seems that procedure 2 might be improved for some situations involving fewer than 50 pairs of duplicates, where data are sufficiently precise that both S 0 and k can be estimated, even if not as rigorously as in procedure 1. 67  ><  (Xl +X2)/2  C\4  >< ><  0  5  10  15  20  25  (Xl +X2)/2  text) for 2 Figure 3.-I. Schematic illustration of Thompson and Howarth’s procedure (see data do not the precision estimation of a set of lithogeochemical data. (A) The duplicate 1% of comply with the 2% error test percentile lines. There are more than 10% and that the plots fall above the 90th and 99th percentile lines respectively. This means on to 3 in this set of data is higher than 2%. (B) After raising the precisi 0 2 precision of A1 Therefore, 4.2%, only 2 out of 18 duplicates plot between the 90th and 99th percentiles. this precision is acceptable.  68  0.8  99t a 2 N 0  th  0.7  50  So  0.6  k  Pc  0.00 0.8  =  =  =  1.6  c4  0.4 >< 0.3 0.2 0.1• 0--a 0  p  2.5 2 (Xl +X2)/2  1.5  1  0.5  I  I  CD  CD  3  3.5  I  —  4.5  4  0.8  0.7  a 2 N 0  0.6  So  =  0.09  ::z—  50th  CD  0.1  ID  0-  0  0.5  I  1.5  1  2  2.5  3  3.5  4  4.5  (Xl +X2)/2  n of lithogeochemical data methods of precision estimatio range of iable standard deviation for constant precision and var using: text for on. See iati variable standard dev variable precision concentration,  Figure  by  3-2.  detailed  Comparison of  (A)  and (B)  the  whole  the  and  explanation.  69  One way of dealing with this problem is the introduction of the detection limit (Cd) of the element of interest to the construction of the corresponding control chart. Commonly, the values of detection limits of each analytical technique for different constituents are provided by the analyst. With the known value of detection limit (Cd), equation (3-18) can be rearranged as follows: = Cd (0.5-k) 0 S  (3-2 1)  substitution of equation (3-21) in (3-19) and (3-20) gives: 90 d  =  326 . 2 C 5 (O. d + k(C-Cd))  (3-22)  99 d  =  643 + k(C-Cd)) . 3 (O.SCd  (3-23)  Now only one variable (k) remains in equation (3-22) and (3-23). Following the same procedure as Thompson and Howarth (1976, 1978) one increases the value of k and moves the 99th and the 90th percentile lines up until no plotted point lies above the 99th percentile line and less than or equal to 10% of the plotted duplicates lie above the 90th 0 can be calculated percentile line. The value (k) can then be estimated. Thus, the value S by using equation (3-2 1). Where the information about detection limits is not available, there is another way 0 and k based on the analytical to deal with this problem, that is, the estimation of S duplicates. A recommended procedure is as follows: (1) Introduce one more empirical precision equation to set one more constraint for taking one more variable (S ) into account, 0 50 d (2) Initially assume S  0 + kC) 0.954(S  (3-24)  0;  (3) Gradually increase the value of k starting from zero in equations (3-20) until no point is above the d 99 line (since 99% of points for a small set of duplicates 10 to 49 pair of duplicates means that all points should be below the 99th percentile line); 0 and k derived from the previous (4) Construct the d 90 line with the current values of S 90 line. If not, continue to step and check whether 90% of the points are below the d 70  increment of k until only 10% of the points are above the d 90 line; 0 and k derived from previous steps 50 line with the current values of S (5) Construct the d and check whether about 50%, or the maximum amount between 10 to 50% of the 50 line are less than 50% or the 50 line. If the points above the d points, are above the d maximum amount value between 10 to 50% of the total plotting points, then reject the initial assumption of S ; 0 (6) Reassign the initial value of S 0 by a small increment; (7) Repeat the steps (2) to (6) until the requirement for all three lines are satisfied; i.e., with certain values of S 99 line, no more than 10% of the 0 and k, no point is above the d 90 line and about 50% or the maximum amount between 10 to points are above the d 50% of the points are above the d 50 line (Figure 3-2B). In brief, this approach helps obtaining reasonable estimates of S 0 and k. Consequently, the precisions of a particular set of lithogeochemical data with wide ranges of concentrations can be estimated in a form consistent with the case for more abundant paired data (i.e., duplicate pairs> 50).  3.4. Propagation of Errors in Calculation of Metasomatic Norms Lithogeochemical data always incorporate some component of random error. Quantitative estimates of losses and gains of components during hydrothermal alteration  are limited by the magnitude of these errors. Errors in analyses of individual components commonly are known. An important concern is the effect these known errors have on various calculated quantities, that is, the propagation of errors (Le Maitre, 1982; Cheng and Sinclair, 1994). In mathematical terms, if the calculated result, z, is a ffinction of a set of measured variables: x ,x 1 , 2  . .  x 2 , 1 z=f(x , ...x)  (3-25)  71  The quantity z will be in error by an amount dz as a consequence of the errors in each of , .x. Then the error dz (as a variable) can be estimated 2 the measured quantities x ,x 1 . .  using the approximation (e.g. Kendall, 1943):  =  )s  --Js. +  (3-26)  where x 1 and Xj are the ith component and thejth component respectively, S is the 0 and k analytical error calculated through equation (3-15) by using corresponding S values; and S, is the value of covariance between the ith andjth variable. It is reasonable to treat the error of lithogeochemical data as independent since the analytical error of one element has no obvious link to the error of the other element. Therefore, a simplified equation used to calculate error propagation is as follow: 2  (3-27)  =  Substitution of equation (3-15) in (3-27) gives: 2  (St,.  +k x 1  )2  (3-28)  =  Since the value of S)q is one standard deviation of a normal distribution, the value of error propagation (Si) derived from it is at the 68% confidence level. Equation 3-27 is commonly used for calculating the variance of a function. As indicated by Le Maitre (1982), with closed data of the constant sum type, not all the covariances can be zero, and their sum must be negative. This means that if the covariance terms in equation 3-27 are ignored, the absence of their overall negative contribution will tend to give an overestimate of the variance. As this is generally more acceptable than an underestimate of the variance, the use of equation 3-27 for closed data would, therefore, seem reasonable as a first approximation.  72  For the calculation of loss or gain of a specific component in a single precursor system the following equation is used:  z  (3-29)  dX=tXdxp  where dx is the value of absolute loss or gain of a component x during the hydrothermal alteration process, Z is immobile during the alteration process, x., and Xd are the mobile element concentrations in the least altered parent rock and altered daughter rock respectively. In equation (3-29) the calculation result (dx) is derived from four analytical measurement values (i.e. Zd, Z,,  Xd  and x.). Each of these four values has its own  uncertainty. The value of dx contains the combination of the errors derived from all former dependent variables. Thus, the error propagation can be evaluated as follows:  0 +kzZd) 2 2 +[_)(S +kZ)  =  0 (S  2 +kXxd)  ,-  =  (3-30)  2  2  (Se, + kZ) 2+ z  +[._] iZxi  2  0 (S  +  )  (S +kx) 2  0 + kzZd )2 (S  0 2 +(S kXxd)  (3-31) +  By using an error determined from equation (3-31) the calculated absolute losses and gains of chemical constituents can be evaluated at an appropriate confidence level. For the calculation of the propagated error of an specific normative mineral, it is first necessary to find the functional relationship between the amount of a specific normative mineral and related chemical constituents allotted to it. A specific normative mineral can be treated as the summation of certain portions of relevant chemical 73  constituents from the whole rock compositions. Therefore, the functional relationship between the percentage of normative mineral and concentration of different components used to construct it can be presented as follows: (3-32) where z is the percentage value of the normative mineral, a is the proportion of the ith 1 is component used to make the normative mineral from the bulk rock compositions, and x the concentration value of ith component in the rock. Substituting equation (3-3 2) in (328), we have: 2 ) x 1 0 +k S =a(S  (3-33)  By using equation (3-3 3) the uncertainty of a metasomatic norm calculation can be estimated through error propagation at the 68 % confidence level. There are two fundamental assumptions for the calculation of propagated errors as outlined above: (i) the errors of lithogeochemical data are assumed to be independent of each other because the error of certain chemical constituent of the whole rock sample has no obvious link to the errors of other chemical constituents of the same rock sample; (ii) the error contributed by a chemical constituent is assumed to be allotted to a normative mineral in the same proportion as the chemical constituent is allotted to the normative mineral. It is hard to prove these assumptions. Their use may lead to small overestimates of the propagated errors, and thus they provide a conservative approach. Furthermore, the propagated errors calculated through equation (3-31) and (3-3 3) can be integrated with the results of the absolute losses and gains of chemical constituents, as well as the normative minerals corrected for the closure to be presented as a comprehensive mass balance equation introduced in the previous chapter. We have:  74  M1neraI,eflt rock ±error + Constituent gained from solution±error =  ineralalted rk±0r + 4  Constituent lost from wall rock±error  (3-34)  Propagated errors provide a basis for screening data for inclusion in the chemico mineralogic model. Abundances less than twice the propagated error are not significantly different from zero and can be ignored.  75  Chapter 4.  Geology of the Silver Queen Mine, Owen Lake Area, Central British Columbia  4.1. Introduction The Silver Queen (also known as Nadina or Bradina) mine is near Owen Lake, 35 kilometres southeast of Houston, and 100 kilometres southeast of Smithers in the Bulkley Valley region of central British Columbia (Figure 4-1). The deposit has had a long history of exploration since its discovery in 1912. It has produced 3160 oz Au, 168,000 oz Ag, 893,000 lbs Cu, 1.55 million lbs Pb, 11.1 million lbs Zn and 34,800 lbs Cd from 210,185 short tons of ore during a brief period from 1972 to 1973. Mine closure was due to overdesign of the mill and complex metallurgy (Cummings, 1987; Dawson, 1985). Geological reserves of the No. 3 vein at the Silver Queen mine presently stand at approximately 500,000 short tons grading 3 g/t Au, 200 glt Ag, 0.23% Cu, 0.92% Pb and 6.20% Zn (Nowak, 1991). Equity Silver mine (total reserves plus production of approximately 30 million tonnes of 0.4% Cu, 110 g/t Ag, and 1 g/t Au) lies 30 km to the east-northeast. Geological mapping of the 20 square kilometre area surrounding the deposit suggests that the stratified rocks (the Upper Cretaceous Tip Top Hill Formation: Church, 1971) hosting this epithermal gold-silver-zinc-lead-copper vein deposit may be correlated with rocks hosting the Equity Silver deposit (Wetherell et al., 1979; Cyr et al., 1984); they are lithologically similar to Kasalka Group rocks of late Early to early Late Cretaceous age (Leitch et al., 1990). Two series of igneous and volcanic rocks have been recognized by their distinctive lithogeochemical characters and K-Ar dating ages. The Silver Queen mine is hosted in the older series of igneous and volcanic rocks and is cut by dikes belonging to the younger series. Therefore, mineralization at the Silver Queen mine occurred during the period after the older series of igneous and volcanic activity, but before the younger one.  76  4.2. Regional Geological Setting The study area lies within the Stikine terrane, which includes submarine calc alkaline to alkaline immature volcanic island-arc rocks of the Late Triassic Takla Group; subaerial to submarine caic-alkaline volcanic, pyroclastic and sedimentary rocks of the Early to Middle Jurassic Hazelton Group; successor basin sedimentary rocks of the Late Jurassic and Early Cretaceous Bowser Lake, Skeena and Sustut groups; and Late Cretaceous to Tertiary calc-alkaline continental volcanic arc rocks of the Kasalka, Ootsa Lake and Endako groups (Maclntyre and Desjardins, 1988). The younger volcanic rocks occur sporadically throughout the terrane, mainly in down-thrown fault blocks and grabens. Plutonic rocks of Jurassic, Cretaceous and Tertiary ages form distinct intrusive belts (Carter, 1981), with which porphyry copper, stockwork molybdenum and mesothermal and epithermal base-precious metal veins are associated. The Silver Queen mine lies on the caldera rim or perimeter of the Buck Creek basin, which is delineated roughly by a series of rhyolite outliers and a semicircular alignment of Upper Cretaceous and Eocene volcanic centres scattered between Francois Lake, Houston, and Burns Lake (Figure 4-1; see also Fig. 59 of Church 1985). The Buck Creek basin has been interpreted as a resurgent caldera, with the important Equity Silver mine located within a window eroded into the central uplifted area (Church, 1985; Church and Barakso, 1990). A prominent 30 km long lineament, trending east-northeasterly from the Silver Queen mine towards the central uplift hosting the Equity mine, appears to be a radial fracture coinciding with the eruptive axis of the Tip Top Hill volcanics and a line of syenomonzonite stocks and feeder dikes to an assemblage of Tertiary ‘moat volcanics’ (Church, 1985). Block faulting is common in the basin, locally juxtaposing volcanic rocks of various ages. Within the basin, a Mesozoic volcanic assemblage is overlain by a Tertiary volcanic succession. The oldest rocks exposed within the basin are at the Equity Silver mine and  77  126°  128°  550  55°  540  540  25  0 KI  50  0netres  Figure 4-1. General geology of central British Columbia, showing the regional setting of the study area (after Maclntyre, 1985). Tpb Tertiary plateau basalt; Eg Eocene granite; KTo Ootsa Lake Group; Kg Cretaceous granite; Kk Kasalka Group; Ks Skeena Group; Jg Jurassic granite; Th Ha.zelton Group. -  -  -  -  -  -  -  -  78  the Silver Queen mine. The sequence at the Equity mine has been characterized by Church (1984) as the Lower Jurassic Telkwa Formation of the Hazelton Group, overlain with angular unconformity by Lower Cretaceous Skeena Group sedimentary rocks. However, Wojdak and Sinclair (1984) correlate the sequence hosting the Equity mine with the Lower Cretaceous Skeena Group sediments, and Wetherell et al. (1979) and Cyr et al. (1984) correlate it with the Lower to Upper Cretaceous Kasalka Group. The Kasalka Group is considered to be a late Early Cretaceous (Armstrong, 1988) or early Late Cretaceous (Maclntyre, 1985; Leitch et al., 1991) continental volcanic succession that is predominantly porphyritic andesite and associated pyroclastic rocks. It is well exposed in the Kasalka Range type section near Tahtsa Lake. Upper Cretaceous rocks with similarities to the Kasalka Group are exposed westwards from the Equity mine to the Owen Lake area, where they host the Silver Queen deposit (Church, 1984). These rocks, which have been dated at 75 to 80 Ma by K-Ar whole rock (Church, 1973; Leitch et a!., 1991) consist of a lower felsic volcanic unit overlain by andesites and dacites of the Tip Top Hill volcanics (Church, 1984). This subdivision is based on ‘rhyolitic volcanic rocks below the Tip Top Hill Formation in the Owen Lake area in extensive drill holes in the vicinity of the Silver Queen min& (Church, 1973), which he considers to be ‘lateral equivalents of quartz porphyry intrusions exposed nearby on Okusyelda Hill’ (Figure 4-2). Recent mapping indicates that the lower volcanic unit exposed in the drill holes may, in part, be a strongly altered equivalent of the Tip Top Hill volcanics (Leitch et a!., 1991). The quartz porphyry of Okusyelda Hill could correlate with dacitic quartz porphyry sills, dikes and laccoliths common within the type Kasalka Group section in the Tahtsa Lake area. Late quartz-feldspar porphyry dikes are also found at the Equity mine (Cyr et a!., 1984; Church, 1985), although these are dated at 50 Ma and thus belong to the younger Ootsa Lake Group. The Upper Cretaceous rocks are overlain by Eocene Ootsa Lake Group rocks, which include the Goosly Lake and Buck Creek formations of Church (1984). The Goosly 79  Lake andesitic to trachyandesitic volcanic rocks are dated at 48.8 ± 1.8 Ma by K-Ar on whole rock, and this is supported by similar dates of 49.6 ± 3.0 to 50.2 ± 1.5 Ma for related syenomonzonite to gabbro stocks with distinctive bladed plagioclase crystals at Goosly and Parrot Lakes between Equity and Silver Queen (Church, 1973). Andesitic to dacitic volcanic rocks of the Buck Creek formation, which directly overlie the Goosly Lake Formation, are dated at 48.1 ± 1.6 Ma by K-Ar on whole rock (Church, 1973). The Goosly Lake and Buck Creek formations correlate with Ootsa Lake Group rocks in the Whitesail Lake area south of Tahtsa Lake dated at 49.1± 1.7 Ma by K-Ar on biotite (Diakow and Koyanagi, 1988), but are slightly younger than dacite immediately north of Ootsa Lake, dated at 55.6 ± 2.5 Ma by K-Ar on whole rock (Woodsworth, 1982). Basalts of the upper part of the Buck Creek formation (Swans Lake Member: Church, 1984) may correlate with the Endako Group of Eocene-Oligocene age. These rocks give dates of4l.7 ± 1.5 to 31.3 ± 1.2 Ma by K-Ar on whole rock samples from the adjacent Whitesail Lake map-area (Diakow and Koyanagi, 1988; cf. the range of 45-40 Ma reported by Woodsworth, 1982). The youngest rocks in the Buck Creek basin are cappings of columnar olivine basalt of Miocene age, called the Poplar Buttes Formation by Church (1984). These have been dated at 21.4 ± 1.1 Ma by K-Ar on whole rock (Church, 1973) and are correlated with the Chilcotin Group.  4.3. Geology of the study area  The preliminary geology of the study area immediately surrounding the Silver Queen mine, as determined by fieldwork and petrological studies completed in 1989-1990, is shown in Figure 4-2 (units are defined in Table 4-1). Relationships between the map units are shown diagrammatically in Figure 4-3. The succession is strikingly similar to that observed in the Kasalka Range (Maclntyre 1985) and on Mount Cronin (Maclntyre and Desjardins, 1988). 80  Okusyelda I-lilt  Sb 4  76 70  2  4 1’.  5b _••_  4  ‘  Emil  2  George  \ 3,  b 0 4  .5  Lake  BartteVebt\  i  *1-47  c  Sear Veki/ 2sf / 2  No. 2 Vein // No.1 Vein7\26 George Lake 5 n CLIneament Vein , 0 4 •[;/ S  0  5 Camp V ns  5  No. 5  :---v  .  -.  A  .  \  \eo.  .  08  ,,  2 V  5  ...  .  3  •.  £  Sw(tchback Veki  .25  5  No. Vein  Ruby Vein S V  -.-.-.-  ci  ,  CF  2  5a  NG 3 Vein 5a  \Cttuci 60  .:  NG 6 Ven  2  .-.  •,,,  2  Lead Ve  11O  —  \.  \7I  3  85  -.,tfll N  •  oleVetri System  ‘  76  —  Q-  Mine  60  6  Lake  ‘k.  78 70  ..  --...  \  Copper Veja  George  26/  i-1&  ‘  \  \3 :°  2  “,>.  holm Veins 2 0 —  0  200  400  1000  •  .  eoo 2000  Boo  1000 metres  3000 f€et  4  4-2. Detailed property geology of the Silver Queen mine, Owen Lake area, central British Columbia (from Leitch et al., 1990). Units are defined in Table 4-1.  Figure  , t, c 5  \0.  7e1  west-  81  Esv :E5E:EEEEEEEESJ7’8  7a V V V  V K  XZfl  V V  LJV % < 7  v  4  t  :  —  :  ÷  V V V V V V  V V  I,  , Owen Lake Figure 4-3. Schematic diagram of stratigraphic and intrusive relationships et al., area, west-central British Columbia. Units are defined in Table 4-1 (after Leitch 1990).  82  Table of formations, Owen Lake area*  Table 4-1. Period  Epoch  Tertiary  Miocene  Age  4a  )  21  Eocene-  45-  Oligocene Eocene  30  5647  Formation  Symbol  Poplar Buttes  MPBV  Endako Group  EOEV  Ootsa Lake Group  E  Mineralization  veins  “Okusyelda”  uKqp uKp  Cretaceous (Late)  uKud 8575  “Tip Top Hill’  formation  Unit  Lithology  8  Olivine basalt Basalt diabase dike  7a  Trachyandesite basalt  7  Bladed feldspar porphyry dike  6  Amygdular dikes  dike  5b  Quartz-eye rhyolite stock,  5a  Intrusive porphyry sills, stocks  4a  “Mine Hill” microdiorite Feldspar-biotite porphyry dike  5  uKfp  4  uKb uKt  2  3  Medium to coarse tuff-breccia  uKc  2a 1  Crystal tuff, local lapilli tuff Fine ash tuff Polymictic basal conglomerate, sandstone and shale interbeds  “Tip Top Hill” andesite  *p.fter Leitch et al., 1990  The rocks of the study area have been subdivided into five major units plus three dike types; Table 4-1 lists the map units defined to date. A basal reddish purple polymictic conglomerate (Unit 1) is overlain by fragmental rocks ranging from thick crystal tuff (Unit 2) to coarse lapilli tuff and breccia (Unit 3), and this is succeeded upwards by a thick feldspar porphyritic andesite flow unit (Unit 4), commonly grading into and locally intruded by microdiorite sills and other small intrusions (Unit 5). The stratified rocks form a gently northwest-dipping succession, with the oldest rocks exposed near Riddeck Creek to the south and the youngest exposed in Emil Creek to the north. All the units are cut by dikes that can be divided into three groups: amygdaloidal dikes (Unit 6), bladed feldspar porphyry dikes (Unit 7), and diabase dikes (Unit 8). The succession is unconformably overlain by basaltic to possibly trachyandesitic volcanics that crop out in Riddeck Creek and further south. These volcanics may be correlative with the Goosly Lake Formation  83  (Church, 1973). The units are described below in detail, to facilitate comparison with other possibly correlative rocks.  Basal Polymictic Conglomerate (Unit 1) The basal member of the succession is a reddish to purple, heterolithic, poorly sorted pebble conglomerate that contains rounded to subangular small white quartz and gray-brown to less commonly maroon tuff and porphyry clasts. Local interbeds of purplish sandstone with graded bedding are found within the unit, as are rare black shaly partings. The matrix is composed of fine sand, cemented by quartz, sericite and iron oxides. The best exposure is found in a roadcut at the southern tip of Owen Lake, where the unit is about 10 m thick and dips 25° to the northwest. The base is not exposed and the unit is in presumed fault contact with the younger volcanic rocks of the Ootsa Lake Group (Goosly Lake Formation; Unit 7) exposed at higher elevations farther south along the road. In drill holes farther north, near the centre of the property, the upper contact of the conglomerate with overlying porphyry is sharp and appears conformable, but the porphyry may be an intrusion rather than a flow.  Crystal-Lithic Tuff (Unit 2) In outcrop, the next major unit is a sequence of mainly fragmental rocks that are mostly fine crystal tuffs with thin interbeds of laminated tuff, ash tuff, lapilli tuff and less abundant breccia. The unit may be as much as 100 m thick. The most widespread rock type is a massive, gray to white, strongly quartz-sericite-pyrite altered, fine crystal tuff that grades imperceptibly into a porphyry of similar appearance and composition; the latter may be partly flow, intrusive sill, or even a welded tuff. Only the presence of broken phenocrysts and rare interbeds of laminated or coarsely fragmental material suggest that the bulk of this unit is tuffaceous. In thin section, the rock is seen to be made up of 1 to 2 mm broken, altered plagioclase relics and 0.5 mm anhedral quartz grains (that may be 84  partly to entirely secondary) in a fine matrix of secondary sericite, carbonate, pyrite and quartz. Drill core exposures show that the basal contact of Unit 2 with the underlying conglomerate is commonly occupied by the porphyry rather than the tuff. The best exposures of Unit 2 are in the area of Cole Creek and the Chisholm vein, where thin (10 cm) interbedded laminated tuff bands occur, many with variable dips to near-vertical, although coarser lapilli tuff lenses, up to 1 m thick, display gentle northerly dips. In drill core, sections of laminated tuffs with faint but discernible layering on a cm scale, may be up to 10 m thick; angles with the core axis suggest a gentle dip for the banding. Outcrops on the northeast side of the George Lake fault have rare interbeds of a very fine, uniform “ash tuff’ that are up to several m thick (Unit 2a). Typically they are dark gray to medium gray-green and have a siliceous appearance. Locally they contain angular fragments of either mixed origins (heterolithic clasts) or of larger blocks that are only barely distinguishable from the matrix (monolithic clasts).  Coarse Fragmental Unit (Unit 3) A distinctive coarse fragmental unit overlies, or in some places is interlayered with, the upper part of Unit 2. It is composed of blocks and bombs(?) (cf. Maclntyre, 1985) of feldspar-porphyritic rock similar in appearance to both the underlying porphyry and the overlying porphyritic andesite. The clasts are mostly angular to subangular and about 2 to 5 cm in diameter, but some are much larger (up to 0.5 m); the matrix makes up a widely  variable percentage of the rock, from almost 0 to 90 per cent. In places the rock has the appearance of an intrusive breccia with little or no rotation of fragments. In other places the fragments are clearly unrelated and “accidental” or unrelated clasts of chert or fine tuff are common, although still volumetrically minor; this has the appearance of a lahar. In outcrop near the Cole veins, this breccia unit forms discontinuous lenses generally less than 10 m thick, with a suggestion of gentle northerly dips. The lenses appear to be conformable with the underlying or enclosing tuffs. In drill core, two 85  distinctly different modes of occurrence are noted for this unit: in one, it appears to be conformably overlain by Unit 4 porphyritic andesites (the total thickness of the breccia unit is up to 30 m); in the other, it appears to have subvertical contacts, implying it is an intrusive breccia. Good examples of the latter distribution are found in the Cole Lake area, the Camp vein system and around the southern end ofNumber 3 vein (Leitch et al., 1991). There is thus a general correlation between the subvertical breccia bodies and mineralized areas, just as there is between the microdiorite and mineralized areas. In thin section, the clasts of the breccia are seen to be composed of highly altered andesite, fine tuff and quartz or quartzofeldspathic rocks, enclosed in a fine tuffaceous matrix. Alteration in the mine area is usually carbonate-sericite-quartz-pyrite.  Andesite (Unit 4) The fragmental rocks appear to be conformably overlain by a thick, massive unit of porphyritic andesite that outcrops over much of Mine Hill and is best developed north of Wrinch Creek. This unit is equivalent to the Tip Top Hill volcanics of Church (1970), although in most places on the property the andesite is coarser and contains sparser phenocrysts than the exposures on Tip Top Hill. At exposures in Wrinch Creek canyon, a distinct flow lamination is developed by trachytic alignment of phenocrysts, best seen on weathered surfaces. This suggests that these andesites are mostly flows, with gentle northerly to northwesterly dips. However, some of the coarsest material probably forms intrusive sills and stocks [cf. the type sections of Maclntyre and Desjardins (1988) and Maclntyre (1985)1 and in many places the andesite grades into intrusive microdiorite. Parts of this unit, particularly in Emil Creek, west ofEmil Lake, and on Tip Top Hill itself, may actually be crystal tuff. In these exposures, the feldspar phenocrysts are smaller, much more crowded and in places broken, and rare lithic fragments are visible. Unit 4 has a Late Cretaceous K-Ar whole-rock date of 78.3 ± 2.7 Ma and 77.1 ± 2.7 Ma reported by Leitch et al. (1992) and Church (1973), respectively. Rhyolite from 86  Tsalit Mountain on the west side of Owen Creek valley, 10 kilometres northwest of the Silver Queen mine, gives a very similar isotopic date of 77.8 ± 3.0 Ma, also by K-Ar on ’ quartz porphyry by (Church, 1 whole rock. This rhyolite is correlated with the Okusye1da 1973). In thin section, the andesite is seen to contain abundant 2 to 3 mm euhedral crystals of andesine. Oscillatory zoning is present, but with little overall change in . Mafic minerals include roughly 35 45 to An composition within a given specimen, from An equal amounts (about 5% each) of 1-2 mm clinopyroxene and hornblende, and euhedral 1 to 2 mm biotite phenocrysts. The groundmass is an aphanitic mesh of intergrown feldspar with minor opaque grains; primary magnetite is abundant in the fresh specimens.  Biotite-feldspar porphyry dikes (Unit 4a) Rare thin (1 m or less) dikes, similar in composition and appearance to the flows of unit 4, probably represent feeders to flows of unit 4. They are distinguished by prominent scattered books of black biotite up to 3 mm across, as well as abundant, 1-2 mm, plagioclase phenocrysts. These dikes have only been recognized near the north end of Cole Lake and on the highway at the north end of Owen Lake, but they could be more extensive (they are difficult to distinguish because of their similarity to unit 4). They are dated by K-Ar on whole rock at 70.3 ± 2.5 Ma, indicating a possible 7-8 Ma span of Tip Top Hill volcanic activity (Leitch et al., 1992).  Microdiorite (Unit 5) Microdiorite forms subvolcanic sills, dikes, and possibly, small irregular stocks on the Silver Queen mine property. These intrusions are centrally located in the two main mineralized areas of the property, the No. 3 Vein and Cole vein areas. Contacts with the andesite are indistinct or gradational. Typically the microdiorite is a medium to fine grained, dark greenish gray equigranular to porphyritic rock characterized by small (1 mm, 87  but locally glomeratic to 4 mm) plagioclase phenocrysts and 0.5 mm mafic relics in a phaneritic pink feldspathic groundmass. Primary magnetite is found in the less altered specimens. It is distinguished in outcrop by its relatively fine-grained, even-weathering texture and lacks the flow structure of the andesite. Because of the gradational relationship to the andesite, distinction is difficult in places. In thin section, the plagioclase is the same as in the andesite (oscillatory zoned andesine, ), 30 and euhedral _ 45 An clinopyroxene phenocrysts, partly altered to carbonate, are the most abundant mafic. Apparent hornblende relics are completely altered to chlorite. No biotite is seen, but rare scattered quartz phenocrysts, displaying late-stage overgrowths of quartz, are observable ranging up to 1 mm in size (these are not visible in hand specimen). The groundmass is composed of fine (0.1 mm) quartz, plagioclase and potassium feldspar. The microdiorite has a K-Ar whole rock age of 78.7 ± 2.7 Ma and 75.3 ± 2.0 Ma reported by Leitch et al. (1992) and Church (1973), respectively. The age of the microdiorite is indistinguishable from the age of unit 4 andesite, in agreement with the gradational contacts between these two rocks.  Porphyry (Unit 5a) Large bodies up to 1000 m across of a coarse feldspar porphyritic rock crop out in the vicinity of Cole Creek and are also found in drill core from the south end of the No. 3 vein system, where the porphyry body usually occurs between Unit 1 and Unit 3. The rock is composed of roughly 50% plagioclase phenocrysts of up to 5 mm diameter and 10 to 20% smaller mafic minerals in a fine feldspathic groundmass. The porphyry is distinguished from the andesite, Unit 4, by its coarser texture and by the absence of flow textures. It probably represents subvolcanic or high-level intrusive bodies that were emplaced below or postdate the extrusive andesite, but are related to the same magmatic event that produced the andesite. Such subvolcanic intrusive bodies, with identical mineralogy to the extrusive porphyritic andesites, have also been noted in the Kasalka 88  Group near Tahtsa Lake (Maclntyre, 1985). No K-Ar whole rock age data is determined for this rock unit because no fresh sample can be found (the outcrops of this unit of rock are always variably saussuritized or sericitized).  Quartz-feldspar Porphyry (Unit Sb) Quartz-feldspar porphyry, which appears to be part of a subvolcanic intrusive stock, crops out along Emil Creek and on Okusyelda Hill to the north of the creek. This unit was called “Okusyeld&’ dacite (rhyolite) by Church (1970). Although its contact relation is uncertain, it appears to intrude Unit 4 (Tip Top Hill volcanics; Leitch et al., 1992). Church (1984) correlates the quartz porphyry intrusions on Okusyelda Hill with felsic volcanic rocks in the Tchesinkut Lake and Bulkley Lake areas, and possibly with the Tsalit Mountain rhyolite of 77.8 Ma. However, in the Kasalka Range, Maclntyre (1985) found sills and dikes of quartz-porphyritic dacite and rhyolitic quartz ‘eye’ porphyry, commonly associated with mineralization, that cut stocks dated at approximately 76 Ma (Carter, 1981). However, the quartz porphyry cannot be significantly younger than the microdiorite-feldspar porphyry in the Owen Lake area; the 84.6 ± 0.2 Ma U-Pb date on zircon shows that it is the same age or older. It is cut by thick calcite veins and quartz sericite-pyrite alteration on the extension of the George Lake vein and so is probably pre mineralization. Thin sections show the quartz porphyry consists of 10 to 15% 2 mm quartz phenocrysts and slightly smaller euhedral andesine plagioclase crystals, plus smaller relic mafic grains, in a microgranular groundmass of roughly equal amounts of quartz, plagioclase and potash feldspar. Quartz, and to a lesser extent, plagioclase also occur as angular fragments.  89  Amygdaloidal Dikes (Unit 6)  Units 1 to 5 are cut by a series of variably amygdaloidal dikes that are concentrated in the two main areas of mineralization (No. 3 vein and Cole vein areas). They generally trend northwesterly parallel to the mineralized veins, but north, east and northeast-trending examples are known. Dips are either subvertical to steep, or else gentle (as low as 200). These dikes are irregular and anastamosing in some parts of the property, for example between the Camp and Switchback vein systems. Highly altered examples are commonly found adjacent to and parallel to veins; elsewhere veins cut through these dikes. These dikes have been referred to previously as ‘pulaskite’ at both the Silver Queen and Equity, but this is an inappropriate term, implying an alkali-rich mineralogy including soda orthoclase, alkali pyroxene or amphibole, and feldspathoids. In underground exposures the dikes range from dark gray-green where fresh, to pale green or creamy-buff where strongly altered in underground exposures; they are purplish in weathered surface outcrops. They are typically fine grained and are characterized by amygdules filled by calcite, or less commonly, iron oxides, particularly at their chilled margins (dikes less than 1-2 m wide commonly lack amygdules), Flow orientations, generally parallel to the walls, provide an indication of attitude in surface outcrops.In the larger dikes (up to 10 m thick) the flow orientations are random. In thin section, the most striking feature of this dike is the abundance of fine, trachytic-textured feldspar microlites that average about 0.25 mm long. Alteration to carbonate and sericite is extensive, but the texture is generally preserved. This dike has an Eocene K-Ar whole rock age ofSl± 1.8 Ma that almost certainly reflects alteration, thus establishing a maximum but likely age of mineralization.  Bladed Feldspar Porphyry Dikes (Unit 7)  A set of trachytic-textured porphyry dikes, 1 to 5 m wide and characterized by coarse (up to 1 cm long) bladed plagioclase phenocrysts, cut and slightly offset the 90  amygdaloidal dikes. The complete lack of alteration in the bladed feldspar porphyry dikes, and the fact that they distinctly crosscut mineralized veins (for example, the Bear Vein, Cole Lake area), indicates that they postdate mineralization. The K-Ar whole rock age of these dikes is 51.9 ± 1.8 Ma, indistinguishable from the K-Ar whole rock isotopic age of the amygdular dikes (Unit 6). Their spatial distribution is also similar to that of the amygdaloidal dikes, with concentrations in the two main mineralized areas; orientations are similar too, but with subvertical dips only. The similarity of these post-mineral bladed feldspar porphyries to the Goosly and Parrot Lake syenomonzonite stocks, and bladed feldspar andesite dikes at Equity dated at 50.7 ± 1.8 Ma by K-Ar on whole rock, suggests that there is a genetic relation among them. In thin section, the bladed feldspar porphyry dikes are composed of large (4-10 mm) plagioclase phenocrysts and rare to locally abundant clinopyroxene crystals up to 5 mm across, set in a dark purplish groundmass of feathery interlocking plagioclase microlites with interstitial quartz, alkali feldspar, opaque and skeletal rutile. The plagioclase forms strongly zoned, oscillatory crystals that range from cores of andesine ). The pyroxene has a strong green color and is probably 15 ) to rims of oligoclase (An 50 (An iron-rich.  Diabase Dikes (Unit 8) Black fine-grained dikes of basaltic composition cut all other units on the property. They are much more limited in distribution than the older dikes, with subvertical dips and northwest or east-west strikes. In thin section, they lack olivine and are composed of diabasic-textured plagioclase set in clinopyroxene, with accessory opaque.minerals The K-Ar whole rock isotopic age of these dikes is 50.4 ± 1.8 Ma, only slightly younger than the dikes of Unit 6 and Unit 7. It is likely that Unit 8 dikes are related to the basaltic Buck Creek Formation (48.1 ± 1.6 Ma; Church, 1973).  91  4.4 Lithogeochemical characters and two series of igneous and volcanic rocks  The various types of igneous and volcanic rocks at Owen Lake area and its peripheral region can be classified into two series according to lithogeochemical features and K-Ar ages. The first series consists of igneous and volcanic units from intermediate to 2 (from felsic composition, and is characterized by having relatively low contents of Ti0 0.36 to 0.8 wt%), MgO (from 0.65 to 4.18 wt%), total iron (from 1.73 to 6.5 wt%) and 5 (from 0.09 to 0.42 wt%) as well as the older K-Ar ages (from 78.8 to 57.2 Ma). In 0 2 P contrast, the second series consists of the igneous and volcanic units from intermediate to 2 (from 0.95 to 1.27 wt%), MgO (from mafic composition, and has higher contents of TiO 5 (from 0.49 to 0.67 wt%) 0 2 2.11 to 7.81 wt%), total iron (from 5.14 to 8.98 wt%) and P as well as younger K-Ar ages (from 48.7 to 21.4 Ma; Table 4-2). The former series predates and hosts the mineralization; the latter is post-mineralization. These two series of 2 binary plot (Figure 4igneous and volcanic rocks can be distinguished by using a Zr-Ti0 4). In Figure 4-4, the amygdaloidal dike composition plots in the middle of the older series of igneous and volcanic rock but has a young age (51.3 Ma). The tentative explanation for this apparent anomaly is that where sampled amygdaloidal dikes were ‘younge& by later hydrothermal activity. It may also be noted that samples of porphyry (Unit 5a) and tuff (Unit 2) plot somewhat off the main trend of the series. These may also arise because of the effects of hydrothermal alteration; dated samples of both of these rock units were not as fresh as the others plotted in Figure 4-4. Lithogeochemical data used to construct Figure 4-4 are selected from relatively unaltered rocks and listed in Table 4-2. Two lithogeochemical analyses with the corresponding K-Ar age known from Church and Barasko (1990) are listed in Table 4-2 to complete the illustration of the relation between the lithogeochemical compositions and the timing of igneous and volcanic activities.  92  —  0  Andesite Porphyry  V  Microdiorite  I  100.00  ArnygdalOidal dike  Ash tuft  0  0  Granite  Rhyolite  Synerrnzonite  Andesitic flow  Diabase dike  Legend  200 Zrppm  300.00  Series I  •1 SeriesIesII  2 binary plot distinguishs two series of igneous and volcanic rocks Figure 4-4. A Zr-Ti0 in Owen Lake area and its peripheral region. Series I has K-Ar age from 78-51 Ma and hosts the Silver Queen vein mineralization. Series II has K-Ar age of 50 Ma or younger and overlies or cuts the veins.  0.00  0.50  [.00-  1.50  29/09/96  Basalt Poplar Buttes  Rock Name Location  SQ-SO  S91-4  213.90 20.80 54.17 922.48 50.4 Ma error on average. 184.40 26.47 99.10 733.87  294.32 26.51 137.16 313.80  220.68 32.69 201.25 423.86 305.64 25.71 92.02 901.97 48.7  30 224.29 29.19 79.54 1148.24 48.8  243.34 27.74 100.61 1187.57  99.19  99.33  99.71  99.58  99.62  98.75  4.73 1.26 0.11 3.15 4.20 4.26 3.16 0.67 0.35 0.90  15.73 6.57 0.99 0.14 2.62 5.31 3.71 3.29 0.63 0.35 2.03 99.64  Granite Nadina Mt.  Rhyolite N Equity  68.03 0.50 14.20 1.04 1.87 0.08 1.76 2.45 3.75 4.68 0.22 0.25 0.36  S91-10  S91-3  72.11 0.36 13.78 1.21 0.52 0.05 0.65 1.27 4.15 4.41 0.09 0.25 0.48  S91-1A Syenmonzonite N. Equity  61.38 0.95 15.38 3.57 1.57 0.06 2.11 4.11 3.96 3.21 0.49 0.60 1.36  60.39 1.06 15.40  55.20 1.24 15.59 3.45 4.33 0.12 4.85 6.65 3.38 1.94 0.59 0.35 1.89  49.64 1.27 15.15 3.34 5.64 0.31 7.81 6.58 2.96 1.53 0.56 1.95 2.88 57.26 1.08  Andesite Riddich Creek  SQ-113  57.2  102.33  67.00 0.67 16.20 2.18 1.58 0.04 1.30 3.30 4.32 3.69 0.28 1.69 0.08  Granite Equity mine  Church-i4  179.31 12.84 122.20 409.23 51.3  9.33 99.38  56.05 0.70 15.14 2.13 2.86 0.09 2.72 4.15 2.53 3.39 0.29  DA48-13 Amygda loidal dike Cole Lake  Lithochemical data of various types of rock at Owen Lake area, central British Columbia  Nadina dike Diabase dike Andesite Nadina Mt. E. Ridge of Wretch Owen Lake Creek  S91-9  4400 Si02 301 Ti02 15.11 A1203 5.11 Fe2O3 7.90 FeO 0.18 MnO 8.62 MgO 9.86 CaO 4.48 Na20 1.73 K20 0.58 P205 3.63 H2O 0.01 CO2 LOl 104.22 TOTAL ppm S Zr Y Rb Sr 21.4 Age (Ma)* * age with about 2 K-Ar dating  wt%  Church-v18  SampleID  Table 4-2.  XLC  99.57 33 191,07 27.95 100.28 592.72 78.3 865 166.44 30.75 92.04 630.05 78.7  57.86 0.65 15.61 3.09 2.89 0.34 2.94 6.07 3.65 3.09 0.38 0.97 2.03  Andesite N. segment of No. 3 vein  x4-4  99.50  57.05 0.69 15.77 2.73 3.77 0.22 4.18 5.78 3.76 2.97 0.42 0.91 1.25  Microdiorite Jack vein  xll-lb  29/09/95  Microdiorite C. segment  of No.3 vein  Rock Name Location  0.18  21 124.27 18.02 77,94 587.77  122.00 158,38 25.75 92.65  153.00 169.80 24.89 118.77 472.32  127  172.67 24.29  119.76 620.61 608.28  100.06  99.54  99.14  100.51  0.27 2.35  573.45  33.05 121.40  29.65 108.22 1071.44  31 178.64  711 168.02  99.60  57.29 0.66 15.70 3.08 2.92 0.25 3.33 5.67 3.39 3.15 0.37 1.04 2.75  99.89  2.16 4.35  3.19 0.28  5.11 3.05  2.50  2.78 7.45 3.22 1.80  2.93  3.43 3.16 0.43  0.16 2.63 6.25  16.04 2.36  56.58 0.67  3.38 0.22  0.13  x2-5  Andesite Andesite South segment N. segment of No. 3 vein of No. 3 vein  x5-6  1.74  56.05 0.80 16.09 4.45  0.93 1.34  2.40  3.09 0.34 1.22  2.18 5.16 3.63  0.26 1.39 1.85  4.92 3.93 3.14  2.78  2.85  2.86 0.14  FeO  MnO MgO CaO Na20 K20 P205 H20 C02 LOl TOTAL ppm S Zr Y Rb Sr Age (Ma)*  0.59 15.98 2.52  0.58 15.11 2.30  Ti02 A1203 Fe203  57.99 0.71 16.53 2.22 3.76  vein  of No.3 vein 59.00  Andesite N. Owen Lake  Microdiorite Switch Back  Microdiorite C. segment  61.25  SQ-119  DA63-1  xlO-6D  0,20 2.64 5.66  0.23 2.61 5.97 3.55 3.04  126.03 18.36 77.13 562.36 75.74 524.71 103.70 597.08  122.52 566.67  607.36  30.36 108.45  24.58 31.91  28.49  445 140.62  180 192.04  160 188.35 180 185.22  2.45 99.50 1.32 99.35 99.70 100.03  1.92 99.50  3.03 4.20 2.62 0.28 5.29 3.81 2.61 0.33  1.82 0.12 3.40  4.76 0.15 2.71  63.22 0.55 14.81 3.00 61.16 0.61 15.53 1.07  porphyry Duck Lake  Ash tuft’ SW Cole hill  2.14  4.09 2.92 0.38 1.27  15.87 2.86 3.05  3.12 2.70  57.97 0.65  S91-15  SQ-77  0.40 2.18 2.34  3.96 3.02 0.39 1.14  0.31 2.87 5.75  0.66 15.85 3.02 2.86  57.20 0.66 16.03  Andesite N. segment of No. 3 vein  Andesite N. segment of No. 3 vein  Andesite N. segment of No. 3 vein 57.75  x3-7  x3-6  x33  Lithochemical data of various types of rock at Owen Lake area, central British Columbia (Continuous)  SiO2  wt%  xlO-6  Sample ID  Table 5-2.  XLC  4.5. Veins: Character and Correlation Mineralization on the property is mainly restricted to 0.1 to 2 m thick quartz carbonate-barite-specular hematite veins that contain disseminated to locally massive pyrite, sphalerite, galena, chalcopyrite, tennantite and argentian tetrahedrite. Locally, in chalcopyrite-rich samples, there is a diverse suite of Cu-Pb-Bi-Ag sulfosalts such as aikinite, matildite (in myrmekitic intergrowth with galena), pearcite-arsenopolybasite, and possibly schirmerite (Hood, 1991). Berryite (Harris and Owens, 1973), guettardite and meneghinite (Weir, 1973), boulangerite (Marsden, 1985) and seligmannite and pyrargyrite (Bernstein, 1987) have also been reported but not yet confirmed. All the Au and much of the Ag are in the form of 60-70 fine electrum, as grains generally less than 50 microns in diameter and hosted in galena that is associated with fine grained pyrite (Hood, 1991). Paragenetically, the mineralization is divided into four distinct stages: Stage I is characterized by fine grained pyrite, quartz and hematite in the central segment of the No. 3 vein. Barite, svanbergite, and binsdalite become abundant towards the south end of the No. 3 vein, with marcasite more abundant towards the north. Stage II is dominated by the presence of massive sphalerite and layered carbonate (calcite in the south, manganoan carbonates in the north). Stage III, however, is more complex. Mineralization consists of chalcopyrite, galena, fahlores (tetrahedrite-tennantite), electrum, quartz and sulfosalts. Included in the sulfosalt assemblage are the unusual Pb-Bi-Cu-Ag species berryite, matildite, gustavite and aikinite. Stage IV is volumetrically minor and is dominated by fine grained quartz, pyrobitumen and calcite (Hood, 1991) The veins cut the amygdaloidal, fine-grained plagioclase-rich dikes (Unit 6), and are cut by the series of dikes with bladed plagioclase crystals (Unit 7). Both these dike types are possibly correlative with the Ootsa Lake Group Goosiy Lake volcanics of 96  Eocene (approximately 50 Ma) age, although chemically the amygdaloidal dikes appear older. The bladed feldspar porphyry dikes cut the amygdaloidal dikes, and both are cut by the diabase dikes that may correlate with Endako Group volcanism of Eocene-Oligocene (approximately 40 to 30 Ma) age. The major veins are concentrated into two main areas on the property centered on the Mine Hill and Cole Lake areas, with an apparently less mineralized area between in which only the George Lake vein has been found to date. However, this intervening area is heavily covered by overburden and more veins may remain to be discovered here (the relatively minor Jack and Axel veins, not shown on Figure 4-2, are located west of the George Lake vein). The most important known vein on the property, both in terms of length and tonnage potential, is the No. 3 which outcrops for over 1000 m on Mine Hill. Its extension to the north appears to taper and die out, but significant potential may exist on faulted extensions to the south where exploration has been hampered by heavy overburden cover. South of Riddeck Creek post-mineralization volcanic cover may preclude further exploration. The predominant strike direction for the main veins is northwesterly, with moderate to steep northeasterly dips. The relatively minor Church, Chisholm and Owl veins also have the dominant northwesterly trend. However, strikes in the Cole Lake, Camp, No. 5 and Switchback vein areas are more variable (see structural analysis below). Dikes and faults on the property have orientations similar to those of the veins, although one major difference is the presence of gently west-dipping dikes; no veins of this orientation are seen. The veins are highly variable in character, ranging from simple massive or banded gangue-rich veins with well-defined walls through irregular massive sulfide veins to ill defined stockwork zones. Note how the No. 3 vein divides into two in its upper part; further division into several sub-parallel thin veins or stringers is common, making correlation difficult even between closely spaced drill holes. In places, the vein pinches 97  out, with the zone of pinching (which correlates with flattening of the vein) raking moderately east in the plane of the vein. Post-mineral shearing is common along the veins, further complicating correlations by attenuating or removing (faulting out) the mineralized section. A strong bleaching alteration envelope (quartz-sericite/kaolinite-carbonate-pyrite alteration) generally accompanies the veining. True thickness of the mineralized structure is also an aid to correlation if the total thickness (e.g. of all the vein strands) is compared from hole to hole. However, the strong lateral and vertical variations make this a less useful tool over longer distances between sections. In general, the tenor of mineralization, as measured by assay composites, is the most reliable correlation tool. Although the assays are necessarily a reflection of vein mineralogy, and mineralogy is useful for correlation, the silver and gold values that have proved to be the most important correlations, cannot be seen visually. Correlation is made more difficult by the presence of one or more hangingwall or footwall veins that are found discontinuously along the length of the major vein structures. The presence of these subsidiary structures has been well established during underground development for exploration of the No. 3 vein; however, in drill core it is difficult to be sure if a given intersection is of a hanging/footwall structure or an en echelon shift of the main vein. In fact, some of the ‘hangingwall’ and ‘footwalP veins are probably en echelon portions of the No. 3 vein; in other places they may be splays off the No. 3 vein (Fig. 4-2). One of the most difficult problems in making correlations is the en echelon character of many of the veins, both along strike and down dip. Resolution of this problem is important because of the implications it has for physical continuity of the vein, and consequently, for tonnage and grade estimations. For example, intersections of veins in the No. 3 vein, George Lake, Camp and Cole Lake areas can be interpreted either as simple tabular bodies or as en echelon lenses (see sections in Fig. 4-5 to 4-9); there may be no vein, or an attenuated vein, in the locations predicted by the simple tabular model.  98  Potential problems are: (1) an increased, non-quantifiable error in tonnage estimation, and (2) disregard for possible different grade character of two en echelon vein segments.  4.6. Structures and the Interpretations The structure of the Silver Queen mine area is dominated by a gently west to northwest-dipping homocline. There is no folding apparent at the scale mapped; the sequence appears to have been tilted 200 to 300 from the horizontal by block faulting. The average bedding plane is 032/25°NW and the most prominent joint set dips steeply, roughly perpendicular to the bedding at 057/77°SE (Leitch et al., 1991). Two prominent sets of faults displace this homoclinal sequence, cutting it into a series of fault panels: a northwest-trending (NW) set and a northeast-trending (NE) set (Fig. 4-2). The former predates or is contemporaneous with mineralization, whereas the latter is mainly post-mineral (a few veins trend east-northeast). The NW faults dip 60° to 80° to the northeast (average 315/75°NE), and the ‘cross’ or NE set appears to be subvertical (070/90°). There are subsidiary trends indicated at 295/85°NE and  085/90°, and a few flat-dipping faults possibly roughly parallel to bedding planes. Most of the mineralized veins and the dikes follow the northwest faults, and in places veins are cut off and displaced by the northeast set. The sense of motion on the northwest faults is such that each successive panel to the east is upthrown, leading to successively deeper levels of exposure to the east. Thus, in the panel between the George Lake and the Emil Lake faults (Fig. 4-2), there is considerably more of the lower fragmental rocks (Unit 2 and Unit 3) exposed than in the next panel to the west, between the Owen Lake and the George Lake faults. There does not seem to be much displacement across the No. 3 vein fault; slickensides seen underground on this structure suggest a reverse sense of last movement with indeterminable horizontal component.  99  SW  0 0  1%  q  wz  00 00 OC  NE  //b  C.,  2600  \O  2500  2400 C C  0  2300  2200  2100  2000  Figure 4-5. Cross-section of Camp vein shows gently dipping dike approximately perpendicular to the steeply dipping vein system. Horizontal scale equals vertical scale. Numbers represent the geological units which are defined in Table 4-1. Thick solid line vein, thin solid line geological contact, ripple line fault, dash line drill, circle drill site. -  -  -  -  -  100  5  2600  116 EEJUT2.8U  5  2500  2400  z  0 >  w  -J Ui  2300  2200  4  2100  Figure 4-6. Cross-section of the southern segment of the No. 3 vein at 21000 E cBU-1 16) to show branching and en echelon character of the vein. Horizontal scale equals vertical scale. Numbers represent the geological units which are defined in Table 4-1. Thick solid line vein, thin solid line geological contact, dash line drill, circle drill site. -  -  -  -  101  22500N  3000  SW 2900  2800  NE 2  -  2700  2  44 2600  2500 b.  i  2400  3 4  2300  U88-06 I  2200  200  U88-075  Figure 4-7. Cross-section of the southern segment of the No. 3 vein at 20,000 E (S-88-3 1) shows branching and en echelon character of the vein. Horizontal scale equals vertical scale. Numbers represent the geological units which are defined in Table 4-1. Thick solid line vein, thin solid line geological contact, dash line drill, circle drill site. -  -  -  -  102  C  Ui -J Ui  >  0  z  2 00  2800  2900  3000  3100  3200  SW  -  -  -  -  later Figure 4-8. Cross-section of Cole vein shows gently dipping dike of unit 6 cut by the dikes of Units 7 and Unit 8. Horizontal scale equals vertical scale. Numbers represent geological units which are defined in Table 4-1. Thick solid line vein, thin solid line geological contact, dash line drill, circle drill site.  NE  NE  SW  2900  2800 0  4  z  0  I  4  2700  > LU -J LU  2600 Lev& X-Cut 2600  4  4  2500  2400  ut, y Figure 4-9. Cross-section of George vein at the 2600 foot level of the Bulkle cross-c ntal with the available intersections interpreted as part of an en echelon system. Horizo in defined are which scale equals vertical scale. Numbers represent the geological units drill, circle Table 4-1. Thick solid line vein, thin solid line geological contact, dash line drill site. -  -  -  —  104  The sense of motion on the northeast faults appears to be south side down, with a small component of sinistral shear. Offsets of No. 1 and 2 veins across the fault along Wrinch Creek (Fig. 4-2) suggest a few m of left-lateral displacement, but the displacement of an amygdaloidal dike near the portals of the 2880 level suggests the south side must have dropped as well. The boundaries of this fault zone, and its dip, are not well constrained; in outcrops in Wrinch Creek, it appears as a vaguely defmed zone up to 10 m wide, with segments that have possible shallow southerly to moderate northerly dips. The Cole Creek fault is not well exposed at surface; a splay from it may cause the change in orientation of the No. 3 vein to the Ruby vein (Fig. 4-2). A considerable left-lateral offset of as much as 200 m is suggested by drill-hole intersections of the NG3 vein, which may be a faulted extension of the No. 3 vein south of the Cole Creek fault. Underground, this fault is exposed at the southernmost extent of drifting as a northeast-trending gouge zone 1 to 2 m thick. Other examples of minor northeast faults are seen underground. Most of the dikes show similar orientations to the veins (310-325160-85°NE), with the pre-mineral amygdaloidal dikes commonly found parallel and adjacent to the veins. Along the No. 3 vein, one such major dike causes significant dilution problems due to the incompetent nature of some of these soft, strongly clay-altered dikes near the veins. There is one major exception to this northwest trend: a prominent gently westdipping (323/33°SW) set of Unit 6 (pre-mineralization amygdaloidal dikes) is well developed in both the No. 3 vein, Camp and Cole Lake areas (Fig. 4-5, 4-7, 4-8 and 49). This gently-dipping set is roughly orthogonal to the main, steeply northeast dipping dikes and veins, and also roughly parallel to the general gentle westerly dip of the host stratigraphy. A similar orthogonal fracture pattern, with steeply dipping fractures better mineralized and with stronger alteration surrounding them than the gently dipping fractures, is also observed in outcrops in Wrinch Creek.  105  4.7. SUMMARY The sequence of rocks exposed in the Silver Queen mine area, mapped as Tip Top Hill Formation (Church, 1984) is petrographically and stratigraphically similar to the Kasalka Group as defined in the Tahtsa Lake area by Maclntyre (1985) and the Mount Cronin area by Maclntyre and Desjardins (1988). The section in all three areas comprises a sequence from a basal, reddish purple heterolithic conglomerate upwards through a sequence of fragmental volcanic rocks, to a widespread, partly intrusive porphyritic andesite, all intruded by a distinctive microdiorite. However, K-Ar dating suggests that the rocks in the Silver Queen mine area are of Late Cretaceous age; both porphyritic andesite volcanics and microdiorite are about 78 Ma. This is younger than the Kasalka Group rocks in the type section near Tahtsa Lake, which give dates of 108 to 107 Ma near the base, and are cut by intrusions dated at 87 to 84 Ma (Maclntyre, 1985). These dates actually straddle the Early to Late Cretaceous boundary (Harland et al., 1989). Thus, there may be two episodes, with the later one as young as 78 Ma (Leitch et al., 1991). Possibly the magmatic front associated with mid- to Late Cretaceous volcanic activity took longer to arrive further inland (i.e. 65 kilometres in 30 Ma gives a rate of advance of 0.22 cm per year, comparable to the rate of 0.25 cm annually suggested by Godwin, 1975; cf. Armstrong, 1988 and Leitch, 1989). Mineralization in epithermal veins at the Silver Queen mine occurred after the time of deposition of the Late Cretaceous Kasalka Group and before the intrusion of Early Tertiary post-mineral dikes dated at about 50 Ma. Some of these dikes may correlate to the Goosly Lake trachyandesite volcanics (49 Ma) of the Ootsa Lake Group and syenomonzonite stocks (50 Ma) found at Equity Silver mine and Parrot Lakes (Church, 1973). Another dike is diabase (50 Ma), which also cuts the vein. It may correlate with the Buck Creek basaltic volcanics, dated at 48 Ma (Church, 1973). Although the main outcrop areas of Kasalka anclesite and microdiorite correlate with the main areas of mineralization, and a genetic link has been postulated between two (Church, 1970), the 106  Late Cretaceous Kasalka andesite and microdiorite must have preceded mineralization by at least 25 Ma. So far there is no evidence at Silver Queen that the Early Tertiary dikes have remobilized older mineralization. Recognition of the fact that significant mineralization at Equity and Silver Queen is Early Tertiary in age, but is found in regionally correlative Upper Cretaceous rocks has important implications for metallogeny of the area. Since no significant mineralization has been found to date in the Early Tertiary rocks, it may be postulated that the Upper Cretaceous rocks represent a regional metallotect for base- and precious-metal mineralization. More significantly, it is possible that only the older (Cretaceous) rocks were sufficiently structurally prepared for ore deposition during a period of widespread magmatism during the Early Tertiary (Leitch et al,, 1991).  107  Chapter 5.  Hydrothermal Alteration at the Silver Queen mine: Field and Petrographic Characters  5.1. Introduction  The aim of this chapter is to describe petrographically the various hydrothermal alteration types, the spatial zonation of alteration associated with precious- and base-metal veins in volcanic sequences and the paragenetic sequences of the alteration mineral assemblage at the Silver Queen mine. Hydrothermal alteration at the Silver Queen mine has been examined in a preliminarily way by other workers. Most of the previous work focused mainly on the alteration types and only briefly discussed the spatial zonation of alteration. Fyles (1984) stated that clay with or without sericite is common at the Silver Queen mine, the principal clay mineral is kaolinite and the principal carbonate is siderite. Bernstein (1987) reported that alteration envelopes associated with Zn-Pb-Cu-Au-Ag sulfide-rich veins at the Silver Queen mine are characterized by silicification and argillic alteration. Church and Pettipas (1990) noted that the veins at the Silver Queen mine are commonly in an argillic envelope within a broader aureole of propylitic alteration. Cheng et al. (1991) presented field descriptions and a preliminary petrographic study of the hydrothermal alteration envelopes. Emphasis in the present chapter is given to the qualitative identification of the alteration mineral assemblages, their spatial zonation in the wall rock, specifically andesite (Unit 4) and microdiorite (Unit 5) of the vein and their paragenetic sequences. Results are based on 20 km 2 field mapping, drill core logging, 72 whole rock sampling, 140 thin section examination and X-ray diffraction analysis. These investigations have defined a specific succession of related alteration and mineralization events at the Silver Queen mine and contribute to the development of a genetic model for this type of mineralization system.  108  5.2. Petrography of Hydrothermal Alteration Types Six types of hydrothermal alteration have been recognized at the Silver Queen mine, viz. (i) propylitization, (ii) carbonatization, (iii) sericitization, (iv) argillization, (v) silicification and (vi) pyritization. They are fhrther classified into three zones on which carbonatization is superimposed to various degrees: propylitic alteration halo, sericitic argillic alteration outer envelope, and silicic-pyritic alteration inner envelope. Detailed descriptions of these hydrothermal alteration types at the Silver Queen mine are given below. Propylitic alteration is typically a weak alteration (Cheng, et al., 1991).  Propylitically altered andesite is black or dark green in color, dense and hard. A strong magnetic character that can be tested easily in the field with a hand magnet indicates the presence of relatively abundant magnetite. The propylitically altered andesite is typical of those with porphyritic texture. A common mineral assemblage for the propylitically altered andesite is: aphanitic groundmass (about 40%), plagioclase (3 5-40%), clinopyroxene (0-6%), hornblende (04%), biotite (0-2%), epidote (0-4%), chlorite (4-8%), carbonates (1-15%), sericite (18%), and accessory magnetite and ilmenite (about 5%) and apatite and zircon (trace). Of these, plagioclase, biotite, augite and hornblende are replaced by epidote, chlorite, carbonate and sericite to various degrees. Pseudomorphs of epidote, chlorite and carbonate after clinopyroxene and hornblende are commonly well preserved. The remaining minerals are not obviously affected by hydrothermal alteration (Figure 5-1). Propylitically altered microdiorite has features roughly equivalent to those of propylitically altered andesite, except that it is paler in color and of granular or porphyroid texture. A common mineral assemblage for the propylitically altered microdiorite is: unidentified fine grain minerals (about 10%), plagioclase (25-35%), augite (0-6%), hornblende (0-4%), K-feldspar (about 10%), quartz (about 10%), epidote (0-2%), chlorite  109  I •“ $fr  *I$ 4W  I -  r.. ‘--:  V  ‘—  i  0.2 mm -  ro ui d -n j S S  C).2 mm  Figure 5-1. Photomicrograph (crossed nicols) of propylitically altered andesite with superimposed carbonatization (SQ-44: surface outcrop sample from the southern segment of the No. 3 vein). Plagioclase (P1) phenocrysts are partially replaced by sericite (Ser) and carbonate (Carb). Augite phenocrysts are completely replaced by epidote (Ep), chlorite (Chi), carbonate and magnetite (mt).  110  (3-10%), carbonate (5-15%), sericite (2-8%), and accessory magnetite and ilmenite (about 5%) and apatite and zircon (trace). The grain sizes of plagioclase, augite and hornblende are relatively coarser. They are commonly replaced by: epidote, chlorite, carbonate and sericite to various degrees (Figure 5-2). Sericitic-argillic alteration commonly appears as a bleached outer envelope around a vein. This type of alteration is called as ‘moderate’ and is more intense than propylitic alteration. Microdiorite and andesite having this type of alteration are softer and paler than their propylitic alteration equivalent. Magnetite is altered to hematite or pyrite. Biotite is unstable in this type of alteration and is progressively replaced by muscovite. Pseudomorphs of primary minerals, especially plagioclase, are remarkably well preserved. Recrystallization, especially of quartz, is obvious in the groundmass. Sericite, kaolinite and carbonates are the major dominant mineral phases and are commonly present with very fine grain size (Figure 5-3). An approximate mode of this type of altered rock is: unidentified fine grain minerals (about 25%), sericite (16-42%), kaolinite (0-28%), quartz (15-20), hematite (2-6%), pyrite (0-5%), siderite and dolomite (4-10%) as well as trace amount of apatite, rutile and zircon. Silicic and pyritic alteration is the most intense alteration type at the Silver Queen mine in terms of the variations of mineral composition and rock texture. It can develop particularly intensely altered zones of hard, pale apple green rock where fresh and orange-yellow on weathered surfaces. No magnetite is present. A distinctive feature of this type of alteration zone is that pseudomorphs of primary minerals are not preserved as well as they are in sericitic and argillic alteration zones. The texture of the silicification and pyritization alteration zone is mosaic or polygonal (Figure 5-4). The rock is characterized by having a simple mineral assemblage. For example, unidentified fine grain minerals (about 20%), quartz (26-30%), sericite (10-28%), kaolinite (0-24%), carbonates (1015%) and pyrite (10-15%) as well as trace amount of apatite, rutile and zircon.  111  • 4-  k  I  0.5 mm  Figure 5-2. Photomicrograph (crossed nicols) of propylitically altered microdiorite with superimposed intense carbonatization (SQ-85: surface outcrop sample from the Cole lake segment). Note rock has an unequal-granular texture. Pseudomorph of carbonate after augite and some plagioclase (P1) crystals partially replaced by carbonate (carb) and sericite (ser) are relatively coarse grained. Compare to Figure 5-1. Primary augite phenocryst is completely replaced by carbonate instead of by epidote, chlorite and carbonate. 112  0.2 mm CO LI fl d mass Ser— Kao  Qtz  Cia LI n d rn ass  Figure 5-3. Photomicrograph (crossed nicols) of sericitized-argillized andesite (X5-3: underground sample from the southern segment of the No. 3 vein). Note pseudomorph of sericite (Ser), kaolinite (Kao) and quartz (Qtz) after plagioclase; pseudomorph of sericite and carbonate (Carb) after mafic phenocryst.  113  0.2 mm  Figure 5-4. Photomicrograph (crossed nicols) of silicified-pyritized microdiorite (X5-1O: underground sample from the southern segment of the No. 3 vein). Note the replacement of sericite (Ser) by abundant quartz (Qtz) and the formation of abundant pyrite (Py). The pseudomorph of sericite and kaolinite (Kao) after plagioclase is not preserved as well as those in the outer sericitic-argillic alteration envelope.  114  Carbonatization superposed on propylitically altered rock is characterized by the  further replacements of epidote, chlorite and plagioclase by carbonates. Where the rock is intensively carbonatized, epidote and chlorite are completely replaced by carbonates which become pervasive in the rock (Figure 5-2). Of the carbonates calcite is an abundant species characterized by reacting with diluted acid fiercely. Carbonatization is also observed in the visible alteration envelope (sericitic and argillic alteration, and silicification and pyritization envelope as described below) as replacements of calcite and chlorite by Fe- and Mg-carbonates such as siderite and dolomite.  5.3. The Spatial Distribution of Hydrothermal Alteration  In general, the zonation of hydrothermally altered rocks in the Silver Queen mine district consists of a broad propylitic alteration halo which gives way as the polymetallic vein is approached to a broad bleached outer sericitic-argillic alteration envelope, which in turn gradates into a narrow inner silicic-pyritic alteration envelope (Figure 5-5). All rocks within the study area, that are older than mineralization, have affected some degree of propylitic alteration. That is, an early stage of propylitic alteration appears ). The least propylitized andesite and microdiorite are 2 to be regional in extent (>20 km  characterized by only slight alteration of plagioclase by sericite and partial replacement of mafic minerals (clinopyroxene and hornblende) by epidote and chlorite with very minor carbonate. A propylitically altered rock with superimposed carbonatization has been recognized at the Silver Queen mine through the examination of a total of 140 thin sections from various successive profiles cross-cutting the No. 3 vein throughout its length and rock samples altered to various degrees from different parts of the Owen Lake area. The spatial distribution of propylitically altered rocks with superimposed carbonatization is controlled by a complicated structure system, rather than by being restricted to the vein and associated mineralized structures. Samples collected a few hundred metres away from a vein commonly have intense propylitic alteration with superimposed carbonatization, 115  ‘  o  /  ,,  / ////  •  .  • / - / / / /  +  +  /  \  /  + +  + +  +  +  +  +  +  +  +  ‘i  ÷  +  ,  4+  +  _—-  •1-  +  ÷  +  ÷  +  +  +  + +  +  S  +\ +  +  + + + + +  •+  4-  +  +  +  +  + -  —  +  +  + \ \  +  ÷.  ÷ ÷  + +  ÷  +  +  ÷  +  +  +  +  ÷  —  —  —  \  +  \+  +  ‘-  +  ,  +  //  “+ + + 4+  /////  /  +  N-  +  //////////////////////  i///////////////////  ÷  +  -  \÷\  +  +  +\÷ +  +  +  -  +  ±  +  /,-.--  ÷  +  7  +  +  +  + 4+ + ‘-f\ + — + +‘ + 4+ + +\+... + + + + + + + + + + + + + + + + + +\— + + + + +  +  \+‘\ i÷ ÷  +  ÷  +  +\+ + + \ + +\ + \+\ + +  -I-  + + + + + + + + + + 4- + ++ +  + + + + + + + -J-- +  I  20000 E  iii ,,,,, ,,,,,,,,,,,, //, _///////////////// /1/ //////////////////  / ,  .-  ÷  +  -I+\ 4+. + + +\ + +  \/  +  -4  +  ///____  m_  /  /  _////  “  + / / ‘  ,k?<4\,8///VV/  .  4-  ‘‘I,,  -“‘I,,  +  +  +  +  -  +  2  I  vein  Sharp contact  Gradational contact  Pyroclastic rock  Propylitic microdiorite  Propylitic andesite  0  ,.  V V 9 V V 7 7 ‘7 V99VV7V7 •••.z••• ‘79 ‘7 ‘7 V ‘7 7 9 SZV -.— 7 7 7 V v-  ‘777999 7 7 7 797 V V V 7 7 7 7 V 7 7 7 7 7 7 V V.’  Underground working  (I Silicic/pyritic inner [j alteration envelope  /  I  21000 E  Figure 5-5. Schematic plan of hydrothermal alteration on the 2600-foot level, Silver Queen mine (modified from Cheng Ct al,, 1991).  I  I  N-.  A  (Northern  ,,  +  +  19000 E  --  + + + ÷ ++ + + + + + + + + + + + + + + + + + + +  +  +  18000 E  ‘,,/‘/,////,//////////+  126 °44  c’  r)  C  (5)  Z  similar to or even stronger than those collected only a few metres from the bleached alteration envelope around the vein. In contrast, there is a tendency for the intensity of carbonatization in propylitically altered rocks at the southern segment of the No. 3 vein to be stronger than that at the northern segment of the No. 3 vein (Figures 5-6 and 5-7). The bleached alteration envelope is characterized by having remarkable zonations both parallel and perpendicular to the vein. Three representative alteration profiles cross cutting the No. 3 vein at the 2600 foot level of the southern, the central, and the northern segments are illustrated in Figures 5-8a, 5-8b and 5-8c. In general, all alteration profiles have the following zonation parallel to the vein: (1) An outer sericitic and argillic alteration envelope commonly has a relative ‘sharp contact’ that grades from a bleached envelope into a dark colored propylitic wall rock within a few centimetres (Figure 5-9). (2) An inner silicification and pyritization envelope immediately adjacent to the vein has a gradational contact with the outer sericitic and argillic alteration envelope (Figure 5-10). Zonation of alteration envelopes perpendicular to the veins are also presented. In detail, the silicic and pyritic inner envelope is almost absent at the northern segment of the No. 3 vein. Also, the alteration envelope is more argillic at the northern segment compared with the southern segment of the No. 3 vein which has more sericite than kaolinite. Silicification and pyritization are more intense at both the central and southern segments than at the northern segment of the No. 3 vein. In addition, the width of the alteration envelope is narrower along the northern segment of No. 3 vein (total width about 7 m wide) than adjacent to the central and southern segments of the No. 3 vein (total width up to 130 m wide). Some alteration envelopes around veins are distributed asymmetrically. For example, the widths of the alteration envelopes at the northern and central cross-cuts of  117  -  ‘  F  :\  ;;:;:  Figure 5-6. Photomicrograph (crossed nicols) of least propylitically altered andesite in the northern segment of the No. 3 vein (X3-7: underground sample from the northern segment of the No. 3 vein). Note primary phenocrysts (augite and plagioclase) are slightly altered along their margin and cleavages. Aug augite; P1 plagioclase, Mt magnetite. -  -  -  118  -4  I.  0.2 mm  C ra u n d rn ass  GroUnd in ass  C roUnd in ass  Figure 5-7. Photomicrograph (crossed nicols) of propylitically altered andesite with superimposed carbonatization in the southern segment of the No. 3 vein (SQ-44: surface outcrop sample from the southern segment fo the No. 3 vein). Note pseudomorph of chlorite (Chi) and carbonate (carb) after augite, partial replacement of plagioclase (P1) by carbonate and sericite (ser). Ap apatite Crossed nicols. -  119  hermally altered wall rock at the northern Tabel 5-la. Estimated modes of alteration minerals in hydrot Columbia segment of the No. 3 vein, Silver Queen mine, central British Mode (Volume %)  Sericitic  Propylitically altered andesite  with  superimposed  carbonatization 6 7 8  and argillic alteration envelope  5  4  3  2  1  0.5  0  25  25 0  25 0  20  0  0  1  0  0  0  0  25 0 0  20  5  25 0  0  0  0  7  7  0  0  0  0  1  3  6  4  4  4  0 5  0 5  0  4  5  5  4  4  0  0  0  0  0  0  0  0  0  0  0  0  4  4  3’  3  3  4  5  feldspar  35  36  39  35  35  0  0  0  0  0  0  0  Muscovite  3  1  1  3  3  27  27  22  22  18  18  16  0  0  0  25  25-  26  26  27  28  28  20  20  22  25  25  100  100  10  9  unknown* augite&Hb  40  40  40  7  9  10  7  Epidote  1  Chlorite  5  2 4  2 2  Carbonate  3  Magnetite  4 5  Pyrite  Distance(m)  0  40  40  0  Kaolinite  0  Quartz  0  0  0  0  0  15  15  Total  100  100  100  100  100  100  100  100  100  100  100  i:i  Quartz  90  I  Kaolinite  80  6  Muscovite  till Feldspar  70 60 -  50  Magnetite  40  Caibonate  30  Chloiite  20  Epidote  /  P3’X & Fib  10 D  0  unknown  Distance from the vei:(m)  _ __________  propylitic alteration halo with superimposed carbonatization  .  .  .  sencitic  &  rn  mode of alteration minerals in hydrothermal alteration profile at northe al including 3 vein at the Silver Queen mine. Unknown unidentifiable materi  Figure 5-8a. Estimated segment of the No.  groundmass and  argillic  alteration envelope  -  extremely fme-grain mineral aggregates.  120  q  CD  0’  CD  CD  D  --  B..  fl  o_  CD  i q  CD  CD CD CD I4)  -t <  a  $-  -z-  CDi  gE  C  0  0  CD  0 CD  co  H  0  C  ::::  CD  Lf  00  0  CD  0 CD  CD  0.  CD  C C  00000  0 U  J1 V  -a ) COO _)  —‘.)  .  CD  0  CD  I  00 CD  ‘  C,  —— 000QCC  CD  l(•)  00 00000. CD  000CCL’  .  u 3 ’ t  .  C Ll  t’J  _ CC000 -)C  CC  00  C 0 tJ  cCCOOCC  C  0.  CDCD  c,  0  —  -1  cv  c f1 ;. IN r! —  —  I  CD 0.  CD  ECD  II  CD  -  CD  H  (g  CD  0  In  CDCD  CD  F’CpD  0  CD  0  CD  T1  1  CD  CD 0  CD  E;.  0  CD 0=  CD  CD  0  Q0O  0)CD — i. CD N N  0 0  CD  CD  0  U)  0  U)  “  L) U) 0  U.  00  U. 0  U) U.  C’  o  —  c  .)  c  U. C  if ru  o  W  Mode vol. % 00  0  C’ 0  C  0  000  C.  .  U)  0  00  00 00 C’ C’  00  00  J 0  00000  00000  0  0  0 J  0 J  00 U) 0 U) 00  00 U) C U) 0 0  0 0 U)  0 0 U)  C’ C’ U) 00  00 U) 0\ 00  0  0 U)  0 00  0 U)  0 t)  I. C)  I  0  CD  0  I CD  rn  CD  H  Figure 5-9. The relatively sharp contact between propylitic alteration and a bleached alteration envelope (Bulkley cross-cut, 2600 foot level underground working).  123  Figure 5-10. Outcrop of the southern segment of the No. 3 vein and its bleached alteration envelope.  124  the No. 3 vein are greater on the footwall than on the hanging-wall. At the cross cuts of the Jack and George veins the situation is reversed (Figure 5-5). These asymmetrical features can be explained by en echelon geometry of individual veins within mineralized zones (Leitch et a!., 1991). The reason for these is that the alteration envelope is developed around the structure zone centering the en echelon veins. Therefore, the alteration envelope may appear in different asymmetrical patterns depending upon where the cross-section cuts the upper or lower part of an individual vein (see Figure 511). This explanation may help exploration for hydrothermal veins developed in en echelon structural patterns.  5.4. Paragenetic Sequence of Hydrothermal Alteration  Propylitization, carbonatization, sericitization, argillization and silicification as well as pyritization, have all taken place in the host rock at the Silver Queen mine. Consistent, systematic sequences of alteration minerals and specific zoned distributions are observed in the host rocks. Many other textures and features in vein-wall-rock profiles strongly support the concept of a consistent sequence in the development of the hydrothermal mineral assemblages at the Silver Queen mine. The distribution of broad propylitic alteration halos suggests that this type of alteration is the product of regional, pre-mineralization hydrothermal activity. Carbonatization controlled by the complicated fracture system developed subsequent to regional propylitic alteration and was superimposed on the propylitically altered rocks. The distribution of bleached alteration envelopes around mineralized structures suggests that the bleached alteration envelopes developed subsequent to, and superimposed on, the broad propylitic alterations referred to above. A series of schematic profiles are constructed to illustrate the spatial distribution pattern and timing sequences of these alteration types (Figure 5-12).  125  Level II  Level I  NE  nship between en echelon Figure 5-1 I Schematic profile illustrates the asymmetrical relatio veins and hydrothermal alteration envelopes, Silver Queen mine.  SW  NE  SW  Stage I: A regional broad pre-mineralization propylitic alteration  Propylitic alteration  Stage H: Carbonatization superposed on the propylitically altered rocks is controlled by fractures  Ckrbonatization  VCIfl  Stage III: Bleached alteration envelopes (sericitic-argillic outer envelopes and silicic pyritic inner envelopes) around the main vein (a NW mineralized fracture zone).  Figure 5-12. A series of schematic profiles illustrate the spatial zonation and sequence of development of various types of alteration at Silver Queen mine.  127  The general sequences of formation of alteration minerals has been established by the replacement relationship between mineral pairs. Microscopic observations indicate the following alteration sequences. Propylitically altered samples show that mafic minerals such as augite and hornblende and plagioclase are initially altered to epidote, chlorite, calcite and sericite along margins and cleavages (Figures 5-1, 5-2, 5-3, 5-6 and 5-7). These replacements are completed where propylitic alteration is intense with superimposed carbonatization; in such cases pseuclomorphs of carbonate, mainly calcite, after primary mafic mineral occur. Early epidote and chlorite are replaced by carbonate (Figure 5-2). Biotite, magnetite, apatite and zircon remain unchanged in the propylitic alteration halo. Quartz is not significantly changed in the propylitic alteration halo. In the bleached alteration envelope near the propylitic alteration halo, primary minerals are completely altered. In particular, plagioclase is completely replaced by sericite and kaolinite along with quartz. Clinopyroxene and hornblende are totally altered to carbonate. No epidote or chlorite pseudomorphs after primary minerals are present in the bleached alteration envelope. Therefore, it appears that epidote, chlorite and calcite pseudomorphs after primary mafic mineral, as well as biotite, are further altered to sericite and siderite. Magnetite is totally altered to hematite and pyrite. Apatite and zircon retain their euhedral forms. Quartz increases in the outer alteration envelope largely due to the decomposition of plagioclase (Figure 5-3). Silicification in the inner envelope is characterized by the progressive replacement of sericite by quartz; eventually sericite occurs as inclusions in pervasive quartz (up to about 30 wt%). Siderite and other carbonates are abundant (up to 10 wt%). Pyrite is disseminated and locally, densely disseminated (content up to about 15 wt%) in the inner alteration envelope. Recrystallization and silicification of the matrix are intense in the inner alteration envelope (Figure 5-4).  128  Note: The solid line and its thickness represent the formation of a mineral and its semiquantitative abundance. The dash line means that the minerals remain stable at certain alteration stages.  Sericitization  Paragenetic Sequence of Mineral Assemblages, Silver Queen mine, Owen Lake Area  Magnetite/ilmenite Apatite Zircon Augite Hornblende Plagioclase K-feldspar Biotite Quartz Epidote Chlorite Calcite Siderite/dolomite Kaolinite Muscovite Pyrite Hematite Rutile  Minerals  Table 5-2.  Combining all the relationships described above leads to a general paragenetic sequence for the alteration around veins at the Silver Queen mine. This sequence is summarized and illustrated in Table 5-2.  5.5 Discussion and Conclusions Hydrothermal alteration patterns, similar to those described above, have been reported in many other deposits [e.g., Waite Amulet (Price and Bancroft, 1948), Creed and Summitville (Hayba Ct al., 1985), Sigma (Robert and Brown, 1984, 1986), Round Mountain (Sander and Einaudi, 1990), Erickson (Sketchley and Sinclair, 1991), Porgera Richards et al., 1991)1. In comparison with the alteration patterns reported by Robert and Brown (1984, 1986) and Sketchley and Sinclair (1991), the propylitic alteration with superimposed carbonatization at the Silver Queen mine shares many similar features with the cryptic alteration at Sigma mine and the carbonate envelope at Erickson mine in terms of alteration mineral assemblages and the mineral paragenetic sequence. For example, primary mafic minerals initially replaced by epidote and chlorite are subsequently replaced  by carbonate. However, there are significant differences in the spatial distribution patterns between the propylitic alteration with superimposed carbonatization at the Silver Queen mine and the cryptic alteration reported at the Sigma mine. The width of the cryptic alteration zone is up to 2 m into the walls of the veins at the Sigma mine (Robert and Brown, 1984). The spatial distribution of propylitically altered rock with superimposed carbonatization at the Silver Queen mine is much more widespread than the Sigma example (Figure 5-5). Propylitic rocks with intense carbonatization have also been found at Goose Lake, about 10 kilometres southwest of the Silver Queen mine, but no vein mineralization was found nearby. In short, the distribution pattern of the propylitic alteration with superimposed carbonatization at the Silver Queen mine is a wide irregular halo, unlike a restricted envelope that locally parallels the veins. In contrast, the intensity 130  of carbonatization, more precisely the completeness of the replacement of epidote and chlorite by carbonate, is weak in the northern segment of the No. 3 vein and stronger to the south. In brief, the distribution pattern of propylitic alteration with superimposed carbonatization at the Silver Queen mine is likely controlled by a complicated fracture system rather than by the mineralized structure zone only. It is suggested that the propylitic alteration at the Silver Queen mine might be related to the hydrothermal activities that immediately followed the volcanic eruption and intrusion of the early Late Cretaceous Kasalka Group equivalent rocks. Carbonatization superimposed on the early propylitic alteration halo may be the product of a CO 2 degassing process. This might be related to the hydrothermal activity associated with mineralization and controlled by a complicated fracture system. Even though the propylitic alteration with superimposed carbonatization at the Silver Queen mine is not an alteration envelope, the distribution pattern of propylitic alteration with superimposed carbonatization does indicate a broad 2 degassing halo that may be used to delineate the hydrothermal alteration anomaly CO associated with mineralization. In summary, the following conclusions about hydrothermal alteration at the Silver Queen mine can be deduced based on observations above: (1) Regional propylitic alteration is characterized by replacement of mainly primary mafic minerals initially by epidote and chlorite as well as minor amount of carbonate and the partial replacement of plagioclase replaced by carbonate and sericite. This type of alteration is interpreted to be the product of hydrothermal activity followed by the initial stage of volcanism, which predates the mineralization. (2) Carbonatization superimposed on the early propylitic alteration halo may be the product of a CO 2 degassing process, which might be related to the hydrothermal activity associated with mineralization; it is controlled by a complicated fracture 131  system. With increasing intensity of superimposed carbonatization on propylitic alteration at Silver Queen, more complete replacement of epidote and chlorite by abundant carbonates occurs. (3) Hydrothermal activity associated with mineralization forms the outer alteration envelopes marked by complete replacement of plagioclase by sericite and kaolinite, chlorite by siderite and magnetite by pyrite or hematite. (4) Inner alteration envelopes are interpreted as maximum stage hydrothermal alteration superimposed on the sericitic and argillic outer alteration envelope; it is marked by the replacement of sericite by quartz and direct precipitation of quartz, sulfide and carbonate. The close association between mineralization and the inner silicification envelope indicates that the ore-forming metals are transported as Si, S and C complexes, and that the precipitation of quartz, sulfide and carbonate through reaction with wall rock and hydrothermal solution might trigger ore deposition.  132  Chapter 6.  Quantitative Model of lEydrothermal Alteration, Silver Queen Mine, Central British Columbia 6.1 Introduction  The Silver Queen mine is an ideal locality to study hydrothermal alteration for the following reasons: (1) The major types of the rocks that host the vein at the Silver Queen mine are andesite and diorite; these are typical wall rocks in many other ore deposits of similar type. (2) The petrographic and timing relations among various rock types and mineralization at the Silver Queen mine are well understood through contact relations, thin section study and isotopic dating. (3) The young ages and short interval between the formation of wall rock and mineralization event (about 78 Ma for the wall rock and 50 Ma for mineralization, respectively) as well as the simple deformation history in the study area exclude the complexities caused by other processes superimposed, but unrelated to, deposit genesis. (4) The uniformity of composition of both the andesite flows and the microdiorite dome, the two host units for veins, is favorable in terms of having a single precursor. (5) Abundant trenches, drill cores and underground workings provide good  access for the study of alteration and its spatial relationship to veins. Silver Queen mine, thus, provides an excellent opportunity to evaluate the quantitative effects of hydrothermal alteration spatially associated with precious- and base metal vein mineralization in volcanic sequences. This chapter discusses a quantitative evaluation of the hydrothermal alteration at the Silver Queen mine, Owen Lake area, central British Columbia by applying the approaches described in previous chapters. I specifically address: 133  (i) optimal sampling and sample preparation method, (ii) estimation of the precisions of lithogeochemical data, (iii) determination of immobile components, and the calculation of absolute losses and gains of chemical constituents during the hydrothermal alteration, (iv) interpretation of the lithogeochemical variations in terms of mineral variations through the use of PER diagrams, (v) calculation of metasomatic norms, (vi) calculation of the propagated errors for the quantitative evaluations of lithogeochemical data, and (vii) integration of the mineralogical variations corrected for closure with the absolute losses and gains of chemical components and the errors at specific confidence levels to provide a quantitative chemico-mineralogic model of hydrothermal alteration.  6.2 Sampling and Sample Preparation The collection and preparation of samples is an often overlooked aspect of data gathering that impacts strongly on the quantitative interpretation of losses/gains in hydrothermal systems. Many published papers related to lithogeochemistry do not document sampling and sample preparation methods in detail. For example, small chips collected from limited drill core may not be of sufficient size to represent the geological unit being sampled; a small sample may not be representative of coarse grained units. As shown in Chapter 3, the larger the sample mass and the finer the sample is ground, the more homogeneous and representative the sample can be made for subsampling. However, for economic reasons it is not desirable to collect too large a sample nor to grind a subsample finer than needed. In order to minimize the artificial sampling and sample preparation errors, equations 3-13 and 3-14 have been applied to samples used to study hydrothermal alteration at the Silver Queen mine. 134  Rock types in study area are massive and porphyritic volcanic flows and high level intrusive rocks. Therefore, the main sources of inhomogeneities at the sampling stage are: (i) the presence of phenocrysts such as plagioclase and augite, and (ii) accessory minerals such as rutile (rich in Ti0 ) and zircon (rich in Zr). The results of calculated optimal 2 sample sizes based on equations in Chapter 3 are presented in Table 6-1. These calculations indicate that the optimal sample size depends on the coarseness of phenocrysts and inhomogeneities of the constituents of interest among the minerals. For instance, plagioclase and augite phenocrysts are the important minerals which determine the size of a field sample because they are the coarsest minerals (v (mm ) = 8 and 1.73 3 respectively); albite and enstatite, as end members of these two mineral series, are rich in 0 and MgO relative to the rest of the rock (the values 2 Na  Of HNa O 2  and  HM  of these two  end member mineral phases are 0.24 and 0.40 respectively, whereas the value of LN o and 2 LMgO for the rest of rock are 0.00 and 0.01, respectively). Therefore, they are the biggest contributors to inhomogeneity of the sample, and nearly 500 grams of sample is needed to reduce the sampling error to about one percent at the 68% confidence level. In contrast, another relatively coarse mineral, quartz (v (nun ) = 3.38), has a high value of H 3 502  (  1)  but also a high value of ( 502 0.4) for the rest of the rock. This means that Si0 L 2 is distributed more homogeneously in the rock than Na 0 or MgO. According to the 2 calculation using equation 3-13 and by treating the rest of bulk rock as the equivalent of ultramafic rock or mafic rock, only 15 grams of sample are necessary to provide an adequately homogeneous sample for analysis of Si0 . Accessory minerals, such as apatite, 2 may have a high value of H (=1) and the rest part of rock has the low value of L  (  0),  but commonly accessory minerals such as apatite have much finer grain size (e.g. 0.0005 ). So if the sample size is just a few grams the homogeneity of P 3 mm 5 in the sample will 0 2 be adequate. Therefore, 500 grams is considered the optimal sample size to provide adequate homogeneity for all components of the samples. This size results in a sampling error of less than or equal to 1% (RE) at the 68% confidence level. 135  Table 6-1.  Estimation of Optimal Sample Size by Using Binomial Function  Component  2 Si0  TiO’,  FeO  MgO  0 2 Na  5 0 2 P  Zr  Mineral  Quartz  Rutile  Pyrite  Enstatite  Albite  Apatite  Zircon  ) 3 v (nun  3.375  0.064  0.125  1.728  8.000  0.0005  0.0003  H  1.000  1.000  0.470  0.402  0.240  0.424  0.498  L  0.400  0.001  0.010  0.010  0.000  0.000  0.000  ) 3 d(gIcm  2.648  4.245  5.011  3.210  2.620  3.180  4.669  ) 3 dL (g/cm  2.87  2.87  2.87  2.87  2.87  2.87  2.87  Pw  0.150  0.005  0.050  0.050  0.300  0.005  0.0003  qw  0.850  0.995  0.950  0.950  0.700  0.995  0.9997  RE  0.01  0.01  0.01  0.01  0.01  0.01  0.01  2 (HdH-LdL)  2.250  17.996  5.413  1.588  0.395  1.818  5.406  2.40x10’  5 3.59x10  3 1.09x10  4 8.75x10  3 5.18x10  6 4.49x10  8 2,28x10  15.0  376.2  60.2  466.7  475.5  3.2  38.9  2 1p+Lq w (g)  Note: the notations used are defined in Chapter 3.  The detailed descriptions of sampling strategy including: sampling locations, the length of the profile that sample represented, rock and alteration type, as well as sample size are listed in Appendix A. An example of sampling strategy along a typical profile is illustrated in Figure 6-1. The samples are collected continuously in the intensely altered zone adjacent to the vein, and discontinuously in the broad moderately and weakly altered zones away from the vein. Using equation 3-14, the optimal fineness of subsamples have been calculated and are listed in Table 6-2. This table shows various components, their principal minerals and  136  5 I  10 m  f  f  + +  +  +  +  [\  +  ‘<  —  I <  ,—1  I  +  >  —  I  +  M  -  I  silicic/pyritic inner envelope  vein  silicic/pyritic inner envelope  -  +  sericitic/argiliic outer envelope  +  +  >>  —  -1  <  >  -  II  CDO  I  I  CON  >  I •Q 0  +  +  ><  —  [ V  +  I  +  +  ><  +  Discontinous chip sample  propylitic microdiorite  +  <  I  000  I  ‘ii  co co  No 3 silicic/pyritic vein inner envelope  \_/+\+  r-.1  I  c’  +  +  + +  +  +  0  +  I  .1  + +  +  + propylitic microdiorite  +  +  /  I  —  0  -d  continuous chip sample  sericitic/argillic outer envelope  ++  -  0  cc) I  +\-  sericitic/argillic outer envelope  +  —  I  0  u) I  the central segment Figure 6-1. A typical sampling profile across the alteration envelope in of the No. 3 vein, Silver Queen mine.  0  Legend  profile  Geological  S ample site  Sample ID  d  Q)  +  +  Table 6.2. Estimated Optimal Fineness of Subsample by Using Binomial Function  Component  2 Si0  TiO,  FeO  MgO  0 2 Na  5 0 2 P  Zr  Mineral  Quartz  Rutile  Pyrite  Enstatite  Albite  Apatite  Zircon  H  1.000  1.000  0.470  0.402  0.240  0.424  0.498  L  0.400  0.001  0.010  0.010  0.000  0.000  0.000  ) 3 dH (g/cm  2.648  4.245  5.011  3.210  2.620  3.180  4.669  ) 3 dL (g/cm  2.87  2.87  2.87  2.87  2.87  2.87  2.87  Pw  0.150  0.005  0.050  0.050  0.300  0.005  0.0003  qw  0.850  0.995  0.950  0.950  0.700  0.995  0.9997  RE  0.01  0.01  0.01  0.01  0.01  0.01  0.04  2 (HdH-LdL)  2.250  17.996  5.413  1.588  0.395  1.818  5.406  2 (Hp+Lq)  4 2.40x10  5 3.59x10  3 1.09x10  4 8.75x10  3 5.18x10  6 4.49x10  8 2.28x10  w (g)  4.00  4.00  4.00  4.00  4.00  4.00  4.00  ) 3 v (mm  0.89765  0.00068  0.00831  0.01481  0.06730  0.00063  0.00041  d (micron)  964.65  87.96  202.54  245.58  406.77  85.81  74.37  Sieve Size (mesh) Note:  <  Common sieve size  12  <  140  Micron  <  60  <  60  Conimon sieve size  <  40  <  140  <  200  Micron  12  1680  80  20  841  140  105  40  420  200  74  60  250  400  37  177  the proportional abundance of each component in the principal mineral (H) and the remainder of the rock (L), as well as the weight proportion of the mineral rich in the constituent of interest (P). These are the key factors in determination of the optimal fineness of a subsample. For instance, the fineness of passing through 80 mesh (i.e. the diameter of grain 177 microns) can provide adequate homogeneity of the major components: FeO, MgO and Na 0. It gives a subsampling error of less than or equal to 2 1% (RE) at the 68% confidence level. In contrast, the homogeneities of minor constituents  138  such as Ti0 2 and P 5 require the fineness of material to be subsampled to pass through 0 2 200 mesh (i.e. the diameter of the grains are 74 microns). This provides a subsampling error of less than 1% (RE) at the 68% confidence level. Zircon has the lowest concentration (about 0.0003 wt%) among the minerals listed in Table 6.2. It is the only common mineral containing Zr (i.e. L = 0), so even a subsample that has been ground to pass through 200 mesh will have a subsampling error four time larger than those of other constituents at the same confidence level. The detailed procedure of subsample preparation is documented below: (1) wash and saw off the mud, veinlets and weathering surface; (2) preserve hand specimen and select a block for thin section; (3) weigh the remaining sample (generally from 480 to 3000 grams); (4) crush sample to grains equal to, or less than, 4 mm by passing through ajaw crusher; (5) homogenize sample thoroughly on rag paper and randomly scoop out a 300  grams subsample; (6) grind this subsample in a swing mill to a particle size less than 75 microns; (7) check the fineness by randomly scooping out a portion of subsample and passing it through a nylon sieve (200 mesh); if not fine enough, randomly scoop out about 100 grams of sample and regrind it until all fines pass the check; and (8) clean the equipment to minimize carryover contamination. In summary, the procedure outlined above minimizes the effects of artificial error arising from improper sampling and sample preparation. It is of a special significance for the determination of immobile components of interest in this study. As indicated in Table 6.1., if the size of a field sample is less than 200 grams (equivalent of a sample from a half drill core with diameter of 4 cm and length of 12 cm), the sampling error for Ti0 2 could be doubled relative to the current sample size (equal to or greater than 500 g). Similarly, 139  if the weight of subsample is reduced from 4 gram to 2 gram, the subsampling error for Zr will increase by  (i.e. from RE  =  4% to RE  4%xl.414  =  5.7%). Consequently, the  difficulty of recognizing and using these potentially immobile components corresponding would be increased significantly.  6.3. Errors in Lithogeochemical Data The lithogeochemical determinations of: Si0 , Ti0 2 , A1 2 , Total Fe 3 0 2 , MgO, 3 0 2 MnO, CaO, Na 0, K 2 0, P 2 , S, Rb, Sr, Y and Zr reported here were obtained by X-ray 5 0 2 fluorescence (XRF) using 4 gram pressed rock powder pellets. This technique is suitable for the purpose here because there is neither the sample dilution problem inherent in borate bead preparation, not the problem of incomplete solution in acid digestion methods (MacLean and Barrett, 1993). In the analytical scheme of XRF the oxidation state of iron (i.e. ferrous and ferric) cannot be distinguished. Thus, the XRF data have been supplemented by determinations for ferrous iron based on titrimetry (Potts, 1987). The determinations of structural water and carbon dioxide were conducted separately by the ignition method (Shapiro and Brannock, 1955, 1962). The quality of lithogeochemical data is a function of various factors including the strategy of the sampling and sample preparation scheme, the skill and experience of the researcher and instrument operator, the operating condition of the instrument, the standards used to calibrate the counting values, the method of converting the counting values to meaningful lithogeochemical data and the concentrations of components/elements. Therefore, the quality of each set of lithogeochemical data should be assessed individually through the use of duplicates that are representative of the range of composition. The duplicates selected for this study were obtained at two different stages. One was at the field sampling stage and other was at the analytical measurement stage. There are 18 sample duplicates and 20 measurement duplicates for major components analyzed 140  by XRF, 10 duplicates for ferrous iron, 10 duplicates for structural water, 10 duplicates for carbon dioxide, 20 duplicates for sulfur and 22 duplicates for trace elements analyzed by methods previously mentioned. The general procedure for assessing errors is presented in Appendix D (Figures 6-2a, 6-2b, 6-2c, 6-2d, 6-3a and 6-3b). The final results of error analysis of lithogeochemical data are listed in Tables 6-3 and 6-4. With the determination of the values of S 0 and k for each component or element, the standard deviation (Se) and the precision (Pc) for each component or element at specific concentration can be calculated by using equation 3-15 and 3-16 introduced in Chapter 3. Table 6-3. Error of lithoeochemical data estimated by usina sample duplicates 9 Si0  TiO,  1 A1,O  Fe,O  FeO  MgO  MnO  CaO  Na,O  So  0.01  0.006  0.01  0.06  0.045  0.074  0.022  0.08  0.09  k  0.012  0.008  0.021  0.018  0.018  0.03  0.007  0.011  0.013  Cd  0.02  0.012  0.021  0.124  0.093  0.157  0.045  0.164  0.185  K,O  P,Oç  CO,  11,0  S  Zr  Y  Rb  Sr  So  0.02  0.02  0.01  0.04  18  0.01  0.3  2.00  5.00  k  0.018  0.015  0.12  0.13  0.07  0.032  0.09  0.035  0.019  Cd  0.041  0.041  0.026  0.108  41.86  0.021  0.732  4.301  10.395  Table 6-4. Error of lithogeochemical data estimated by using measurement duplicates SiO,  TiO,  A1,O.  The  MgO  MnO  CaO  Na,O  K,O  P,Oç  So  0.001  0.006  0.001  0.042  0.07  0.007  0.028  0.02  0.005  0.001  k  0.002  0.008  0.007  0.025  0.008  0.01  0.012  0.003  0.009  0.04  Cd  0.002  0.012  0.002  0.088  0.142  0.014  0.057  0.04  0.01  0.002  Analytical precision for all components can be seen to be much less than field sampling precision. The reason for this is that the duplicates at the field sampling stage 141  contain more sources of variability, including the artificial errors caused by insufficient sample size, inhomogeneity of sub samples and inconsistent analytical measurements. On the other hand, measurement duplicates reveal only the error caused by inconsistent analytical measurements. The purpose of lithogeochemical data is to reveal lithogeochemical variations at scales larger than sample size. Therefore, the sum of all sources of variability of the samples should be known for interpretation purposes.  6.4. Lithogeochemical Data of Altered Rock and Determination of Immobile Components  The analytical results of the whole rock samples collected from four representative 2 alteration profiles at the Silver Queen mine are listed in Appendix E (Table 6-5). A Ti0 versus Zr binary plot (Figure 6-4) is constructed with these data and the lithogeochemical data are listed in Table 4-2. The two distinctive series of volcanic and intrusive rocks around Owen Lake area (Chapter 4) are evident in Figure 6-4. Compositions of altered rocks from four alteration profiles form linear patterns which converge toward the origin. These patterns indicate that the hydrothermally altered samples were derived from a multiple precursor system along the fractionation trend of the older series of igneous rocks 2 and Zr are likely immobile in the hydrothermal at Owen Lake area. Therefore, Ti0 alteration system at the Silver Queen mine. The lithogeochemical data indicate that hydrothermally altered rocks are related to a multiple precursor system on the scale of the entire property. However, samples from each local hydrothermal alteration profile exhibit the attribute of a single precursor system -Zr binary plot. This linear 2 that is a linear trend going through the origin of the Ti0 pattern results from dilution or concentration of Ti0 2 and Zr in proportion to the gain or loss of the total mass of the sample during the hydrothermal alteration (Figure 6-4). In other words, before wall-rock hydrothermal alteration at the Silver Queen mine, rocks that are hundreds of metres apart from each other have significant differences in their 142  H —  0  0 error  100  Switch Back vein  south No. 3 vein  central No. 3 vein  north No. 3 vein  Unaltered rock  Legend  Zr ppm  200  300  Pre mineralization igneous series  Post mineralization igneous series  400  Figure 6-4. Immobile component/e1ementscatter plot, Silver Queen mine, central British Columbia.  0.00  0.50  1.00—  1.50  lithogeochemical compositions, but those within a few tens of metres from each other are not significantly different in composition. Therefore, each individual hydrothermal alteration profile can be treated as a single precursor system. Furthermore, Ti0 2 and Zr are mineralogically and geochemically incompatible, hence both are used as immobile constituents with which to quantifj the mobilities of other components. Theoretically, there should be no significant difference in the recognition of mobile components using both immobile components (Ti0 2 and Zr). In reality, this is not so. Thus, the question is, which should be used to correct for closure to provide the most accurate quantification of losses and gains? The sampling (+analytical) variability for Ti0 2 ranges from 3 to 5.6% at 95% confidence level in the abundance range of interest (0,3 to 0.9 wt% Ti0 ). Comparable variability for Zr is 6.4% or more at 95% confidence level in 2 the abundance range of interest (120 to 220 ppm Zr). It therefore is reasonable to deduce that Zr has contributed more to the dispersion of the immobile linear trend for each profile than has Ti0 . This conclusion is also consistent with what is expected based on the 2 calculations of the optimal sample size and the optimal fineness of subsample (Tables 6-1 and 6-2). As a result, Ti0 2 is chosen to be the preferred immobile component. It is used to remove the closure of lithogeochemical data in this study.  6.5. Calculation of Absolute Losses and Gains of Chemical Constituents and Their Spatial Variations The total mass change of each sample can be visually and qualitatively evaluated from the Ti0 -Zr plot (Figure 6-4) after knowing the composition of the precursor. Most 2 of the hydrothermally altered samples at the Silver Queen mine plot between the primary Late Cretaceous fractionation trend and the origin of the plot. This means that these hydrothermally altered rocks have gained mass during alteration, so that the immobile constituents Ti0 2 and Zr are diluted proportionally. For example, most of the hydrothermally altered samples from the southern and central profiles of the No. 3 vein, 144  and Switch Back vein plot in this fashion. In contrast, the samples that plot further from the origin reflect loss of the mass and thereby proportional concentration of the immobile 2 and Zr. The specific amounts lost and gained remain to be determined. constituents Ti0 Equation 1-9 is used to calculate the absolute losses and gains of individual chemical constituents. The mass of precursor is assumed to be around 100 grams and the mass loss or gain is also presented in an extensive unit (grams), which are the absolute mass change relative to the mass of the precursor (100 grams). The results are listed in Appendix E (Table 6-6). Moreover, to see what lithogeochemical variation is significant and what variation is caused by error propagation, equation 3-31 is applied to calculate the propagated error. If the variation of a constituent between two samples is obviously larger than its propagated error, then this variation is thought to be significant; otherwise, it is not significant. A selected example of these calculations are combined with the previous calculation result are present in Figure 6-5a and rest of the results in Appendix D (Figures 6-5b, -5c, -5d, -5e, -5f, -5g, -5h, -5i, -5j, -5k, -51, -5m, -5n, -5o, -5p). The absolute losses and gains of chemical constituents indicated by the samples from different hydrothermal alteration profiles at the Silver Queen mine have many features in common and show some systematic variations from the southern segment to the northern segment of the No. 3 vein and from different levels (from 2600-foot level to 2880-foot level). The general feature shared by all profiles may represent the common attributes of ore-forming hydrothermal solutions in this district. Whereas the differences from place to place may illustrate the spatial variations of the properties of ore-forming hydrothermal solutions. Both are important in the study of ore deposits, but the latter is of specific significance to exploration. The systematic variation in fluid/rock interaction may help to interpret the migration direction of ore-bearing hydrothermal fluid. Therefore, both the general features and the spatial variation of absolute losses and gains of each chemical constituents in various hydrothermal alteration profiles at the Silver Queen mine are described below. 145  di  :  -60  4(  60  x3-7  *  ....  x3-6  .  x3-5  •..  x3-2  .  .  x3-2  x3-3d  x3-3  x2-5  -.  .—  .  —  alteration outer\ s envelope  *  .j .::z::zzz ........—_  —  Central segment of the No. 3 vein  fice Tv F  —-----———  _—.--  x3-1  \veinalteration envelope \ propylitic andesite  x3-4  Northern segment of the No. 3 vein  *  \0 altera ion inner envelope  alteration outer’. propylitic “ nsicrodiorite envelope  xi-8 sl-6 xl-4 xl-2c1 al-i xlO-l xll-3x10-3dxiO-4 dO-S clO-6x10-6D xi-7 al-SD xi-3 xi-2 xbO-l xlO-2 ,clO-3x10-3dxlO-4 xlO-5 xlO-6x10-6D  —-  -  !..L  propylitic andesite\  x4-4  ..  .  I  0  -60  60  ....*  Switch Back vem  \  xS-1  alteration inner envelope  \vein  x5-10  ‘\  xS-2  xS-4  x54  xS-5 envelope  alteration outer  x5-3  x5-8 microdiorite alteration  x5-6d  propylitic niicrodiorite  sericitic ‘\ propylitic”\  x5-6  -  alteration outer envelope”\  DA63-8 DA63-5D DM34 DA63-3D DA63-3 DA63-1 DA63-6 DM3-S DM34 DA63-3D DA63.ID alteration inner”\ envelope  z  absolute loss or gain  —  uncertainty at 95 % confidence level  2 from four alteration profiles at the Silver Queen mine, central British Columbia. The Figure 6-5 a. Absolute losses and gains of Si0 blank part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) and a range representing ± 2 standard deviations.  0  c-i  80  bc  -60  40  -2:  20  4o)  absolute loss or gain  uncertainty at 95 % confidence level  80  iou  : In general, this constituent is added from hydrothermal solution to wall rocks 2 Si0 in all alteration envelopes discussed here, except in the alteration envelope of the northern segment of the No. 3 vein and in the outmost subzone of the alteration envelope at the central and southern segment of the No. 3 vein. The greatest addition of Si0 2 is at the 2600-foot level of central segment of the No. 3 vein, and the 2600-foot level of southern segment of the No. 3 vein. In turn, mildly intensive addition of Si0 2 occurs at the Switch 2 occurs at the northern segment of the No. 3 vein and Back vein. In contrast, a loss of Si0 in the outmost subzone of the alteration envelope at the central and southern segments of the No. 3 vein (Figure 6-5a). . In general, A1 3 0 2 A1 3 has a loss-gain pattern similar to that of Si0 0 2 2 but the changes are less obvious than are those of 5i0 2 (Appendix D, Figure 6-5b). : Ferric oxide is depleted or reduced to various extents in most portions of 3 0 2 Fe the alteration envelopes. A moderate increase in Fe 3 commonly occurs immediately 0 2 adjacent to the veins, probably due to the occurrence of hematite veinlets (Appendix D, Figure 6-5c). FeO: Ferrous oxide is ‘added’ (probably by reduction of ferric iron) prominently in all alteration envelopes. This ‘addition’ is strongly intensified at the Switch Back vein and in the central segment of the No. 3 vein (Appendix D, Figure 6-5d). MnO: Manganese addition and depletion patterns are two-fold. Type one is characterized by a pervasive addition of MnO to the wall rocks in the alteration envelopes at the northern segment of the No. 3 vein and the Switch Back vein. Type two involves the addition of MnO to most portions of the alteration envelopes, but there is a narrow depletion ‘valley’ adjacent to the vein at the 2600-foot level of central segment and southern segment of the No. 3 vein (Appendix D, Figure 6-5e). MgO: Magnesium is moderately depleted in the alteration envelopes. There is no significant systematic addition and depletion pattern in the profiles (Appendix D, Figure 65f). 147  0 and CaO: Sodium and calcium depletions from the wall rocks are prominent 2 Na and intense in all alteration envelopes. In particular, the depletion of Na 0 is almost 2 complete in all alteration envelopes (Appendix D, Figures 6-5g, 6-5h). 0 and Rb: Potassium and rubidium additions to the wall rocks are prominent 2 K but variable in intensities from the southern segment to the northern segment of the No. 3 vein. Additions of K 0 and Rb are most intense in parts of the alteration envelopes at the 2 2600-foot level of the central and southern segment of the No. 3 vein, and moderately intense in the alteration envelope at the Switch Back vein. In contrast, only one sample shows a slight addition of K 0 and Rb, the rest indicate depletion or no significant mass 2 0 and Rb in the alteration envelope at the northern segment of the No. 3 2 change, of K vein. K 0 and Rb depletions occur at the outmost parts of the alteration envelopes at the 2 central and southern segments of the No. 3 vein (Appendix D, Figures 6-5i, 6-5j). 0, CO 2 H 2 and S: Volatile constituents are prominently added from hydrothermal solution to wall rocks in all alteration envelopes discussed here except the southern segment of the No. 3 vein. The spatial variation of addition of H 0, CO 2 2 and S are described as follows. The additions of H 0 and CO 2 2 are the most intense in the alteration envelopes at the Switch Back vein and the central segment of the No. 3 vein, the second most intense in the alteration envelope at the northern segment of the No. 3 vein. There is almost no significant addition of H 0 and CO 2 2 in the alteration envelope at the southern segment of the No. 3 vein. In contrast to the addition of H 0 and C0 2 , the addition of 2 sulfur reaches its peak in the alteration envelope about the southern segment of the No. 3 vein, as well as at the central segment of the No. 3 vein. The addition of sulfur is minor along the Switch Back vein profile. There is very little addition of sulfur in the alteration envelope at the northern segment of the No. 3 vein (Appendix D, Figures 6-5k, 6-51 and 6-5m). Sr: Strontium is depleted in the alteration envelopes in a pattern similar to those of 0 and CaO but the intensity of depletions vary from profile to profile. It appears to be 2 Na 148  more intense at the southern segment of the No. 3 vein than at the northern segment of the No. 3 vein. In addition, the subzone adjacent to the vein in the alteration envelope at the central segment of the No. 3 vein shows strong addition of Sr (Appendix D, Figure 6-5n). Y: Yttrium in the alteration envelope have gained a small amount of mass from the hydrothermal solution, but lost its mass in part of the alteration inner envelope in the central and southern segment of the No. 3 vein. These changes may not be significant since yttrium has a large analytical error (Appendix D, Figure 6-5o). : Phosphorous is probably a locally immobile component during the 5 0 2 P hydrothermal alteration process because it has no significant loss or gain in the sericitic and argillic outer alteration envelope; its depletion is mild in the silicic and pyritic inner alteration envelopes at the Silver Queen mine (Appendix D, Figure 6-5p). In brief, wall rock alteration is most intense in the alteration envelope at the central segment of No. 3 vein and least intense at the northern segment of No. 3 vein in terms of absolute losses and gains of chemical constituents according to the lithogeo chemical data from the current four profiles. The total mass change of each altered sample is largely the result of the depletions of CaO and Na 0, and the addition of 5i0 2 ,K 2 0, 1120 and CO 2 . 2  6.6. Application of PER Diagram to the Interpretation of Hydrothermal Alteration  Knowing the absolute losses and gains of chemical constituents during the hydrothermal alteration process, we can infer corresponding mineralogical changes. For example, an addition of K 0 along with the depletion of CaO and Na 2 0 of andesitic 2 volcanic rock samples might be intuitively interpreted as the replacement of plagioclase or K-feldspar by muscovite. This can be illustrated by the following equations: Si 3CaA1 8 O 2  +  Anorthite  3NaAlSi 8 O 3 Albite  +  2K  +  4H = 2 (OH) S 2KA1 1 O 3 0 i + 3Ca Muscovite  K +2W  =  (OH) S KA1 1 O 3 2 0 i + 3Na Muscovite  +  2 6SiO  (6-1) (6-2)  149  3KAISi 8 O 3 K-feldspar  +  2H  =  (OH) S KA1 1 O 3 2 0 i + 2K Muscovite  +  2 6SiO  (6-3)  0, CaO and Na 2 In another case, the depletions of K 0 along with no mass changes of 2 2 might indicate the occurrence of argillic alteration. This can be represented as follows: Si0 Si 2 CaAl 8 O Anorthite  +  2W + H 0 2  2NaA1Si +2W + 1120 8 O 3 Albite 2KA1Si +2W +1120 8 O 3 K-feldspar  =  =  =  4 S A1 ( 5 0 2 OH i Kaolinite  +  Ca  (6-4)  4 S Al ( 5 0 2 0H i Kaolimte  +  2Na + 4Si0 2  (6-5)  4 S A1 2 ( 5 0 OH) i Kaolimte  +  2K  +  2 4Si0  (6-6)  A previous petrographic examination documents the existences of propylitization, carbonatization, argillization, sericitization and silicification in the study area. These alteration processes lead to the replacement of primary minerals such as plagioclase, augite and hornblende by epidote, chlorite, carbonates, kaolinite and sericite, with the addition of quartz. These processes can be tested in detail for each analysis using PER diagrams (Russell and Stanley, 1990a; Stanley and Russell, 1989a, 1989b, 1989c, 1990). There are two preconditions that must be satisfied before applying this PER diagram to the interpretation of the lithogeochemical data. The first is that the chemical composition and mineral assemblage of parent rock or precursor of alteration derivatives must be known or predictedable. This has already been demonstrated in Figure 6-4 and the related discussion. The lithogeochemical composition and mineral assemblage of a propylitic rock can be treated as the precursor of the altered rocks in the superimposed alteration envelope. The second precondition is that the proportion of primary minerals converted into alteration product must be reasonably estimated. The microscope observations indicate that primary minerals are completely replaced by altered minerals including mainly sericite, kaolinite, quartz, carbonate and pyrite within the alteration envelope, and partially replaced by epidote, chlorite, carbonate and sericite in propylitic alteration halo.  150  The PER diagram designed previously (Figure 1) is used to test (i) whether feldspar and augite fractionations are still the main contributors to lithgeochemical variation among the propylitically altered rocks; (ii) whether either carbonatization, sericitization, argillization or siicification is the dominant alteration type at the Silver Queen mine. The propylitically altered samples on the PER diagram are characterized by a scattered trend with a slope approximately equal to one within the error range at the 95% confidence level. This implies that the total mass of corresponding chemical constituents used to construct this PER diagram have had no significant changes during the propylitic alteration process. In other words, primary feldspar and augite crystal fractionations may be still the major causes for the lithogeochemical variations of the corresponding chemical constituents among the propylitically altered samples (Figure 6-6a). However, it is not certain whether the unchanged mass means that the mass of each constituent is unchange or that the masses of corresponding constituents do change but the total mass remain unchange by compensation. In general, all the samples from the alteration envelope (not including propylitic alteration) plot far from the primary fractionation trends on this PER diagram. This implies that there are significant mass changes of the corresponding chemical constituents among these samples relative to the propylitically altered samples. Also, all the samples from the alteration envelope spread between sericitic trend and argillic trend rather than concentrating around one alteration trend, indicating that the lithogeochemical variation of altered rocks is not entirely controlled by either carbonates, sericite, kaolinite or quartz at the Silver Queen mine. Instead, the lithogeochemical variations among these samples have to be interpreted as due to the complete replacement of primary minerals as well as the ‘propylitic’ minerals by different proportions of sericite, kaolinite, carbonate, pyrite and quartz. According to petrographic observations one of the possible alteration paths is deduced as follows (Figure 6-6b): all primary minerals and propylitical minerals in the least 151  r.J  C  -  -  -  -  -  -  2 Si!TiO  -  -  -  -  -  S.No.3 v.  A  C. No.3 v.  x  SWBK v.  *  N. No.3 v.  +  unaltered  error  Legend  -  -  Figure 6-6a. PER plot to discriminate the alteration types associated with precious- and base-metal vein mineralization in volcanic sequences at the Silver Queen mine. Qtz quartz, Carb carbonates, Kao kaolinite, An anorthite, Ab albite, Or, K-feldspar, Chl chlorite, Aug augite, Mus muscovite, Ep epidote, N. No. 3 v. the northern segment of the No. 3 vein, SWBK v. Switch Back vein, C. No. 3 v. central segment of the No. 3 vein, S No. 3 v. southern segment of the No. 3 vein, see text for detailed discussion.  0.2  0.4  0.6  0.8  1.2  1.4  1.6  1.8  r3  C  ,/  t  -  I— I ——I  ,/  /1,/  b2  -  1  /  ,/  /  b3  P  -  2  b4  a2  S i/Ti0 2  3  -  Ca rb  b5  error  Alteration path  -  4  Kao  -  Ab,O r,Chl  Ep  Legend  -  -  -  Figure 6-6b. One of the possible alteration paths on PER diagram designed to discriminate the alteration types associated with precious- and base-metal vein mineralization in volcanic sequences at the Silver Queen mine. Qtz quartz, Carb carbonates, Kao kaolinite, An anorthite, Ab albite, Or, K-feldspar, Chi chlorite, Aug augite, Mus muscovite, Ep epidote.  0.4  0.8  1  1.2  1.4  1.8  2  or propylitically altered wall rocks are completely replaced (from P to b 1) by carbonatization (from b 1 to b2), argillization (from b2 to b3, sericitization (from b3 to b4) and silicification (from b4 to b5). Another PER diagram is used to further test alteration types at the Silver Queen mine. This PER diagram has a A1/Ti0 2 as x-axis and (2Ca+Na+K)/Ti0 2 as y axis (Stanley and Madeisky, 1993). The displacement vectors of primary minerals (feldspar and hornblende) are defined to have slopes equal to one, the displacement vectors of carbonates are vertical, that of kaolinite horizontal, that of muscovite has a slope equal to 1/3, and that of quartz is perpendicular to the paper (Figure 6-6c). The alteration samples of Silver Queen mine on this PER diagram show again that least or propylitically altered samples plot along the fractionation trend of slope equal to one within the error range (at the 95% confidence level). This means that lithgeochemical variation of least or propylitically altered wall rock is caused mainly by feldspar. The displacement vector of augite is vertical on this PER diagram (Figure 6-6d). Compared to the previous PER diagram, this PER diagram shows a more understandable dispersion of plotted points; the alteration patterns are more distinguishable because the effect of quartz has been removed and only carbonates, muscovite and kaolinite alteration are presented on this PER diagram. In addition, a bubble plot superimposed on this PER diagram is used to investigate the effect of silicification (Figure 6-6e). With regard to the alteration intensity relative to the spatial distribution, the plots of the samples from the alteration envelopes of the northern segment of the No. 3 vein, the Switch Back vein, the southern segment of the No. 3 vein and the central segment of the No. 3 vein are presented in turn from the lowest left portion to the highest right portion of this PER diagram. This plotting pattern indicates that samples from the alteration envelope of the central segment of the No. 3 vein are affected by the most intense alteration including sericitization, carbonatization, pyritization and silicification. In contrast, the alteration intensity of the samples from alteration envelope of 154  LI UI  Ce  z+  +  C  0  -  I  0.2  0.4  I  0.8 0.6 2 A1/Ti0 -  1  +  Legend  1.2  -  1.4  -  -  -  -  -  -  Figure 6-6c. PER diagram designed to discriminate the alteration types without considering the effect of quartz. Qtz quartz, Carb carbonates, Kao kaolinite, An anorthite, Ab albite, Or, K-feldspar, Chi chlorite, Aug augite, Mus muscovite, Ep epidote. P protolith; augite replaced (al) by carbonates (a2); primary minerals are completely replaced (b) by carbonates (c), muscovite (d) or kaolinite (e).  0  0.8-  0.9  -  L)  z+  +  -  0.2  -  0.4  -  -  -  -  -  -  -  -  -  -  -  1.4 1.2 1 0.8 0.6 Al/TiOa Figure 6-6d. PER plot to discriminate the alteration types associated with precious- and base-metal vein mineralization in volcanic sequences at the Silver Queen mine (the displacement vecotor of quartz is perpendicular to the paper). qtz. Qtz quartz, Carb carbonates, Kao kaolinite, An anorthite, Ab albite, Or, K-feldspar, Chl chlorite, Aug augite, Mus muscovite, Ep epidote, N. No. 3 v. the northern segment of the No. 3 vein, SWBK v. Switch Back vein, C. No. 3 v. central segment of the No. 3 vein, S No. 3 v. southern segment of the No. 3 vein, see text for detailed discussion. 0  V.  V.  C. No.3 v. A S.No,3 v.  x  SWBK  N. No.3  +  unaltered  error  Legend  LI  +  L)  z+  2  Figure 6-6e. PER diagram superimposed by Si/(immobile element) bubble plot. The size of bubble represents the relative molar amount of Si corrected for closure.  A1/TiO  the northern segment of the No. 3 vein is the mildest relative to others. Its alteration types are mainly carbonatization and argillization plus sericitization. All these are consistent with the conclusions drawn from the calculations of absolute losses and gains of chemical constituents in the previous section.  6.7. Application of Metasomatic Norm Methodology  For the purpose of a general examination of the types and intensities of hydrothermal alteration associated with precious- and base-metal vein deposit in volcanic sequence by using the lithogeochemical data, the PER diagram, described above, is a useful tool. However, projections of multicomponents systems can be ambiguous and may not involve all variables, partly because of its 2-dimensional limitation. For example, an altered sample plotted on the PER diagram, above, could be interpreted as either the combined product of argillization, carbonatization, sericitization and silicification or simply the product of carbonatization plus intense silicification. A more complicated system has to be taken into account to reduce the ambiguities or to test other hypotheses. In the example mentioned above, the product of carbonatization plus intense silicification will lead to the content of CO 2 in the bulk rock composition being more abundant than in the case of silicification, argillization and sericitization. In contrast, the combined product of silicification, argillization, carbonatization and sericitization will contain more 1120 in the bulk rock composition than in the product of carbonatization plus intense siliciflcation. One means of reducing these ambiguities is through use of the methodology described by Cheng and Sinclair (1994) and in Chapter 2. The lithogeochemical data of four hydrothermal alteration profiles at the Silver Queen mine have been processed by applying the approach of metasomatic norm calculation. The minerals listed in Table 2-1 are chosen to be the standard normative minerals for the metasomatic norm calculation. These mineral occurrences are based on the petrographic observations and XRD examination of the samples (Cheng et al., 1991). 158  Finally, all the calculated metasomatic norm values have been corrected for closure by using Ti0 2 as an immobile component and equation 1-9. The metasomatic norms corrected for the closure and the absolute loss and gain values of chemical constituents of the northern segment of the No. 3 vein profiles as the selected examples are presented in units of mole and gram in Tables 6-7a and 6-8a, respectively. The calculations of other profiles are listed in Appendix E, Table 6-7b, 6-7c and 6-7d and Tables 6-8b, 6-8c and 68d, respectively. Residuals have been used to monitor how closely the masses of parent-daughter losses and gains balance. A residual is defined as metasomatic normftered rock  -  (  metasomatic normprecsor rock + zMass change). The residuals of metasomatic norm calculation after the correction for the closure range from 0.16 to -0.49 gram relative to the mass of precursor rock (about 100 gram). This indicates that the mineral assemblages chosen here represent the bulk rock composition well. The data listed in Tables 6-8a, 6-8b, 6-8c and 6-8d are illustrated in Figures 6-7a, 6-7b, 6-7c and 6-7d. For the purpose of comparison, the scales of y-axes are uniform in Figures 6-7a, 6-7b, 6-7c and 6-7d. Thus, the type and intensity of wall-rock hydrothermal alteration in different profiles can be quantitatively evaluated and objectively compared. The propylitic altered rock is characterized by a metasomatic normative mineral assemblage composed mainly of plagioclase, K-feldspar, pyroxene, quartz, epidote, chlorite and carbonate. There is no systematic spatial variation of the abundances of these minerals relative to the vein. This attribute is convincing evidence that propylitic alteration is related to pre-mineralization volcanic activity rather than the ore-fluid. The carbonatization is relatively intense in hydrothermal alteration envelopes and is indicated by the increase in the content of carbonate from 5.6 gram on average in the propylitic alteration halo to about 15 gram on average in the bleached alteration envelope. Of the four profiles the alteration envelope of the Switch Back vein is the most strongly  159  Table 6-7a. SmpIeJd Afteration  and gains of components (in moles) Metasornatjc norms corrected for closure and absolute losses Owen Lake, central BC at northern segment of the No. 3 vein, Silver Queen mine, x3-3 x2-5 x3-3d x3-2 x3-2 x3-1 x3-4 x3-5 x3-6 x3-7 x4-4 w-alt w-alt w-alt rn-alt rn-alt ms-alt ms-alt rn-alt w-alt w-alt w-alt  mole Pyroxene  0.02  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.01  0.02  0.02  Plagioclas  0.14  0.16  0.10  0.00  0.00  0.00  0.00  0.00  0.11  0.15  0.15  0.00  0.00  0.00  0.07  0.06  0.07  K-feldspar  0.07  0.06  0.06  0.00  0.00  Quartz  0.20  0.22  0.26  0.46  0.68  0.59  0.58  0.58  0.23  0.19  0.24  Carbonate  0.05  0.05  0.05  0.09  0.16  0.13  0.10  0.10  0.04  0.05  0.06  Epidote  0.04  0.02  0.02  0.00  0.00  0.00  0.00  0.00  0.03  0.03  0.01  Chlorite  0.00  0.01  0.02  0.00  0.00  0.00  0.00  ,‘O.OO  0.02  0.01  0.01  Sericite  0.00  0.00  0.02  0.04  0.11  0.06  0.07  0.07  0.01  0.00  0.00  Kaolinite  0.00  -0.00  0.01  0.06  0.02  0.07  0.05  0.05  -0.00  0.00  0.00  Pyrite  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  Hematite  0.00  0.01  0.01  0.00  0.01  0.01  0.01  0.01  0.00  0.00  0.01  Magnetite  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  Ilinenite  0.00  0.01  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  Rutile  0.01  0.00  0.01  0.01  0.01  0.01  0.01  0.01  0.01  0.01  0.01  Apatite  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  Total  0.53  0.55  0.56  0.67  1.00  0.87  0.83  0.82  0.52  0.52  0.58  dSiO2  0.00  0.00  -0.03  -0.24  0.11  -0.04  -0.05  -0.06  -0.00  -0.02  -0.02  dAl+3  0.00  0.01  0.00  -0.04  0.08  0.03  0.02  0.02  0.00  -0.00  -0.00  dTi+4  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  dEe +3  0.00  -0.00  -0.00  -0.03  -0.02  -0.02  -0.01  -0.01  -0.00  -0.00  -0.00  dFe+2  0.00  0.00  -0.00  -0.00  0.05  0.04  0.01  0.01  0.00  -0.00  -0.00  dMn+2  0.00  -0.00  -0.00  0.01  0.02  0.02  0.00  0.00  0.00  -0.00  -0.00  dMg+2  0.00  -0.01  -0.01  -0.06  -0.04  -0.05  -0.05  -0.05  0.00  -0.00  0.01  dCa+2  0.00  -0.01  -0.00  -0.07  -0.09  -0.10  -0.08  -0.08  -0.01  -0.01  dNa+  0.00  0.01  -0.00  -0.11  -0.10  -0.11  -0.11  -0.11  0.00  0.01  -0.03  0.03  -0.01  -0.00  -0.00  0.00  -0.00  0.00  0.00  0.00  -0.00  dK+  0.00  -0.00  -0.00  dP+5  0.00  0.00  0.00  /  -0.01 -0.01  -0.00  -0.00  -0.00  -0.00  -0.00  -0.30  -0.01  -0.15  -0.17  -0.17  -0.00  -0.01  -0.01  0.05  0.01  0.00  Sum 0=  0.00  -0.01  -0.02  dH2O  0.00  0.02  0.07  0.13  0.12  0.16  0.15  0.14  dCO2  0.00  0.00  0.01  0.04  0.11  0.08  0.04  0.04  -0.01  -0.00  0.02  dS  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  -0.00  dTotal  0.00  0.01  0.01  -0.69  0.26  -0.15  -0.25  -0.27  0.04  -0.03  -0.03  160  Table 6-8a. Sample Id  and gains of components (in grams) Metasomatic norms corrected for closure and absolute losses Owen Lake, central BC at northern segment of the No. 3 vein, Silver Queen mine, x3-3 x3-3d x2-5 x3-2 x3-2 x3-1. x3-4 x3-5 x3-6 x3-7 x4-4 w-alt  w-alt  w-alt  rn-alt  ms-alt  ms-alt  rn-alt  rn-alt  w-alt  w-alt  w-alt  5.11  1.22  0.90  0.00  0.00  0.00  0.00  0.00  1.80  4.33  33  Plagioclase  36.01  41.63  26.19  0.25  1.12  0.53  0.89  0.08  28.51  39.58  40.72  K-feldspar  18.26  17.26  16.00  0.00  0.00  0.00  0.08  18.50  17.58  18.34  Quartz  12.02  13.40  15.88  14.21  Carbonate  4.86  5.85  5.35  Epidote  18.70  9.79  11.07  1.78  0.00  Chlorite  3.05  7.28  11.35  0.00  0.00  Sericite  0.00  0.02  7.39  17.28  44.29  25.43  Kaolinite  0.00  -0.00  1.56  16.28  6.06  17.77  Pyrite  0.02  0.03  0.03  0.04  0.27  Hematite  0.00  1.24  1.24  0.65  1.44  Magnetite  0.00  0.00  0.00  0.00  0.00  Ilmenite  0.00  1.20  0.00  0.00  0.00  Rutile  0.65  0.02  0.65  0.65  Apatite  0.90  0.90  0.93  Total  99.58  99.83  dSiO2  0.00  dAI+3  AIteraon  gram Pyroxene  0.00 27.38  40.90  35.35  34.72  34.76  13.87  11.17  9.81  17.14  14.14  10.25  10.21  3.98  5.10  5.53  0.00  0.00  0.00  15.49  13.55  3.89  0.00  0.00  ,.0.00  11.71  4.16  7.65  28.75  29.59  3.96  0.00  0.00  13.92  12.95  -0.00  0.17  0.01  0.13  0.10  0.09  0.05  0.03  0.01  1.21  2.00  2.10  0.25  0.74  2.39  0.00  0.00  0.00  0.00  0.00  0.00  0.43  0.00  0.00  0.00  0.08  0.01  0.65  0.42  0.65  0.65  0.65  0.61  0.64  0.48  0.51  0.46  0.56  0.55  0.92  0.91  0.86  98.53  74.60  112.38  95.86  91.83  91.06  99.69  98.01  98.09  0.11  -1.53  -14.19  6.76  -2.32  -2.99  -3.50  -0.27  -0.99  -1.44  0.00  0.14  0.09  -1.10  2.16  0.70  0.61  0.51  0.10  -0.00  -0.08  dTi+4  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  dFe+3  0.00  -0.16  -0.01  -1.50  -1.16  -1.31  -0.77  -0.69  -0.20  -0.08  -0.04  dFe+2  0.00  0.12  -0.18  -0.10  2.88  2.14  0.35  0.31  0.15  -0.06  -0.01  dMn+2  0.00  -0.11  -0.09  0.51  1.19  0.92  0.16  0.16  0.01  -0.03  -0.07  dMg+2  0.00  -0.18  -0.22  -1.37  -0.98  -1.14  -1.24  -1.23  0.08  -0.07  0.20  dCa+2  0.00  -0.29  -0.14  -2.90  -3.74  -3.83  -3.23  -3.22  -0.33  -0.29  dNa+  0.00  0.33  -0.11  -2.54  -2.34  -2.50  -2.47  -2.48  0.03  0.19  dK+  0,00  -0.14  -0.08  -1.11  1.34  -0.33  -0.00  -0.01  0.03  -0.10  0.01  dP+5  0.00  0.00  0.01  0.00  0.00  -0.01  -0.35 .  -0.23  -0.08  -0.07  -0.08  -0.06  -0.06  -4.78  -0.21  -2.40  -2.70  -2.76  -0.01  -0.17  -0.20  0.87  0.16  0.05  Sum 0=  0.00  -0.10  -0.25  dH2O  0.00  0.30  1.18  2.31  2.10  2.82  2.63  2.58  dCQ2  0.00  0.11  0.27  1.86  4.70  3.55  1.91  1.85  -0.38  -0.14  0.68  dS  0.00  0.00  0.00  0.01  0.13  0.06  0.04  0.03  0.01  0.00  -0.01  dTotal  0.00  0.14  -1.05  -24.98  12.76  -3.73  -7.76  -8.52  0.10  1.57  -1.49  Residual  0.00  0.11  -0.00  0.00  0.03  0.01  0.01  0.01  0.00  0.00  161  -0.00  C)  c9.  1•  C)  C)  C)  .  c  C  0-. 0 —,  •  -t  C)  0  0  o  c  S  gram  Q’j’  B  Pt  B  Pt  B  Pt  S  gram  (  ,  0 CD  -t  0  0  CD  CD  0 0< CD CD  II.  CD  —  -i  0  ijcj  liI Ct  gram  fi1 Pt  B  B  gram  •  CD  CD 0  -t  .  s  0  BCD  CD  CD  o  0  Pt  < CD 0  CD  CD  0  0  =  -t  —  CD  •  .  L  CD  0  :t. 0  0  oo  i1  I  ii  .  wji  Pt  Pt  B 5’  Pt  B  S 5’  B  Pt  Pt  Pt  (I,  Pt  B  Pt  B  gram  jfl1  1ii  5’  5’  5’  B  Pt  B  B 5’  Pt  B  5’  Pt  5’  Pt  5’  C’,  Pt  B  gram  •  CD  —  o  CD  CD  CD -t  -C  o  —j  CC  CM  O CD  II I  0,  CD  CM  CM  0  CD  0  -  0  0  0  pJ  0  —  0  C-CC  OIj  (1C  o  I  CM  gram  1!  C-  (C  CM  (C  CM  gram  carbonatized. The carbonatization of the alteration envelope at the southern segment of the No. 3 vein is the mildest. Argillization is extensively developed in the narrow alteration envelope at the northern segment of the No. 3 vein. The alteration envelope of the Switch Back vein is characterized by an inner extensive argillic subzone. The broad alteration envelope at the central segment of the No. 3 vein has an inner argillic subzone similar to that of the Switch Back vein but much narrower than that of the Switch Back vein. There is also an argillic alteration outer subzone adjacent to the boundary between the alteration envelope and propylitic halo at the central segment of the No. 3 vein. A similar outermost argillic subzone is present in the alteration envelope of the southern segment of the No. 3 vein too. Sericitization is extensive in all four alteration envelopes but is strongest in the alteration envelope of the southern segment of the No. 3 vein (the content of sericite is up to about 61 gram relative to 48 gram on average). In contrast, the content of sericite in the alteration envelope of the northern segment of the No. 3 vein is relatively low (up to 44 gram and 29 gram on average, respectively). Potassic alteration is indicated by the presence of normative K-feldspar in the alteration envelopes of the central and southern segments of the No. 3 vein. In contrast, there is no normative K-feldspar present in the alteration envelopes of the Switch Back vein and the northern segment of the No. 3 vein. Silicification is strong in the alteration envelopes of the central and southern segments of the No. 3 vein. It is weakest in the alteration envelopes of the northern segment of the No. 3 vein and the Switch Back vein. In brief, the results of the metasomatic norm calculations of four alteration profiles provide a comprehensive, quantitative view of mass and mineralogical changes that are associated with hydrothermal alteration at the Silver Queen mine. The ambiguities of the interpretation have been largely reduced by considering all constituents of the geochemical 166  system, and by using mass balance and known minerals as constraints. The metasomatic norm profiles documented in this section link the lithogeochemical variations with the mineralogical variations. They present the hydrothermal alteration associated with precious- and base-metal vein mineralization in an easily understood way.  6.8. Propagated Error Analysis and Confidence Level of the Quantitative Evaluations To decide which chemical and mineralogical variations discussed in the previous sections are significant, the propagated errors are calculated using equations 3-31 and 333 and the values of S 0 and k of each chemical constituent (derived from the duplicate analyses, cf. Table 6-3). The propagated error calculation of the northern profile of the No. 3 vein are listed in Tables 6-9a as a selected example. The calculation results of other three profiles are listed in Appendix E, Table 6-9b, 6-9c and 6-9d. Only the chemical or mineralogical variations that are larger than the corresponding propagated errors can be safely considered as significant. Smaller apparent variations may be caused entirely by artificial factors. By using this technique the words ‘significant’ and ‘insignificant’ are used to describe the variations according to an objective criterion. Based on the calculation of propagated error, the four alteration profiles can be interpreted with respect to significant chemical variations. For example, the propylitic altered samples from the alteration profile at the northern segment of the No. 3 vein have absolute losses and gains of Si0 2 ranging from -0.11 to 1.53 gram, and the propagated errors of Si0 2 for these samples range from ± 1.76 to ±1.80 gram at 68% confidence level. Thus, Si0 2 mobility in the propylitically altered rock is not significant. In contrast, the altered samples x3-5 and x3-4 in the alteration envelope have absolute losses and gains of Si0 2 equal to -14.19 and 6.76 gram respectively. These changes in Si0 2 contents are much greater than their propagated errors (±1.38 and ±2.03 gram at the 68% confidence level, respectively). The other three samples (x3 -1, x3 -2 and x3 -3d) in the alteration 167  ed for closure and absolute losses/gains of components Table 6-9a. Propagated errors of metasomatic norms correct nt of the No. 3 vein, Silver Queen mine, central BC in grams at the 68% confidence level, the northern segme x2-5 x3-3 x3-3d x3-2 x3-2 x3-1 x3-4 x3-5 x3-6 x3-7 x4-4 San,pleid w-alt w-alt w-alt rn-alt rn-alt ms-alt ms-alt rn-alt w-alt w-alt w-alt AlteTation  gram  0.28  0.19  Pyroxene  0.17  0.04  0.03  0.00  0.00  0.00  0.00  0.00  0.16  Plagioclase  0.95  1.10  0.69  0.01  0.04  0.02  0.04  0.00  0.75  1.04  1.08  K-feldspar  0.48  0.45  0.42  0.00  0.00  0.00  0.00  0.00  0.49  0.46  0.48  Quartz Carbonate  0.33  0.36  0.43  0.71  1.15  0.96  0.93  0.93  0.38  0.30  0.39  0.40  0.36  0.34  0.60  1.05  0.86  0.65  0.65  0.24  0.34  0.40  Epidote  0.50  0.26  0.29  0.05  0.00  0.00  0.00  0.00  0.41  0.36  0.10  Chlorite  0.11  0.28  0.41  0.00  0.00  0.00  0.00  0.00  0.42  0.15  0.27  Serjcite  0.00  0.00  0.20  0.47  1.26  0.71  0.79  0.82  0.11  0.00  0.00  Kaolinite  0.00  0.00  0.05  0.51  0.21  0.58  0.45  0.42  0.00  0.01  0.00  Pyrite  0.00  0.00  0.00  0.00  0.01  0.01  0.01  0.01  0.00  0.00  0.00  Hematite  0.00  0.06  0.06  0.04  0.10  0.09  0.10  0.10  0.01  0.03  0.11  Magnetite  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  0.00  Ilmenite  0.00  0.04  0.00  0.00  0.00  0.01  0.00  0.00  0.00  0.00  0.00  Rutile  0.02  0.00  0,02  0.02  0.02  0.01  0.02  0.02  0.02  0.02  0.02  Apatite  0.04  0.04  0.04  0.02  0.05  0.04  0.03  0.03  0.04  0.04  0.03  Total dSiO2*  2.99  2.99  2.98  2.44  3.89  3.29  3.01  2.98  3.04  2.94  3.16  1.73  1.73  1.68  1.33  1.95  1.66  1.63  1.61  1.72  1.70  1.69  ciAl+3  0.32  0.32  0.32  0.28  0.38  0.33  0.33  0.32  0.32  0.31  0.31  0.01  0.01  0.01  0.01  0.01  0.01  0.01  0.10  0.11  0.11  0.12  0.12  0.12  0.12  0.12  0.12  dTi+4  0.01  0.01  0.01  0.01  dFe+3  0.13  0.12  0.13  0.09  0.11  dFe+2  0.12  0.12  0.12  0.11  0.20  0.17  0.13  0.12  dMn+2  0.03  0.03  0.03  0.03  0.05  0.04  0.03  0.03  0.03  0.03  0.03  dMg+2  0.14  0.14  0.14  0.11  0.12  0.12  0.11  0.11  0.15  0.14  0.15  dCa+2  0.18  0.18  0.18  0.12  0.13  0.12  0.13  0.13  0.18  0.18  0.17  dNa+  0.16  0.16  0.16  0.11  0.13  0.12  0.12  0.12  0.16  0.16  0.15  dK+  0.11  0.11  0.11  0.08  0.15  0.10  0.11  0.11  0.11  0.11  dP+5  0.02  0.02  0.02  0.01  0.02  0.01  0.01  0.01  0.02  0.02  Sum 0=  0.65  0.65  0.65  0.53  0.70  0.62  0.60  0.60  0.65  0.65  0.65  dH2O  0.24  0.27  0.36  0.49  0.48  0.56  0.54  0.53  0.33  0.25  0.24  dCO2  0.36  0.37  0.39  0.54  0.87  0.74  0.55  0.33  0.35  0.43  dS  0.00  0.00  0.00  0.00  0.01  0.01  0.01  0.01  0.00  0.00  0.00  dTotal  4.19  4.23  4.28  3.87  4.41  4.37  4.25  4.15  4.20  *  5.31  -  4.72  0.55  /  between the least altered and altered rocks. prefixe d stands for the absolute difference of corresponding constituent  168  0.11 0.02  2 ranging from 2.32 to 3.5 gram, respectively. This is close to envelope have gained Si0 their propagated errors of Si0 2 ranging from ±1.68 to ± 1.73 gram at the 68% confidence level and is almost equal to the propagated error at the 95% confidence level (from ±3.36 2 at the sites where these three sample were to ± 3.46 gram). Therefore, the gains of Si0 collected are very small. Similar examination of the other chemical and mineralogical variations can be carried on by comparing the data listed in Tables 6-8a, with the corresponding propagated errors listed in Tables 6-9a.  6.9. A Comprehensive Model of Hydrothermal Alteration  A comprehensive model is suggested here to illustrate the process of hydrothermal alteration at the Silver Queen mine. A set of comprehensive, mass balanced reaction equations can be constructed by combining the data listed in Tables 6-7a, 6-8a, and 6-9a. For instance, if sample x4-4 is the precursor rock of sample x3 -5, the hydrothermal alteration of sample x3-5 can be interpreted as follows. The primary minerals such as pyroxene (0.023 mole or 5.11±0. 17 gram), plagioclase (0.136 mole or 36.01± 0.95 gram) and K-feldspar (0.066 mole or 18.26±0.48 gram) as well as some of propylitic altered minerals including chlorite (0.004 mole or 3.05±0.11 gram) and epidote (0.039 mole or 18.7±0.5 gram) are mainly replaced by sericite (0.044 mole or 17.28±0.47 gram), kaolinite (0.063 mole or 16.28±0.5 1 gram), carbonate (increased from 0.053 mole or 4.86±0.34 gram to 0.093 mole or 9.81±0.6 gram) and quartz (increased from 0.2 mole or 12.02±0.3 3 gram to 0.456 mole or 27.3 8±0.71 gram). These replacements are accompanied by the mass losses of Si0 2 (-0.236 mole or -14.19±1.38 gram), A1 (-0.041 mole or -1.1±0.22 3 gram), Fe (-0.027 mole or -1.5±0.04 gram), Mg 3 2 (-0.056 mole or -1.37±0.03 gram), (-0.072 mole or 2.9±0.07 gram), Na (-0.110 mole or -2.54±0.04 gram), K(-0.029 2 Ca mole or -1.11±0.06 gram) from wall rock to hydrothermal solution and the mass gains of 0 (0.129 mole or 2.31±0.1 gram) and C0 2 H (0.042 mole or 1.86±0.12 gram). All these 2 exchanges can be presented as a comprehensive reaction equation as follows: 169  Primary minerals  0.O23pyroxene +0. l36plagioclase 5.11±0.17 g 36.01± 0.95 g  Propylitic alteration  +  +  0.066K-feldspar 18.26±0.48 g  0.O04chlorite + 0.O39epidote 3.05±0.11 g 18.7±0.5 g  +  +  0.2quartz 12.02±0.33 g  0.O53carbonate 4.86±0.34 g  2 0.236SiO 0.04 1A1 3 3 0.027Fe 2 0.072Ca 0.056Mg 2 0.11Na mass 0.029K -1.5±0.04 losses -14.19±1.38 g -1.1±0.22 g g -1.37±0.03 g -2.9±0.07 g -2.54±0.04 g -1.11±0.06 g -  -  -  mass gains  +  sericitic, argillic, carbonatized, silicified alteration  =  -  -  -  -  0. 129H 0 + 0.042C0 2 2 2.31±0.1 g 1.86±0.12 g  0.O44sericite + 0.O63kaolimte + 0.O93carbonate + 0.456quartz 17.28±0.47 g 16.28±0.51 g 9.81±0.6 g 27.38±0.71 g  The chemical constituents have been converted from oxides into ionic species. There are two reasons for these conversions. One is to correct for the effect of sulfur on the value of the total weight of the sample. Analytical measurements provide the results of most constituents in  the form of oxides but report sulfur in elemental form. In reality,  however, sulfur is in the form of an anion combined principally with Fe. Thus, Fe 2 may not combine with oxygen anion entirely as an oxide but may combines partly with sulfur anion . As a result, the total weight of the sample may be exaggerated 2 as a sulfide, such as FeS when abundant sulfides exist in the sample and their cations are analytically reported as oxides. In contrast, calculations of a metasomatic norm allot cations to critical minerals and take corresponding required amounts of necessary anions to form each normative mineral according to the stoichiometries of the mineral. Consequently, the total value of normative minerals will not be balanced with the total value of analytical constituents when sulfur is present in an analysis. The extra oxygen will be easily taken out during the conversion of oxides to ionic species. The other reason for converting oxides to ionic species except Si0 2 is that a mass balanced equation is commonly presented in the forms of solid mineral phases and soluble ionic species or complexes rather than oxides. Si0 2 is an exception because it exists both in a solid form as quartz and as an aqueous species. It is also possible that these species can  170  be further converted to any probable form of aqueous complex such as HC0 , Al(OH) 2 , 2 etc., if there is sufficient evidence to support the existences of these complexes in the hydrothermal fluid.  171  Chapter 7  Conclusions and Recommendations  The aim of this thesis is to extend quantitative methods in the evaluation of material exchanges during hydrothermal alteration associated with precious- and basemetal vein deposit in volcanic sequences. Of the methods currently used, Gresen& equation and Pearce element ratio diagrams are the most popular and most useful. Gresens’ equation and Pearce element ratio diagrams are superficially different but are fundamentally similar in principle. That is, they both remove the closure effect in order to decipher the true chemical variations during alteration. Gresens’ procedure emphasizes chemistry. Pearce element ratios provide the ability to discuss losses and gains mineralogically. The first requirement of applying these quantitative techniques to the estimation of absolute losses and gains in a metasomatic system is to determine immobile components from lithogeochemical data. The determination of immobile components is recommended through a two-fold consideration of: (i) the ratio of two immobile components remains constant in a single precursor system regardless of the nature of the alteration, and (ii) two immobile components must not be mineralogically or geochemically compatible with each other during the hydrothermal alteration process. In reality, there is no perfectly constant ratio of a pair of immobile components. Minor variation in ratios may result from improper sampling and sample preparation procedure as well as analytical error. Analytical error can be quantified to provide a basis for recognizing significant variation, such as ratio variability that is too large to be attributed to analytical error (thus, too large to accept the two components of the ratio as being immobile). This rule is to be used cautiously. If a PER ratio is constructed with one of the components being mobile and the other having poor analytical precision, then the latter component will contribute more to the final propagated error of the ratio, especially 172  where it is used as the denominator of the ratio. As a result, mobility of the former component might be obscured and the plot might lead to the incorrect conclusion that both numerator and denominator are immobile. Therefore, ‘immobil& components of relatively high analytical quality should be accepted in preference to those with poor analytical precision. The second requirement of applying these quantitative techniques for estimating losses and gains in metasomatic system is that a suite of samples for which loss/gain variations are to be evaluated, must be the alteration products of either: (i) a single parent rock characterized by chemical and mineralogical homogeneity (single precursor system), or (ii) a suite of rocks with determinable pre-alteration chemical compositions (multiple precursor system). This requirement can be met conventionally through the careful investigation of the field and petrographic relationships in the study area. Rock derivatives altered to various degrees from a common homogeneous parent rock commonly are in close spatial proximity and may show gradational contacts between each other. Primary textural and structural features may remain identifiable in least-altered to more intensively altered derivatives. To examine these types of variations rigorously it is recommended that samples be collected systematically along alteration profiles from the strongly altered rock adjacent to, or within, a mineralized zone, to the least altered rock far from the ore deposit itself. Such sampling should be done after a careful field investigation of the profile. Even though the altered rocks are our main concern, equal attention should be paid to the least altered or unaltered rocks because they provide important information about the parent rocks before hydrothermal alteration. This gives insight into the possibilities of a single precursor system versus a multiple precursor system. The PER approach to examining a metasomatic system has an advantage over other procedures in not only removing the closure effect of lithogeochemical data by using immobile components, but also by explaining the corrected chemical variations in terms of mineralogical variation. Two specific PER diagrams have been designed to discriminate 173  the hydrothermal alteration types commonly associated with epithermal vein deposits in volcanic sequences. The first one is constructed with Si/(immobile component) as its x axis and [l/4A1 +1 1/4(Na+K)+3/2Ca+1/2(Fe+Mg)J/(immobile component) as its y-axis. The displacement vectors of primary minerals such as augite, anorthite, albite and Kfeldspar, and alteration mineral chlorite are defined to have slopes equal to one, the displacement vectors of carbonates and pyrite are parallel to the y-axis, the slope of muscovite is 7/6, the slope of kaolinite is 1/4 and the slope of quartz is zero. Therefore lithogeochemical variations cuased by either primary feldspar and augite fractionation, intense carbonatization, argillization, sericitization or silicification can be discriminated if either of them is the dominant contributor to the lithogeochemical variation. The second PER diagram is designed to deal with more complicated types of alteration. It has A1/(immobile component) as its x-axis and (2Ca+Na+K)/(immobile component) as its y axis. The displacement vector of quartz is designed to be perpendicular to the diagram. As a result, the discriminations of carbonatization, argillization and sericitization from primary crystal fractionations are relatively easier on this PER diagram These specifically designed PER diagrams can be used to test the hypotheses that chemical variations are due to variations in amounts of a particular set of minerals, but the amount of each mineral can not be determined explicitly because the total displacement on a PER diagram commonly is the sum of the displacements of different minerals when a complicated multiple variable system is considered. In other words, ambiguity arises where too many variables are summarized in two dimensional space. A metasomatic norm approach has been developed in this thesis to quantitatively and objectively evaluate material exchange in complicated hydrothermal alteration systems associated with precious- and base-metal vein deposits in volcanic sequences. A metasomatic norm is a quantitative and objective approach to estimating mineral abundances from the lithogeochemical data since the mineralogy and chemistry of a rock are intimately linked through mineral abundances and the compositions of individual 174  minerals. The normative approaches, originally designed principally for igneous rocks, are rigid in their application and in general, do not utilize important alteration minerals. The different approach here, to the determination of norms of hydrothermally altered rocks combines petrographic and lithogeochemical data. Metasomatic norm calculation uses the same principles as the calculation of CIPW norms, but different mineral phases including volatile component-bearing minerals are used as the normative standard minerals that represent hydrothermal alteration systems. Another distinctive difference between a metasomatic and a conventional igneous norm is that the calculation of a metasomatic norm does not proceed along as fixed a hierarchical path as in the case of an igneous norm. More flexibility is necessary because of the wide range in both rock and mineral compositions. In some cases, where constrained by known mineralogy, the calculations must alternate back and forth following a loosely defined sequence in order to eventually balance or best fit a calculated mineral assemblage with the fixed chemical composition of an altered rock (i.e., to make the chemical masses and the mineral masses balance). In addition, the calculation of a metasomatic norm take into account possible incompatible mineral pairs in a hydrothermal system. A possible approach to the application of the norm concept to metasomatic rocks is to constrain the calculated normative mineralogy by a priori knowledge of existing minerals (i.e. to approximate the mode as closely as possible). The selection of a set of standard minerals for metasomatic norm calculation is based on geological observations. A set of standard normative minerals based on the author’s experience are given in this thesis. This set of normative minerals should not be considered exhaustive. It can be extended by the addition of new standard normative mineral(s). Other identified mineral species can be substituted to meet specific requirements. The general procedural scheme for metasomatic norm calculation is inefficient for manual calculation. Consequently, a computer-based procedure using Quattro Pro 5.0, a 175  sophisticated and readily available spread sheet program, has been devised to process norm calculations. It can be easily converted to other spread sheet software (Appendix C). The procedure involves the use of a built-in module  —  Optimizer in the software. The  general procedure of using Optimizer is to decide on the solution destination, choose the variables (standard minerals) to be included in the calculation, and set up the constraints. Then the Optimizer module can adjust the amounts of the variables and adhere to the constraints to provide a final best-fit solution. Unlike other black box’ types of software, this calculation model is transparent. Users can easily adjust and develop it according to their own purposes. With the recognition of an immobile component, the metasomatic norms for precursor and altered rocks, and the constituents lost or gained, can be further recast into the absolute amounts of minerals and chemical constituents relative to a given mass of parent rock by using Gresens’ equation. Consequently, the calculated results can be used to construct a comprehensive mass balanced and easily understood chemico-mineralogical model to interpret a hydrothermal alteration system in terms of initial and final normative mineral assemblages (corrected for closure) plus absolute losses and gains of chemical constituents. It does not matter whether the system is closed or open, or whether it represent equilibrium or disequilibrium assemblages. All lithogeochemical data contain errors. Therefore, errors have been propagated in this thesis to the final results of all calculations of absolute losses and gains, including metasomatic norm in intensive units (percentage) and metasomatic norm in extensive units (grams relative to a specific amount of precursor rock) after correction for closure. Such propagated errors also have been integrated with the results of the chemico-mineralogic model for material exchange (including absolute losses and gains of chemical constituents as well as the normative minerals) formulated in this work as follows: Mineralparent rocic  ± error + Constituent gained  from so1uon± error  Mineralaite rk± error + Constituent lost from wall rock±  error  (7-1) 176  The value of such an equation is that it provides useful, quantitative information about the hydrothermal system and limits the properties of the hydrothermal solution that effected the metasomatism, provided the equation represents a simple and unique alteration process. In reality, this type of reaction equation may more likely represent the final result of a series of sequential and/or superimposed processes. Nevertheless, the form of the equation is particularly useful because it is both quantitative and easily comprehensible. Specifically, the equation includes starting and ending rock mineralogies that may be partly evident in the field. It documents gains and losses of specific chemical constituents in space. Also it includes the uncertainties of each item at certain confidence level, which indicate what variations are significant. In brief, this chemico-mineralogical model: (i) provides an objective and quantitative basis for a mineralogical classification of hydrothermally altered rock; (ii) maps spatial distribution of normative minerals from lithogeochemical data; (iii) interprets lithogeochemical variations in terms of mineralogical variations (iv) recasts norms to mass units relative to a specified amount of the parent rock (v) then combines norms with the absolute losses and gains of lithogeochemical constituents to form a comprehensive mass balanced equation; (vi) integrates the propagated errors to indicate what variation is significant. The methodology for this approach is a natural extension of the use of Pearce element ratio (PER) diagrams for the study of metasomatic rocks. The metasomatic norm approach is quantitative in the same way as Pearce element ratio diagrams. The common principle is the correction for closure that provides true relative lithogeochemical and mineralogical variations between parent and daughter rocks. The normative approach is a useful supplement to PER analysis; the two procedures have much in common and contain much the same information presented in different ways. The strategy of a PER diagram is 177  to test whether chemical changes between two rocks can be explained purely by the variation(s) of certain mineral(s) as demonstrated by disposition of plotted points along predefined trends (slopes) according to the partial mass balance relationship. Metasomatic norms are displayed more explicitly as equations or profiles showing the spatial distributions of normative mineral assemblages, as well as the absolute losses and gains of chemical constituents based on comprehensive mass balance relationships. In brief, metasomatic norms solve the problems of multiple variables in multiple dimensional space. In a quantitative evaluation of hydrothermal alteration, it is essential to know the quality of data so that conclusions can be derived with confidence. The major causes for the variations of lithogeochemical data are classified as primary causes (such as crystal fractionation, mixing and assimilation), secondary causes (such as metamorphism, hydrothermal alteration and weathering) and artificial causes (insufficient sample size, improper sample preparation, analytical error, etc.). Ideally, variations generated by artificial processes should be eliminated. In practice, however, they can only be minimized through quality control, such as the estimation of the optimum sample size, the necessary fineness of the ground grain size, and quality assessment of analytical results in terms of precision, accuracy and detection limit. To estimate the optimum size for a sample or the necessary fineness of the particle size for a subsample, the model of’two-mineral mixture of uniform grain size’ and binomial distribution function are used in this thesis to simulate the distribution of major and compatible trace elements during sampling and subsampling processes. Because the rock types in the study area (Silver Queen mine) are massive and porphyritic volcanic flows and high level intrusive rocks, the inhomogeneities of various constituents at the sampling stage are mainly caused by phenocrysts, such as plagioclase and augite. Calculations indicate that the optimal sample size depends on the coarseness of phenocryst and homogeneities of the constituents of interest in the rock; 500 grams of sample are needed to reduce the sampling error to around one percent at the 68% confidence level. The 178  optimal particle fineness of the subsample depends on the variable being considered: both the abundance of an element in a mineral of interest and the amount of the mineral are important parameters. The quality of lithogeochemical data is a function of various factors including: (i) strategy of sampling, (ii) the sample preparation scheme, (iii) the skill and experience of the researcher and/or instrument operator, (iv) the operating condition of the instrument, (v) the standards used to calibrate the counting values and (vi) the method of converting the counting values to meaningful lithogeochemical data as well as (vii) the concentrations of components/elements. Therefore, the quality of each set of lithogeochemical data must be assessed individually through the use of duplicates. To assess the quality of lithogeochemical data the method of Thompson and Howarth (1976, 1978) has been used to treat precision as a function of concentration; the method has been modified slightly to deal with small sets of duplicate lithogeochemical data. Duplicates selected for the Silver Queen study are arranged at two different stages. One is at the field sample stage and the other at the analytical measurement stage. Analytical errors are consistently much lower than field sampling variability. The reason for this is that the duplicates arranged at the field sampling stage contain more sources of errors and include the artificial errors caused by insufficient sample size, inhomogeneity of subsample and inconsistent analytical measurements. Because the purpose of using lithogeochemical data is to reveal real geochemical variations it is essential to include sampling variability (i.e. using duplicates samples) as a basis for recognizing meaningful variation. The application of the approach described in the first part of this thesis to the study of the Silver Queen mine reveals that there are two distinctive series of volcanic and intrusive rocks in Owen Lake area. The first series consists of igneous and volcanic units from intermediate to felsic composition. They are characterized by having the lower content of Ti0 , MgO, total iron and P 2 5 as well as the older K-Ar dating ages (range 0 2 179  from 78.8 to 57.2 Ma). The second series consist of igneous and volcanic units from intermediate to mafic composition. They have higher contents of Ti0 , MgO, total iron 2 and P 5 as well as the younger K-Ar dating ages (range from 48.7 to 21.4 Ma). The 0 2 former predates and hosts the mineralization. The latter is post-mineralization. The hydrothermally altered samples at the Silver Queen mine derive from a multiple precursor system defined by the fractionation trend of the older series of igneous rocks of the Owen Lake area. However, each local, individual hydrothermal alteration profile exhibits the attributes of a single precursor system. These are characterized by a linear trend going through the origin of a Ti0 -Zr binary plot. Furthermore, the 2 mineralogical and geochemical incompatibility of these two potentially immobile constituents are examined to eliminate any possibility that Ti0 2 and Zr could be mobile. Of these two immobile components, Ti0 2 is used to remove the closure of lithogeochemical data because its lithgeochemical error is smaller than that of Zr. Six types of hydrothermal alteration at the Silver Queen mine have been described. They are propylitic alteration, sericitic and argillic alteration, silicification, pyritization and carbonatization. In general, the wall rock alteration in the study area is composed of a widespread regional propylitic alteration which gives way as the vein is approached to an outer envelope of sericitic and argillic alteration + carbonatization and an inner envelope of silicification and pyritization + sericitic or argillic alteration + carbonatization. Widespread regional propylitic and carbonatic alteration, sericitic and argillic outer envelope and silicification and pyritization inner envelope developed sequentially in that order. Most of the hydrothermally altered samples in alteration envelopes at the Silver Queen mine have gained mass during the hydrothermal alteration. In contrast, samples from the profile of the northern segment of the No. 3 vein have lost mass. Other spatial variations of hydrothermal alteration from the southern segment to the northern segment of the No. 3 vein and from different levels (from 2600-foot level to 2880-foot level) have 180  been recognized. In brief, the wall rock alteration is most intense in the alteration envelope at the central segment of the No. 3 vein and mildest at the northern segment of the No. 3 vein. The total mass change of each altered sample is largely the result of depletions of CaO and Na 0, and additions of Si0 2 ,2 2 K 0 , 1120 and CO . 2 In addition, the width of the alteration envelope is very much narrower along the northern segment of the No. 3 vein (total width about 7 m wide) compared to the central and southern segments of the No. 3 vein (total width up to 130 m wide). In some places, alteration envelopes around veins are distributed asymmetrically, principally because of the presence of other veins and because the No. 3 vein is, in reality, an en echelon vein zone. In brief, the hydrothermal alteration at the Silver Queen mine can be summarized as follows: (1) The regional propylitic alteration is characterized by the replacement of mainly primary mafic mineral initially by epidote and chlorite as well as minor amount of carbonate and the partial replacement of plagioclase replaced by carbonate and sericite. This type of alteration is interpreted to be the product of hydrothermal activity that followed the initial stage of volcanism and predates the mineralization. (2) Carbonatization superimposed on the early propylitic alteration may be the product of a CO 2 degassing process, which might be related to the hydrothermal activity associated with mineralization, and is controlled by complicated fracture systems. With increasing intensity of superimposed carbonatization on propylitic alteration, more complete replacements of epidote and chlorite by abundant carbonates occur. (3) The hydrothermal activity associated with mineralization leads to the complete replacement of plagioclase by sericite and kaolinite, chlorite by siderite and magnetite by pyrite or hematite to form the outer alteration envelope. (4) The inner alteration envelope is interpreted as the product of the process superimposed on sericitic and argillic alteration outer envelope at a maximum stage 181  of ore-forming hydrothermal activity. This is marked by the replacement of sericite by quartz and by the direct precipitation of quartz, sulfide and carbonate from the hydrothermal solution. The close association between mineralization and the inner silicification envelope is clear. This implies that ore-forming metals are transported as Si, 5, C complexes, and that the precipitation of quartz, sulfide and carbonate by the reaction between wall rock and hydrothermal solutions might trigger ore deposition. 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Megascopic Description of Altered Samples, Silver Queen Mine  196  Table A-i. Megascopic Description of Altered Samples, Silver Queen Mine Sample Description No.  Weight* (g)  the main cross-cut (also named Bulkley cross-cut) of 2600 foot level of  610  X1-1  underground working; 0-0.3 m from the footwall of the No. 3 vein (1.2 m wide, 325fNEL47°) to walirock; strongly silicffied and pyrilized microdiorite; pale apple green, not magnetic, fine grain porphyroid texture, quartz, clay minerals  and abundant disseminated pyrite. X1-2  same location as above; 0.3-0.6 m from the footwall of the No. 3 vein to wallrock;  1260  strongly silicified and pyritized microdkrite; petrographic features are same as above except containing less pyrite. X1-2d  same location as above; 0.6-0.8 m from the footwall of the No. 3 vein to wallrock;  645  moderately silicffied microdionte, petrographic features are same as above. X1-3  same location as above; 0.8-1.6 m from the footwall of the No. 3 vein to wallrock;  1196  sericitic-argillic altered nricrodiorite, it is getting away from the vein, the intensity of alteration seems weaker than above samples; the color of the rock looks pale white to grey white or yellowish grey, the rock has more clay (can be tasted) and less_quartz_and pyrite than the_above_samples. X1-4  same location as above; 1.6 2.4 m from the footwall of the No. 3 vein to -  1085  walirock; sericitic-argillic altered microdiorite; its petrographic features are similar to the above sample. X1-5.  same location as above; 2.4- 3.2 m from the footwall of the No. 3 vein to wallrock;  1522  sericitic-argillic altered microdiorite; its petrographic features are similar to the above sample. X1-6.  same location as above; 5-7 m from the footwall of the No. 3 vein to wallrock  2143  (inaccessible for sampling between 3.2-Sm); sericitic-argillic altered microdiorite; its petrographic features are similar to the above sample. X1-7.  same location as above; 7-14 m from the footwall of the No. 3 vein to walirock;  2216  sericitic-argillic microdiorite; it seems having more sericitic and less clays. Primary textrue is well preserved. X1-8.  same location as above; 14-27 m from the footwall of the No. 3 vein to wallrock;  3051  moderate sericitic-argillic microdiorite; the alteration intensity looks obviously weaker than the samples above; ther is a post-mineralization structure zone at the place of 27 m.  197  X2-1  the northern cross-cut of 2600 foot level underground working; 6.4-8.9 m from  880  the hanging-wall of the No. 1 vein to wall-rock (at the footwall side of the No. 2 vein), propylitic andesite, black or dark grey, massive and dense, detectable magnetism, reacting with diluted acid, porphyritic and flow texture, feldspar, hornblende and augite are identifiable phenocrysts, their sizes range from 0.5 to 2 mm,_there are about 40% of aphanitic grounchnass. X3 -1  the northern cross-cut of 2600 foot level underground working; 1 m of horse rock  920  between two veins (belong to No. 2 vein system), strong sericitic-argillic andesite; pale green, no magnetic, not reacts with diluted acide, alteration is relatively strong characterized by intensed fracture and poorly preserved primary texture; disseminated pyrite and other sphalerite are oberserved; all primary minerals are altered to_clay minerals_(stick tongue). X3-2  same location as above; 0-2.5 m from the footwall of the No. 2 vein to wall rock;  580  moderate sericitic-argillic andesite; petrographic features are similar to the above sample. X3-2d  same location as above; 2.5-6 m from the footwall of the No. 2 vein to wall rock;  840  moderate sericitic-argillic andesite; .pale white or grey white, no magnetic, no reaction with diluted acide, primary porphyritic and flow texture is well preserved, primary minerals such as feldspar, hornblende and augite are all altered to clay minerals. X3-3  same location as above; 6-8 m from the footwall of the No. 2 vein to wallrock;  1380  propylitic andesite, its petrographic features are similar to those of sample X2-1. X3-3d  same location as above; 8-16 m from the footwall of the No. 2 vein to wallrock;  995  propylitic andesite, its petrographic features are similar to those of sample X2-1. X3-4.  same location as above; 0-0.4 m from the hanging-wall of the No. 2 vein to  990  wallrock; strong sericitic-argillic andesite; its petrographic features are similar to sample X3-l. X3-5.  same location as above; 0.4-1.4 m from the hanging-wall of the No. 2 vein to  770  wallrock; moderate sericitic-argillic andesite. Its petrographic features are similar to X3-2d. X3-6.  same location as above; 1.4 4.4 m from the hanging-wall of the No. 2 vein to -  860  wallrock; propylitic andesite. Its petrographic features are similar to X3-2d. X3-7.  same location as above; 4.4-15 m from the hanging-wall of the No. 2 vein to  967  wallrock; propylitic andesite. Its petrographic features are similar to X2-1.  198  X4-4  same location as above; 3-12 m from the footwall of the No. 3 vein to wall rock,  980  propylitica andesite. Its petrographic features are similar to X2-1. X5-1  the southern cross-cut of 2600 foot level underground working; 0-0.3 m from the  1350  hanging-wall of the No. 3 vein to walirock, silicic and pyritic andesite. It is intensely fractured and altered. X5-2.  same location as above; 0.3-1.1 m from the hanging-wall of the No. 3 vein to wall  1320  rock, moderate silicic and pyritic andesite, similar to the sample above but less intensely fractrued. X5-3.  same location as above; 1.1-1.6 m from the hanging-wall of the No. 3 vein to  1110  walirock, sericitic and argillic andesite, pale brown, massive, primary texture well preserved, no magnetic and no reaction with diluted acide. X5-4.  same location as above; 1.6-3.1 m from the hanging-wall of the No. 3 vein to  1615  wallrock, sericitic and argillic andesite, X5-5.  same location as above; 3.1-14 m from the hanging-wall of the No. 3 vein to  1058  wallrock, sericitic and argillic andesite. X5-5d  same location as above; 14-33 m from the hanging-wall of the No. 3 vein to  908  wallrock, sericitic and argillic andesite. X5-6.  same location as above; 33-36 m.from the hanging-wall of the No. 3 vein to  893  wallrock, propylitic andesite. X5-6d.  same location as above; 36-38 m.from the hanging-wall of the No. 3 vein to  860  walirock,_propylitic_andesite. X5-7.  same location as above; 38-56 m from the hanging-wall of the No. 3 vein to wall-  956  rock, sericitic and argillic andesite. This alteration envelope may be related to a non-mineralized breccia zone (see the description below). X5-8  same location as above; 56-70 m from the hanging-wall of the No. 3 vein to wall-  1512  rock, sericitic and argillic andesite. The rock at the working face (70 m) is intensely fractured_(breccia_zone). X5-9  same location as above; 0-0.5 m from the hanging-wall of the Footwall vein to  1528  wall-rock, silicic and pyritic andesite, pale apple green, abundant disseminated pyrite. X5-10  same location as above; 0.5-6.5 m from the hanging-wall of the Footwall vein to  1715  the footwall of the No. 3 vein, silicic and pyritic andesite, similar to the sample above but less abundant disseminated pyrite.  199  X10-1  the main cross-cut (also named Bulkley cross cut) of 2600 foot level of  487  underground working; 0-1.2 m from the hanging-wall of the No. 3 vein to wall rock, silicic and pyritic niicrodiorite, pale apple green, abundant hematite veinlets cut pyrite veinlets and altered wallrock with abundant disseminated pyrite. It is also intensely fractured. X10-2  same location as above; 1.2-4 m from the hanging-wall of the No. 3 vein to wall-  950  rock, moderate silicic and argillic microdiorite. Its petrographic features are similar to the above but less adundent of veinlets, disseminated pyrite and not intensely fractured. X10-3  same location as above; 4-5.5 m from the hanging-wall of the No. 3 vein to wall-  830  rock, sericitic and argillic microdiorite. Its petrographic features are similar to above but there_is_much_less veinlets_than above_sample. X10-3d  same location as above; 5.5-7.5 m from the hanging-wall of the No. 3 vein to  815  wall-rock, sericitic and argillic microdiorite, buffer brown. There is no veinlets. X10-4.  same location as above; 7.5-20 m from the hanging-wall of the No. 3 vein to wall-  803  rock, sericitic and argillic microdiorite, similar to the sample above. Xl0-5.  same location as above; 20-38 m from the hanging-wall of the No. 3 vein to wall-  847  rock, moderate sericitic and argillic microdiorite, similar to the sample above. X10-6  same location as above; 38-44 m from the hanging-wall of the No. 3 vein to wall-  651  rock, propylitic microdiorite, black, dark grey, magnetic. It has a ‘sharp contact’ (gradational contact in the range of 2 cm) with the sample above. X10-6d  same location as above; 44-56 m from the hanging-wall of the No. 3 vein to wall-  545  rock, propylitic microdiorite, similar to the sample above. DA63-1  Switch back vein, 32-44 ft of drill 87-S-04, propylitic andesite contacts with a  488  post-mineralization dike (DA63-2). DA63-3  same location as above, 460-469 ft of drill 87-S-04, sericitic and argillic andesite  720  DA63 -4  same location as above, 472-496 ft of drill 87-S-04, sencitic and argillic andesite,  610  DA63 -5  same location as above, 497-499 ft of drill 87-S-)4, silicic andesite  620  DA63-6  same location as above, 500-504 ft of drill 87-S-04, silicic andesite. There is  720  hanging-wall sphalerite-galena-pyrite-barite vein (DA63-7) between sample DA63-6 and DA63-8. DA63-8  same location as above, 506-514 ft of drill 87-S-04, silicic andesite contacs the  770  hanging-wall of the main vein at 514 ft. *  sample weight after sawing out the weathering surface and veinlets.  200  Appendix B. Lithogeochemical Duplicate Analyses, Silver Queen Mine  201  C  mdi.  X1-5D  xl-90d  -  m. dl.  mdl. mdl. m. dl.  Nadiandk Nd granite m. dl.  mdl.  -  andesite; w-alt.  ALTERATION w-alt rn-alt s-alt s-alt w-alt rn-alt wm-alt wm-alt rn-alt w-alt w-alt w-alt w-alt w-alt rn-alt s-alt w-alt rn-alt w-alt rn-alt s-alt s-alt w-alt rn-alt wrn-alt wrn-alt rn-alt w-alt w-alt w-alt w-alt w-alt rn-alt s-alt w-alt rn-alt  -  weakly altered; rn-alt.  main x-cut  maIn x-cut  LOCATION main x-cut Swtch bk V. 87-S-4 Camp v. 88-S-29 Swtchbkv.87-S-4 Swtch bk v. 87-S-4 Colelkv.88-S-5 Duck lake Cole 1kv. 88-S-5 Cole 1kv. 88-S-5 N No3 v. x-cut FWJackv, NadlnaMt.E.slo NadlnaMt.E.slo malnx-cut mainx-cut maIn x-cut malnx-cut mainx-cut malnx-cut Swtch bk v. 87-S-4 Carnpv.88-S-29 Swtch bk v. 87-S-4 Swtchbkv.87-S-4 Colelkv.88-S-5 Duck lake Colelkv.88-S-5 Cole 1kv. 88-S-5 N No3 v. x-cut FWJackv. NadlnaMt.E.slo Nadina Mt. E. sb main x-cut rnalnx-cut malnx-cut  -  15.15  15.02  A1203 15.43 16.24 15.69 15.34 16.53 18,88 15.34 16.81 21.94 15.85 15.70 15.15 14,20 15.06 17.76 14.67 15.33 16.15 15.98 16.20 16.43 14.95 16.63 18.95 15,24 17.05 20.75 15.80 15.77 15.03 14.28 15.98 17,99 14.29 moderately altered; s-alt.  64.51  61.87  S102 59.05 51.19 58.11 54.41 57.99 52.68 60.05 54,71 52,77 57.75 57.01 49.64 68,03 61.20 63.27 59.10 61.89 63.85 59.00 51.68 55.69 54.59 57.72 52.63 60.64 54.20 53.82 57.59 57.05 49.82 67.46 59.00 63.52 59.20  -  3.19  2.61  FeO 2.89 11.24 3.49 9.14 3,76 6.43 2.42 3.20 3.60 2.86 3.77 5.64 1.87 2.86 3.11 9.11 2.44 3.33 2.85 11.24 3.49 9.13 3.76 6.43 2.42 3,20 3,60 3.08 3.77 5,64 1.87 2.85 3.11 9.17  -  CrOSS  0.86  2.47  MgO 2.69 1.35 0.38 0.80 2.63 1.16 2.76 2.14 0.92 2.87 4.29 7.81 1.76 2.81 1.05 0.85 2.25 1.22 2.18 1.34 0.39 0.87 2.62 1.16 2.62 2.15 0.84 3,07 4.18 7.64 1.86 2.18 1.06 0.83 strongly altered; x-cut  1.52  1,83  Fe203 2.64 0.66 2.73 2.15 2.22 0.81 2.59 2,46 2.02 3,02 2.69 3.34 1.04 2.36 0.99 0.51 1.99 1.33 2.52 0.41 2.81 2.02 2.32 0.81 2.54 2.41 2.02 2.81 2.73 3.23 1.05 2.52 1.02 0.67 cut;  1K  -  V.  -  3.72  4.19  K20 3.15 4.27 3.57 3.34 3.16 6.39 2.37 4.34 3.05 3.02 2.98 1.53 4.68 3.15 4.98 2.75 3.69 4,55 3.09 4.24 3.78 3.29 3.26 6.37 2.36 4.42 3.05 3.13 2.97 1.51 4.69 3.09 5.03 2.78 vein.  0.00  3,54  Na20 3.70 0.25 0.03 0.04 3.43 0.14 3.83 2.66 0.13 3.96 3.76 2.96 3.75 3.96 0.32 0.05 3.52 0.31 363 0,03 0.05 0.02 3.28 0.14 3.90 2.59 0.16 3.69 3.76 2.98 3.83 3.63 0.32 0.07 laKe;  1.81  3.97  CaO 5.10 1.25 1,00 1.24 6,25 2.16 5,02 5.67 4.95 5.75 5.80 6.58 2.45 4.90 1.60 0.66 4.09 1.56 5.16 1.24 1.55 1.04 6.45 2.04 4.98 5.68 4.65 5.61 5.78 6.50 2.44 5.16 1.62 0.68  Sample Duplicates of Major Components at Silver Queen mine, central British Columbia  ROCK TYPE rn. di.* rn. di. and. mdi. m. di. mdi. porphyry m. dl. m. dl. and. mdi. Naciiandk Ndgranlte rn.di. m.di. m. di. m.dl. m.dl. m.di. m. dl. and, m. di. m.dl, m.dl. porphyry mdl. m. dl. and,  microdiorite; and.  Table B-i SAMPLE ID xlO-6d DA63-3 DA8-3 DA63-5 DA63-1 DA48-2 S91-15D DA48-5 DA48-4 x3-3 xll-1 S91-9 S91-10 xlO-6 xlO-3d xl-1 xl-90 xl-5 xlO-6D DA63-3D DA8-3D DA63-5D DA63-1D DA48-2D S91-l5Dd DA4B-5D DA48-4D x3-3d xll-lb S91-9D S91-1OD xlO-6d xlO-3D X1-1D  0.44  0,43  T102 0.59 0.58 0.54 0.45 0.71 0.61 0.59 0.58 0.51 0.66 0.66 1.27 0.50 0.58 0.40 0.34 0.43 0,41 0.56 0.56 0.55 0.46 0.72 0.60 0,59 0.57 0.53 0.65 0.69 1.26 0.51 0.56 0.40 0.35  1.14  0.19  MnO 0.18 0.98 4.09 0.69 0.16 1,16 0.41 0.21 0.31 0.31 0.21 0.31 0.08 0.14 0.49 1.08 0.16 1.06 0,18 0.98 4.27 0.63 0.16 1.18 0.36 0.21 0.31 0.35 0.22 0.31 0.08 0.18 0.49 1.06  0.20  0.22  P205 0.28 0.28 0.30 0.31 0.43 0.32 0.29 0.41 0.31 0.39 0,42 0.56 0.22 0.27 0.13 0.17 0.23 0.12 0,34 0,25 0.30 0.29 0.43 0,32 0.29 0.41 0.33 0.39 0.42 0.56 0.21 0.34 0.14 0.17  C  SNo3v.x-cut Duck lake mainx-cut mainx-cut malnx-cut malnx-cut main x-cut Cole 1kv. 88-S-S Cole 1k V. 88-S-S Swtchbkv.87-SSwtchbkv.87-SSNo3v.x-cut SNo3v.x-cut S No3 V. x-cut SNo3v.x-cut S No3 V. x-cut N No3 V. x-cut malnx-cut N No3 v. x-cut N No3 V. x-cut  s-alt wm-alt rn-alt s-alt rn-alt rn-alt s-alt wm-alt rn-alt rn-alt rn-alt rn-alt rn-alt w-alt w-alt rn-alt w-alt w-alt w-alt rn-alt  and. porphyry mdi. m.di. m.dl. m.di. m. di. m. dl. m. di. m.di. mdi. and. and. and. and. and. and. m.di. and. and.  x5-9 S91-15 xlO-3 xlO-2 xlO-5 xlO-4 xl-3 DA48-5 DA48-4D DA63-4 DA63-3D x5-5d x5-5 x5-6d x5-6 x5-4 x2-5 xlO-6 x3-7 x3-2  .  LOCATION SNo3v.x-cut Duck lake mainx-cut malnx-cut main x-cut mainx-cut main x-cut Cole 1k v. 88-5-5 Cole 1kv. 88-S-S Swtchbkv.87-SSwtch bk v. 87-SS No3 v. x-cut SNo3v.x-cut S.No3 v. x-cut S No3 v x-cut SNo3v.x-cut N No3 v. x-cut mainx-cut N No3 V. x-cut N No3 V. x-cut  ALTERATION s-alt wm-alt rn-alt s-alt rn-alt rn-alt s-alt wm-alt rn-alt rn-alt rn-alt rn-alt rn-alt w-alt w-alt rn-alt w-alt w-alt w-alt. rn-alt  ROCK TYPE and. porphyry m.di. mdi. m, di. mdi, m. di. m. di. m. di. mdi. m. di. and, and. and. and. and. and. mdi. and. and. -  0.19 0.28 0.11 0,19 0.19 0.14 0.19 0,41 0.34 0.29 0.26 0.28 0.26 0.30 0.28 0,20 0.37 0,27 0.38 0.26 0.08 0.12 0.96 1.66 0.30 0.37 0,83 0.21 0.31 0.90 0.98 0.48 0.69 0.19 0.22 0.36 0.25 0.14 020 0.60 0.44 0.56 0.39 0.41 0.58 0.45 0.4G 0.58 0.54 0.59 0.57 0,69 0.78 0.64 0.67 0.51 0.66 0.58 0.65 0.72 4.69 2.64 5.61 1.29 3.38 4.37 3.96 4.34 3.06 4.05 4.26 3.94 3.62 275 3.19 4.69 3.15 3.15 2.92 3.41 0.35 4.26 0.31 0.03 0.29 0.27 0.20 2.66 0.15 0.06 0.05 0.82 0.33 4.22 3.05 0.34 3.39 3.96 4.09 0.34 1.14 3.40 1.00 0.93 1.47 1.25 0,78 2.14 0.85 1.21 1.36 2,13 1.86 3.43 2.50 1.24 3.33 2.81 2.64 0.99 3.35 1.82 3.52 4.20 3,43 2.75 4.68 3.20 3.60 12.68 11.24 3.60 4.00 3.58 3.38 2.62 2,92 2.86 3.05 3.65 2,20 3.01 0.85 2.93 1.44 1.19 1.24 2.46 2.09 1.01 0.59 1.85 1.86 2.23 2.36 1,49 3.08 2.36 2.86 2.33 16.09 14.89 17.37 16.35 17.87 17.07 15.68 16.81 20.81 18.07 16.29 16.87 17.50 15.42 16.04 16.05 15.70 15.06 15.87 18.35 64.31 63.00 63.39 59,19 59.90 64.27 64.14 54.71 53.44 48.43 51.36 53.63 55.40 56.64 56.58 66.43 57.29 61,20 57.97 60.21  0.35 3.07 0.67 0.70 2.72 1.60 1.00 5.67 4.69 1.02 1.24 6.23 4.38 4.44 5.11 0.66 5.67 4.90 5.66 1.73  MnO P205 0.19 0.08 0.28 0.12 0.12 0.95 0.10 1.41 0.19 0.31 0.15 0.36 0.15 0,81 0.42 0.21 0.33 0.31 0.29 0.90 0.25 0.98 0.28 0.47 0.26 0,67 0.26 0.19 0.25 0.22 0.20 0.37 0.37 0.26 0.26 0.14 0.38 0.20 0.26 0,59 Ti02 0.45 0.55 0.39 0.39 058 0.46 0.39 0.58 0.53 0.59 0.56 0.69 0,78 0,64 0.67 0.51 0.66 0.58 0.65 0.71 K20 4.73 2.62 5.67 4.45 3.34 4.36 4.02 4.31 3.05 4.04 4.24 3.93 3.58 2,70 3.15 4.56 3.09 3.14 2.83 3.37 Na20 CaO 0.33 0.35 4.20 3.03 0.31 0.66 0.29 0.63 0.31 2.71 0.28 1.60 0.14 0.95 2.69 5.73 0.16 4.65 0.06 1.02 0.03 1.24 0.81 6,42 0.33 4.34 4.19 4.56 3,00 5.31 0.33 0.66 3.36 5.91 3.93 4.92 4.10 5.85 0.35 1.70 MgO 1.10 3.40 1.01 1.28 1.48 1,25 0.92 2.12 0.84 1.21 1.34 1.93 1.71 3.42 2.49 1.26 3.23 2.78 2.57 0.97 FeO 3,35 1.82 3.52 5.40 3.43 2.75 4.70 3.20 3.60 12.79 11,24 3.60 4.26 3.58 3.38 2.62 2.92 2.86 3.05 3.65  Fe203 2.23 3.00 0.88 2.45 1.43 1.22 1.35 2.41 2.02 0.86 0.41 1.81 1.57 2.22 2.40 1.48 3.09 2.30 2.89 2.18  A1203 16.00 14.81 17.41 15.71 18.16 17.08 15.50 16.77 20.75 18.16 16.20 16.58 17.51 15.34 15.94 15.90 15.76 15.11 15.82 18.30  S102 64.10 63.22 63.27 60.43 59.71 64,19 64.23 54,61 53.82 48.40 51.68 53.53 55.24 56.68 56.54 66,30 57.18 61.25 57.91 59.94  Measurement Duplicates of Major Components at Silver Queen mine, central British Columbia  Table B-2. SAMPLE ID x5-9 S91-15 xIO-3 xlO-2 xlO-5 xlO-4 xl-3 DA48-5 DA48-4D DA63-4 DAG3-3D x5-5d xS-5 x5-6d x5-6 x5-4 x2-5 xlO-6 x3-7 x3-2  Table 8-3. SAMPLE ID  Queen mine, central British Columbia Duplicates of C02, H20 & S at Silver S (ppm) H20 C02 SAMPLE ID C02  3.64 3.75 2.35 4.15 1.85  xlO-2 xl-2 xl-90 xlO-3 xlO-6 xlO-4 xlO-5 x5-4 x5-5 xll-1 x3-3 xS-6 S91-10 391-9 SQ-119 xl-2 x3-2  Table 8-4. SAMPLE ID DA48-4D xl-1 xl-2 xl-20 xl-3 xlO-2 xlO-3 xlO-3D xlO-6 xlO-6D x3-2 S91-l5Dd DA48-2D DA48-4D DA48-5D DA63-ID DA63-3D DA63-5D DA8-2D DAB-3D X1-1D xl-2D X1-5D xl-9Oci xll-lb x3-3d S91-9D SQ119D  H20  1.95 1.86 1.39  3.30  2.12  1.92 4.35 0.25  0.90 1.14 2.16 0.36 2.88 2.93  S (ppm)  898 800 128 458 127 421 357 1635 751 970 181 711 21 800 559  x10-2 xl-2d xl-90d xlO-3d xlO-6d x10-4 xlO-5 x5-4 x5-5 xll-lb x3-3d x5-6d S91-1OD S91-9D SQ119D xl-2 x3-2  4.69 3.26 2.40 4.04 2.40 3,40 1.85 4.15 0.35  ‘1.90 2.27 1.22 2.02 0.91 1.64 1.28 0.58 3.19 3.19  n mine, central British Columbia Duplicates of Trace Elements at Silver Quee ZR 127 133 135 159 158 150 177 178 172 170 198 125 135 127 124 165 112 99 152 163 133 159 156 167 166 180 182 124  V 29 20 18 22 21 19 26 26 24 25 27 17 30 30 28 25 24 20 31 31 18 22 24 21 31 24 25 18  RB 116 110 148 166 172 199 206 206 120 119 123 82 260 116 179 104 179 120 177 127 113 166 177 136 92 117 99 71  SR 217 35 201 220 208 69 179 179 511 472 376 397 196 220 446 636 143 87 23 182 32 220 111 421 630 606 732 557  SAMPLE ID DA48-4D xl-1 xl-2d xl-2d xl-3 xlO-2 xlO-3d xlO-3d xlO-6d xlO-6d x3-2 S91-15D DA48-2 DA48-4 DA48-5 DA63-1 DA63-3 DA63-5 DA8-2 DA8-3 xl-1 xl-2 xl-5 xl-90 xll-1 x3-3 S91-9 SQ-119  ZR 145 131 159 159 162 155 178 178 172 172 198 116 142 127 138 158 114 91 152 164 132 135 160 165 166 185 184 145  V 30 20 21 21 26 21 27 27 27 27 27 17 31 30 28 26 25 21 31 30 19 18 25 24 28 32 26 18  867 732 124 659 154 423 349 1610 720 865 250 1056  5 768 504  RB 116 105 165 165 169 204 177 177 121 ‘121 123 77 265 116 188 93 173 123 177 121 110 148 179 135 90 104 99 78  SR 220 42 219 216 209 79 172 172 462 462 376 398 200 220 454 608 141 74 23 176 32 201 114 422 595 597 734 588  204  Appendix C Metasomatic Norm Calculation Using Quattro Pro for DOS 5.0  205  Instruction of using Quattro Pro for DOS 5.0 to calculate metasomatic norm  Page A. This is the title page of metasomatic norm calculation using Quattro Pro for DOS 5.0  Page B. The first block of this page contains lithogeochemical raw data. For example, the block B: B3..126 contains the raw data in following page.  The second block of page B converts the lithogeochemical raw data into their corresponding molar amounts. For example, the content of Si0 2 of sample x4-4 in cell C7, 57.86, divided by the molar weight of Si0 , 60.09 g/mole in cell A32 gives its molar 2  amount of 0.962889 in cell C32.  Page C. Absolute losses and gains of lithogeochemical constituents are calculated in the first notebook block of this page using Ti0 2 as immobile component and sample x4-4 as equivalent of least altered parent rock. For example, the value in cell C :D6 is calculated by Gresen& equation (cf. equation 1-9. in chapter 1): X 0 dXX  (C1)  In detail, dX is the value of absolute loss or gain of Si0 2 of sample x3-5, z 0 is the immobile component Ti0 2 of sample x3-5 (B:E9), z the immobile component Ti0 2 of sample x4-4 (B:C9), x 0 (B:E7) and x (B:C7) are 2 Si0 wt.% of the altered sample x3-5 and the least altered sample x4-4 respectively.  206  The second block of page C presents lithogeochemical data corrected for closure using the equation as follows: 0 X=--x  (C-2)  Clearly, the equation above is derived from equation (C-i). It converts the intensive value of x 0 (wt.%) to X with an extensive unit (such as gram).  Page D and E Page D and E contain the formulas to calculate metasomatic norms using Optimizer, oneof the powerful tools provided in Quattro Pro for DOS 5.0. In general, Optimizer can (i) evaluate more than one formula; (ii) solve sets of linear and nonlinear equations and inequalities; (iii) find a minimum or maximum solution instead of an exact target; (iv) find values that satisfy limits. To use Optimizer, a notebook model is created. It contains the realistic estimates and define the elements of metasomatic norm calculation as follows: 1. The results of calculated metasomatic norms, which are given on page E. The formulas in this notebook block are based on equations introduced in Chapter 2; 2. A set of variables Optimizer can change to produce the results above, which is listed in the block of Adjust Factor Matrix on page D; and 3. The constraints, or limitations, the solution must accommodate, which are listed in the block of Constraint Matrix on pageD. For example, dTotal = 0, dH2O  <  0.3 and >-0.3, dCO2 <0.3 and >-0.3 etc. All formulas in these notebook blocks are based on the equations introduced in Chapter 2 and attached on the pages following page D and E. After the problem is properly defined, Optimizer can adjust the variables, recalculates the notebook, and then, based on the new results, continues these adjustments until it finds a solution that meets the requirements.  207  Page F This page contains the notebook blocks calculating propagated error. The formulas in each notebook blocks on this page are based on the equations introduced in Chapter 3 and attached on the pages following page F for reference.  Page G This is the last notebook page of this program. It presents the final results of metasomatic norm calculation in units of mole and gram respectively. A set of comprehensive, mass balanced reaction equations can be constructed by combining the results listed on page F and G. For example, sample x4-4 is the least altered precursor rock of altered sample x3 -5, the hydrothermal alteration of sample x3 -5 can be presented as follows: Primary minerals  0.O23pyroxene 5.11±0.17 g  Propylitic alteration  +  +  0. l36plagioclase + 0.066K-feldspar + 0.2quartz 36.01± 0.95 g 18.26±0.48 g 12.02±0.33 g  0.O04chlorite 3.05±0.11 g  +  0.03 9epidote 18.7±0.5 g  +  0.O53carbonate 4.86±0.34 g  mass 2 0.236SiO 0.04 1Al 3 0.027Fe 2 0.056Mg 3 2 O.11Na 0.072Ca 0.029K losses -14.19±1.38 g -1.1±0.22 g -1.5±0.04 g -1.37±0.03 g -2.9±0.07 g -2.54±0.04 g -1.11±0.06 g -  -  -  mass gains  +  sericitic, argillic, carbonatized, silicified alteration  =  -  -  -  -  0. 129H 0 + 0.042C0 2 2 2.31±0.1 g 1.86±0.12 g  0.O44sericite + 0.O63kaolinite + 0.O93carbonate 17.28±0.47 g 16.28±0.5 1 g 9.8 1±0.6 g  +  0.456quartz 27.38±0.7 1 g  Unlike other ‘black box’ types of software, this Quattro Pro program is transparent. User can easily adjust and develop it according to his own purpose, such as add or replace some standard norm minerals, set different constrains. In addition, user should keep in  mind when using Optimizer that calculations of metasomatic norms are complex nonlinear problems and could have many different solutions. Depending on the values user start  208  with, Optimizer’s recommended solutions vary. User should use his knowledge to well constrain the problem and treat his negative results as a case that his hypothesis is rejected and his positive results as the case that his hypothesis is not rejected rather than approved.  209  Notebook page A.  METASOMATIC NORM By Xiaolin Cheng and A. J. Sinclair Dept. of Geological Sciences University of British Columbia 1995  210  Notebook page B. Al  B Sample_id Alteration rock location N Si02 A1203 Ti02 Fe203 FeO MnO MgO CaO Na20 1(20 P205 H20 C02 S LOl Total Zr Y Rb Sr  Molar wt 60.09 101.96 79.90 159.70 71.85 70.94 40.31 56.08 61.98 94.18 141 .94 18.00 44.01 32.06 90.03  CI  DIEt  Fl  G  Lithogeochemical Raw Data  1  H  x3.3d x3-1 x3-4 x3-5 x3-7 x4-4 w-alt ms-alt nis-alt ni-alt w-alt w-alt and. and, and. and. and. and. v. x No3 v. N x No3 V. N x No3 v. N x No3 No3 v. x N No3 v. x N 57.59 57.25 56.67 58.45 57.97 57.86 15.80 17.45 17.27 18.11 15.87 15.61 0.65 0.67 0.57 0.87 0.65 0.65 2.81 1.25 1.26 1.26 2.86 3.09 3.08 5.82 5.78 3.69 3.05 2.89 0.35 1.57 1.65 1.34 0.20 0.34 3.07 1.09 1.15 0.90 2.64 2.94 5.61 0.73 0.73 2.69 5.66 6.07 3.69 0.29 0.44 0.31 4.09 3.65 3.13 2.77 4.12 2.34 2.92 3.09 0.39 0.20 0.19 0.27 0.38 0.38 1.84 3.9 2.69 4.39 1.27 0.97 1.65 5.75 5.9 5.2 2.14 2.03 0.025 0.073 0.127 0.029 0.018 0.013 3.52 9.72 8.72 9.62 3.43 3.01 99.69 98.81 98.55 99.85 99.72 99.58 180.19 188 163 220 192 191 23.62 23 12 32 30 28 117.16 114 172 96 108 100 605.75 630 231 238 607 593  Conversion of wt% to x4-4 Sample_id w-alt Alteration 0.962889 Si 0.306199 Al 0.008135 Ti 0.038698 Fe+3 0.040223 Fe+2 0.004793 Mn 0.072935 Mg 0.108238 Ca 0.11778 Na 0.065619 K 0.005354 P 0.107411 OH0.046126 C03= 0.000415 S 2.122293 Zr  molar amount x3-5 x3-7 rn-alt w.alt 0.96472 0.972708 0.311299 0.355237 0.008135 0.010889 0.035817 0.01578 0.04245 0.051357 0.002819 0.018889 0.065492 0.022327 0.100927 0.047967 0.131978 0.010003 0.062009 0.049692 0.005354 0.003804 0.141111 0.487778 0.048625 0.118155 0.000549 0.000895 2.133067 2.445851  x3-4 ms-alt 0.943085 0.33876 0.007134 0.01578 0.080445 0.023259 0.028529 0.013017 0.014198 0.087492 0.002677 0.298889 0.13406 0.003949 1.813284  x3-1 ms-alt 0.952738 0.342291 0.008385 0.015654 0.081002 0.022131 0.02704 0.013017 0.009358 0.058824 0.002818 0.4.33333 0.130652 0.002283 2.086082  x3-3d w-alt 0.958396 0.309925 0.008135 0.035191 0.042867 0.004934 0.07616 0.100036 0.119071 0.066468 0.005495 0.204444 0.037491 0.000780 2.001444  I 2 3 x2-5 4 w-alt 5 and. N No3 v. x 6 7 57.29 15.70 8 0.66 9 3.08 10 2.92 11 0.25 12 3.33 13 5.67 14 3.39 15 3.15 16 0.37 17 1.04 18 2.75 19 0.003 20 3.79 21 99.60 22 178.64 23 33.05 24 121.40 25 573.45 26 27 28 x2-5 w-alt 0.953403 0.307964 0.00826 0.038572 0.04064 0.003524 0.08261 0.101106 0.10939 0.066893 0.005213 0.115211 0.062486 0.000097 1.984227  30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46  211  Notebook page C. AIBICDIEI  FIGIH  Absolute loss or gain calculation  Sample_id Alteration dSiO2 dA12O3 dTiO2 dFe2O3 dFeO dMnO dMgO dCaO dNa2O dK2O dP2O5 dH2O dCO2 dS dLOI dTotal dZr dY dRb dSr  (by using Gresens’s/MacLean’s Equation) x3-1 x3-4 x3-5 x3-7 x4-4 ms-alt ms-alt rn-alt w-alt w-alt -2.32 6.76 -14.19 0.11 0.00 1.32 4.08 -2.08 0.26 0.00 0.00 0.00 0.00 0.00 0.00 -1.88 -1.65 -2.15 -0.23 0.00 2.76 3.70 .0.13 0.16 0.00 1.18 1.54 0.66 -0.14 0.00 -1.88 -1.63 -2.27 -0.30 0.00 -5.36 -5.24 -4.06 -0.41 0.00 -3.37 -3.15 -3.42 0.44 0.00 -0.40 1.61 -1.34 -0.17 0.00 -0.19 -0.16 -0.18 0.00 0.00 2.82 2.10 2.31 0.30 0.00 3.55 4.70 1.86 0.11 0.00 0.06 0.13 0.01 0.00 0.00 6.42 6.93 4.18 0.42 0.00 -3.72 12.80 -24.98 0.14 0.00 -8.87 -4.91 -26.55 0.97 0.00 -5.69 -14.29 -3.88 2.41 0.00 10.33 95.59 -28.33 8.17 0.00 18.37 3 -328.9 8 -414.5 14.64 0.00  x3-3d w-alt -0.27 0.19 0.00 -0.28 0.19 0.01 0.13 -0.46 0.04 0.04 0.01 0.87 -0.38 0.01 0.51 0.11 -10.88 -4.33 16.88 13.03  Lithogeochemical Data Corrected for Closure Sample_id Alteration dSiO2 dAl2O3 dTiO2 dFe2O3 dFeO dMnO dMgO dCaO dNa2O dK2O dP2O5 dH2O dCO2 dS dLOI dTotal dZr dY dRb dSr  x4-4 w-alt 57.86 15.61 0.65 3.09 2.89 0.34 2.94 6.07 3.65 3.09 0.38 0.97 2.03 0.01 3.01 99.58 191.07 27.95 100.28 592.72  c3-7 w-alt 57.97 15.87 0.65 2.86 3.05 0.20 2.64 5.66 4.09 2.92 0.38 1.27 2.14 0.02 3.43 99.72 192.04 30.36 108.45 607.36  x3-5 rn-alt 43.67 13.53 0.65 0.94 2.76 1.00 0.67 2.01 0.23 1.75 0.20 3.28 3.89 0.02 7.19 74.60 164.52 24.07 71.95 178.14  x3-4 ms-alt 64.62 19.69 0.65 1.44 6.59 1.88 1.31 0.83 0.50 4.70 0.22 3.07 6.73 0.14 9.94 112.38 186.16 13.66 195.87 263.79  x3-1 ms-alt 55.54 16.93 0.65 1.21 5.65 1.52 1.06 0.71 0.28 2.69 0.19 3.78 5.58 0.07 9.43 95.86 182.20 22.26 110.61 611.09  x3-3d w-alt 57.59 15.80 0.65 2.81 3.08 0.35 3.07 5.61 3.69 3.13 0.39 1.84 1.65 0.03 3.52 99.69 180.19 23.62 117.16 605.75  2 3 4 x2-5 5 w-alt -1.44 6 -0.15 7 0.00 8 -0.06 9 -0.01 10 -0.09 11 0.34 12 -0.49 13 -0.31 14 0.01 15 -0.02 16 0.05 17 0.68 18 -0.01 19 0.72 20 -1.49 21 -15.14 22 4.60 23 19.28 24 -27.96 25 26 x2-5 w-alt 56.42 15.46 0.65 3.03 2.88 0.25 3.28 5.58 3.34 3.10 0.36 1.02 2.71 0.00 3.73 98.09 175.93 32.55 119.56 564.76  28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49  212  Notebook page D.  Al  Dl ci Adjust factor matrix 81  x4-4 Sample_id w-alt Alteration 0.043 Calcite 0.000 Mg-chl 0.472 Mg-pyx 0.535 Fe-chl 0.312 Fe-pyx 1.000 Or 0.156 An 1.000 Ab 0.000 te ilmeni 0.000 Ca-pyx 0.000 magnetite 89 0.4723 I4-p Mg-ch Fe-chl+py 0.846492  x3-5 rn-alt 0.763 0.000 0.000 0.000 0.000 0.000 0.000 0.127 0.000 0.000 0.000 1 0.000479 0 0.270079 x3-7 w-alt 0.393 1.000 0.000 0.000 0.270 1.000 0.191 1.000 0.969 0.000 0.000  Residual Matrix Sample_id Alteration dSiO2 dAl2O3 dTiO2 dFe2O3 dFeO dMnO dMgO dCaO dNa2O dK2O dP2O5  x4-4 w-alt 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000  x3-7 w-alt 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000  3.5 rn-alt 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000  Constraint matrix dH2O dCO2 dS dLOI dTotal Carbnate Epidote Sericite KaoI ChI Pyx Or P1 Pyrite Qtz  0.294 -0.299 0.000 0.004 0.001 4.857 18.700 0.000 0.000 3.052 5.106 18.264 36.013 0.025 12.017  0.128 -0.240 0.000 0.112 0.108 5.850 9.787 0.016 -0.000 7.280 1.222 17.260 41.628 0.033 13.395  0.244 -0.251 0.000 0.007 0.000 13.129 2.388 23.128 21.789 0.001 0.000 0.000 0.334 0.054 36.654  El  Fl  Gi  H  0 0  x2-S w-alt 0.271 0.339 0.000 0.805 0.195 1.000 0.416 1.000 0.011 0.522 0.000 1 0.339311 0 / 1 0 0.535345  x3-4 ms-alt 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000  x3-3d w-ait 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000  x2-5 w-alt 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000  -0.076 0.069 0.000 0.007 0.000 3.981 15.489 3.961 -0.000 11.711 1.802 18.501 28.508 0.047 13.867  0.073 -0.075 0.000 0.001 0.000 5.615 3.952 0.000 0.008 7.771 3.884 18.619 41.346 0.006 14.434  x3-1 ms-alt 1.000 0.000 0.000 0.000 0.000 0.000 0.000 0.221 0.349 0.000 0.000  x3-4 ms-alt 1.000 0.000 0.000 0.000 0.000 0.000 0.000 0.265 0.000 0.000 0.000  0.178 -0.209 0.000 0.032 0.000 15.027 0.000 38.839 5.318 0.000 0.000 0.000 0.985 0.237 35.863  x3-1 ms-alt 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000  0.148 -0.166 0.000 0.018 0.000 14.570 0.000 26.216 18.313 0.000 0.000 0.000 0.542 0.137 36.433  —  2 3 4 5 6  x3-3d w-ak 0.149 1.000 0.000 0.535 0.000 1.000 0.000 0.913 0.000 0.171 0.000  8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36  -  38 39 40 41 42 43 44 45 46 47 48 49  213  Notebook page E.  I  A  B  Molar wt 100.09 483.24 232.34 278.22 84.32 555.78 200.80 115.86 713.48 263.88 398.30 278.34 382.20 262.24 151.75 79.90 258.14 60.09 114.95 502.21 119.97 159.70 231.55  Sample_id Alteration Calcite Epidote Ca-pyx An Mg-carb Mg-chl Mg-pyx Fe-carb Fe-chl Fe-pyx Muscovite Or Na-mica Ab ilmenite rutile Kaol qtz Mn-carb apatite pyrite hemtite magnetite total  I FIG Metasomatic Norms (closed) CJ  x4-4 w-alt 0.350 18.700 0.000 5.126 3.245 0.000 3.459 0.712 3.052 1.647 0.000 18.264 0.000 30.887 0.000 0.650 0.000 12.017 0.551 0.896 0.025 0.000 0.000 99.581  DIE  x3-7 w-alt 2.626 9.787 0.000 7.029 0.000 7.280 0.000 2.900 0.000 1.222 0.000 17.260 0.016 34.599 1.196 0.020 -0.000 13.395 0.324 0.896 0.033 1.243 0.000 99.825  x3-5 rn-alt 3.177 2.388 0.000 0.000 1.882 0.001 0.000 5.898 0.000 0.000 19.792 0.000 3.336 0.334 0.000 0.870 21.789 36.654 2.171 0.637 0.054 0.865 0.000 99.849  x3-4 ms-alt 0.856 0.000 0.000 0.000 2.406 0.000 0.000 9.092 0.000 0.000 34.848 0.000 3.991 0.985 0.000 0.570 5318 35.863 2.674 0.448 0.237 1.260 0.000 98.547  I  x3-1 ms-alt 0.833 0.000 0.000 0.000 2.280 0.000 0.000 8.913 0.000 0.000 23.429 0.000 2.786 0.542 0.444 0.436 18.313 36.433 2.544 0.472 0.137 1.250 0.000 98.813  Hill 2 x3-3d w-alt 1.127 15.489 1.802 0.000 0.000 8.466 0.000 2.287 3.245 0.000 0.000 18.501 3.961 28.508 0.000 0.650 -0.000 13.867 0.567 0.920 0.047 0.251 0.000 99.685  Final Metasomatic Norms (Closed) Sample_id Alteration apatite ilmenite magnetite pyroxene plagioclase orthoclase quart epidote chlorite sericite kaolinite carbonate rutile hemtite pyrite total  x4-4 w-alt 0.896 0.000 0.000 5.106 36.013 18.264 12.017 18.700 3.052 0.000 0.000 4.857 0.650 0.000 0.025 99.581  x3-7 w-alt 0.896 1.196 0.000 1.222 41 .628 17.260 13.395 9.787 7.280 0.016 -0.000 5.850 0.020 1.243 0.033 99.825  x3-5 rn-alt 0.637 0.000 0.000 0.000 0.334 0.000 36.654 2.388 0.001 23.128 21.789 13.129 0.870 0.865 0.054 99.849  x3-4 ms-alt 0.448 0.000 0.000 0.000 0.985 0.000 35.863 0.000 0.000 38.839 5.318 15.027 0.570 1.260 0.237 98.547  x3-1 ms-alt 0.472 0.444 0.000 0.000 0.542 0.000 36.433 0.000 0.000 26.216 18.313 14.570 0.436 1.250 0.137 98.813  3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29  x2-5 w-alt 0.608 3.952 2.844 12.659 4.602 3.116 0.000 -0.000 4.656 1.039 0.000 18.619 0.000 28.686 0.013 0.653 0.008 14.434 0.405 0.873 0.006 2.427 0.000 99.600  30  x3-3d w-alt 0.920 0.000 0.000 1.802 28.508 18.501 13.867 15.489 11.711 3.961 -0.000 3.981 0.650 0.251 0.047 99.685  x2-5 w-alt 0.873 0.013 0.000 3.884 41 .346 18.619 14434 3.952 7.771 0.000 0.008 5.615 0.653 2.427 0.006 99.600  31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48  214  A  lB  I  C  Error Propagation So k  DI  F  El  Cd  G So  I  HI k  —  2 Cd  3  S102  0.010  0.012  0.020  K20  0.020  0.018  0.041  4  AL203  0.012  0.020  0.025  P205  0.020  0.015  0.041  5  T102  0.006  0.008  0.012  H20  0.040  0.130  0.108  6  0.010  0.120  0.026  7 8  FE203  0.060  0.018  0.124  C02  FEO  0.045  0.018  0.093  S  0.002  0.070  0.004  MNO  0.022  0.007  0.045  Zr(ppm)  0.010  0.032  0.021  9  MGO  0.074  0.030  0.157  Y(ppm)  0.300  0.090  0.732  10  CAO  0.080  0.011  0.164  Rb(ppm)  2.000  0.035  4.301  11  NA2O  0.090  0.013  0.185  Sr(ppm)  5.000  0.019  1.395  12  Standard Deviation at 68% confidence level Sample_id  x4-4  x3-7  x3-5  x3-4  13  x3-1  x3-3d  14  x2-5  0.1037  0.1008  0.0784  0.0416  15  0.0358  0.0000  0.0000  0.3735  0.0952  16  0.0061  0.0000  0.0000  0.0333  0.0524  17  0.0013  0.0000  0.0000  0.0000  0.2270  15  0.0000  0.2144  0.2613  0.2516  0.0000  0.4119  19  0.1024  0.3620  0.0000  0.0000  0.0000  0.3982  0.1512  20  Mg-pyx  0.0000  0.0000  0.0034  0.0000  0.0000  0.0000  0.0000  21  Fe-carb  0.0039  0.1864  0.3591  0.5657  0.5544  0.1557  -0.0000  22  Fe-chi  0.0000  0.0000  0.0000  0.0000  0.0000  0.1226  0.1857  23  Fe-pyx  0.0821  0.0323  0.0094  0.0000  0.0000  0.0000  0.0247  24  Muscovite  0.0000  0.0000  0.3479  0.6067  0.4095  0.0000  0.0000  25  Or  0.2891  0.2742  0.0000  0.0000  0.0000  0.2926  0.2943  26  Na-mica  0.0174  0.0003  0.1516  0.1316  0.1152  0.0740  0.0000  27  Ab  0.5104  0.5722  0.0000  0.0375  0.0274  0.4796  0.4899  28  ilmenite  0.0153  0.0296  0.0000  0.0000  0.0094  0.0000  0.0003  29  rutile  0.0057  0.0003  0.0130  0.0106  0.0074  0.0112  0.0112  30  Kaol  0.0113  -0.0000  0.7336  0.1811  0.6116  -0.0000  0.0003  31  Calcite  0.0000  0.1706  Epidote  0.0025  0.2544  Ca-pyx  0.0937  0.0000  An  0.2666  0.1186  Mg-carb  0.4208  Mg-chl  0.2657  qtz  0.1607  0.1611  0.4456  0.4367  0.4436  0.1688  0.1757  32  Mn-carb  0.0507  0.0389  0.1327  0.1581  0.1516  0.0518  0.0429  33  apatite  0.0406  0.0409  0.0401  0.0542  0.0559  0.0413  0.0404  34  pyrite  0.0005  0.0006  0.0010  0.0037  0.0021  0.0009  0.0001  35  hemtite  0.0589  0.0438  0.0704  0.0827  0.0825  0.0099  0.0910  36  magnetite  0.0788  0.0000  0.0000  0.0000  0.0000  0.0000  0.0000  37  Sc_SiO2  0.704  0.706  0.711  0.690  0.697  0.701  0.697  38  Sc_A1203  0.324  0.329  0.374  0.357  0.361  0.328  0.326  39  Sc_Ti02  0.011  0.011  0.013  0.011  0.011  0.011  0.011  40  Sc_Fe2O3  0.116  0.111  0.083  0.083  0.083  0.111  0.115  41  Sc_FeO  0.097  0.100  0.111  0.149  0.150  0.100  0.098  42  Sc_MnO  0.024  0.023  0.031  0.034  0.033  0.024  0.024  43  Sc_MgO  0.162  0.153  0.101  0.109  0.107  0.166  0.174  44  Sc_CaO  0.147  0.142  0.110  0.088  0.088  0.142  0.142  45  Sc_Na20  0.137  0.143  0.094  0.096  0.094  0.138  0.134  46  Sc_K2O  0.076  0.073  0.062  0.094  0.070  0.076  0.077  47  Sc_P205  0.026  0.026  0.024  0.023  0.023  0.026  0.026  45  Sc_H20  0.166  0.205  0.611  0.390  0.547  0.279  0.175  49  Sc_C02  0.254  0.267  0.634  0.718  0.700  0.208  0.340  50  Sc_S  0.003  0.003  0.004  0.011  0.007  0.004  0.002  51  Sc_Zr  6.124  6.155  7.056  5.234  6.020  5.776  5.726  52  215  Notebook page F. jc B Al Table 7Samplejd Calcite Epidote Ca-pyx An Mg-carb Mg.chl Mg-pyx Fe-carb Fe-chl Fe-pyx Muscovite Or Na-mica Ab ilmenite rutile Kaol qtz Mn-carb apatite pyrite bemtite magnetite Total Table 7-  .  Sample_id dSiO2 dAl+3 dTi+2 dFe+3 dFe+2 dMn+2 dMg+2 dCa+2 dNa+ dK+ dP+5 dH2O dCO2 dS dO=  I  HI FjG level) ence confid 68% at D grani(S in for closure Error propagation of norms corrected BC central Lake, Owen mine, Queen at northern segment of No.3 vein, Silver x2-5 x3-3d x3-1 x3-4 x3-5 x3-7 x4-4 0.043 0.083 0.100 0.121 0.189 0.192 0.025 0.133 0.531 0.000 0.000 0.070 0.336 0.638 0.085 0.055 0.000 0.000 0.000 0.000 0000 0.376 0.000 0.000 0.000 0.000 0.213 0.155 0.420 0.000 0.250 0.306 0.168 0.000 0.307 0.167 0.448 0.000 0.000 0.000 0.403 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.132 0.000 0.165 0.577 0.696 0.304 0.209 0.052 0.214 0.146 0.000 0.000 0.000 0.000 0.144 0.035 0.000 0.000 0.000 0.000 0.041 0.056 0.000 0.000 0.678 1.220 0.425 0.000 0.000 0.531 0.537 0.000 0.000 0.000 0.502 0.531 0.000 0.122 0.129 0.189 0.114 0.000 0.000 0.838 0.844 0.029 0.051 0.013 1.019 0.915 0.000 0.000 0.014 0.000 0.000 0.041 0.000 0.019 0.019 0.012 0.020 0.018 0.001 0.019 0.000 0.000 0.732 0.257 0.656 0.000 0.000 0.386 0.378 0.957 1.148 0.707 0.365 0.327 0.043 0.054 0.159 0.196 0.106 0.040 0.052 0.045 0.047 0.055 0.063 0.032 0.046 0.046 0.000 0.001 0.004 0.008 0.001 0.001 0.001 0.107 0.012 0.085 0.101 0.045 0.057 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 3.4443 3.4430 3.7823 4.3782 2.8480 3.4662 3.4013  I  DIE  I  in gram (SD at 68% confidence level) Error propagation of absolute losses & gains mine. Owen Lake, central BC at northern segment of No.3 vein, Silver Queen x2-5 x3-3d x3.1 x3.4 x3-5 x3-7 x4-4 1.686 1.720 1.660 1.946 1.330 1.729 1.726 0.313 0.318 0.333 0.381 0.279 0.319 0.315 0.013 0.013 0.013 0.014 0.013 0.013 0.013 0.125 0.122 0.100 0.107 0.093 0.122 0.126 0.119 0.123 0.172 0.200 0.111 0.123 0.120 0.027 0.028 0.042 0.051 0.032 0.026 0.027 0.150 0.147 0.117 0.125 0.108 0.140 0.145 0.174 0.176 0.122 0.128 0.124 0.176 0.182 0.154 0.159 0.122 0.131 0.115 0.165 0.159 0.109 0.109 0.100 0.147 0.081 0.105 0.109 0.016 0.016 0.015 0.016 0.014 0.016 0.016 0.240 0.328 0.563 0.481 0.49 1 0.265 0.235 0.425 0.330 0.737 0.874 0.545 0.372 0.362 0.003 0.005 0.007 0.013 0.004 0.004 0.004 0.647 0.653 0.618 0.696 0.533 0.650 0.652  54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82  83 84 1.000  85  0.529  86  0.599  87  0.699  88  0.777  89  0.774  90  0.603  91  0.715  92  0.742  93  0.830  94  0.436  95  1.000  96  1.000  97  1.000  98  1.000  99  216  Notebook page G. 1H AIBICIDIEIFIG  & absolute losses and gains Table 7a. Metasomatic norms corrected for closure mine. Owen Lake, central BC at northern segment of No. 3 vein, Silver Queen x2-5 x3-3d x3-l x3-4 x3-S x3-7 x4.4 S.nip4ld øjwiaion  w-alt  w-alt  rn-alt  ms-alt  ms-alt  w-alt  w-alt  0.0060  2 3 4 5  Epidote  0.0387  0.0203  0.0037  Ca-pyi  0.0000  0.0000  0.0000  Au  0.0184  0.0253  0.0000  0.0000  0.0000  0.0000  Mg-carb  0.0385  0.0000  0.01 67  0.0325  0.0262  0.0000  0.0538  Mg-chl  0.0000  0.0131  0.0000  0.0000  0.0000  0.0152  0.0055  Mg-pyx  0.01 72  0.0000  0.0000  0.0000  0.0000  0.0000  0.0000  6 7 8 9 10 11 12 13  Fe-carl,  0.0061  0.0250  0.0380  0.0895  0.0746  0.0197  -0.0000  14  Fe-cht  0.0043  0.0000  0.0000  0.0000  0.0000  0.0045’  0.0064  Fe-pyx  0.0062  0.0046  0.0000  0.0000  0.0000  0.0000  0.0039  15 16  Muscovite  0.0000  0.0000  0.0371  0.0998  0.0571  0.0000  0.0000  17  Or  0.0656  0.0620  0.0000  0.0000  0.0000  0.0665  0.0659  Na-mica  0.0000  0.0000  0.0065  0.0119  0.0071  0.0104  0.0000  Ab  0.1178  0.1319  0.0010  0.0043  0.0020  0.1087  0.1077  ilmenite  0.0000  0.0079  0.0000  0.0000  0.0026  0.0000  0.0001  nitile  0.0081  0.0003  0.0081  0.0081  0.0053  0.0081  0.0080  KaoL  0.0000  -0.0000  0.0631  0.0235  0.0688  -0.0000  0.0000  18 19 20 21 22 23  qtz  0.2000  0.2229  0.4557  0.6806  0.5882  0.2308  0.2366  24  Mn-carb  0.0048  0.0028  0.0141  0.0265  0.0215  0.0049  0.0035  apatite  0.0018  0.0018  0.0009  0.0010  0.0009  0.0018  0.0017  25 26  pyrite  0.0002  0.0003  0.0003  0.0023  0.0011  0.0004  0.0000  bemtite magnetite  0.0000  0.0078  0.0040  0.0090  0.0076  0.0016  0.01 50  0.0000  0.0000  0.0000  0.0000  0.0000  0.0000  0.0000  Total  0.5313  0.5522  0.6731  0.8713  0.5238  0.5790  dSiO2  0.0000  0.0018  -0.2362  0.1126  -0.0386  -0.0045  -0.0239  dAI+3  0.0000  0.0051  -0.0408  0.0801  0.0259  0.0037  -0.0029  dTi+4  0.0000  0.0000  0.0000  0.0000  0.0000  0.0000  0.0000  dFe+3  0.0000  -0.0029  -0.0269  -0.0207  -0.0235  -0.0035  -0.0007  dFe+2  0.0000  0.0022  -0.0019  0.0515  0.0384  0.0026  -0.0002  dMn+2  0.0000  -0.0020  0.0093  0.0217  0.0167  0.0001  -0.0013  dMg+2  0.0000  -0.0074  -0.0563  -0.0404  -0.0467  0.0032  0.0084  dCa+2  0.0000  -0.0073  -0.0724  -0.0934  -0.0956  -0.0082  -0.0087  dNa+  0.0000  0.0142  -0.1103  -0.1016  -0.1087  0.0013  -0.0100  dK+  0.0000  -0.0036  -0.0285  0.0342  -0.0086  0.0008  0.0003  27 28 29 30 31 32 33 34 35 36 37 38 39 40  dP+5  0.0000  0.0000  -0.0025  -0.0023  -0.0026  0.0001  -0.0002  41  Sum 0=  0.000  -0.006  -0.299  -0.013  -0.150  -0.001  -0.012  dH2O  0.000  0.017  0.129  0.117  0.156  0.049  0.003  dCO2  0.000  0.002  0.042  0.107  0.081  -0.009  0.015  dS  0.000  0.000  0.000  0.004  0.002  0.000  -0.000  44 45  dTotal  0.000  0.014  0.256  -0.154  0.035  -0.034  46  mole Calcite  0.0035  0.0262  0.0237  0.0098  0.0081  0.0113  0.0000  0.0000  0.0321  0.0081  0.0000  0.0000  0.0078  0.01 21 0.0448  -0.694  0.9987  42 43  47 48 49  217  Notebook page G.  GIH  AB)CIDJEIF  & absolute losses and gains Table 7b. Metasomatic norms corrected for closure Owen Lake. central BC at northern segment of No. 3 vein, Silver Queen mine. x2-5 x3-3d x3-1 x3-4 y3-5 x3-7 x4-4 sarnp4.W w-alt  w-alL  w-alt  w-alt  rn-alt  ms-alt  ms-alt  Calcite  0.3499  2.6257  2.3738  0.9765  0.8079  1.1 268  0.5989  Epidote  18.6998  9.7869  1.7840  0.0000  0.0000  15.4890  3.8918  Ca-pyx  0.0000  0.0000  0.0000  0.0000  0.0000  1.8023  2.8013  Au  5.1 260  7.0290  0.0000  0.0000  0.0000  0.0000  1 2.4674  Mg-carb  3.2447  0.0000  1.4059  2.7432  2.2120  0.0000  4.5324  Mg.chl  0.0000  7.2799  0.0009  0.0000  0.0000  8.4656  3.0685  Mg-pyx  3.4591  0.0000  0.0000  0.0000  0.0000  0.0000  0.0000  Fe-carb  0.7117  2.9001  4.4068  10.3677  8.6472  2.2868  .0.0000  Fe-chl  3.0522  0.0000  0.0000  0.0000  0.0000  3.2449  4.5852  Fe-pyx  1.6470  1.2220  0.0000  0.0000  0.0000  0.0000  1.0237  Muscovite  0.0000  0.0000  14.7874  39.7390  22.7300  0.0000  0.0000  Or  18.2644  17.2596  0.0000  0.0000  0.0000  18.5008  18.3369  Na-mica  0.0000  0.0156  2.4924  4.5513  2.7033  3.9605  0.0000  Ab  30.8866  34.5992  0.2498  1.1231  0.5259  28.5076  28.2518  ilmenite  0.0000  1.1961  0.0000  0.0000  0.4312  0.0000  0.0130  rutile  0.6500  0.0202  0.6500  0.6500  0.4230  0.6500  0.6432  Kaol  0.0002  -0.0001  16.2790  6.0642  17.7660  -0.0004  0.0078  qtz  12.0169  13.3950  27.3848  40.8959  35.3457  13.8670  14.2150  Mn-carb  0.5509  0.3241  1.6222  3.0489  2.4681  0.5671  0.3990  apatite  0.8963  0.8963  0.4758  0.5111  0.4577  0.9199  0.8595  pynce  0.0249  0.0329  0.0401  0.2701  0.1329  0.0468  0.0057  hemtite  0.0001  1.2428  0.6466  1.4368  1.2127  0.2506  2.3903  magnetite  0.0000  0.0000  0.0000  0.0000  0.0000  0.0000  0.0000  total  99.5809  99.8254  74.5996  112.3777  95.8636  99.6854  98.0914  dSiO2  0.0000  0.1100  -14.1905  6.7637  -2.3190  -0.2700  -1.4380  dAl+3  0.0000  0.1376  -1.1005  2.1613  0.6981  0.1006  -0.0783  dTi+4  0.0000  0.0000  0.0000  0.0000  0.0000  0.0000  0.0000  dFe+3  0.0000  -0.1609  -1.5028  -1.1563  -1.3131  -0.1958  -0.0396  dFe+2  0.0000  0.1244  -0.1035  2.8770  2.1425  0.1477  .0.0111  dMn+2  0.0000  -0.1084  0.5120  1.1939  0.9163  0.0077  -0.0726  dMg+2  0.0000  .0.1809  -1.3675  -0.9822  -1.1353  0.0784  0.2048  dCa+2  0.0000  -0.2930  -2.9018  -3.7432  -3.8320  -0.3288  -0.3473  dNa+  0.0000  0.3264  -2.5359  -2.3355  -2.4990  0.0297  -0.2310  dK+  0.0000  -0.1411  -1.1138  1.3350  -0.3343  0.0332  0.0102  dP+5  0.0000  0.0000  -0.0778  -0.0713  -0.0812  0.0044  -0.0068  Sum 0=  0.000  -0.095  -4.777  -0.207  -2.397  -0.010  -0.199  dH2O  0.000  0.303  2.313  2.101  2.817  0.873  0.054  dCO2  0.000  0.110  1.855  4.698  3.548  -0.380  0.678  dS  0.000  0.004  0.008  0.131  0.058  0.012  -0.010  dTotal  0.000  0.137  -24.982  12.765  -3.731  0.102  -1.487  Residual  0.000  0.108  0.001  0.032  0.014  0.002  -0.003  Ajt.ratton  gram  50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96  97 98  218  +E:D241E:$A$24)125)  0 ROUND(B: E20-B:$A$20’ E: E25*2/E;$A$255)  D:037: (F3)  D:F3: (F3) +B:G21 -@SUM(B:G1 8.G20)-@SUM(F35F37)  D:E38: (F3) +B:F21-@SUM(B:F18..F20)-@SUM(E35..E37)  D:D38: (F3) +B:E21-@SU(B:E18..E2O)-@SUM(D35,,D37)  D:C38: (F3) ÷B:D21-@SUM(B:D18.D20)-@SUM(C35,,C37)  D;B38: (P3) +B:C21-SUM(BC1BC2O)-@SUM(B35.B37)  D:A39: “dLOI  E:12 2 /E:$A$255) 0 AOUND(B: 120=B:$A$20* t 5  ROUND(B:IOB:$A$2O* E:F-5’2/E:$A$255)  D:G37: (P3)  D: H37 (F3)  0 ROUND(B:G20.B:$A$20* E:G25’2/E:SA$265)  D:F37: (F3)  D:E37: (P3) @ROUND(B:F2OB:$A$2O*E:F252/E:$A$255)  020-B:$A$20 E;D25’2/E:$A$255) @ ROUND(B: t  D:C37: (F3)  E:C25’2/E:$A$256)  @ ROUND(B:C20-B:$A$20  D: B37: (F3)  D:A37; “dS  D:H36: (F3) @ROUND(B:II9-B:$A$19(E:I5/E:$A$5+E:I9/E:$A$94-E:I12/E:$A$12+E:I23 /E:$A$23),5)  D:G36: (F3) @ROUND(B:H19.B:$A$19*(E:It5/E:$A$5+E:H9JE:$A$9+E:H12/E:$A$12+E:H23/E:$A$23)S)  D:F36: (F3) @ROUND(B:G19-B:$A$19(E:G5/E:$A$5+E:G9/E:$A$9+E:G12/E$A$l 2÷E:G23/E:$ A$23)5)  D:E36: (F3)  D:D36: (F3) @ROUND(9’:E19-S$A$9’(E:E5/E:$A$5-i-E:E9/E;$A$9+E:E12/E:$A$t2+EE 23)E$A23)5)  D:C36: (F3) @ROUND(B:D1 9-B;$A$1 9(E:DS/E:$A$5+ E:D9/E:$A$S+ E:D1 2/E:$A$l 2-t-E:D23/E: $A$23)5)  D:B36: (F3) @ROUND(B:C9B:$A$19*(E:C5/E:$A$5+E:C9/E:$A$9+E:C12/E:$A$12+E:C23/E:$A$23),5)  DD35: (F3) @RUND(B:E1B:$A$18(E:E6/E:$A$6+E:E1O*8/E$A$1O÷E:E1 t 38/E:$A$13+ 4 /E E:E152/E:$A :$ $15+E;Ej7’2 A$2 /E:$A$17+E :E21 +E:E24)E:$A$24)/26) 1 D:E35: (F3) ÷EF24IE:$A$24)/25) D:F35: (P3) @ROUND(B:G18B:$A$18*(E:G6/E:$A$6÷E:GIO*8/E:$A$1O+E:G13*8/E:$A$13+E:G1 5e2/E:$A$16+E:G17*2/E :$A$17+E:G21*4/E:$A$21 +E:G24/E:$A$24)/25) D:G35: (F3) +E:I-Q4/E:$A$24)/25) D:H35: (P3) @ROUND(B:I18B:$A$19(E:l6/E:$A$6+E:I1O*8/E:$A$1O+E:Il 3*81E:$A$13+E:115*2/E;$A$l5+E:I1 72/E:$ 4 t /E:$ A$17+ A$2 E:I2l 1 +E;I41E:$A$24)125) D:A36: “dCO2  Q:B35: (F3) @AOUND(B:Cl8-B:$A$18(E:C6/E:$A$6+E;C1 8 t O’8/E; /E;$A$ $A$1O 13+E:G +E:C11 5 2 /E:$A$1 5+E:C17’2/E:$A$1 7+E:C21’4/E:$A$21 ÷E:024/E:$A$24)/2S) 3t D:C35: (F3)  D:A35: “dH2O  D:B4: Constraint matrix  C  k)  D:H42: (F3) +E:115+E:117 D:A43: KaoI D:B43: (F3) +E:C21 D:C43: (F3) +E:D21 D:D43: (F3) +E:E21 D:E43: (F3) +E:F21 D:F43: (F3) +E:621 D:G43: (F3) +E:-1 0:1-443: (F3) +E:121 D:A44: ‘ChI  D:A39: “dTolaI  D:B39: (F3) @ABS(+B:C22-E:C28)  D:C39: (F3) @ABS(+B:D22-E:D28)  D:D39: (F3) @ABS(+B:E22-E:E28)  D:E39: (F3) @ABS(+B:F22-E:F28)  D:F39: (F3) @ABS(+B:G22-E:G28)  D:G39: (F3) @ABS(+8:I-22-E:H28)  D:H39: (F3) @ABS(+B:122-E:128)  D:A40: “Carbnat  D:B40: (F3)  0:C44: (F3) +E:D1O+E:013 D:D44: (F3) +E:E1O+E:E13 D:E44: (F3) ÷E:F1O+E:F13 D:F44: (F3) +E:G1O+E:G13 0:644: (F3) -t-E:H1O+E:H13 D:H44: (F3) +E:IlO+E:113 D:A45: ‘Pyx 0:845: (F3) +E:C7+E:C11+E:C14 D:C45: (F3) +E:D7+E:D11+E:D14 0:045: (F3) +E:E7+E:E11+E:E14 D:E45: (F3) +E:F7+E:F1I+E:F14 D:F45: F3) +E:G7+E:G1 1 +E:G14 D:G45: (F3) ÷E:H7+E:Hl1+E:H14 D:H45: (F3) +5:17+5:111 +E:114 D:A46: “Or D:848: (F3) +E:C16 D:C46: (F3) +E:D16 D:046: (F3) +5:516  D:D-4O: (F3) +E:E5+E:E9+E:E12+E:E23  D:E40: (F3) +E:F5+E:F9+E:F12+EF23  E:GS+E:G9+E:G1 2+E:G23  D:F40: (F3)  D:G40: (F3) +E:-+E:H9+E:H12+E:H23  D:H40: (F3) +E:15+E:19+E:112+E:123  D:A41: “EpIc1ot  D:B41: (F3) +E:C6  D:C41: (F3) +E:D6  D:D41: (F3) +E:E6  D:E4: (F3) +E:F6  D:F41: (F3) +E:G6  0:641: (F3) +E:H6  D:H41: (F3) +E:16  D:A42: (F3) “SrlcIte  0:842: (F3) +E:C15+E:C17  D:C42: (F3) +E:D15+E:D17  D:D42 (F3) +E:E15+E:E17  D:E42: (F3) +E:F16+E:F17  +  D:844: (F3) +E:C1O÷E:C13  D:040: (F3) +E:D5+E:D9+E:D12+E:D23  E:C5+E:C9+E:C1 2+ E:C23  0:642: (F3) +E:H15+E:H17  D:H38: (F3) +B:I21..@SUM(8:18,i2O)-@SUM(H35.H37)  +  D:F42: (F3) +E:G1S+E:G17  D:G38: (F3) -i-9:H21 -gSUM(B:H1 8.i-O)-@SUM(G35.,G37)  D:H49: (F3) +E:122  D:G49: (F3) ÷E:I-2  D:F49: (F3) +5:622  D:E49: (F3) +E:F22  0:049: (F3) +5:522  D:C49: (F3) +E:D22  0:849: (F3) +5:022  D:A49: “Qtz  0:1-148: (F3) +5:125  D:G48: (R3) +E:H26  D:F48: (F3) +5:625  D:E48: (F3) +E:F25  0:048: (F3) +E:E25  D:C48: (F3) +5:025  D:B48: (F3) +E:C25  D:A48: “Pyrite  D:H47: (F3) +E:18+E:118  D:G47: (F3) +E:H8+E:H18  D:F47: (F3) +E:G8+E:G18  D:E47: (F3) +E:F8+E:F18  D:D47: (F3) +E:E8+E:E18  D:C47: (F3) +E:D8+E:D18  D:847: (F3) +E:C8+E:C18  D:A47: “P1  D:H46: (F3) +5:116  D:G46: (F3) +E:H16  D:F46: (F3) +5:616  0:E46: (F3) +E:F16  -4  I—’)  4AS24)*SA$7)2 0:01 4*(B:E39.E8/SA$8.E24*5  0:98. (WI0) “An 0:08: (P3) +0:8i*G.C40*$A$8 E:08: (P3) +0:C11*8:040*$A68  0:04 (P0) U “ms-all  E.H4. (P0) U “w-alt  w-all  **A$S  0:35* (8:H39.H7*2/$A$7il8I$A$8H24*5f$A$24)*SA  +  E:GS: (P3)  0:1-IS: (P3)  A$7.D9/$A$8.024*54A$24)*$A$6/2 E:06: (P3) (1 .0C5)*(8039.07*21$  0:06: (P3)  *5/SA$24)*$A6/2 (10:B5)*(B:C39.C7*2/$A$7.C8f$A$8.C24  0:86: IW1O) “Epidote  E:A6: (P2)  40.08*2+55.85+26.98*2+28.09*3+16*12+17  S8.l24*S/SAS24)*SA$5 E:15: (F3) + 0:H5*(B:l39l7*2/$A$7le,$A  $5  4)*$A$5  0:F5*(8:039.07*21$AL7.G8/$A$e.024*6/$AS2  +  E:F5: (P3)  0:ES* (8:P39. F7*2f$A$7P8/A$8.F24*S/$A$24)  +  38*$A$9 E:H9: (P3) (1 .036.037)*BH  SAS9 E:39: (P3) (l.0:P60:P7)*9:Q38*  E:P9: (P3) (10:E60:E7)*B:F38*$A$9  0:09: (P3) (1.D:060:D7)*8E38*SAS9  9 0:09: (P3) (1.D:C6D:C7)*B:088*$A$  *$A$9 0:09: (F3) (t.0.86.0:87)*B.C30  0:89: (Wl0) “Mq-carb  E:A9: (P2) 24.31+60.01  E:18: (P3) +D:Hll*8140*$A$8  E:H8: (P3) +0:31 l*B.ll40*SA$8  0:38 (P3) +0:Fll*B:040*SA$8  E:F8: (P3) ÷0:Ell*B:F40*SA$8  E:85: (W10] “Catdte  8)$A$8.C24*5/SA$24)*$A$5 0:05: (F3) + 0:85 (B:C39C7*2/$A$7.C )$A$7.09/A$8.024*5f$A$24)*$A$5 0:05: (P3) +D:C5*(B:D39D7*2 E8/$A$8E24*5/$A$24)*$A$S 0:05: (P3) +D:D5*(B:E39.E7*2/$A$7.  E:E8: (P3) +0:0l1*8:E40*$A$8  0:A5: (F2) 40.08+ 1201 +16*3  0.14: (P0) U  AS7/2  0314* (8:H39H8f$A$8.H24*5f$A$24)*$  l24*5/$A$24)*SA$7)2 0.17: (P3) + D:H1 4 *(8l39I8/SA8  +  6*8 E:A8: (P2) 4008+26.98*2+28.09*2+1  mall  E:H7 (P3)  E:F4 (F0)U “ms-all  004 (P0) U  0:04 (P0) U “w-alt  A$8G24*5/$A$24)*$A$7/2 0:37: (P3) +D:F14(8:G39.G8/$  +  0:04. (P0) U “w-aIl  0:07 (P3)  A$24)*$A$7/2 0:C1 4*(B:039D8/$A$8024*S/$  S8.F24*5/A$24)*A$7,2 E:F7: (P3) + 0:014* (B.F39.PB,$A  Molar wt%  +  A$7/2 0:814* (B:039C8f$A$8C24*5f$A$24)*S  E:B4: [WI0) “Alteration  E:A4:  0:07: (P3)  x2-5  0:13: (P0) U  +  0:87: W10] “Ca-pyx  0:33: (P0)14 “x3-l  E:C7: (P3)  6*6 E:A7: (F2) 40.08*2+28.09*2+1  E:F3:(F0)U “x3-4  x3-3d  t8f$A$8.t24*5/$A$24)*SA$6/2 0:16: (P3) (l.D:H5)*(9:l39l7*2/SA$7  0:03: (P0)14 “x3-S  E:H3: (P0) U  2/SAS7t18/t,AL8.H24*5/$ E:H6: (P3) (1.0.05)*(8:H39.H7*  003: (F0)U “x3-7  AS24)*$A$6/2  2/$A$7.G8/$A$8.02 E:06: (P3) (1.0:F5)*(B:339.07*  4*5/$A$24)*$AS6/2  AS7E8J$AS8.E24*5/A$24)*$A$6/2 0:06: (F3) (1 0:D5)*(B:E39.E7*2f /$A$7.F8f$AS8F24*5/$A$24)*AS6/2 E:P6: (F3) (I .D:E5)*(G:F39F7*2  0:03: (P0)U “x4-4  0:93. [Wl0] “Sample_Id  E:C2: MelasornaticNcms (dosed)  0:013: (P3)  +  0:813: [WiG)  D:98*(9:036.0l 9/SAIl 9-C25/IAS25.C27/5A$27)/5$A$1 3  Pe-chi  E:A1 3: (P2) 55.85*5+26.98*2+28.09*3+16*10+17*8  E:li 2: (P3) (1. D:H8.0:H9)*(9:136.Il 9/SAIl 9.125/$A$26.127/$A527)*$A$l 2  E:H12: (F3) (1 .DG9.OG9)*(8H36H19/$A519.H25,SA$25.H27/$A$27)*$A5j 2  0:012: (P3) (I -D:F8.0:P9)’(B:036-G1 9/SAIl 9.G25/$A525.027/5A127)*$A$ 12  0:Pi 2: (P3) (1 -D:E8-D:09)(B:P36.FI 9/SA$19.F25/$A525-F27/$A527)’$A5i2  0:012: (F3) (1 .D:08.0:D9)*(B:035.Ei 9/$A$19.E25/$A$25.0271$A$27)*$A$i 2  0:012: (P3) (1 -0:C8-D:C9)(B:036.Di 9/SAIl 9.025/$A525.027/$A$27)*$A$1 2  0:012: (P3) (1 .D:98.0:99)*(B:C36.Ci 9/SASI 9.C25/$A$25.027/$A$27)*$ASI2  0:812: Wl0) Fe-carb  E:A12: (P2) 55.85+60.01  0:111: (P3) +D:H7*9:138/2*$A$1 1  E:H11: (P3) +D:07*8:H38/2*$A$ii  0:011: (P3) +D:F7*9:G38/2*SA$il  E:FI1’ (P3) +D:E7*8:P38/2*SA$ii  0:011: (P3) +D;D7*B:03812*SA$ii  0:011: (P3) +0.C7*8:038/2*$A$li  0:011: (F3) +0:87*8:C3812*$A$1i  E:8l1: Wi0] “Mg.pyx  E:Ail: (P2) 24.31*2+28.09*2+16*6  0:110: (P3) +0:H6*8:138/5*$A$lO  0:HI0: (P3) ÷D:06*8:H38/S*$A$iO  0:010: (P3) +D:F6*0:038/5*$Af.iO  E:Pi0: (P3) +0:E6*8:F38/6*$A$lO  E:Ei0: (F3) +D:D6*B:E3815*$A$10  0:010: (P3) +D:C6*8:038/S*$A$iO  0:010: (P3) +0:B6*0:C38/s*$A$IO  0:810: [WiG) Mg.chI  E:AI0: (P2) 24.31*5+26.98*2+28,09*3+16*lO+ 17*8  0:19: (P3) (I.D:H6.D:H7)*9:138*$A$9  + +  D:H8 (0:136.11 9/SAIl 9.125/1A525.l27/$AS27)/5*$A$1 3  0:013: (P3) E:H1 3: (P3) 0:113: (P3)  O:08(B:H36.H1 94A519.H25/$A$25.H27/$A$27)/5*$A5 13  D:P8’(8:036-Gi 9/SAIl 9.025/$A525.027/SA$27)/5*SAS1 3  D:E8*(9:F36.P1 9/SAIl 9.P25/$A$25.P27/$A527)15*$A$1 3  +  + +  D:H9*(B:136.I1 9/SA$19.125/SA$25.127/$A$27)/2*$A$1 4  +  0.014: (F3) E:EI 4: (P3) E:Fl 4: (P3) E:0l 4: (F3) E:Hi 4: (P3) 0:114: (P3)  O:G9*(B:H35.H1 9/SAIl 9.H25/SA$25.H27/$A$27)/2*$A$l 4  0:F9*(9:036.GiS/$A$19.025/SA$25.027f$A$27)/2*$AIi 4  D:E9*(9:F36.Pi 9/SAIl 9F25/5A525.P27/$A$27)/2*$A$1 4  0:016: (F3) +D:Fl0*9:041*$A616  E:P16: (P3) +0:El0*8:F41*SA$16  0:016: (P3) +D:Dl0*8:041*IA$16  E:DI6: (P3) +D:0i0*B:D41*$A$16  0:016: (P3) +D:BIQ*B:C41*SA$16  0:816: [WIG) “or  E:Al6: (P2) 39.09÷26.98+28.09*3+16*8  0:115: (P3) (1.D:Hl0)*B:141*SASI5  E:H15: (P3) (1.D:Gl0)*B:II4l*5A$I5  0:015: (P3) (I -D:Pl 0)B:G4 I 165  E:P15: (P3) (1.0:Ei0)*B:F41*$A$15  E:ElS:.(F3) (l.D:DI0)*8:E41*SASIS  0:015: (F3) (1 D010)*B’041 *SAII S  0:015: (P3) (1.D:B10)*B:041*$A515  0:815: (WiG) Muscov1te  E:A15: (P2)39.09+26,98*3+28,09*3+16*10+17*2  +  D:C9*(9:D36OI 9/SAIl 9.025/$A525.027/SA$27)/2*$A$i 4  +  0.09*(B:E36.Ei 9/SA$19.E25/$A$25.E27/$A$27)/25A$I 4  D:99 (B:C36.Ci 9/$-A$1 9.C25/$A$25.C27/SA$27)/2*$A$l 4  +  0:014:  (P3)  0:914: [WIG) Pe.pyx  E:A14: (P2) 55.85*2+28,09*2+16*6  +  +  0:Pl 3: (P3)  D:D8*(B:E36.E1 9/SAIl 9.E25/$A$25.E27/$A$27)/5*$AS1 3  +  0:013: (P3)  D:C8*(8:036.0i 9/SAIl 9.025/$A$25.D27/$A$27)/5*SA$i 3  +  0:013: (P3)  I-)  l8f$ASI8)/2t$A$2l (P3) (:D33-D62/SAS6-DS2/SAt8-D1 02/$A$lO-DI 321$A$13-DI53/$A$15-D16/$At16-DI 7*3/$A$l7D  Pl7t3f$AS17.PI 8f$A$18)/2*$A$21 (P3) (B:P33P6*2/SA$6.F8*2/$A$8PlO*2/$A$IOP1 3’2/$A$1 3.PlS*3/$ASI5P16/$ASl6  E:P23: (P3) +E:P375A523  E:E23: (P3) +8,E37*$A523  5:023: (P3) +B.D37*IA$23  5:023: (P3) + 9:037*5A523  5:923: Wl0) 4i-carb  E:A23: (P2)54,94+12.01+16*3  1)*5A$22  SI6.H17*3/$A$17.Hl8*34ALl8.H2I*2/$A$2l)*SA522 I 2/$A$1 I.Hl3*3/IASI3.H14*2/SAII4HI5*3/SA$l5H16*3/$A  I1 Il4*2/$AIl4II5*3/$A515.ll6*3/5A516.Il7*3/SA$17.l18*3/SA$18.i2I*2/$A52 5:122: (P3) (+ B:I32.I6*3/SAS6i7*2/SAS7.l8*2/5A58Il0*3f5A$I0 I 2/5AI1 Ill3*3/$A$I3  E:H22: (P3)  8EI0*3/$A$10.E1 I 2/$MI I-El 3*3/SA513 E14*2/$A514.El5*3/5A515 EI6’3/SA$l6-517’34A$I 7El8*3/$A$l8E2l*2f5A$21)*SA522 5:522: (P3) (+ B:E32.E6*34AS6.E7*2/SAS7E8*2/$AS l7P18*3/$A518.P2l*2/5A521)*5A$22 .P1 1 2/SAII I PI3*3/5A5I 3PI4*2/5A$l4PI5*3/5A5I5.Pl6*3/5A5l6Pl7*3/SA5 t E:P22: (P3) (+ B:P32P6*3/SA$6.P7*2/$A57P8*2/IA$8PI0*3/$ASl0 7.018*3/SA51802l *24A$21)*$A522 2/SA$l 1 -01 3*3/5AS1301 4*24A$l4GI5*3/SA515016*3/$A116Gl7*3/5A$1 t 5:022: (P3) (+0.G3206*3/$A56G7*24AS708*2/5A58.0l0*3/5A5l0GI 1  8Dl0*3/SAS10DI 4*2/SAIl I E:D22: (P3) (+ B:DS2D6*34AS6.D7*24AS7D8t2/SAS  AS ID-Oil *2/SAIl ICl3*3/SASi3CI4*2/SASl4.Ol6*3/SASI5O16*3/SASl6.Cl 7*3/$A5170I8*3/SA$18021*2/5A521)t$A522 5:022: (P3) (+ G’C32.C6*3/SA$6.C7*2/SA$7.C8*2/SA$8.CI0*3/$  E.822: [W10] “qtz  E:A22: (P2) 28.09+16’2  3f5A517.118/5A518)/25A52I t 5:121: (P3) (9:I33I6*2/SA56l8*2/SAS8.lI0*2/$ASl0II 32/SASI 3ll5’3/SA$l5-II6/SA$I6-I1 7  E:H21. (P3)  7*3/SAIl 7-018/SAIl 8)/2*SAS2 I E:021. (P3) (S:O33G6*2f$AS6G8*2f$A$B.G1 02/SA$ I 0-GI 3*2/SASI 3-GI 5*3/SAS I 5-01 6/SM I 6-GI  EF21  E.E21: (P3) (B:E33-E6’2/$A$6-E82/$A$8-E102/$A$1O-E13’2/$A$l3-El5’3/$A$I S-El6/$A$16-E1 73/LA$1 7.EIBJSA$18)/2’SAS2I  E:D21  $A$21 E:C21: (P3) (8.C33.C6*2j$At6.C8*2/SAS8.CiO*2/$A$lOC132/$A$l 3•0153/$AS15-C16J$A$16.C1 73/$A$17-CI8J$A$18))2  E:921: [WiOl “Kact  E;A21: (P2) 26S8’2+28.092+165+1?’4  E:120: (P3) (1 -D:Hl 3)* B:l34SAS2O  E:H20 (P3) (1-D:013)8:H34’$At20  E:020: (PS) (l-D:P13)’B:034$A$20  E:P20: (F3) (l-D:E13)’8:F34$A$20  E:E20: (P3) (ID:D13)tB:E34t$A$2O  E:D20. (P3) (I-D:C13)B:034SA$20  E;C20: (P3) (I -D:Bl 3)B:C34$A$20  E:820: (P3) fWlO) -rutI[e  E:A20: (F2) 47.9+16’2  E:119: (F2) +D:H13*B:i34*$AS19  E:I-419: (F3) +0:0l3*B:H24*$A$19  E:G19: (F3) +D:F12’9:GB4’A$19  E:F19: (F) +D:E’B:F24’$AS1  E:E19: (Fe) +D:0I2’8:E24’$ASI  E:019: (F3) +D:C13’8:D34’$A$19  E,Cl9: (F3) +0:B12’B:C4’$A$I9  E919: [WIO] ‘IIrneriite  EA19: (F2) B5.85÷47 9+l6’  E118 (Fe) +0H12’B:140’$A518  EH18 (F$) ÷0.G12’BH4O’Al8  EGI8 (F) +DF12’:G4O’1A$18  E FIB (F3) +D.E12’B F4O’$A18  EE1B: (F3) +D.Dl2*B:E4O*Ai8  E,D18: (Fe) +D.CI2’B:D40’$ASI8  E,C18: (F3) +0 8I2’B:C40’$A$18  E:B18: tWIO] Ab  E:A18: (F2) 22.99+26.98+28.O’3+16’8  E:117: (Fe) (1-0:H12)’G:140’SA$17  E:H 17: (F3) (I -0.012)’ B:H40’SA$l 7  E:GI 7: (Fe) (1 -D:F1 2)B:040’SA$l 7  E:F17: (Fl) (l.D:E12)’B:F40’$A$17  E:E17: (F3 (1-D:0I2)’B:E40’$ASI7  E.D17: (F3) (l0:Cl2)*B:D4O*SASI7  E:Cl 7: (Fe) (I -D:BI 2)’B:C40’SASI 7  E:B17: (WlO] Na-rnIca  E:A17: (F2) 22gg+26.98*+2eo9*+l6*lO+17*2  E:I16: (F3) +D:H1O’B:I4l’A$l6  E:Hl6: (FI) +0:GlO’B:H4l’SA$l6  +  +  B:G45/2’SAS2S  B:P45J2*$AS25  +  B:145J2’$A$25  E:A27: 55.85’3+I6’4  E:126: (F3) (I -0:HI 5)’(+ B:135-16/SA$6)’$A$26/2  E:H26: (P3) (1-0:31 5)*(+ 0:I-135-H6/$AS6)’$AS26/2  E:026: (P8) (1D:P15)*(+B:G35.G6I$A$6)*$A26/2  E:P26: (P3) (I -D:E1 5)’(+ 8:F35.P6/$A$6)’SA$26/2  E:E26: (P8) (I -0:01 5) (+ B:E35-E64A$6)’SA$26/2  E:026: (P8) (I -D:C I S)’(÷ B:035-D6/$A$6)’SAS26/2  E:C26: (P3) (lD:B15)*(+B:C35-C6/$A$€)’SA$26/2  E:826: [W1O] ‘hernBte  E:A26: (P2) 55.85’2+16’3  E:125: (P3)  E:H25, (P3) +B:H45/2’$A$25  E.1325: (F3)  E P25: (P3)  E:E25: (P3) +8.E45/2’SA$25  E:D25: (P3) +8:045/2$A$25  E.C25: (P3) +B:C45/2’SAS2S  E:B25: (WiOl ‘pyIIte  E:A25: (P2) 55.85t-2’32.06  E:124: (P3) +9:142/3’$A$24  E:H24. (P3) +B:H42/3’$A$24  E:024: (P3) +B.042)3*SAS24  E:F24: (F3) +8:F42/3’SAS24  E:E24: (P3) +B:E42/3’$AS24  E:024: (P3) +B.D42/3’SA$24  E:C24: (P3) +B:C42/3’$A$24  E:B24: WIO) apatIt  E:A24: (P2) 40.0654-BO.97’3+16’12+ 17  E:123: (P3) +B:137’$A$23  E:I-123: (P3) +B:H37’AS23  E:323: (P8) +B:G37’$A$23  +  D:3I 5’(+ a:H35-I-46f$M6)’$A$27/2  0:H1 B’ (+ B135-16/$A$6)’SA$27J2  +  E:128: (P3) @SUM(5,.I27)  E:H28: (P3) @SUM(H5.,H27)  E:028: (P3) @SUM(G5..327)  E:F28: (F3) @SUM(F5,.P27)  E:E28: (F3) @SUM(E5..E27)  E:028: (P3) @SUM(05..D27)  E:C28: (F3) @SUM(C5..C27)  E:B23: [WIO] totaI  E:127: (P3)  E:H27: (P3)  E:027: (P3) +D:FI5*(+B:33506f$A$6)SA$27/2  E:P27: (F2) +0:ElS’(+B:F35-F6/$A$€)’$A$27/2  E:E27: (F3) +0:01 5’ (+ B:E35-E64AS6)’SA527/2  E:027: (P3) +0:C15’(+B:D35-D6/$A$6)’SA527/2  E:C27: (F8) +0:B15’(+a:C35-C6/$A$6)’SA$27/2  E:927: CWIO] ‘rnagnetite  +  +  F:Cl 5: (P4)  F: Dl 5: (P4)  E: E5/E:$A5*(B:$Al 4/B: El 4*D45+ B:$Al9/B: El9*D50)  E:D5/E:$A5*(B:$Al 4/B: Dl 4*C45+ B:$Al 9/B: Dl 9*C50)  E:C5/E:$A5*(B:$Al 4/8:C1 4*B45+ B:$Al 9/B:Cl 9*850)  E: 15/E:$A5*(B:$Al 4/8:11 4*H45+ B:$Al 9/8:11 9*H50)  E:l_5/E:$A5*(B:$Al 4/B: F-Il 4*645+ B:$A1 9/B:1_1l9*G50)  +  F:Cl6: (P4)  E:D6/E:$A6*(2*B:$Al4*C45/B:Dl4+0.5*B:$AlO*C4l/B:D1C+ B:$A8*C39/B:D8+3*B:$A7*C38/B:D7+0.5*B:$Al8*C49/B:D18)  E:C6/E:$A6*(2*B:$Al4*B45/B:C1 4+0.5*B:$AlC*B4l/B:C1C+B:$A8*B39/B:C8÷3*B:$A7*B38/B:C7+0.5*B:$A18*B49/B:C18)  +  +  +  +  +  F: 817: (P4)  P:C1 7: (P4)  P: Dl 7: (P4)  P: El 7: (P4)  E:F7/E:$A7*2*(B:$A1 4/B:F1 4*E45+ B:$A7/B:P7*E38)  E: E7/E:$A7*2*(8:$Al 4/B: El4*D45+ B:$A7/B: E7*D38)  E: D7/E: $A7*2*(B:$A1 4/B:D14*C45+ B:$A7/B:D7*C38)  E:C7/E:$A7*2*(B:$A1 4/B:C1 4*845+ B:$A7/B:C7*B38)  P:A17: Ca-pyx  P1-116: (P4)  F:G1 6: (P4) +E:H6/E:$A6*(2*B:$A14*G45/B:Hl4+0.5*B:$A10*G41/B:H10+ B:$A8*G39/B:H8+3*B:$A7*638/B:H7+0,5*B:$Al8*G49/B:lI18)  P:P16: (P4) +E:66/E:$A6*(2*B:$Al4*P45/B:Gl 4+05*B:$AlO*P41/B:GlO+8:$A8*P39/B:G8+3*B:$A7*P38/B:67÷0.5*B:$Al8*P49/B:G18)  F:El6: (P4)  P:Dl6: (P4) 4E:E6/E:$A6*(2*B:$A14*D45/8:El4 +C5*B:$AlC*D4l/B:ElC+B:$A8*D39/B:E8+3*B:$A7*D38/B:E7+C.5*8:$A18*D49/B:E18)  +  F:8l6: (P4)  ‘Epidote  +  F: Rl 5: (P4)  P:A16:  +  F:G1 5: (P4)  F:E15: (P4) ÷E:F5/E:$A5*(B:$A14/8:P14*E45+B:$A19/8:F19*E50) F: P15: (P4) + E:65/E:$A5*(B:$Al 4/8:61 4*45 B:$Al 9/8:61 9*F50)  +  F: 815: (P4)  F:A15: Calcite  F:Hl4: (PC) ‘x2-5  F:G14: (FO) ‘x3-3d  P:F14: (P0) “x3-l  P:E14: (PC) ‘x3-4  P:D14: (PC) “x3-5  P:C14: (P0) ‘x3-7  F:814: (P0) “x4-4  P:A14: Sample_id  P:813: Standard Deviation at 68% confidence level  +  E:G7/E:$A7*2*(B:$A14/B:Gl 4*45 B:$A7IB:G7*F38)  +  +  +  +  F:Ci 8: (F4)  F: Die: (P4)  F: El 8: (P4)  F:Fi 8: (P4)  E:G8/E:$A8*(B:$Ai 4/B:G14*F45+ B:$A8/B:G8*F39÷2*B:$A7/B:G7*F38)  E: E8/E: $A8*(B:$A1 4/B: El 4*D45 + B:$A8/B: E8*D39 + 2*B: $A718: E7*D38) E: P8/E:$A8*(B:$Ai 4/B: Fl 4*E45+ B:A8/B: P8*E39+2*B:$A7/B: F7*E38)  E:C8/E:$A8*(B:$A1 4/B:Ci 4*B45+ B:$A8/B:C8*B39+2*B:$A7/B:C7*838) C38) 4 E: D8/E:$A8*(B:$Al 4/B: Di 4*C45 + B:$A8/B: D8*C39 +2*B:$A7/B: D7  +  +  F:F19: (P4)  E:G9/E:$A9*(B:$A13/B:G1 3*F44 + B:$A19/B:Gi9*P50)  +  F: 821: (P4)  +  E:C1 1 *2/E$A1 1 *(B:$A1 3/B:C13*B44÷ S:$A7/B:C7*B38) F:C21: (P4) + E:Di 1 *2/E:$Ai 1 *(B:$/j 3/B: Di 3*044 + B:A7/B: D7*C38)  P:A21: “Mg-pyx  A7JB:17*H38+4*B:$Ai8/B:1i8*R49) F:H20: (P4) +E:IiO/E:$AiO*(5*B:$Ai3/B:1i3*H44+B:$A8/B:l8*H39+3*B:$  $A7/B:G7*F38+4*B:$A18/B:Gi8*F49) P:F20: (P4) +E:GiO/E:$A10*(5*B:$Ai3/B:G13*F44+B:$A8/B:G8*F39÷3*B: A7/B:H7*G38+4*B:$A18/B:H18*G49) P:G20: (P4) +E:H1OIE:$A10*(5*B:$A13/B:H13*G44÷ B:$A8/B:H8*G39+3*B:$  8÷4*B:$AiS/B:Ei8*D49) F:D20: (P4) +E:Ei0/E:$A10*(5*B:$A13JB:Ei3*D44+ B:$A8/B:E8*D39+3*B:$A7/B:E7*D3 $A7/B:P7*E38+4*B:$Ai8/B:Fl8*E49) F:E20: (F4) +E:F10/E:$Ai0*(5*B:$Ai3/B:Fi3*E44+B:$A8/B:F8*E39÷3*B:  7/B:C7*838+4*9:$Ai8/B:C18*B49) F:920: (P4) +E:C10fE:$Ai0*(5*G:Ai3/B:Ci3*944÷B:$A8/B:C8*839+3*8:$A A7f9:D7*C38+4*B:$Ai’8/B:Di8*C49) F:C20: (P4) + E:DiO/E:$A10*(5*B:$A13/B:Di3*C44+ B:$A8/B:D8*C39.i3*B:$  F:A20: “Mg-chi  P:G1 9: (F4)  E:H9/E:$A9*(B:$Al 3/B: Ri3*G44 + B:$A19/B:R19*G50) F: Hi 9: (P4) + E:19/E:$A9*(B:$A13/B:Ii 3*H44 + G:$Ai 9/B:119*H50)  +  F: 819: (P4)  E:C9/E:$A9*(B:$Ai3/B:C1 3*844 + B:$Ai 9/8:019*850) F:0i9: (P4) + E: D9/E:$A9*(B:$Ai 3/B:Di3*C44 + B:$Ai 9/B:D19*C50) F: Di 9: (F4) + E: E9/E:$A9*(B:$A13/B:E13*D44 + B:$Ai 9/B: E19*D50) F:E1 9: (P4) + E: P9/E:$A9*(B:$A1 3/B:Fl 3*E44 + B:$Ai 9/B: Fi9*E50)  P:A19: “Mg-carb  F:Gi 8: (F4)  E: H8/E:$A8*(B:$Ai 4/B: Hi 4*Q45 B:$A8/B: H8*G39÷2*B:A7/B: H7*G38) F: Hi 8: (P4) + E:18/E:$A8*(B:$Ai 4/B:1i4*H45+ B:$A8/B:18*H39+2*B:$A7/B: 17*R38)  +  +  F: 818: (P4)  F:A18: “An  F: Gi 7: (F4)  E: H7/E:$A7*2*(B:$Ai 4/B: Hi 4*G45 + B: $A7/B: H7*G38) F: Ri 7: (P4) + E: 17/E:$A7*2*(B:$Ai 4/B: Ii 4*H45+ B:$A7/B:17*H38)  F: Fl 7: (F4)  +  F: E21: (P4)  38) E:El 1 *2/E:$Ai 1 *(9:$A13/8: El 3*D44+ 2$A7/8:E7*D E: Fl 1 *2/E:$Al 1 *(:$4j 3/B:Fl 3*E44 + B:$A7/B: F7*E38)  +  +  +  +  Eli 4*2/E:$A1 4*(9:$Al 1/8:111 *H42+ B:$A7/8:17*H38)  Muscovite  +  F: H24: (F4)  F:A25:  +  F: 824: (F4)  E:C1 4*2/E:$A14*(B:$Al 1/8:011*842+ B:$A7/8:C7*838) B:$A7J9:D7*C38) F:C24: (P4) + E:Dl 4*2/E:$Ai4*(8:A1 1/B:D1 1*042+ E7*D38) F:D24: (F4) + E: El 4*2/E:$Al 4*(8:$Ai 1/8: Eli *D42+ 8:$A7/B: 7/9: F7*E38) F:E24: (P4) + E:Fi 4*2/E:$Al 4*(B:$Al l/8:Fl 1*E42+B:$A *F42+ 8:$A7/8:G7*F38) F:F24: (F4) + E:Gi4*2/E:$A14*(B:$Al 1/B:Gl 1 8:$A7/8:H7*G38) F:G24: (P4) + E:Hl 4*2/E:$Ai4*(9:$A1 1/B:Hl 1 *G42+  F:A24: “Fe-pyx  F:F23: (F4)  Gl8*F49) E:Gi3/E:$A13*(B:$Al l*5/B:Gl i*P42+ B:$A8/8:G8*F39+3*8:$A7/8:G7*F38+4*9:$A18/B: 8/B:HB*G39+3*8:$A7/B:H7*G39+4*8:$A18/8:H18*G49) F:G23: (P4) +E:Hi3/E:$A13*(B:$Ai i*5/B:H1 1*G42÷B:$A B:A8/8:I8*H39+3*B:$A7/B:I7*H38÷4*B:$Al8/B:I18*H49) F:H23: (P4) + E:1i3/E:$A13*(8:$A1 1*5/8:11 1*H42+  ) 42+ B:$Ae/B:C0*939+3*B:SA7/B:07*838+4*B:$Al8/B:Cl8*849 F:B23: (P4) +E:C13/E:$A13*(B:$Ai 1*5/8:011*8 9) 18*04 8:A8/8:DB*C39+3*B:$A7/B:D7*C38+4*B:$A18/9:D P:C23: (P4) + E:D13/E:$Ai3*(9:$Al l*5/9:D1 l*C42+ B:$A8/B:E8*D39+3*8:$A7/B:E7*D38+4*B:$Al8/B:El8*D49) F:D23: (P4) +E:8l3/E:$A13*(B:$A1 1*5/B:E1 1 *D42+ 8:$A8/B:F8*E39+3*8:$A7/9:F7*E38+4*8:$A18/B:Fl8*E49) F:E23: (P4) +E:F13/E:$A13*(B:$Ai l*5/B:Fl 1*E42+  F:A23: “Fe-chi  F:F22: (P4)  9*P50) E:Gl 2/E:$Al 2*(B:$Al l/9:G1 1 *F42+ B:$A19/9:G1 9/B:Hl 9*G50) F:G22: (F4) + E:Hl 2/E:$A12*(9:$Ai 1/8: Hi 1 *G42+ B:$Al 9*H50) F:H22: (P4) + E:1l2/E:$A12*(9:$Ai 1/8:111 *H42+ 9:$A19/9:11  F:822: (P4)  9*850) E:012/E:$Al 2*(B:$Ai 1/9:011*842+ B:$A19/9:Ci 9*050) F:C22: (F4) + E:Dl 2/E:$A12*(B:$Ai i/B:Dl l*C42+ B:$A19/B:Dl 9*D50) F:D22: (P4) + E: El 2/E:$Al 2*(9:$A1 l/8:El 1 *D42+ B:$Ai 9/B: El 9*E50) F: E22: (F4) + E:Fl 2/E:$Al2*(B:$Al 1/8: Fl 1 *E42+ B:$Ai 9/B:Fi  F:A22: “Fe-carb  F: F21: (F4)  F38) E:G1 1 *2/E:$Al l*(B:$Al3/B:G13*F44÷ B:$A7/8:G7* *(:$,j 3/8:Hl 3*G44 + B:$A7/B: H7*G38) F:G21: (P4) + E: Hi i*2/E:$Al 1 4+ B:$A7/B:17*H38) F: H21: (P4) + E:li 1 *2/E:$Ai l*(8:$A13/8:1l3*H4  +  F: D21 (F4)  +  E:G15/E:$A15*(O,5*B:$A16/B:G16*P47÷O.5*B:$A8/B:G8*F39+3*B:$A7/B:G7*P38f B:$A18/B:G18*F49)  E:D16/E:$A16*(O5*B:$A16/B:D16*C47+O5*B:$Ae/B:D8*C39+3*B:$A7/B:D7*C38)  +  +  +  +  F:C26: (P4)  F:D26: (P4)  P:E26: (P4)  F: P26: (P4)  +  E:E17/E:$A17*(O.S*B:$A15/B:E15*D46÷O5*B:$A8/B:E8*D39+3*B:$A7/B:E7*D38+ B:$A18/B:E18*049)  +  +  E Dl 8/E:$A1 8*(O.5*B:$A1 5/B: Dl 5*C46+O,5*B:$A8/B: D8*C39+3*B:$A7/B: D7*C38)  P:G28: (P4) +E:Hl8/E:$Al8*(O5*B:$Al5/B:F1l5*G46+O,5*B:$A8/B:[18*G39+3*B:$A7/9:F7*G36)  P:P28: (F4) +E:G18/E:$A18*(O,5*B:$A15/B:G15*P46+O.5*B:$A8/B:G8*P39+3*B:$A7/B:G7*F38)  P:E28: (P4) ÷E:Fl8/E:$Al8*(O,5*B:SA15/B:P15*E46+O5*B:$A8/B:P8*E39+3*B:$A7/B:P7*E38)  P:D2e: (P4) +E:El8/E:$A1e*(O.5*B:$A15/B:E15*D46+O.5*B:$A8/B:E8*D39i3*B:$A7/B:E7*D38)  P:C28: (P4)  P:B28: (P4) +E:C18/E:$A18*(O.5*B:$A15/B:C15*B46+O.5*B:$A8/B:C8*B39+3*B:$A7/B:C7*B38)  F:A28: “Ab  P:H27: (P4) +E:I17/E:$A17*(O,5*B:$A15/B:l15*H46+O.5*B:$A8/B:l8*39+3*B:$A7/B:I7*I_3O+ B:$A18/B:118*H49)  F:G27: (P4)  F:P27: (P4) +:G17/E:$A17*(O,5*B:$A15/B:G15*F46+O.5*8:$A8/B:G8*P39+3*B:$A7/B:G7*P38+ B:$A18/B:G18*F49)  P:E27: (P4) ÷E:F17/E:$A17*(O,5*B:$A15/B:F15*E46÷O5*B:$A8/B:P8*E39+3*B:$A7/B:F7*E38÷B:$A1B/B:F1B*E49)  P:D27: (P4)  P:C27: (P4) +E:D1 7/E:$A17*(O.5*B:$A15/B:D15*C46+O.5*B:$A8/B:08*C39+3*B:$A7/9:D7*C38+ B:$A18/B:D18*C49)  P:B27: (P4) -t-E:C17/E:$A1 7*(O 5*B:$A15/BC15*B46+O 5*B.$A8/B.C8*B39+3*B.$A7/9C7*B38+ B:$A18/B:C18*B49)  P:A27: “Na-mica  P:I-26: (P4) +E:I16/E:$A16*(O5*B:$A16/B:l16*H47+O.5*B:$A8/B:I8*H39÷3*B:$A7/B:I7*I36)  P:G26: (P4) ÷E:H1 6/E:$A16*(O5*B:$A16/B:FU6*G47+O.5*B:$A8/B:H8*G39+3*B:$A7/B:l17*G38)  E:G16/E:$A16*(O.5*9:$A16/B:316*P47÷O.5*B:$A8/B:G8*P39+3*B:$A7/B:G7*F38)  E:F16/E:$A16*(O,5*B:$A16/B:P16*E47+O.5*B:$A8/B:P8*E39i3*B:$A7/B:P7*E38)  E:E16/E:$A16*(O,5*B:$A16/9:E16*D47÷O.5*B:$AB/B:E6*D39+3*B:$A7/B:E7*D38)  E:C16/E:$A16*(O.5*B:$A16/R:C16*B47+O.5*B:$A8/B:C8*B39+3*B:$A7/B:C7*B38)  +  F:B26: (P4)  P:A26: “Or  P:H25: (P4) +E:I15/E:$A15*(O,5*B:$A16/B:I16*H47+O.5*B:$A8/B:I8*H39+3*B:$A7/B:I7*Il38+B:$A18/B:t18*H49)  F:G25: (P4) +E:H15/E:$A15*(O.5*B:$A16/B:lI16*G47+O5*B:$A8/B:H8*G39+3*B:$A7/B:H7*G3S+ 9:$A18/B:[118*G49)  P:P25: (P4)  F: P25: (P4) +E:F15/E:$A15*(O.5*B:$A16/B:F16*E47+O.5*B:$A8/B:PB*E3943*B:$A7/B:P7*E38÷B:$A1B/B:P18*E49)  F:D25: (P4) +E:E15/E:$A15*(Q,5*:$A16/B:E16*D47+O,5*B:$A8/B:E8*D39+3*B:$A7/B:E7*D38fB:$A18/B:E18*D49)  P:C25: (P4) ÷E:D15/E:$A15*(O.5*B:$A16/B:D16*C47+O.5*B:$A8/B:D8*C39+3*B:$A7/B:D7*C38÷ B:$A18/B:D18*C49)  P:25: (P4) +E:C15/E:$A15*(O,5*B:$A16/B:C16*47+O,5*:$A8/S:C8*B39+3*B:$A7/B:C7*B38÷B:$A18/9C18*B49)  +  F:C29: (P4)  E: Dl 9/E:$Al S*(B:$A9/S:D9*C40+ B:$Al 1/B:D1 1*042)  E:0l 9/E:$Al 9*(B:$A9/B:C9*B40÷ B:$Al 1/B:Cl 1 *4)  +  +  +  F: P29: (P4)  F:G29: (P4)  P: H29: (F4)  E:Il 9/E:$A19*(B:$A9/B:19*H40+ B:$A1 1/B: Ill *42)  E: I-l 9/E:$Ai9*(B:$A9/B:H9*G40+ B:$Al 1/B: I-Ill *G42)  E:Gl9/E:$A19*(B:$A9/S:G9*F40+ B:$Al l/B:Gl 1 *F42)  +  +  F: C30: (P4)  F: D30: (P4)  E: E2OJE: $A20*B: $A9/B: E9*D40  E: D20/E: $A20*B: $A9/B: D9*C40  E:020/E: $A20*B: $A9/B:C9*B40  +  F: G30: (P4)  E: H20/E:$A20*B: $A9/B: Il9*G40  E:G20/E:$A20*B:$A9/B:G9*P40  E:C21/E:$A21 *(B:$A8/B:C8*B39+2*B:$A7/B:07*B38÷2*B:$A18/B:Cl 8*B49)  +  +  +  F: P31: (P4)  P:G31: (P4)  P:H31: (P4)  E121/E:$A21 *(B:$A8/B:t8*H39+2*B:$A7/B:17*H38+2*B:$A18/B:Il 8*H49)  E: F-121/E:$A21 *(B:$A8/B:H8*G39+2*B:$A7/B:H7*038÷2*B:$A1 8/B: I-1 8*649)  E: P21/E:$A21 *(B:$A8/B: P8*E39÷2*B:$A7/B: F7*E38÷2*B:$A1 8/B: P1 6*E49) E:G21/E:$A21 *(B:$A8/B:G8*P39÷2*B:SA7/B:G7*F38+2*B:$A1 8/B:G1 8*P49)  E:E21/E:$A21 *(B:$A8/B: E8*D39÷2*B:$A7/B:E7*D38+2*B:$A1 8/B:E1 B*D49)  P:E32: (P4) +E:P22f9:F7*E38  P:D32: (P4) +E:E22/B:E7*D38  F:032: (P4) +E:D22/B:D7*C38  P:B32: (P4) ÷E:022/B:C7*B38  ‘qtz  +  F: E31: (P4)  F:A32:  +  F: D31: (P4)  F:C31: (P4) +E:D2i/E:$A21*(B:$AB/B:D8*C39+2*B:A7/B:D7*C38÷2*B:$A18/B:D18*C49)  --  ‘KaoI  F: B31: (P4)  P:A31:  F:H30: (P4) +E:120/E:$A20*B:$A9/B:19*H40  +  F: P30: (P4)  P:E30: (P4) +E:P20/E:$A20*B:$A9/B:P9*EA0  +  F: B30: (P4)  F:A30: (P3) rutiIe  +  F: D20: (F4)  E: El 9/E:Al 9*(B:$A9/B: E9*D40+ B:$Al 1/B: Eli *D42) F: E29: (F4) + E: F19/E:$A19*(B:$A9/B: F9*E40+ B:$Al 1/B:Fl 1 *E42)  +  ilmenite  F: B29: (F4)  F:A29:  F:H28: (F4) +E:Il8/E:$A18*(0,5*B:$A15/B:I15*H46+0.5*B:$A8/B:I8*39+3*B:$A7/B:I7*H38)  C  E: D23/E:$A23*(B:$Al 2/9,: Dl 2*C43 + B: $Ai 9/B: Di 9*C50)  +  +  +  F: P33: (F4)  F:G33: (P4)  F: H33: (P4)  E: 123/E:$A23*(9,:$A12/9,: Il2*H43tB:$Al 9/B:1i9*H50)  E: H23/E:$A23*(B: $A1 2/B: Hi 2*G43 + B: $Ai 9/B: Hi 9*G50)  E:G23/E: $A23*(B:$Ai 2/B:Gl 2*F43 + B:$Ai 9/B:Gl 9*F50)  +  E:C24/E:$A24*(5*B:$A14/B:C14*B45+i .5*B:$A1 7/B:C17*948+O,5*B:$A18/B:C18*B49)  +  E:E24/E:$A24*(5*B:$A14/B:E14*D45+ 1 .5”B:$Ai 7/B:Ei7*D48+O,5*B:$Al8/B:lB*D49)  +  E:H24/E:$A24*(5*B:$Ai4/B:H14*G45+ 1 .5B:$Ai7/B:Hi 7*G48+05*B:$A18/B:Hi8*G49)  E: D25/E:$A25*(B: $Ai i/B: Dli *C42 + 2*B:$A20/(B: D20*i 0000)*C51)  +  F: H35: (F4)  E: 125/E:$A25*(B:$Al 1/B: Iii *H42 + 2*B:$A20/(B: 120*1 0000)*H51)  E: H25IE:$A25*(B: $Al 1/B: Hi 1 *G42 + 2*B:$A20/(B: H20*l 0000)*G51)  F:C36: (P4) +E:D26/B:D10*C41  F:836: (F4) +E:C26/B:Cl0*B41  hemtite  +  F:G35: (F4)  F:A36:  +  F: E35: (P4)  E: F251E:$A25*(B: $Al 1/B: Fl 1 *E42 + 2*B:$A20/(B: F20*i 0000)*E51) F: F35: (F4) + E:G25/E:$A25*(B:$Ai 1 /B:Gl 1 *4 +2*9,:$A20/(B:G20*i 0000)*F51)  F:D35: (P4) ÷E:E25/E:$A25*(B:$A1 1/B:El 1 *D42+2*B:$O/(B:0*l0000)*D51)  +  F:C35: (F4)  E:C25/E:$A25*(B:$Al 1 /B:Ci *9,4 2*B:$A20/(B: C20*l 0000)*B51)  pyrite  +  ‘  F: B35: (P4)  F:A35:  F:H34: (F4) +E:124/E:$A24*(5*B:$A14/B:114*H45÷ 1 .5*B:$A17/B:117*H48+O.5*B:$A16/B:118*H49)  F:G34: (P4)  F:E34: (P4)  + E:F24/E:$A24*(5*B:$Al4/B:Fl4*E454l 5*B.$Al 7/B:Fl 7E48+O.5*B:$Al8/B:F18*E49) ÷E:G24/E:$A24*(5*B:$A14/B:014*F45+ F:F34: (P4) 1 5*:,4j 7/B:G17*F48÷O.5*B:$A18/B:Gl8*F49)  F:D34: (P4)  F:C34: (F4) ÷E:D24IE:$A24*(5*B:$A14/B:D14*C45÷ 1 5*B:$A17/B:D17*C48+05*B:$A18/B:D18*C49)  F:B34: (P4)  F:A34: apatite  +  F: D33: (F4)  E: E23/E:$A23*(B: $Ai 2/B: El 2*D43 + B: $A1 9/B: El 9*D50) F: E33: (P4) + E: F23/E:$A23*(B:$Al 2/B: Fl 2*E43 + B:$Al 9/9, Fl 9*P50)  +  F:C33: (F4)  :C23/E:$A23* (B: $Ai 2/B: Cl *9,43 + B:$A1 9J9:C1 9*B50)  Mn-carb  +  ‘  F: B33: (P4)  F:A33:  F:H32: (F4) +E:122/B:17*H38  F:G32: (P4) +E:H22/9,:H7*G38  F:F32: (P4) +E:G22/B:G7*F38  Ui  +  +  +  +  +  +  +  F:C37: (P4)  F: D37: (F4)  F: E37: (P4)  F: P37: (P4)  F:G37: (P4)  P:I-137: (P4)  B:$A1 1/8:111 *H42)  E: l27/E:$A27*(B:$Ai 0/B: Ii O*F4i +  +  E: 27/E:$A27*(B:$AiO/B:FlO*G4i  B:$Ai i/B:Ri 1 *G42)  B:$Al i/B:Gl 1 *P42)  +  E:G27/E:$A27*(fl:$AiO/B:Gi O*F41  B:$Al 1/B: Eli *042)  B:$Ai i/B: Ph *E42)  +  E: E27/E:$A27*(B:$A1 O/B:E1 O*D41  9:$A1 i/B: Dli *C42)  S:$A1 1/B:C1 1 *B42)  +  +  E. D27/E:$A27*(B:$Ai O/B:DlO*C41  E:F27/E:$A27*(B:$Ai O/B:Fl O*E41  +  E:C27/E:$A27*(B:$AiO/B:Ci O*B41  magnetite  F: B37: (P4)  P:A37:  F:R36: (P4) ÷E:T26/B:I1O*F4l  RG36: (P4) +E:F426/B:H1O*G41  F:F36: (P4) lE:G26/B:G1O*F4i  F:E36: (P4) +E:F26/B:PiO*E41  P:D36: (P4) +E:E26/B:EiO*D41  P:H40: (P3) +$6÷B:I9*$C6  P:040: (P3) +$B6+B:-9$C6  F:P40: (F3) +$B6+B:G9*$C6  F:E40: (P3) +$6+B:P9*$C6  P:D40: (P3) +$B6÷B:E9*$C6  P:C40: (P3) +$96+9:D9*$C6  P:B40: (P3) +$B6+B:C9*$C6  P:A40: So T102  P:H39: (P3) +$55÷B1B*$C5  P:G39: (F3) +$5fB:H8*$C5  P:P39 (P3) +$B5+:G8*$C5  P:E39: (P3) +$B5+B:F8*$C5  F:D39: (F3) +$S5+B:E8*$C5  F:C39: (P3) +$B5+B:D8*$C5  P:839: (P3) +$B5+B:C8*$C5  P:A39: Sc_A1203  F:H38: (F3) +$B4+B:17*$C4  F:G38: (P3) +$B4+B:F17*$C4  F:F38: (P3) ÷$4+BG7*$C4  F:E38: (P3) +$4+:F7*$C4  F:D38: (P3) +$B4+B:E7*$C4  P:C38: (P3) +$94+B:D7*$C4  P:B38: (P3) +$B4+B:C7*C4  P:A38: So Si02  F:H43: (P3) +$9+B:I12*$c9  F:G43: (P3) ÷$B9+B:Ii12*$C9  F:F43: (P3) +$B9+B:G12*$C9  F:E43: (P3) +$9+B:P12*$C9  P:D43: (P3) +$B9+B:E12*$C9  P:C43: (P3) +$B9+B:D12*$C9  P:43: (P3) +$B9+B:C12*$C9  F:A43: Sc_MnO  F:H42: (P3) t$B8÷B:I11*$C8  P:G42: (P3) +$98+B:H11*$C8  P:P42: (P3) ÷$58+8:G11*$Ce  P:E42: (P3) ÷$8÷B:P11*$C8  P:D42: (P3) +$B8÷B:E11*$C8  P:C42: (P3) +$B8+B:D11*$C8  P:B42: (P3) +$56+B:C11*$C8  P:A42: Sc_PeO  P1-141: (P3) +$97+B:I1OA$C7  P:G41: (P3) +$B7÷fl:F11O*$C7  P:P41: (P3) i$B7+B:G1O*$C7  P:E41: (P3) +$B7+:P1O*$C7  P:D41: (P3) +$97+B:E1O*$C7  P:C41: (P3) +$B7+B:D1OC7  P:B41: (PS) +$B7÷B:C1O*$C7  P:A41: So_Pe203  P:H46: (P3) +$912+8:115*$C12  P:G46: (PS) +$B12+9:H15*$C12  P:P46: (P3) +$B12+B:G15*$C12  P:E46: (F3)+$B12+P,:15*$C12  P:D46: (PS) +$B12+B:E15*$C12  F:C46: (P3) i$G12+B:D15*$C12  P:B46: (P3) +$B12+B:C15*$C12  F:A46: ‘Sc_Na20  F:H45: (P3) +$S11+B:I14*$C11  P:G45: (P3) +$B11+B:l_114*$C11  F:P45: (P3) +$B11+B:G14*$C11  P:E45: (P3) +$B11÷B:P14*$C11  P:D45: (P3) +$B1 1 +:E14*$C1 1  P:C45: (P3) +$B11+:D14*$C11  F:B45: (P3) +$B11÷B:C14*$C11  P:A45: ‘Sc_CaO  P1-144: (P3) +$1O+B:l13*$C1Q  P:G44: (P3) +$B1O+8:H13*$C1O  F:F44: (P3) +$1O+:G13*$C1O  F:E44: (P3) +$810+B:P13*$C1O  P:D44: (P3) +W1O+B:E13*$C1O  F:C44: (P3) +$B1O+B:D13*$C1O  F:G44: (P3) +$B1O÷B:C13*$C1O  P:A44: Sc_MgO  L,.)  P:C50: (P3) +$67+B:D19*$H7 P:D50: (P3) +$G7iB:E19*$H7 P:E50: (F3) +$G7+B:F19*$H7 P:F50: (P3) +$G7+B:G19*$[-7  P:C47: (P3) +$G4+B:D16*$I14  P:D47: (P3) t$G4+B:E16*$H4  F:E47: (P3) +$G44B:F16*$H4  F:F47: (P3) +$G4+:G16*$)I4  P1-149: (P3) +$G6+S:118*$H6  F:&49: (P3) +$G6+:l118*$li6  F:F49: (P3) +$G6+B:G18*$116  F:E49: (P3) +$G6+B:F18*$[6  F:D49: (P3) +$G6+B:E18*$H6  F:C49: (F3) +$G6.iB:D18*$H6  F:849: (F3) +$G6tB:C18*$H6  F:A49: Sc_H20  F: [-148: (P3) +$G5+S:l17*$115  F:G48: (P3) +$G5+:l117*$1l5  P:P48: (P3) +$G5+B:G17*$H5  P:E48: (P3) +$G5+B:F17*$Ii5  F:D48: (P3) +$35+8:E17*$H5  F:C48: (P3) +$G5+8:D17*$I15  F:48: (F3) +$G5+a:c17H5  F:A48: Sc_P205  P1-147: (P3) +$G4+8:I16*$I14  P:H52: (P3) +$G9iB:I23*$[-19  F:G52: (P3) +$G9+B:1123*$H9  P:F52: (F3) +$G9+8G23*$H9  P:E52: (P3) ÷$G9iB:F23*$H9  P:D52: (P3) +$69÷B:E23*$H9  P:C52: (P3) +$G9+B:D23*$H9  F:B52: (P3) +$G9+2C23*$H9  F:A52: sc_Zr  P1-151: (P3) +$G8÷B:120*$H8  P:G51: (P3) +$G8+B:H20*$H8  F:P51: (P3) +$G8+:G2O*$H8  P:E51: (P3) ÷$G8iB:P2O*$Il8  P:D51: (P3) +$G8+fl:2O*$Il8  F:C51: (P3) +$G8+B:D2O*$II8  F:551: (F3) +$G8+B:C20*$H8  F:A51: Sc_S  F:H50: (F3) +$G7+B:I19*$[l7  F:G50: (P3) +$G7÷B:I119*$H7  F:B50: (P3) +$G7+B:C19*$H7  F:947: (P3) +$G4+B:C16*$H4  P:G47: (P3) +$G4+B:H16*$H4  F:A50: Sc_C02  F:A47: Sc_K20  “  2/B:E$9 2*$B$4O2+ B:$C$9 2*E:E5 2/B:E$9 4*D4O 2+B:$C$9  2/B:E$92*D15 2)  “  2*G1 6” 2)  2+B:$C$9 “ 2/B:G$9” 2*P16 2) 2+ B:$C$9 “ 2*E:H6 2/B:H$9 “ 4*G$40 “2+ B:$C$9” 2/B:H$9  2*E:G6 2/B:G$9” 4*p$4  F:C59: (P3) @SQRT(+ E: D7 “2/B: D$9” 2*$B$40 “2+ B:$C$9 2*E: D7  “  4*B$4O2+B:$C$9 2/B:C$92*B17 “2)  2/B:D$9” 4*C$4O2+ B:$C$9”2/B: D9 2*C1 7” 2)  P:B59: (P3) @SQRT(+ E:C7”2/B:C$9” 2*$B$4O2+ B:$C$92*E:C72/B:C$9  P: H58: (P3) @SQRT(÷ E: 16” 2/B:l$9 “ 2*$B$40 “2+ B:$C$9 2*E:l8 2/B:l$9 4*H$4O 2+ B:$C$9 “2/B: l$9 “ 2*H16 “2) F:A59: “Ca-pyx  P:G58: (P3) @SQRT(+ E: H6 “2/B:F-l$9 2*$B$4O  F:F58: (P3) @SQRT(+ E:G6 “ 2/B:G$9 “ 2*$8$40 “2+ 8:$C$9  P:C58: (P3) @SQRT(+ E: D6 “2/B: D$9  2*$B$40 “2+ 8:$C$9 “ 2*E:D6 2/B:D$9” 4*C$40 “2+ B:$C$” 2/B:D$9 2’C16 “2) F:D58: (P3) @SQAT(+ E: E6” 2/B:E$9” 2*$B$4O2+ B:$C$9 2’E:E6 “ 2/8:E$9 “ 4”D$40 “2+ B:$C$9 “2/B:E$9 2D16 “2) F:E58: (P3) @SQRT(+ E: P6” 2/B:F$9 “ 2*$B$40 “2+ B:$C$9 2*E: P6” 2/B:P$9 4*E$40 “2+ B:$C$9 “2/B: F$9 “ 2*E16 “2)  P:B58: (P3) @SQRT(+E:C6 “2/B:C9 2*$B$4O “2+8:$C$9” 2*E:C6  F:A58: “Epidote  F:H57: (P3) ©SQRT(÷E: 15” 2/B:l$9 2*$B$4O2+B:$C$9 2*E:l5 2/B:l$9” 4*F14O 2+ B:$C$9”2/B:l$9 2*ll152)  F:E57: (P3) @SQRT(+ E:P5  2*E:F5 2/B:F$94*E4O “2+ B:$C$9 “2/B:P$9 “ 2*E152) “ 2fB:P$9 2*$B$4O 2+B:$C$9 P:P57: (P3) @SQRT(+E:G5 “ 2/B:G$9 2*$B$4O2+ B:$C$9 “ 2*E:G5 2/B:G$9 4*p4Q 2+B:$C$9 “ 2fB:G$92*F15 2) F:G57: (P3) @SQRT(+E:H5 “ 2/B:H$9 “ 2*$B$40 “2+ B:$C$9 2*E: H5 “2/B: H$9 “ 4*G4O21 B:$C$9 “ 2/B: I—1$9’ 2*G15 ‘2)  P:D57: (P3) @SQRT(÷ E:E5  F:C57: (P3) @SQRT(÷ E:D5  “  2*$B$40 “2+ B:$C$9 2*E:C5 2/B:C$9” 4*B4O 2+ S:$C$9 2/B:C$9” 2*815 “2) 2/8:D$9 2*$B$4O “2+ B:$C$9 2*E:D5 2/B: D$9 “ 4*C4O 2+ B:$C$9 “2/B: D$9 “ 2*C15 “2)  F:957: (P3) @SQRT(÷ E:C5 “ 2/B:C$9  F:A57: “Calcite  P:F-156: “x2-5  F:G56: “x3-3d  P:P56: “x3-1  P:E56: “x3-4  F:D56: “x3-5  P:C56: “x3-7  P:B56: “x4-4  “  at northern segment of No.3 vein, Silver Queen mine, Owen Lake, central BC  F:A56: sample_id  F:855:  F:954: Error propagation of norms corrected for closure in gram(SD at 68% confidence level)  P:A54: Table 7-  2/B:E$9  2*$B$40 “2+ B:$C$9” 2*E:E7 2/B:E$94*D$40 “  2+B:$C$9” 2/B:E$9” 2*D17 “2)  ‘An  ‘  “  “  2E:C8 “  2/8:C$9 4*B$402÷ B:$C$9 “2/B:C$9  2*818 “2)  “  “  “  A 2/B:D$9 A2*$B$40A2÷ B:$C$9 2E: D8 2/B:D$9” 4*C$40 “2+ B:$C$9” 2/B:D$9 2’C1 8” 2) 2/B:E$9 2*$B$40 “2+ B:$C$9” 2*E:E8 2/B:E$9” 4*D$40 “2+ B:$C$9 2/B:E$92*Dl82)  2/B:C$9 2*$B$402÷ B:$C$9  “  ‘  “  2/8:C$9  “  A  2*E:18  A  2*E:P9 A  A  2*E: D9  2*$B$40 A2÷ B:$C$9 A2*E:E9  2’$B$4O “2+ B:$C$9  ‘  “  4*C$40 A  2/B: P$9  4*E$40 “2+ G:$C$9  “  2/B:D$9  2”Cl 9 “2)  2/B:C$9A2*B192)  2/B:F$9  “  2*El9 2)  2/B:E$92*D192)  “  A  2+ 8:$C$9  2/B:E$94*D$4O 2÷B:$C$9  2/B:D$9 A  ‘  2f8:I$9 A4*I.j$40 “2+ B:$C$9” 2/B:l$9 A2*R1BA2)  2*$B$40 “2+ B:$C$9” 2*E:C9 2/B:C$9’4*B$4OA 2+B:$C$9  2*$B$40 “2+ B:$C$9  “  2*$8$40 2÷ B:$C$9  “  “  “  2/B:l$9  2’B20” 2)  21-1l9 “2)  2*$B$40 “2+ B:$C$9 A 2*E:C10 “ 2/B:C$9 “ 4’B$40 “ 2+B:$C$9 A 2/B:C$9  A  “  “  P:A63: “Mg-pyx  P:G62: (P3) @SQRT(+ E:Hl0 “2/B:I-1$9 “2’$B$40 “ 2÷B:$C$9 A2*El-Il0 “2/B:I-1$9 4*G$40 “2+ B:$C$9 “2/8:1*9 A2*G2OA 2) P:H62: (P3) SQRT(+E:I10 “2/B:I$9” 2*$B$40A2+ B:$C$92*E:Il0 2/B:I$94*H$40 A2÷B:$C$9A2/B:I$9A2*20A2)  F:C62: (P3) @SQRT(÷ E:Dl 0  A 218:D$9 A 2*$B$40 “2+ B:$C$9 2*E: Dl C” 2/B:D$9 4C$40 “2+ B:$C$9” 2JB:D$9 2C20 2) A A P:D62: (P3) @SQRT(+ E: El 0” 2/B:E$9” 2*$B$40 “2+ B:$C$9 2*E:El0 2/9:E$9 4*D$40 2+B:$C$9 “2/B:E$9 2’D20 “2) P:E62: (P3) @SQRT(÷ E:Fl0 A 2/B:P$9” 2*$B$40 “2+ B:$C$9 “ 2*E:Pl0 2/B:P$9 4*E$40 “2+ B:$C$9 2/B:F$9 2*E20 2) P:F62: (P3) @SQRT(÷ E:Gl0 A 2/B:G$9 A2*$B$40 “2+ B:$C$9 2*E:G10 2/8:G$9 4’P$40 “2+ B:$C$9 2/B:G$9 2*F20 “2)  A  2*$B$40 A 2+ B:$C$9 A 2*E:19 A 2/8:I$9 4*I_I$40 “2+ B:$C$9  F:862: (P3) @SQRT(+ E:Cl0” 2/B:C$9  P:A62: “Mg-chl  P:H61: (P3) @SQRT(+ E: 19 A 2/B:I$9  “  A4*$4Q ‘2+B:$C$9 2/B:G$92*P19A2) P:F61: (P3) @SQRT(+ E:G9 A2/9:G$9A2*$B$40A 2+ B:$C$9 A2*E:G9 A2/B:G$g A A P:661: (P3) @SQRT(+ E:H9 2/B: $9 A 2*$B$40 “2+ B:$C$9” 2*E:H9 2/B:H$9 4*G$40 2+ B:$C$9 “2/8:1*9” 2*Gl9 2)  P:E61: (P3) @SQRT(+ E:P9 A 2/B: $g  P:D61: (P3) @SQRT(÷E:E9”2/B:E$9  P:C61: (P3) @SQRT(+ E: D9 “2/B:D$9  P:B61: (P3) @SQRT(+E:C9  P:A61: “Mg-carb  P1-160: (P3) SQRT(+ E:18” 2/B:I$9  “  A  F:E60: (P3) @SQRT(+ E: PB” 2/B: F$9 2*$B$40 “2+ B:$C$9 2*E: P8” 2/B:F$9 4”E$40 “2+ B:$C$9 2/B:P$9 2*E18. 2) F:F60: (P3) @SQRT(÷ E:08 2/8:G$9 2*$B$40 “2+ B:$C$9 2’E:G8” 2/B:G$9 4’P$40 “2+ B:$C$9” 2fB:G$9 A 2*F18 “ 2) F:G60: (P3) @SQRT(+ El-IS” 2/B:H$9” 2*$B$40 “2+ B:$C$9 2E:1-48 2/8:H$9 4kG$40 “2+ B:$C$9 2/B:F-I$9 2*G18A 2)  P:D60: (F3) SQRT(+ E:E8  F:C60: (P3) @SQRT(÷ E: D8  F:860: (P3) @SQRT(+ E:C8  P:A60:  “  F: E59: (F3) @SQRT(+ E:F7 “2/B: P$9 “ 2*$E$40 “2+ B:$C$9  2’E: P7” 2/B:P$9 4E$40 “2+ B:$C$9” 2/B:P$9 2E1 7 “2) 2*E:G7 “2/B:G$9 A 4*F$40A 2+ B:$C$9 “ 2/B:G$92*P17 “2) P:F59: (P3) @SQRT(+ E:G7 2/B:G$9 2*$B$40 “2÷ B:$C$9 F:G59: (P3) @SQRT(+ E: H7 “2/B:l-l$9 2*$B$402+ B:$C$9 2*E:ll7 2/B:H$9” 4*G$40 “2+ B:$C$9 2/9.:H$9” 2*G1 7 “2) A F: R59: (P3) @SQAT(+ E: 17” 2fB: $9 2*$B$402+ B:$C$9” 2*E:I7 2/B:l$9 4*H$40 “2+ B:$C$9 2/B:1$9 A2*Hl 7 “2)  F:D59: (F3) SQRT(÷ E:E7  “  2+B:$C$9” 2*E:Cl 1 2/B:C$94*B$4O2+ B:$C$92/B:C$92*B2l “2)  “ “  2/B:G$9 2*F21 “2)  2*EHl 1 “2/B:H$9” 4*G$40 “2+ B:$C$9 “ 2/B:H$9” 2*G21 “2)  2*$B$40 “2+ B:$C$9  2*E21 “2)  2$B$4O “2+ B:$C$9  2/B:F$9  2*E:Gl 1 “2/B:G$9” 4*p$4Q “2+ B:$C$9  ‘  4*D$40 “2+ B:$C$9 “2/B: E$9 2*D2l “2) 4*E$4O2+ B:$C$9  2*$B4O “2+ B:$C$9 2*E:Dl2  “  “  2’$B$4O “2+ B:$C$9 “  “  4*D$4O 2+B:$C$9”2/B:E$9 2*D222)  4E$4O 2+9:$C$9” 2/B:F$9” 2*E222) 2/B:G$9 4*$4() “2+ B:$C$9 “2/B:G$9 2*F22 “2)  2/B:F$9  “  “  2*E:612  2*E:P12  “  2+B:$C$92/B:D$92*C222)  4*B$4O 2+ B:$C$92/B:C$92*B222)  “  “  “  “  2*$B$40 “2+ B:$C$9  “  2*E: P13” 2fB:F$9  “  2*E:El 4” 2/B: E$9  “  4*D$40 “2+ B:C$9  “  2/B:E$9  2*D24 “2)  4*G$40 “2+ B:$C$9 2/B:H$92*G24 “2) “  2*$B$40 “2+ B:$C$92*E:Hl4 “2/B:H$9  P:G66: (P3) @SRT(+ E:Hl 4” 2/B:H$9  4*P$4O2+ B:$C$92/B:G$92*P24 “2)  P:P66: (P3) @SQRT(÷ E:G14 “2/B:G$9 2*$B$4O 2+ B:$C$92*E:G14 “2/B:G$9  F:E66: (P3) @SQRT(4-E:P14 “2/B:P$9 2*$B$4O 2+ B:$C$92*E:Fl 4 “2/B:F$9 4*E$4O 2+B:$C$9”2/B:F$9 2*E242)  F:D66: (P3) @SQRT(÷ E: El 4” 2/B:E$9 “ 2*$B$4O2+ B:$C$9  2/B:D$O  2+B:$C$9” 2/B:D$9 2*C24 “2)  P:C66: (P3) @SQRT(+ E:D14  2*$B$4O 2+ B:$C$9 2*E:D14 “2/B:D$9 4*C$4O  2/B:I$9” 2*H23 “2)  2/B:H$9 2*G23 “2)  2÷B:$C$9”2/B:C$9 2*B242)  “  “  F:B66: (P3) SQRT(+ E:C14 “2JB:C$9 “ 2*$B$40 “2+ 9:$C$9 2*E:C14 “2/B:C$9 4*B$4O  F:A66: “Fe-pyx  4*H$40 “2+ B:$C$9  2*E: Hl3 “2/B: H$9 4*G$4O2+ B:$C$9  P:H65: (P3) @SQRT(+ Eli 3” 2/B: I$9” 2*$B$4O2+ B:$C$9 2*E:Il 3” 2/B: I$9  P:G65: (P3) @SQRT(÷ E:H13” 2/B:H$9 2*$B$4O “2+ B:$C$9  F:E65: (P3) @SQRT(+ E:P13 “2/B:F$9  4E$4O “2+ B:$C$9” 2/B:F$9 2*E23 “2) F: P65: (P3) @SQRT(+ E:G13” 2/B:G$9 2*$B$4O2+ B:$C$9” 2*E:Gl 3 2/B:G$9” 4*P$4Q “2+ B:$C$9 “ 2/B:G$9” 2*P232)  2*$B$40 “2+ B:$C$9  2+S:$C$9”2/B:E$9 2*D232)  4*C$40 “2+ B:$C$9 “ 2/B:D$9 2*C23 “2)  2/B:E$9” 4*D$40  2*E:Dl 3 2/B:D$9  F:D65: (P3) @SQRT(+E:El3 “2/B:E$9” 2*$B$4O 2+ B:$C$92*E:El3  F:C65: (P3) @SQRT(+ E:Di 3” 2/B: D$9  F:B65: (P3) @SQRT(+E:Cl3” 2/B:C$9 “ 2*$B$40 “2+ B:$C$9” 2*E:Cl32/B:C$9 4*B$40 “2+ B:$C$9”2/B:C$9” 2*B232)  F:A65: “Fe-chi  “  F;G64: (P3) (SQRT(+ E1-112” 2/B:H$9 2*$B$40 “2+ B:$C$9” 2*E:H12 “2/B:1-1$9” 4*G$4O2+B:$C$92/B:H$92*G22 “2) P1-164: (P3) @SQRT(+ E:112 2/B:I$9” 2*$B$40 “2+ B:$C$9 2*E:Ii2 2/B:I$9 4*F1$4O “2+ B:$C$9 2/B:I$9 2*f122 2)  F:F64: (P3) @SQRT(÷ E:G12 “2/B;G$9  2/B:F$9  “  2/B:D$9” 4*C$40  2/B:C$9  2*$B$4O2÷ B $C$9  “  2’E:Cl2  P:E64: (P3) @SQRT(+E:Fl2  2/B:D$9  2+B:$C$9  2*$B$4O 2+ B:$C$9” 2*E:El2 2/B:E$9  “  “  P:D64: (P3) @SQRT(+ E:E12” 2/B:E$9  F:C64: (P3) @SQRT(+ E:D12  F:B64: (P3) @SQRT(+ E:C12” 2/B:C$92*$B$4O  F:A64: “Fe-carb  F:H63: (P3) @SQRT(+ E:Il 1 2/B:I$92*$B$4O 2+ B:$C$92*E:Il 1 2/B:I$94*H$4O 2+B:$C$9 2/B:I$9A2*H2l “2)  FG63 (P3) @SQRT(+ EHi 1 “2/B:F-1$9  FF63 (F3) cSQRT(+ EGi 1 “2/B:G$9  F:E63 (F3) SQRT(+ E:Fl 1 “2/B: F$9  2*$B$40 “2+ B:$C$9” 2*E:Pl 1 “2/B: F$9  F:D63: (P3) @SQRT(+ E:E1 1 “2/B: E$9 2*$B$4O “2 + B:$C$9” 2*E: El 1 “2/B:E$9  P:C63: (P3) @SQRT(i-E:D1 1 “2/B:D$9 2*$B$4O2+ B:$C$92*E:D1 1 “2/B:D$9” 4*C$4O2+ B:$C$92/B:D$92*C21 “2)  F:B63: (P3) @SQRT(+E:C1 1 S2/B:C$92*$B$4O  A  “  “  “  “  “  “  “  2+ B:$C$9  “  A  “  “  ‘  A  2+ B:$C$9  “  “  A  2*E:116A 2/E:I$9  A  A  A  2*$9$40 A  2+ B:$C$9’’ 2*E:Ei7 “  A  4*C$40A 2+ B:$C$9” 2/B:D$9” 2*C27 “2)  4”B$40 “2+ B:$C$9 “2/B:C$9” 2*B27 “2)  2/B:E$9” 4*D$40 “2÷ B:$C$92/9:E$92*D27 “2)  A  “  “  2’E:I17  A  A4*H$40A  “  2÷ B:$C$9” 2/B: I$9” 2*H27  A  2)  2/8:H$9 4*G$40 “2+ B:$C$9 “2/B:H$9 A2*G27A2) 2/B: I$9  A  4*B$40A2+B:$C$9A2/B:C$9A2*B28A2) F:B7O: (F3) @SQRT(÷E:Cl8” 2/B:C$9’2*$B$4OA 2+ B:$C$92*E:C16’ 2/B:C$9” 4*C$40 A 2+ B:$C$9 2/B:D$9” 2*028 “2) F:C70: (F3) @SQRT(+ E:Dl 8 2/B:D$9” 2*$B$40 “2+ B$C$9 A2*E:D18A 2/B:D$9 A E$9 4*D$40A2÷B:$C$9A2/B:E$9A2*D28A2) FD7O (P3) @SQRT(+EEl8A2JB:E$92*$B$4O 2+B:$C$9” 2*E:El82/B: 4*E$4O 2+ B:$C$9 2/B:F$9 A2*E28A 2) F: E7O: (P3) @SQRT(+ E:Fl 8 A 2/B: F$9A2*$B$OA 2+ B:$C$9 A 2*E: Fl 8 A 2/B:F$9”  F:A70: “Ab  F: H69: (F3) SQRT(+ E: (17 “2/B: $9 2*$B$40 2+ B:$C$9  F:G69: (F3) @SQRT(÷ E:Hl 7” 2/B:H$9” 2*$B$40” 2÷B:$C$9 A2*E:Hl 7  A  B:$C$92/B:F$92*E27 2) F:E69: (P3) @SQRT(÷ E:F17 “2/B:F$9” 2*$B$4O 2+ 9:$C$9” 2*E:Fl 7 “2/B:F$9” 4*E$40 “2+ A A 4*F$40 2+B:$C$9” 2/B:G$9” 2*F27 “2) F:P69: (P3) @SQRT(÷ E:G17” 2/B:G$9” 2*$9$40 2+ 9:$C$9 2*E:G1 7 A2/9:G$9A  F:D69: (F3) @SQRT(÷ E:Ei 7” 2/9:E$9  4kD$4O A2÷B:$C$9A2/B:E$9A2*D26A 2)  4*H$40A 2+ 9:$C$9 “2/B: $9” 2*H26s2)  F:969: (P3) @SQRT(+E:Cl 7” 2/9:C$92*$B$4O “2+ B:$C$9 A2*E:Cl 7” 2/B:C$9 F:C69: (F3) @SQRT(+ E:D17 2/B:D$9” 2*$B$4O 2+ B:$C$92*E:D1 7 2/B:D$9  F:A69: “Na-mica  F:H68: (P3) @SQRT(+ E:116” 2/9:I$9 A2*$B$40  “  49$4O A 2+B:$C$9” 2/B:C$9” 2*B26 “2)  2*E:Fl6 2/B:F$9” 4”E$40 A2+ B:$C$9 A 2/B:F$9” 2*E26S 2) A A 2*$B$40 2÷ B:$C$9” 2*E:G16 A 2/B:G$9” 4*$4Q A 2+ B:$C$9 A 2/B:G$9 2*F26 2) 2*$9$4O 2+ B:$C$9 2’E:Hl 6 “2/B: H$9” 4*G$40 2+ B:$C$9” 2/B:F-($9” 2*G26 2)  2*$B$40 “2+ 9:$C$9  “  “  2/9:G$9  2/B:F$9  “  2*E:Di6 2/9:D$9” 4*C$4O2+ B:$C$9”2/B:D$9” 2*C262)  2/B:C$9  2/9:E$9 A2*$B$40 “2+ B:$C$9” 2*E:E1BA 2/B:E$9  F:G68: (P3) @SQRT(÷ E: Hi 6” 2/9: H$9  F:F68: (P3) @SQRT(÷ E:G16  F:E68: (F3) @SQRT(+ E:F16  F:D68: (P3) @SQRT(÷E:El6  ‘  “  A A 2’E: Hi 5 “2/B: H$9 4*G$40.2+ B:$C$9 “2/9:H$9 2*G25 2) A *)(5 A A “2) 2’E:Ii 5”2/B: $9” 4*f($4Q 2+ B:$C$9 2/9:I$9  A  2/B:O$9_2*$B$4OA 2+ B:$C$9” 2*E:C16  A  F:C68: (P3) @SQRT(+ E:Dl 6” 2/B:D$9” 2*$B$40 “2+ B:$C$9  F:B68: (P3) @SQRT(+E:Cl6  F:A68: “Or  “  2/B:H$9A2*$B$40 “2+ B:$C$9  A F:H67: (F3) @SQRT(÷ E:tl 5” 2/9:I$9 2*$B$40  F:G67: (F3) SQRT(+ E: Hi 5 A  2*D25A 2)  2’E25 “2)  “  ‘  2+ B:$C$9” 2/B:E$9  2C25 A2)  2/B:C$92*S25 “2)  2*E: Di 5” 2/B:D$9” 4*C$40 “2+ B:$C$9 “2/B:D$9  2*$B$40 “2+ B:$C$9” 2*E: El 5” 2/B: E$9” 4*D$40  2*$B$40 “2+ B:$C$9  “2+ B:$C$9  2+B:$C$9” 2fB:I$9A2*H24 “2)  4*E$40 “2+ B:$C$9” 2/B:F$9 F:E67: (F3) @SQAT(+ E:Fl 5” 2/B:F$9” 2*$B$40 “2+ B:$C$9 2*E: F15 “2/B: F$9” F:F67: (F3) @SQRT(+ E:Gl5s 2/9:G$9 2*$B$40 2+B:$C$9”  F: D67: (F3) @SQRT(+ E: El 5” 2/9: E$9  F:C87: (F3) @SQRT(÷ E:Dl 5” 2/B:D$9  ‘  A4*$4Q  2/B:I$9” 4*H$40  2*$B$40 “2± B:$C$92*E:Ci5 2/B:C$9  2/B:l$9” 2*$B$40 “2÷ B:$C$9 2*E:Il4  F:B67: (F3) @SQRT(+ E:Cl5” 2/B:C$9  F:A67: “Muscovite  F:H66: (F3) @SQRT(+ E:l14  “  2/B:G$92*$B$40.’ 2+ B:C$9 2*E:G18 2JB:G$9_S 4*$4Q _‘  2+B:$C$9 “2/B:G$9” 2*F282)  “  2/B:E$9  2*$B$40 2+ B:$C$9” 2*E:E19A2/B:E$9. 4*D$40. 2+8:$C$9 A2/B:E$9A2*D292)  2+9:$C$9  “  “  ‘  “  4*G$40.2÷B:$C$9 _2/B:H$9.2*G29A2)  2*E:C20S2/B:C$9 4*B$40 2+B:$C$92/B:C$92*B302)  2/B:H$9  2/S:D$9 .2*$B$40 “2+ B:$C$9 s2*E;D20 “2/B:D$9 4*C$40 “2+ B:$C$92/B:D$92*C3OS2) 2/B;E$9 2*$B$40 “2+ B:$C$9 2’E: E20 A 2/B:E$9 4’D$40 “2+ B:$C$9 “ 2/B:E$9 2kD30 “2)  2/B:C$9 2*$B$40 “2+ 8:$C$9  “  “  ‘  “  “  2$B$40 “2+ B:$C$9  A 218:D$9 2*$B$40 2+ B:$C$9  Aq  A  2/B: I$9 A 2*$B$40 “2+ B:$C$9  2+ B:$C$9  “  2/B:E$9  2kD31 “2)  2*E:121  A  2/B: [$9” 4*G$40 “2+ B:$C$9 “ 2/B: -($9”’ 2*G31 “2)  “  2/B: I$9 “ 4*H$40 “2+ B:$C$9 “2/B: I$9” 2*H31 “2)  A  A A A A F:B74: (P3) @SQRT(+EC22 A2/B:C$9A 2*$B$40A 2+ B:$C$9” 2*E:C22 2/B:C$9 4*B$40A 2+B:$C$9” 2/B:C$9 2*B32 2) A A F;C74: (P3) iSQRT(+ E;D22 “‘2/B; D$9 F2*$B$40 “2 + B:$C$9 2*E; D22 2/B;D$9 4*C$40 2+ B:$C$9 “-2/B:D$9 2*032 “2)  P:A74:  F:[-173: (P3) @SQRT(+ E: (21  2*$B$40 “2+ B:$C$9 2*E:I(21  2+ B:$C$9  F:G73: (P3) @SQRT(÷ E: H21 “2/B:[-1$9  A  A  2B31 “2) 2+B:$C$9 A 2/B:D$92*C31 “2)  4B$40 A 2+ B:$C$9 “ 2/B:C$9  “  2/B:P$9 A4*E$40 2÷B:$C$9 “2/B:F$9 A2*E31 “2) 2*E:G21 “2/B:G$9 A 4*$4Q “2÷ B:$C$9 2/B:G$9 A 2*F31 “‘2) A  2*$B$40  A  2/B:C$9  -  2*E: E21 “2/B:E$9 A 4*D$40  F: P73: (P3) @SQRT(+ E:G21 “2/B:G$9  2/B: E$9” 2*$B$40 “2+ B:$C$9  “  “  “  2*E:D21 ‘2/B:D$9” 4*C$40  2$B$0 “2÷ B:$C$9 A2*E:F21  “  A  2*E:C21  F:E73: (P3) @SQRT(÷ E:F21 “‘2/B:F$9  F: D73: (P3) @SQRT(+E: E21  F:C73: (PS) @SQRT(-t- E: D21  “  “  F: B73: (P3) @SQRT(+ E:C21 “2/B:C$9  F:A73: “-KacI  F: E72: (P3) @SQRT(+ E: F20  A 2/B:F$9 “ 2*$B$40 “2+ B:$C$9 ‘ 2*E:F20 2/B:F$9 4*E$40A2+ B;$C$9 2/B:F$9A 2*E30’. 2) F:F72: (P3) @SQRT(+ E;G20 2/B:G$9 2*$$4O “2+ B:$C$9 A2*E:G2OA 2/B:G$9” 4*F$40 A2÷B:$C$9A 2/B:G$9 2*F302) F:G72: (P3) @SQRT(+ E: H20 2/B:l-l$9 A 2*$B$402+ B:$C$9 2*E: H20”2/B; [I$9 4G$40 “2+ B;$C$9 “2/B:[-1$9 2*G30 “2) A A A P1-172: (P3) @SQRT(+ E: 120 “2/B:l$9 A 2*$B$40 2+ B:$C$9 “ 2*E:I20 2/B: I$9 4*H$40 2+ B:$C$9 2/B: I$9 A2*[-(30A 2)  F: D72: (P3) @SQRT(-t- E: E20  F:C72: (ES) @SQRT(÷ :D20  F;B72: (P3) @SQRT(+ E:C20  F;A72: (P3) “rutile  P1-471:  F:G71: (P3) SQRT(+E:H19 2/B:I4$9A 2*$B$40 2+ B:$C$92*E:H19  “  A F:E71 (P3) @SQRT(+ E:E1 9,’ 2/B:F$9” 2*$B$40 2+B:$C$9 2*E:F19 2/B:F$9 4*E$40A 2+ B:$C$9S2fB:F$92*E292) 4*p$4QS 2+B:$C$9 “2/B:G$9 _s2*F29s2) F:F71: (P3) @SQRT(+ E:G19 “2/B:G$9 A2*$B$40A2+ B:$C$9” 2*E:G19 2/B:G$9  F:D71: (P3) @SQRT(÷E:19  “  2/B:D$92*C29 “2)  2’$B$40 “2+ B:$C$9  2*E: D19 “2/B:D$9” 4*C$40  “  2+B:$C$92/B:C$92*B292)  2/B:C$9S2*$B$40s 2+B:$C$9 2*E:C19 “2/B:C$9” 4’B$40  F:C71 (F3) @SQRT(+ E: D19 A2/B:D$9  F:B71: (P3) @SQRT(+E:C19  F:A71: “ilmenite  “  F:G70: (P3) @SQRT(+E:H18 2/B:[*92*$B$40 “2+ B:$C$9 A2*E:H18 “2/B:H$9” 4*G$40A2+B:$C$92/B:[l$9/.2*G28A2) F: [-470: (F3) @SQRT(+ E:I1 8” 2/B:I$9 “ 2*$B$40.2+ B:$C$9 2’E:I1 8” 2/B: I$9 4*R$40 “2+ B:$C$9 “2/B:I$9” 2*H28 “2)  F:F70: (P3) @SQRT(4-E:G18  2/B:G$9  4*G$40 “2+ B:$C$9” 2/B:F-l$9  4’F$4O “2+ B:$C$9  2/B:F$9 2*G32 “2)  2F32 “2)  2E32 “2)  “  2/B:C$9  2’B33 “2)  4*C$40 “2+ B:$C$9 “2/B: D$9 “ 2*C33 “2)  B4O “2+ B:$C$9 4  ‘  4*D$4O 2+ B:$C$9” 2/B:E$92*D33 2)  “  “  “  “  2/B:E$92*$9$4O 2+B:$C$9  4*C$40 “2+ B:$C$9 “2/B:D$9” 2*C34 “2)  2’E:E24 “2/B:E$9” 4*D$40 “2+ B:$C$9 “ 2/B:E$92*D34 “2)  2*E: D24 “2/P:D$9  “  “  2÷ B:$C$9 “ 2/B:I—1$9  2’G34 “2)  2/B:l$9” 4*1440 “2+ B:$C$9 “2/B:I$9 2*H34 “2)  ‘  “  4D$40 “ 2+B:$C$9 “2/B:B$9 “ 2’D35” 2)  P:A78: “hen,tite  F:G77: (P3) @SQRT(+ B:R25 “ 2/B:I—1$9 2*$B$40 “2+ B:$C$9 2*B -125 “2/B:I-19 “ 4*G$40 “2+ B:$C$9 “ 2/B: 149” 2*G35 “2) P:H77: (PS) @SQRT(+ E:125 “2/B:I$9 2*$B$40 “2+ B:$C$9 “ 2*E:125 “ 2/B:l$9 “ 4*lI$40 “2+ B:$C$9 “2/B:I$9 2*H35 “2)  P:P77: (PS) @SQRT(+ E:G25 “ 2/B:G$92*$B$40 “2+ B:$C$9 “ 2*E:G25  2/B:P$9 2’E35 “2) 4*$4Q “2+ B:$C$9” 2/B:G9 2*P35 “2) 2/B:G$9”  P:B77: (P3) @SQRT(÷ B: P25 “2/B: F$9” 2*$B$402+ B:$C$9 2*B: P25” 2/B:P$9” 4*E$40 “2+ B:$C9  P:D77: (P3) @SQRT(÷ B: E25 “2/B: E$9 2*$B$40 “2 + B:$C$9 2*E:E25 “2/B:B$9  F: B77: (P3) @SQRT(+ E:C25  2/B:C$9 2*$B$40 “2+ B:$C$9” 2*E:C25 2/B:C$9” 4*B$40 “2+ B:$C$9” 2/B:C$9” 2*B35 “2) P:C77: (P3) @SQRT(÷ B: D25 “2/B: D$9 2*$B$402+ B:$C$9 “ 2*E:D25 2/B:D$9” 4*C$40 “2+ B:$C$9 “ 2/B:D$9” 2*C35 “2)  P:A77: “pyrite  P1-176: (P3) @SQRT(+ B: 124 “2/S:l$9” 2*$B$40 “2+ B:$C$9” 2*B:124  P:G76: (P3) @SQRT(+ E: -124 “2/B:H$9 2*$B$4O2+ B:$C$9 2*E: 1-124 “2/B: H$9 “ 4*G$40  F: E76: (P3) @SQRT(+ B: P24 “2/B: F$9  2*$2,$4O2+ B:$C$9 “ 2*E:P24 “2/B: F$9” 4*E$40 “2+ B:$C$9 “2/B:P$9” 2*E34 “2) P:P76: (P3) @SQRT(÷ E:G24 “2/B:G$9” 2*$B$40 “2+ B:$C$9” 2*E:G24 “2/B:G$9” 4*$4Q “2+ B:$C$9 “ 2/B:G$9 2*F34 “2)  F:D76: (P3) @SQRT(+ E:E24  P:C76: (P3) @SQPT(+ E: D24 “2/B:D$9” 2*$B$40 “2+ B:$C$9  2/B:C$9” 2*B34 “2)  2*E: 123 “2/B: I$9 4*I1$4O “2+ B:$C$9 “2/B:I$9” 2*I_133 “2)  F:B76: (P3) @SQRT(÷ E:C24 “2/B:C$9 2*$B$4O2÷ B:$C$9 “ 2*E:C24 “2/B:C$9” 4*B$40 “2+ B:$C$9  P:A76: “apatite  F: -175: (P3) cSQF1T(+ E:123 “2/B:I$9 “ 2’$B$4O “2+ B:$C$9  “  “ 2fB:P$9” 4*E$40 “2+ B:$C$9 “ 2/B:F$9 “ 2*E332) 2*$B$40 “ 2*E:G23 F:P75: (PS) @SQRT(+ E:G23 “ 2/B:G$9 “2+ B:$C$9 “2/B:G$9 “ 4*P$4O2÷ B:$C$9 “2/B:G$9 2*P33 “2) F:G75: (F3) @SQRT(+ B: H23”2/B: H$9 2*$B$4O “2+ B:$C$9 “ 2*E:H23 “2/B1-1$9 4G$4O “2+ B:$C$9” 2/B:F-$9 2*G33 “2)  F:E75: (P3) @SQRT(+ E:F23 “ 2/B:F$9” 2*$B$4O2 + B:$C$9 2*E:F23  2/B:E$9  2*E: D23”2/B: D$9  2/B:D$9 2*$B$4O “2+ B:$C$9  F:C75: (PS) @SQRT(÷ E: D23  F:D75: (P3) @SQRT(+E:E23” 2/B:E9 2*$B$4O 2+ B:$C$9 “ 2*E:E23  2*E:C23 “ 2/B:C$9  “  “  4*E$4O2÷ B:$C$9  2’D32” 2)  4*IH$40 “2+ B:$C$9 “2/B:I$9 “ 2*H322)  2/B:C$9 2*B$4O “2 + B:$C$9  “  F: B75: (P3) @SQRT(+ E:C23  F:A75: “Mn-carb  2*E: 122” 2/B:l$9  21B:G$9  2E: H22 “2/B: H$9  F: H74: (P3) @SQRT(+ E: 122”2/B: l$9” 2*$B$40 “2+ B:$C$9  “  F:G74: (P3) @SQPT(+ E: H22 “2/B: H$9” 2*$B$4O2+ B:$C9  2*E: P22 “2/B:F$9 2*E:G22  2*$B$4O 2+ B:$C$9  F: P74: (F3) @SQRT(+ E:G22” 2/B:G$9 2*$B$4O “2+ E:$C$9  P:E74: (P3) @SQRT(+ E: P22 “2/B: P$9 “  F:D74: (P3) @SQRT(+ E:E22 “2/B: E$9” 2*$B$4O2+ B:$C$9” 2*E: E22” 2/B:E$9” 4*D4O “2± B:C$9 “2/B:E$9  2*$B$4O2 + B:$C$9  P:P78: (P3) @SQRT(+ E:G26” 2/B:G$9  4*$4Q  4*D$4O 2+ B:$C$9 “  2/B:E$9  2+ B:$C$9” 2/B:D$9  2/B:C$9  2)  2*C362)  2*D36 2)  “  2*B36  2JB:F$9” 4*E$40 “2+ B:$C$9 “2/B:F$9 2*E36 “2) 2*E:G26 2/B:G$9” 4*$4Q “2+ B:$C$9” 2/B:G$9 2*F36 “2)  2*E:E26 21B:E$9 2*E:P26  “  “  2+ B:$C$9  “  “  “  “  2*E: P27 “2/B: P$9 4*E$4O2+ B:C$9  “  2B37 “2)  2/B:E$9” 2*D372) 2/B:F$9 2*E37 “2)  “  4*C$4O2+ B:$C$9 “2/B:D$9 2*C37 “2)  “  F:H80: (P4) @SUM(H57.H79)  P:GOO: (P4) @SUM(G57G79)  F:F80: (P4) SUM(P57..P79)  P:E80: (P4) @SUM(E57.E79)  F:D8O: (P4) @SUM(D57.D79)  F:C80: (P4) @SUM(C57,C79)  F:B80: (P4) @SUM(B57..B79)  F:A80: (P4) Total  F:I-179: (P3) @SQRT(+ E:127 “2/B:I$9” 2*$B$4O 2+ B:$C$9” 2*E:127 “2/B:l$9  “  4*ll.$4O 2+B:$C$9 “2/B:l$9  “  2”F-137 “2)  4*p$4Q 2+ B:$C$9”2/B:G$9 2’P37 “2) F:P79: (F3) @SQRT(+E:G27 “2/B:G$9 2*$B$4O2+ B;$C$9 2*E:G27 2/B:G$9” P:G79: (PS) @SQRT(+ E:H27 2/B:H$9 .2*$B$4O 2+ B:$C$9 2*E:II27 2/B:H$9” 4*G$40 “2+B:$C$9 2/B:F-l$9 2*G37 “2)  P:E79: (P3) @SQRT(+ E:P27 “2/B: F$9” 2*$B$40 “2 + B:$C$9  “  “  2*E:C27 “2/B:C$9 4*B$4O “2+ B:$C$9 “2/B:C$9  “  P:C79: (PS) @SQRT(+ E: D27 “2/B: D$9 2*$B$4O2+ B:$C$9 2*E:D27 2/B:D$9 F:D79: (P3) @SQRT(+ E: E27 2/B:$9 2*$B$4O2 + B:$C$9 2*E: E27 “2/B:E$9 4*D$4O2+ B:$C$9  F:979: (P3) @SQRT(÷ E:C27 “2/B:C$9” 2*$B$40 “2+ B:$C$9  F:A79: “magnetite  F:G78: (PS) @SQRT(+ E: H26  2/B:I-l$9” 2*$B$40 “2+ B:$C$9 2*E:H26 2/81-4$9” 4’G$4O “2+ B:$C$9 2/B:H$9 2kG36 “2) P:[-178: (P3) @SQRT(+ E: 26” 2/B:l$9 2*$B$4O2+ B:$C$9 2*E: 126” 2/B:I$9 4*H$4O2+ B:$C$9 2/B:I$9 2’)-l36 “2)  “  2*$B$40 “2+ B:$C$9  2+ B:$C$9  P:E78: (F3) @SQRT(+ E: P26” 2/B: P$9  F:D78: (P3) @SORT(+ E:E26 “2/B:E$9 2*$B$4O  “  “  P:C7e: (P3) @SQRT(+ E: D26  2/B:C$9  2/B:D$9 2*$B$4O2+ B:$C$9” 2*E:D26 2/B:D$9” 4*C$40  “  2/B:C$9 2*$B$4O2+ B:$C$9 2*E:C26  F:878: (P3) @SQRT(+ E:C26  ‘  at northern segment of No.3 vein, Silver Queen mine, Owen Lake, central BC  Error propagation of absolute losses & gains in gram (SD at 68% confidence level)  2*C$40) 2+(B;$C$9/B:D$9*C38) 2÷$B38 “2)  F;C85; (F3) +$185*@SQRT((B;D7/B; D$9*$$40y 2+(B;$C$9*B; D7/B;D$9  +  P;G85: (P3) 2+(B;$C$9B; l7/B:l$9 “  2*G$40) “2 + (B;$C$9/B: H$9*G38) “2 + $B38 “2)  2*D$40) 2+(B;$C$9/B:E$9*D39) 2+$B39 “2) 2*E$40) 2÷(B;$C$9/B:P$9*E39) 2+$B39  F; D86; (P3) +$186*@SQAT((B; E6f8;E$9*$B$40) 2+(B;$C$9*B;E8/B; E$9  F; E86; (P3) +$186*@SQRT((B; P8/B: P$9*$B$40) 2÷(B;$C$9*B;F8/B; P$9  +  F:A87; “dTi÷2  F;l86; (P3) 26.98*2/B:$A$8  F;086; (P3)  $166*@ SQRT((B; HO/B; Fl$9*$B$40)2 + (B; $C$9*B; HO/B; H$9 2*G$40) “2 + (B; $C$9/B; Fl$9*G39) “2 + $R39”2) P:H86: (P3) +$186*@SQRT((B; l8/B;l$9*$B$40) 2÷(B;$C$9*B: 18/B; $9” 2*H$0) 2+(B;$C$9/B:l$9*Fl39y 2+$B39”2)  2) F; P86; (F3) +$l86*@SQRT((B;G8/B;G$9*$B$40) 2+(B;$C$9*B:GO/B;G$9 2*P$40) 2÷(B;$C$9/B:G$9*F39) 2+$B39 “2) “  2+(B;$C$9/B:C$9B39)”2+$B39”2) 2*C$40) 2+(B:$C$9/B;D$9*C39) 2÷$B39 “2)  F;C86; (P3) +$l86*@SQRT((B;D8/B;D$9*$B$40) 2+(B;$C$9*B; D8/B;D$9  “  2*H$40) 2÷(B;$C$9/B;l$9*H38) 2+$B38 “2)  “  F;B86; (P3) +$l86*@SQRT((B;C8/B;C$9*$B$40) 2+(B;$C$9*B:C8/B;C$9 2*B$40)  F:A86: “dAI-i-3  P:l85: (P3) 1  “  $185*@ SQRT((; H7/B; H$9*$B$40)2 + (B; $C$9*B; H7/B: F-l$9  F:l-185: (P3) +$185*@SQRT((B; l7fB;l$9*$B$40)  +  P:D65; (P3)  $l85*@SQRT((B;E7/B; E$9*$8$40) 2+(B;$C$9*B; E7/B; E$9” 2*D$40y 2+(;$C$9/B:E$9*D38) 2+$B38 “2) F: E85; (P3) + $185*@ SQRT((B; P7/B; F$9*$$4Q) 2 + (B; $C$9*B; P7/B; F$9” 2*E$40) “2 + (B;$C$9/B: F$9*E38y 2 + $B38 “2) F; P85; (P3) +$l85*@SQRT((;O7/B;G$9*$B$40) 2÷(B;$C$9*B;G7/S:G$9 2*P$40) 2+(B;$C$9/B;G$9*F38) 2-t-$B38 “2)  2*B$40y 2+(B;$C$9/B:C$9*B38y 2-i-$B38 “2)  F; B85; (P3) ÷$l85*@SQRT((B;C7IB;C$9*$B$40Y 2÷(9;$C$9*B;C7/B;C$9  P;A85; “dSiO2  F;H84; (P0) “x2-5  F;G84; (P0) “x3-3d  F;F84; (P0) “x3-1  P;E84: (P0) “x3-4  F; D84: (FO) “x3-5  F:C84: (FO) “x3-7  F:84; (P0) “x4-4  F:A84: ‘Sampleid  F;B83:  P;B82:  F:A82: Table 7-  +  $i87*@ SQRT((B:C9/B:C$9*$8$40)  2 + (B:$C$9*B: C9/B:C$9  2*S$40) “2 + (8:$C$9/B:C$9*840) “2 ÷$840 “2)  +  “  “  +  “  “  B:C1 2/B:C$9 2*B$40y 2+(8:$C$9/S:C$9*B43)2+$843 “2) F: 890: (P3) +$I90*@SQRT((8:C1 2/B:C$9*$B$4O) 2+(B:$C$9* + “ 2*C$40)2 + (8: $C$9/B: D$9*C43) “2 +$843”2) F: COO: (PS) + $I9O SQRT((B: Di 2/8: D$9*$8$40) “2 (B:$C$9*B: Di 2/B: D$9 :Ei 2/B: E$9” 2*D$40) 2+(8:$C$9/B: E$9*D43) 2÷$843 “2) F:D9O: (F3) ÷$190*@SQRT((B: El 2/B: E$9*$B$4O) 2÷(B:$C$9*B  F:A90: “dMn+2  F:189: (P3) 55.85/B:$A$ii  :C1 l/B:C$9 2*B$40) 2+(B:$C$9/B:C$9*B42) 2÷$B42”2) F:889: (PS) ÷$I89*@SQRT((8:Ci i/S:C$9*$B$40) 2÷(B:$C$9*B B:Dl l/B:D$9 2*C$40) 2+(B:$C$9/B:D$9*C42) 2.4842” 2) F:C89: (P3) + $189*@SQRT((8:Dl l/B:D$9*$B$40) 2+(B:$C$9* B:Ei i/B:E$9 2*D$40y 2i (B$C$9/B:E$9*D42) 2+$B42 “2) F: D89: (F3) +$189*@SQRT((B:El l/9:E$9*$B$40) 2+(B:$C$9* B:Fl l/B:F$9 2*E$40) 2+(B:$C$9/B:F$9*E42)2+$B42 “2) F:E89: (F3) +$189*@SQRT((B:Fl l/8:F$9*$B$40) 2+(B:$C$9* B:Gl l/B:G$9 2*F$40) 2+(B:$C$9/B:G$9*F42) 2+$842”2) F:F89: (PS) ÷$189*@SQRT((B:Gl l/B:G$9*$B$40) 2+(B:$C$9* B:Hl l/B:H$9 2*G$40) 2+(B:$C$9/B:H$9*G42)A 2-4842” 2) F:G09: (F3) +$189*@SQRT((B: Hi i/B:H$9*$B$40) 2+(B:$C$9* 2+(B:$C$g*B:Il i/B:I$9 2*H$40) 2+(B:SC$9/B:I$9*H42) 2+$B42 “2) F:H89: (F3) +$189*@SQRT((B:Ii 1/B:$9*$B$40)  F:A89: “dFe+2  F:188: (F3) 5585*2/B:$A$i0  F: B88: (P3)  0) 2÷(B:$C$9/B:C$9*B41)2+$B4i “2) $188*@SQRT((B:C1 0/B:C$9*$B$40) 2+(8:$C$9*8:C10/B:C$9 2*B$4 B:Di 0/B:D$9 2*C$40) 2÷(B:$C$9/B:D$9*C41)2÷$B4l “2) F:C88: (P3) +$188*@SQRT((B:Dl 0/B: D$9*$B$40) 2+(B:$C$9* + (B:$C$9/B:E$9*D4l) 2+$B41 “2) F:D88: (F3) +$188*@SQRT((B: El 0/B:E$9*$B$40) 2+(B:$C$9*B:ElO/B:E$9 2D$4O)” 2 2*E$40) 2 +(B:$C$9/B:F$9*E4l) 2+$841 “2) :Fl F: E88: (P3) +$188*@SQRT((B: Fl 0/B:F$9*$B$40) 2 +(B:$C$9*B 0/8: F$9 :G1OIB:G$9 2*F$40y. 2÷(B:$C$9/B:G$9*F4l)A 2+$B4l “2) F: F88: (PS) + $188*@SQRT((B:G1 0/B:G$9*$8$40) 2 +(B:$C$9*B Hl0/B:$9 2G$40y’ 2+(B:$C$9/B: I1$9*G41) 2÷$84l “2) F:G88: (P3) + $188*@SQRT((B: Hl 0/B:H$Q*$B$40) “2 ÷(B:$C$9*8: 2*H$40) 2÷(B:$C$9fB:I$9*H4i) 2.4841 “2) B: F:H88: (P3) +$188*@SQRT((9: 10/B: I$9*$B$40) 2+(B:$C$9* I10/8:I$9  F:A88: “dPe+3  F:187: (P3) 47.9/B:$A$9  F: C87: (F3)  D$9*C40) 2 + $840 “2) $187*@ SQRT((8: D9J8: D$9*$8$40) “2 + (9:$C$9*B: D9/B: D$9 2*C$40) “2 + (B: $C$9/B: :E$9*D40) 2+$940 “2) B:E9/B:E$9 2*D$40) 2+(B:$C$9/B F: D87: (F3) ÷$I87*(SQRT((B: E9/B:E$9*$B$40y 2+(B:$C$9* F$9*E40) 0)2 “2+ $840”2) 2*E$4 + (B: $C$9/B: F: E87: (F3) + $187*@ SQRT((B: F9/B: F$9*$B$40) 2 + (B: $C$9*B: F9/B: F$9 :G$9*F40) 2+$840” 2) B:G9/B:G$9 2*F$4O) 2+(B:$C$9/B F: F87: (P3) +$I87*@SQRT((B:G9/B:G$9*$B$40) 2+(B:$C$9* (B:$C$9*B: H9/B: I-1$9 2*G$40) “2 + (B: $C$9/8: H$9*G40) 2 + $840 “2) F: G87: (F3) + $107*@SQRT((B: Hg/B: H$0*$B$40) “2 + *$B$4Oy 2÷(B:$C$9*B:19/B:I$9 2*H$40) 2+(B:$C$9/B:I$9*H40) 2+$840” 2) F:H87: (F3) +$I87*SQflT((B:I9/2,:I$9  F: 887: (F3)  “  ‘  “  ‘  “  “  “  46) 2+$B46 “2) $4O) 2÷(B:$C$9*B:Cl 5/B:C$9 2*B$4Oy 2i(B:$C$9/B:C$9*B F: B93: (P3) ÷$I93*@SQRT((B:Cl5/B:C$9*$B 46)2 + $B46 “2) B$4O)2 + (B:$C$9*B: Dl 5/B: D$9 2*C$4O)2 + (B:$C$9/B: D$9*C F: C93: (P3) + $193*@ SQRT((B: Dl 5/B: D$9*$ E$9*D46) “2 4-$846”2) + (B:$C$9*B: El 5/B: E$9 “ 2*D$40) “2 + (B: $C$9JB: F: D93: (P3) + $193*@ SQRT((B: El 5/B: E$9*$B$40) “2 2 + (B:$C$9*B: P15/B: P$9” 2*E$4O)2 + (B:$C$9/B: F$9*E46) “2+ $B46 “2) F: E93: (P3) + $193*@ SQRT((B: P15/B: P$9*$B$4O) 4O) 2 +(8:$C$9*B:Gi5/B:G$9 2*P$4O) 2÷(B:$C$9/B:G$9*F46) 2+$B46”2) F: P93: (P3) +$193*@SQRT((B:G1 5/B:G$9*$B$ 46) 2+$946 “2) B$4O) 2+(B:$C$9*B: Hi 5/B: H$9 “ 2*G$40) 2+(B:$C$9/B:H$9*G F:G93: (P3) +$193*@SQRT((B: Hi 5/B: H$9*$  F:A93: “dNa+  P:192: (P3) 40.08/B:$A$14  “  “  :C$9*B45) 2+$B45”2) 9*$B$4Oy 2 +(B:$C$9*B:Cl4/B:C$9 2’B$4O)” 2+(B:$C$9fB P: B92: (P3) +$192*@SQRT((B:C1 4/B:C$ C45) 2+$B45 “2) B$4O) 2+(B:$C$9*B: Dl 4/B: D$9 2*C$4O) 2+(B:$C$9/B:D$9* P:C92: (F3) +$192*@SQRT((B: Dl 4/B: D$9*$ B45 2) 4O) 2+(B:$C$9*B:El 4/B:E$9 2*D$4O) 2+(B:$C$9/B:E$9*D45)2+$ F: D92: (P3) +$I92*cSQRT((B:El 4/B:E$9*$B$ 45) “2 + $B45 “2) B$4O)2 + (B: $C$9*B: P14/B: F$9” 2*E$40) “2 + (B:$C$9/B: F$9*E F: E92: (P3) + $192*@SQRT((B: P14/B: P$9*$ 45) “2 +$B45”2) 40) 2 + (B: $C$9*B:Gl 4/G:G$9 2*P$4O) “2 + (B: $C$9/B:G$9*P F: P92: (P3) i$l92*@ SQRT((B: Gi 4/G:G$9*$B$ 45y 2+$845 “2) $40) 2+(B:$C$9*B: Hi 4/B:H$9 2*G$4Oy 2+(B:$C$9/B:H$9*G P:G92: (F3) +$192*@SQRT((B: Hi 41B:H$9*$B )2÷$B452) $4O) 2+(B:$C$9*S:114/B:l$9 2’H$4O)”2÷ (B:$C$9/B:J$9*H45 F: H92: (P3) +$192*@SQRT((B: l14/B1$9*$B  F:A92: “dCa+2  P191: (F3)24.31/B:$A$13  44)Is 2+$B44”2) B$4O) 2÷(B:$C$9*B:Cl3/B:C$9 2B$4O)” 2+(B:$C$9/B:C$9*B F:B91: (P3) ÷$191 *@SQRT((B:C13/B:C$9*$ *C44) 2+$B44 “2) 4O) 2+(B:$C$9*B: Di 3/B:D$9 2*C$4O)2÷(B:$C$9/B:D$9 P:C91: (P3) +$191 *@SQRT((B.Dl 3/B:D$9*$B$ 44) 2+$B44 2) B$4Oy 2+(B:$C$9*B: El 3/B: E$9” 2*D$4O) 2+(B:$C$9fB:E$9*D F: D91: (P3) +$191 *@SQRT((B: El 3/B: E$9*$ 44) 2+$B44 “2) 40)S 2+ (9:$C$9*B:F13/B:F$9 2’E$4O)” 2+(B:$C$9/B:F$9*E F: E9l: (P3) +$l91 *@SQRT((B: Fl 3/B:F$9*$B$ P44) 2+$B44 “2) 4O) 2+(B:$C$9*B:Gl 3/B:G$9 2*F$4O) 2+(B:$C$9/B:G$9* F:F91: (P3) + $191 *@SQRT((B:Gl 3/B:G$9*$B$ 44). 2+$B44 “2) 40) 2 +(B:$C$9*B:Hl 3/B:H$9” 2*G$4O) 2+(9:$C$9/B: H$9*G F:G91: (P3) +$I9l *@SQRT((B: Hi 3/B:H$9*$9$ ) $4O) 2+(B:$C$9*B: Ii 3/B:l$9” 2*F1$4O) 2 + (B:$C$9/B:l$9*H44 2+$B44 “2) F: H91; (P3) +$191 *@sQRT((B. 113/B: l$9*$B  P:A9l: “dMg+2  P:190: (P3) 54.94/B:$A$12  +  2*E$40)2 + (B: $C$9/B: F$9*E43) 2 + $B43 “2) $I90*@ SQRT((B: El 2/B: P$9*$B$40) “2 + (8:$C$9*B: P12/B: F$9 F43) 2+$B43 2) 4Oy 2+(B:$C$9*B:G1 2fB:G$9” 2*F$4O) 2+(B:$C$9/B:G$9* F:F90: (P3) +$I9O*SQRT((B:G1 2/B:G$9*$B$ G43y 2÷$B43 “2) 9*$B$4Oy 2+(B:$C$9*B: Hl2/B:H$9 2*G$4O) 2+(B:$C$9/B:H$9* F:G90: (P3) +$l9O*@SQRT((B:I1l 2/B:H$ 4O) 2÷(B:$C$9*B: 112/B:l$9” 2*H$4O) 2+(B:$C$9/B:l$9*l143) 2+$B43 “2) P:H90: (P3) +$190*@SQRT((B:I1 2/B:l$9*$B$  F: Ego: (P3)  +  +  +  F: C94: (F3)  F: D94: (P3)  F: E94: (P3)  F: P94: (F3)  $194*@ SQRT((B:Gl 6/B:G$9*$B$40)  2)  2 + (B:$C$9*B: Gi 61 B:G$9 A2*F$40) “2 + (8: $C$9/B:G$9*F47) “2+ $847” 2)  2 + (B: $C$9/8: F$9*E47)  2 + $847  2)  2+ $847 “2)  A  2 +$847 “2)  2 + (B:$C$9/B: D$9*C47)  2*E$40)  ‘  2*C$40)  $194*@ SQRT((B: P16/B: F$9*$B$40) “2 + (B:$C$9*B: Fl 6/B: F$9  (B:$C$9*B: Dl 6/B: D$9 2*D$40)2 + (B: $C$9/B: E$9*D47)  2 +  $194*@ SQRT((B: El 6/B: E$9*$B$4Oy 2 + (B:$C$9*B: El 6/B: E$9  $194*@SQRT((B: Dl 6/B: D$9*$B$40)  ‘  ‘S  2*H$4O) 2+(B:$C$9/B: I$9*FI47)F 2+$B47 ‘2)  +  $195*@SQRT((B: El 7/B:E$9*$B$40)  2+(E:$C$9*B: El 7/B: E$9  2*D$40)’S 2+(B:$C$9/B: E$9*D48)S 2÷$B48 “2)  2+(B:$C$9/B: D$g*C48y5 2+$948”2)  +  ‘5  2+(B:$C$9/B:I$9*H48)’5 2+$B48”2)  2*C$40y5 2+(B:$C$9/B: D$9*C49)  “  2+$B49 ‘52)  F:A97: ‘SdCO2  P:196: (P3)1  F: R96: (F3) ÷$196*@SQRT((B:1l8/B: I$9*$8$40)’5 2÷(B:$C$9*B:Il 8/B: $9’ 2*H$40)’S 2+(B:$C$9/B:I$9*IF49)A 244849” 2)  2)  P:G96: (P3)  2 +$B49  2*G$40) ‘2 + (B: $C$9/B: H$9*G49)  $196*@ SQRT((B: F—Fl 8/B: IF$9*$B$4O)2 ÷ (B:$C$9*B: I—Fl 8/B: H$9  +  F: F96: (P3)  “  2*F$40)2 + (B:$C$9/B:G$9*F49) “2 + $849 “2)  $196*@ SQRT((B: Gl 8/B:G$9*$B$40) “2 + (B:$C$9*B:Gl 8/B:G$9  +  2 + $849 “2)  $196*@SQRT((B: Fl 8/B: F$9*$B$40) “2 + (8:$C$9*B: P18/B: F$9” 2*E$40)A2 + (B:$tD$9/B: F$9*E49)  +  2*D$40)5 2+(B:$C$9/B:E$9*D49)’ 2-44849 “2)  ‘S  F: E96: (F3)  F: D96: (F3) +$196*@SQRT((B: El 8/B:E$9*$B$40)5 2+(B:$C$9*B: E18/B: E$9  F:C96: (P3) +$196*@SQRT((B:Dl 8/B: D$9*$B$4Oy 2+(B:$C$9*B:D1 8/9:D$9  5 2+(B:$C$9*B:Cl 8/B:C$9” 2*B$40)’5 2+(B:$C$9/B:C$9*849y5 2+$B49 “2) F: 896: (P3) +$196*@SQRT((B:Cl 8/B:C$9*$B$40y  F:A96: “dF-2O  F:195: (F3) 3097*2/B:$A$17  5 2 +(B:$C$9*B: Ii 7/B:I$9’5 2*H$40) F:H95: (PS) +$195*@SQRT((B:Il 7/B: I$9*$B$40y  2*G$40)’5 2+(B:$C$9/B:FI$9*G48) 2+$B48 “2)  $195*@SQRT((B:Gl 7/B:G$9*$B$40)’5 2+(B:$C$9*B:Gl 7/B:G$9’5 2*P$40)’S 2+(B:$C$9/B:G$9*F48) 2+$B48”2)  F:G95: (P3) +$195*@SQRT((B: F-Il 7/B:F1$9*$B$4O) 52+(B:$C$9*B: F-Il 7/B:F-l$9  F: P95; (P3)  F: E95: (P3) +$195*@SQRT((B: Fl 7/B: F$9*$B$40y5 2+(B:$C$9*B: Fl 7/B: F$9” 2*E$40)’S 2+(B:$C$9/B:F$9*E48) 2+$B48 “2)  F:D95: (P3)  ‘5  2+(B:$C$9*B:Cl 7/B:C$9” 2*B$40)A 2+(B:$C$9/B:C$9*B48y5 2+$848 “2)  2+(B:$C$9*B:Il 6/B:I$9  F:C95: (P3) +$F95*@SQRT((S: Dl 7/B: D$9*$B$40)’S 2+(B:$C$9*B: Dl 718:D$9” 2*C$40)  F: 895: (F3) +$F95*@SQRT((B:Cl 7/B:C$9*$B$40)  F:A95: “dP+5  F:194: (P3) 3909*2/B:$A$16  F: H94: (PS) ÷$194*@SQRT((B:Il 6J8:I$9*$B$40)  F:G94: (F3) ÷$I94*@SQRT((B:IIl 6/B:II$9*$B$4O) 2+(B:$C$9*B:FIl6/B:H$9A 2*G$40)A 2+(B:$C$9/B:I_F$9*G47)A 2+$B47 “2)  +  2)  2*B$4O) 2+(B:$C$9/B:C$9*B47) 2+$947  2*[1$4Oy 2+(B:$C$9/B:I$9*H46y 2+$846  F: B94: (F3) +$I94*@SQRT((B:Cl6/B:C$9*$B$4O) 2÷(B:$C$9*B:Cl6/B:C$9  P:A9’l: “dK+  R193: (F3) 22.99*2/B:$A$15  F:H93: (F3) +$193*@SGRT((B:ll 5/B: I$9*$B$4O) 2÷(B:$C$9*B:Il 5/B:I$9  2*D$40y. 2+(B:$C$9/B:$9*D5O) 2+$B50 “2)  F: D97: (P3) +$197*@SQRT((B: E19/B:9$9*$B$4O) 2+(B:$C$9*B:Ei 9/B:E$9  + ‘S  2+(B:$C9*B:li9/B:t$9 ‘S  2kH$40y 2+(B:$C$9/B: l$9*H50)’S 2+$B50 “2)  2*G$4OyS 2+(B:$C$9/B: H$9*G50)2+$B502)  ‘S  2*G$40)’S 2÷(B:$C$9/B:H$9*G51)5 2+$B51 “2)  2F$40)’S 2+(B:$C$9/B:G$9*F51) 2+$B51 “2)  +  C92/40,08 + C93/46 + C94/78.i 7 + 5/62*C95)  892/40.08 + B93/46 + B94/78. 17 + 5/62*995)  +  P199: (F3) 1  F: H99: (P3) 1 6*(3/54*H86 + 2/47.9*H87 + 3/ill .7*H88 + H89/55.85 + H90/54.94 + H91 /24.31  +  G93/46 + G94[78. 17 + 5/62*G95) H92/40.08 + H93/46 + H94/78. 17 + 5/62*H95)  + G92/40.08 +  P92/40.08 + P93/46 + P94/78.17 + 5/62*F95)  F: G99: (P3) 1 6*(3/54*G86 + 2/47.9*G87 + 3/111 7*G88 + G89/55.85 + G90/54.94 + G91 /24.31  F: P99: (P3) 1 6*(3/54*P86 + 2/47,9*F87 + 3/111 .7*F88 + P89/55.85 + P90/54.94 + P91/24.31  F: D99: (P3) 1 6*(3/54*D86+2/47.9*D87+3/i 11 .7*D88+ D80/55.85+ D90/54.94 + D91/24.3i ÷ D92/40.08+D93/46÷ D94/78.1 7+5/62*D95) F: E99: (P3) 1 6*(3/54*E86÷2/47.9*E87+3/l ii .7E88+ E89/55.85+ 990/54.94+ 991/24.31 + 992/40.08+ E93/46+ E94/78.17÷5/62*E95)  F: 099: (P3) 1 6*(3/54*086 + 2/47.9*087 + 3/111 7*088 + 089/55.85 + 090/54.94 + 091/24.31  +  2’H$40)’S 2 +(9:$C$91B:I$9*H5i )‘S 2+$951 “2)  “  2*E$40). 2+(B:$C$9/B:F$9*E51)’S 2+$B51 “2)  F: 899: (F3) 1 6*(3/54*B86 + 2/47,9*987 + 3/ill 7*B88 + B89/55.85 + B90/54.94 + B9i /24.31  F:A99: “d0  F:l98: (P3) 1  F H98: (P3) @SQRT((B: 120/B: l$9*$B$40)’S 2+ (B:$C$9*B:120/B:i$9  F:G98: (PS) @SQRT((9: H20/B: H$9*$B$40)’S 2+(B:$C$9*B:H20/B:H$9  F: P98: (P3) ©SQRT((B:G20/B:G$9*$B$40)’S 2+(B:$C$9*B:020/B:G$9  F: E98: (F3) @SQRT((B: P20/B: F$9*$B$40)’S 2+(B:$C$9*B: F20/9:F$9  F:C98: (F3) @SQRT((B: D20/B: D$9*$B$40) ‘S2+(B:$C$9*B:D20/B: D$9” 2*C$40)’S 2+(B:$C$9/B: D$9*C51)’S 2+$B5i “2) F: D98: (P3) @SQRT((8:E20/B: E$9*$B$40)’S 2+(9:$C$9*B:E20/B: E$9 2*D$40)’S 2+(B:$C$9/B:E$9*D5i)’S 2+$B5i “2)  2+(B:$C$9*B:C20/9:C$9 2*B$40)’S 2+(B:$C$9/B:C$9*B51)’S 2+$B51 “2)  $197*@SQRT((B: 119/B: l$9*$B$40)  F: 998: (P3) @SQRT((B:C20/9:C$9*$B$40)  F:A98: ‘SdS  F:197: (F3) 1  F: H97: (P3)  F:G97: (F3) +$197*@SQRT((B: Hi 9/B:H$9*$B$40) 2+(B:$C$9*B: Hi 9/B: H$9  F: F97: (F3) ÷$197*@SQRT((B:G1 9/B:G$9*B$40y 2 +(B:C$9*B:Gi9/B:G$9 2*F$40) 2+(B:$C$9/B:G$9*F50) 2+$950”2)  F: E97: (P3) +$197*@SQRT((B: Fl 9/B:F$9*$B$4O) 2÷(B:$C$9*B: P19/B: F$9 2*E$4O) 2+(B:$C$9/B:F$9*E50)Fs 2+$B50 “2)  “  2*C$4Oy 2÷(B:$C$9/B:D$9*C5Oy2÷$B5O 2)  F:C97: (F3) ÷$197*@SQRT((B: Dl 9/B: D$9*$B$4Oy 2+(B:$C$9*B:D1 9/B:D$9  2)  2*B$4Oy 2+(B:$C$9/B:C$9*B5O) 2+$B50  F: 997: (P3) +$I97*SQRT((B:C19/B:C$9*$B$4O) 2 +(B:$C$9*B:C1 9/B:C$9  Appendix D. Diagrams of Alteration Evaluation, Silver Queen Mine  246  x  x  (Xl +X2)12  (Xl ÷X2)/2  s XRF analyses. Figure 6-2a. Error of major components estimated by sample duplicate of  (Xl +X2)/2  (Xl +X2)/2  x  >$  c’J  0.03  0,1  0.2  0.3  0.4  PC I  0.5  Cd =  1  1  0i848  So=0.09 k = 0013  N*ZO  I  1.5  1.5  (Xl +X2)/2  (Xl +X2)/2  I  2  C  3,5 3  I  C  Figure 6-2b. Error of major components estimated by sample duplicates of XRF analyses.  (XI +X2)/2  (Xl +X2)/2  ><  0.5  0.7  4  50th  90th  99th  4.5  x  x  x  (Xl÷X2)/2  (Xl +X2)12  Figure 6-2c Error of ferrous iron and voJatile components estimated by measurement d u p Ii cat es.  (Xl i•X2)/2  (Xl +X2)/2  x  x  C”  (Xl +X2)12  (Xl +X2)/2  Figure 6-2d. Error of trace elements estimated by duplicates of XRF analyses,  (Xl +X2)/2  (Xl 4-X2)12  ><  >  0.05  Di  0.15  0.25  0,25  0.4  0.45  0  [  0.5  1  2  (Xl +X2)/2  1.5  0 0  0  2.5  0  3  60th  90th  3.5  01  0.2  0.3  0.4  0.5 =  0.c17  0.5  1  k = 0.cD75 Cd = 0.1421  So  1.5  0  (Xl +X2)12  2  (Xl +X2)!2  0  3  00  2.5  Figure 6-3a. Error of major components estimated by measurement duplicates of XRF analyses  So0.042 k=0.023 Cd = 0.0884  [Ft203  (Xl +X2)/2  >  c’J  3.5  50th  99th  Lt  x  ><  Figure 6-3b. analyses.  Frior of  (Xl +X2)/2  (Xl +X2)/2  0  1  L1  Li)  OS  0  i  k=0.YD3 = 0.0402  So = 0.02  -.  15  2  (Xl +X2)/2  2.5 3 (Xl +X2)/2  C  maor components estimated by measurement duplicates of XRF  x  0.02  0.04  0.06  0,08  01  0.12  0.14  016  o. is  3.5  4  0  4.5  50th  90th  99th  15.6  1.1  —  propylitic  ,2-5  ——  .1.7  ,i 4  .1-SD  0  ‘  ‘alteration outer\ alteration inner ‘ envelope envelope  \  vein  propytitic microdiorite  .105 06 .10613 ,l03 5.3d ,l64 il-I 0 I 3d .10.5 xml 0060 till .10-Id .104 abS xli .10  .13  alteration oute-. envelope  .1.8  Central segment of the No. 3 vein  —  t  .1-3d  0  or gain  13-2  t  absolute loss  .3-2  0  C  43-I  alteration envelope  \  vein  43.4  8  s  .3.7  propylitic andesite \  .4.4  Northern segment of the No. 3 vein  t  0  8  1:  20  .  13.561-8  -20  .3-9 .5 II  .5-I  DAIS-S  .52  alteration inner envelope  \ \..  vein  DA63-SD  .5.3  OAIS-4  DA63-tD  DAIS 3D  0.563-3  .5 9  .54  x3 5  .3-5  Southern  \  456  9SId  ,34  x54  propylitic’s. sericitie microdiorite alteration  .5-Id  segment of the No.3 vein  absolute loss or gain  uncertainty at 95 % confidence level  propylitic microdiorite  DAIS-I  jjzz..zz:z.zzzz  El  DA63-ID  Switch Back vein  ‘alteratIon outer envelope  0A63-4  alteration outer envelope  alteration inner envelope  veils  0A65 6  : :zjj  50  .15  absolute loss or gain  Figure 6-5b. Absolute losses and gains of A1 3 from four alteration profiles at the Silver Queen mine, central British Columbia. The 0 2 blank part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) and a range representing ± 2 standard deviations.  0  0  8  absolute loss or gain  uncertainty at 95 % confidence level  uncertainty at 95 % confidence level  25-0  xi-)  2 z3  230.3  2102  t0tiytiii  1131220.52  1103d 004 005 00.6 xI06D 00-3 xio-3d 00-4 2105 x10-6 xi0-Oi)  -.  x3-5  S 05  alteration outer\  envelope  ‘—. alteration outer’ alteration inner— envelope envelope  \  vein  —  propylitic noicrodiorite  ii.  xi-)  xJ.2  alteration envelope  0-I  C  21-3D  .  Vet is  xs-2  a.  xi)  23 2  a.  C  0  S  xi-)  propylitic andesite  0.1  Nortltcin scgmcnl of the No.3 vein  95 % contidcrici level  absolute loss or gain  uncertainty at  \  DA6O-$D 0.563 5  03-i)  -  \  x5-i  envelope  --  xS-2  x3-3  -  22.563-1  0.563-SD  bA6i-s  x5-4  -  ....  DAIS-)  in  niicrodiorite  propyiitic  0.563-i  x5-4  25-0  -  envelope  xS-$  -  xS-6  -  x3-8  alteration  2$-)  sericitic  -  propylitic’  x3-6d  microdiorite  x3-6d  Southern segment of the No.3 vein  DA6S  Switch Back vein  —alteration outer envelope  DA63-4  alteration outer  alteration inner envelope  cciii  0.563-6  alteratioss inner  veil)  x3.0  0.5658  I  E absolute loss or gain  uttce rtai sty at 95 % confide nec level  3 from four alteration profiles at the Silver Queen mine, central British Columbia. The 0 2 Figure 65c. Absolute losses and gains of Fe blank part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) and a range representing ± 2 standard deviations.  a.  C  V  2  131  Northern segment of the No. 3 vein  31.  uncertaiitty at  95% confidence level  .1  envelope -  envelope  alteration outer alteratton inner envelope  \  vein -...  microdiorite  propylitic  .10.6 .00 6D ,I0.3 .10 3 .10-Id .00.6 .30 -4 .1-24 .3.0 l.2 .10-5 .30-6 .1060 .103 £10.34 .304 £10.2 £32 iISD 13.3 £10.1  3 alteration oute-  1 1  Central segment of the No. 3 vein  a.  0  pro1,ylilic andosito  0  .  0 a.  a  c absolute loss or gain  alieralion envelope  .3-6.4.3.2,3.34,2.3 .3.1 .12 xii .1 5  llrOPYtiiiC aiiolesiln  £44  polo  % coafideoce tenet  a  1:  -is  absotule tool or  uncertainty a195  :  .5-10  envelope  .5-3  0*03-  DA63.33  aS-a  propylitic microdiortte  DA63-l  loss or gain  uncertainty at 95 % confidence level  a..  DAli. II)  n5-4  alteration outer  .3-5  .3.3 .5-6  .5-64  aS-i .3-6  propylitic\ sericitic microdiorite alteration  aS 64  Soutltern segment of tlte No.3 vein  E  envelope  0*62.1  Switch Back vein 0*63-3D  a. alteration outer  0A634  envelope  inner  3*63-3  a  .5-2  \.  .5- I  envelope  alteratioti inner  \  aS-P  vein  01*61-3D  alteration  veil  IiAs1 6  absolute toss or gain  DA65-  LJ  Juncertarntyat5%conridencelevei  11  Figure 6-5d. Absolute losses and gains of FeO from four alteration profiles at the Silver Queen mine, central British Columbia. The blank part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) and a range representing ± 2 standard deviations.  0  C  L.J  vettt  iz  veitt  propyti tie unilvoite  S  cj  al-S  gala  Central segment of the No 3  Oilier  envelope  alteration liner envelope  alteration outor  \.  nticroclioriie  peopylttic  .10-i .10.5 .iO.3d .10.4 .10-5 .106 410 00 ,i .4 .11 0 .2d vi -6 *106 .1060 .105 .10-2 .10.3 hOld .10.4 *1.2 *101 .1-3 .1-50  alteration envelope  .1-8  absolute loss or  Jaecertaioty at 95% confidence level  ‘V  alteration envelope  an-S  0  ‘.  .3-3  Northern segment of the No.3 vein .10x3.4x3.tes.Sd .32 . .3.1 e31  propylilic attdosite  4.4  absolute loss or gain  oncortainlyal9t%coofidencelovel  ‘a  ‘V  : ..:  -  —  vs  r .0  S  -  0  S  I  06  0:  \  \  .  ttAO3-5i) 0A63-5  gaiu  .510  43.2  alter  \:.  .5-i  :  \..  ttA6l.4  % coufidettce bud  .5-5  53-6  43.53  el-S  propylitic \\ mkrediorile  .5-5*5-ed  sericilic alteration  45.8  Southern segment of the No.3 vein  alteration outer envelope  454  0195  toss or gale  unteeltoinly atnotate  necrodiorite  0A03-3 0A01-l DAOS-OD DA63-ID 0,66330  . -.. alteration ouler envelope  DAO3-4  .5-355-4  alteralioa toner envelope  vein  DAOt 6  alteration olive lope  vein  53.9  0,603-8  absolale loss or  witch Back vein  i••ii  j nncerlainly 6195 % confidence level  !I  Figure 6-5e. Absolute losses and gains of MnO from four alteration profiles at the Silver Queen mine, central British Columbia. The blank part of each bar includes the mean estimate (a horizontal irnagii]uy line through the centre of the blank bar) and a range representing ± 2 standard deviations.  0  0,  S  r,  at  Cl-S  al-C  -to  \.• olin raiivli eiivelolio  at I  at 2  .  propyitlic aiidnnjte  Cit  alteration inner envelope  U alteration ootor envelope  propylitie niicrodiotiie  I  -..  asia  aOl  alteration inner envelope  attO  cOt  eO.4 aS-S  elternilen outer envelope  aS-C  aSS  aS-6  aS-ed  propylitic  oticrodiorite  nO.?  sericitic alteration  CS-S  No.3 vein  propylitic uticrodiorite  cO-ed  Sonlhern segment of the  jh  alteration outer envelope  uueoriainay at 95 % confidence level  \ \  on ii  eS.9  LI  alteration totter etivelope  Vt Ill  Figure 6-5f Absolute losses and gains of MgO from four alteration profiles at the Silver Queen mine, central British Columbia. The blank part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) and a range representing ± 2 standard deviations.  --  OO.t elt-td atii.4 i0-S 00-6 atll.6t7 ait-l et-2d ,t i ci0-t ait-t alt-Id alt 4 alt-S at 0.6 alt-Or) cit-i al-2 cit  alteration outer envelope  at.?  itropylitic aedesite  ,t 7  cc  Lit  lvi  ‘0  L)  0  vS 1  —.  ,00d  .2-5  irsIltylilic suclasslo  vi->  of the No 9 vt_in  \.  i...  alteration inner  envelope  0\  -  envelope  alteratlois outer  ‘-.  microdiorile  proltylitic  0.5 itO-S .10 61) 004 .10 3d 00 4 vi l 00. .1.22 vi .4 vt6 .50 6 .1061) t 0.3 .10 2 .10 3 ,I0.Sd .10.4 .10.1 .1.0 .1-2 .1-SD  alteration outer envelope  .1.0  (‘e nlral segroc 61 of Ito No. 3 vei it  .IPiIHflIE*H  j obsolute loss or galls  I I  Northern vegment  e cttvelo , alteration 1  Eluncertninty at 95% confidooce level  .5-8  Ii  ifl[9 I!l I’I I ti I°I  1  .06.34,02 .3 I .3-5  .  propylitic atidesite  i”  fl.  2  6 ‘N  tiA6i SD  envelope  .0-I  alteration inner envelope  \ \  Ye it,  .3-In  loss or gals  \.  .5 2  is-S  vein  envelope  -  ‘  P  rnicrodioute  propyliiic  .04’  .55  .60  .566  .366  -  nsiriodiorise  \. propylisir  .56  sericitic alteration  .38  Soulhc no scgerctsl of hoe NI) 3 vein  alteration outer envelope  .5-4  ck B s 5  DAebB DA6J 3 t)A63 2) 0A63 ID 0A61 315  Silch  Ipj  vb,olule  95 %  .  DA6O 4  alteration outer  DAIS a  confidence level  2)063 5  alit raison loller  0A63 6  I ccl  HH  cairliltriac  lute lc,si Or sin  liily 6195  uncertainty at  tAO> B  abs  uiscvrs  Columbia. The Figure 6-5g. Absolute losses and gains of CaO from four alteration profiles at the Silver Queen mine, central British and a range blank part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) representing ± 2 standard deviations.  ‘0  0  9  0  9115  at 95 % cotttidv,ico lava  abvolusv loss or  IlIl005lililily  ‘  -0  a3-S  .  at-I  at-S  alteration envelope  vein  4 at-  at 2  at  td  c2.$  3  vein  propylitie audesito  at-S  Northern segment of the No. 3 vein  %  bA6t-sri  DAunt  envelope  alterattoti toner  vein  DM5-n  at-S  -.  Central segment of the No.  -.  alteration inner eovelope  alwratiao outer envelope  S  \\ propylitic tnicraelinrite  xIs t ala-Sd 00-4 xIS-S 00-6 als-6D t-n 0-4 xl 2d 0- I’ 00 ate-S cIO-O cm-el) al-S al-S clOt ala-S clOt ate-3d ,tO-4 at -SD  alteration outer envelope  at-a  level  .  DA63-4  level  \  at-tO  envelope  ct-S  \\  at-I  alteration inner  vein  aS-S  absolute  at-s  tsMt-to  DA6O-.ttt  aS-4 cS-S  allerntioe outer envelope  a$-4  cS-S  ‘v  cS-6  -  aS-6d  N  nmicrodiorite  \  at-S  -  alteration  sericitic  cs-n  vein  n,icrodiorite  propylitic  DA6S-l  No.3  propylilic  et-6d  Southern segmenl of the  \  DA6t-ID  Switch Back vein  DAO5-3  -alterastos outer envelope  t)AOO-4  confidence  uncertainty at 95% confidence level  DA6t-S  fl  utOS  IHIIHiIHIz: I ininty  absolute loss or gain  unce I  IUHi11IUI1OHiEz 1 ILl]  at-S  0195% confidence  absolute toss or gain  cjuecertatnty  J  aSs  propylitie undesite  c4.4  LJE  uhf -  loss or gain  E  Figure 65h. Absolute losses and gains of Na 0 from four alteration profiles at the Silver Queen mine, central British Columbia, The 2 blank part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) and a range representing ± 2 standard deviations.  z  0  E  bsolu to  noes rlviuty at 95 % confidence level  Northern segment of the No.3 vein  envelope envelope  alteration inner  vein  envelope  alteration outer  naicrodioeite  propylitic  ta- on-3d 00-4 ,in-$ in- eo.eb i -6 rt-4 0-3d ri-i i3cit st-SO ci .3 st-i clOt eta-i itO-S ate-3d 033-4 riO-S at 0-n sin-un  alteration oatee  -S  absoluto loan or pain  U U  peopylitic andenite  Central segment of the No. 3 vein  iiIh  uncertainty at 95% confidence level  •  ..,  0  0  P  \  eS-tO  \  eS-i  envelope  alteration letter  vein  eS-S  aS-i  e$-3  eO-4 55-5  alteration Outer  a3-4  DAna-3D  eS-S  \  eS-6  5S-Oit  \  aSS  DA63-1D  propylitic nilerodiorite  eS-ed  alteration outer envelope  DA63 4  envelope  DA63-5  alteration inner envelope  vein  DAO3.n  sericitic alteration  55-S  peopylitic  naicrodiorite  Figure 6-5i. Absolute losses and gains of K 0 from four alteration profiles at the Silver Queen mine, central British Columbia. The 2 blank part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) and a range representing ± 2 standard deviations.  0  ii  alteration envelope  e3.6t.43.Ze3.3di2.5 3t 3 2 Cciii  propylitic andesitn  4.4  0  0  H  P  absoluterossoigarn  P  3  uncertaintY at 95 confidence level  t  .01  .100  nOt  (116  propylitic uridesile  e4.4 ntS  C  et.5  .15.2 5.5d  Central segment of the No. 3 vein  —  propylitie andrsite  sOt  [DODD  eOn  000010100  alteration toner envelope  vein alteration outer envelope  I500pylitic nticrodiorioe  .2nd et.t tOt ,tO.3 stOOd to.4 uet .ts.e .io.OD st.4 dO sinS ,lOu .20.60 nI 2 .10-i duO .10-0 ntt.0d .104 at .50 sIt  uttetation outer  .t.e  absolute toss or gain  nOt  Northern segment of the No. 3 vein  alteration envelope  .  5.4  uncertainty at 95% confidence level  .55_._—__  200  :  .101  .5(1  .  Inn  fl  too  50  zoo  .100 DAst.$tt  OtA6t.5  or guilt  envelope  alteration tuner  vein  DA6O.6  olute loss  nS 5 sO tO  et t  alteration inner en ye to 1w  veil’  1  .00  toss or gum  .53  DM320  DAOOtD  0A60.3  nO 4 s5.5  envelope  alteration outer  a 4  \.  DA6O.tD  mierodiorite  propytitie  0A53t  Switch Back vein  eS-S  n.%.6  5.ud 5  aSS  prupylitic tnicrodiorile  ,.c.ud  sericitic alteration  .5-S  Southern segment of the No. 3 vein  uueeronitety us 95 % confidence lee.et absolute  .  0A52.4  \nlteruttou Outer envelope  0A634  95 % confide ore level  i1111  0A638  v  uneurtaiitry at  1áiiiJ  20  Figure 6-5j. Absolute losses and gains of Rb from four alteration profiles at the Silver Queen mine, central British Columbia, The blank part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) and a range representing ± 2 standard deviations, -  -o  S  ubsolute loss or guiit  E]  icy at 1)5 % confidence level  1111CC liii  ct-i  do el-i  et.4  cl-SD  el-6  —  cl.n  ci.2d cli  aitniation 001cr envelope  51.1  4 c6  ci S  Central segment of the No. 3 vein  propylitic andeslir  cit  el-id cii  the No. 3 vein  segment of  alteration inner envelope  vein alteration outer envelope  s  proPYliiiC nsjcrodiotile  On-I 05-n ctO-6t) l5 e-t lt- sIn-3d 00.4 sinS sin-n clouD 1n-4 ,l-i clvi sin-3d 5  cit-I  cl-I  uncertainty at 95% confidence level absolute lots or gain  cl-C  cit  alteration envelope  si-i  Northern  ..  i__i iI  ——1-  propylitic andesitn  -t-t  U  1...._J absolute lost or gaul  x  0 ‘0  I  :  4  -  b.56a.SD OASiS  alteration inner envelope  vein  ctAai-6  DAeS-4  ci- It  el-n  \-.  nt-i  alierarioll inner C 1 ye In ltC  \  n5.9  vein  cii  cS-C cii  alteration outer envelope  ci-4  propylitic  cii  56-6  si-ed  eS-I  microdiorite  propylitic  ci-6d  ‘  —  alteration  sericitic  cS-C  uncertainty at 95 % confidence level absolute loss  J  Swltchflackvein DA6i-l DAO3DA6S3D bAet-ID DAdi-tD  ‘alteration outer envelope  DAunt  -  Soulhern segnsent of the No. 3 vein  DA6S-8  J;bstiUt;io5;;io  uncertainty at 95% confidence level  PIIIIIIEE  -...--.  0 from four alteration profiles at the Silver Queen mine, central British Columbia. The 2 Figure 6-5k. Absolute losses and gains of H blank part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) and a range representing ± 2 standard deviations.  z  0  :i  g  Central ncgnhenl of the No. 3 veio  ——.. . .  propylitic undetite  ‘.  alteration inner envelope  ‘  envelope  “-. niteration outer  “ uticeodiorite  propylilic  00.2 00.3 dO-3d ,tO.4 00-S 00.6 ett:6t) t.e 0.4 l.2d 0 1 ate-I 00-2 00-0 alOud alt-4 aIS-S at0-6 stOOD l :2 et.7 al-3D xiS veil’  —19-  alteration outer envelope  a) .S  —  i ii  Thsoluto foosorgaie  o-.——---  ‘°  eS-t  nlterntiott envelope  vein  uucertuittty at 95% cottfideuce level  propylitic audeulte  eS 7  0 U  ‘0  Ca  I tO  l2  E1  II  DAO3-SD  envelope  \  aS. tO  \  et-t  alteration inner elite lope  vein  et-t  tAilS-S  0-2  aS-S  nO.4  nticrodioeitn  .5.3  aS-S .5-6  -  nticrodiorite  propyjitic  sS.6d  \..  alteration  sericitic  sS.6  Southern segment of the No.3 vein  uiteratiou Outer envelope  0.4  Swllch Back vein DAd3-t DA6S-3 DAOS-SD DAOS-lD tAnS-tO  -alteration outer envelope  tAOS-a  coufialcttm level  alleratton tuner  DAns-6 vein  uncoeointy ut95  DAOO-  DA6I-4  uncertainty at 95% confidence level absolute loss or gait)  Figure 6-51. Absolute losses and gains of CO 2 from four alteration profiles at the Silver Queen mine, central British Columbia. The blank hart of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) and a range representing ± 2 standard deviations.  ‘0  0 U  0iII  .3-7  21-4  nI-SD  l-6  alteration outer envelope  .34  —  .2-0  \.  S  propylilic usicrodiorite  :  -  \  0A62-3t5  .3-In  \  .3-I  e,Ivelope  \.  45-2  .5-4  N  DM3.4  2 standard deviations.  Switch Back vein  83-4 .5-3  envelope  N  mivrodiorite  blank  \ \\ propylilic N sericitic microdiorite - alteration  alteration outer envelope  DA63-I DM33 DAO3-30 DM3-ID DA63-4 DAO3-3D  nllernlion Outer  .5-3  DM3-S  alIeeaa inner envelope  vein  DM1-n  ulteealion inner  vein  ,v-9  DM3-S  % confidence levol  gain  uncertainty 0395  absolute loss or  In —----.——-—---—-.--—.—  I1  I!  25  The blank representing ± bar) and a range  from four alteration profiles at the Silver Queen mine, central British Columbia.  alteration Outer ‘ envelop.  gains of  alteration inner envelope  \  vein  3D  Central segment of the No. 3 vein .1-3d .10-I .20-3 .30-3d 210-4 .30-3 .tn-e .10-61) .3-I .10-I 020-0 .10-3 .10-3d .30-4 .30-3 .30-6 810 .3.2 .2-3  •-....---...-------..-----------.--.-.—.--...--....---------.-........-.-.--....--------.-.-—  absolnle loss er  uncertaioty 0395% confidence level  alteration envelope  t-3  propylilie andovite  .3-6.5-4,3-2.3-3d .3-2 . 03-I -3  .—  Norfhcrn segme itt of the No. 3 vci it  part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the  Figure  e  .3-7  propylisic aodosite  84-4  —-------.-  6-5m. Absolute losses and  I!  0  It  Zn  In  %  al,0oIotrtoororolt  confidence level  uilcvr(ain  1000  -500  I  Ste  loon  I 306  -1500  -3000  :. at-S  a3-l  —  \\  a3-5  —  C  et -S  13-3d  an-s  veils  ..———......—..——..——.  —  propylitic audesite  13-3  Central segment of the No. 3  —...—-.-*.....—,...  wH  .- —  ,3-l  envelope envelope  alieratine 11111cr .  envelope  ulteralioll outer  \. S.-  nlicendiociee  peopylitic  110-3 aIO-3d ItO-I sIn-S sIn 6 alO-0D 13-4 11.20 13-3 130-I 13-6 dO-I sIC-S sIC-3d ale-4 ate-S aIO-6 adO 60 sI-SD Il-S Il-n sin-I  alteralion Outer  al-n  absolute Jots or gain  a3-2  eIlvOtOpe  aS-I  alteratioii  \  .  ,3-4  veIn  HWUL1  propylilic andesite  U-4  Northern segment of the No.3 vein  Er s.... r.: Err  Duncertainty at 95% confidence level  —  -—-  absoluLe loss or gain  noccrtaioty 0395 % confidence level  t  -‘$00  .1000  500  1000  ‘$00  -Iso  Sn:  uncertaitlly 0195%  confidence level  Switch Back vein  ollrt,I in,ner etivelope  veill  aS-IS  aS-I  envelope  alieration inner  \ \  eS-9  —--.  Ollt 9  5$-n  103506  --—--•--“•--•--  absolute  15-4  e$-4 eS-S  envelope  alteration Dater  eS-t  —  53-3  as-n  eS-6d  “..  a3-7  microdiorite  propylitic  aS-6d  Se  sericilic - alteration  a3-4  Southern segment of the No.3 vein  —  —.....,-.---....-—.....  alteration outer envelope  DM33 DA63-SD DM33 DA63-$D DM34 DM3-ID DM3-3D DA63-5 DA6O-4 DM36  uncertainty at9S % confidence level  DAO3.8  —  absolute loss or gall,  .*..! 1.1 !.! I.If . .-—- - —-. -  -  Figure 6-5n. Absolute losses and gains of Sr from four alteration profiles at the Silver Queen mine, central British Columbia. The blank part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) and a range representing ± 2 standard deviations.  0  (IS  50  9  1000  503  I 500  LZJ  loner  I 4  ci -SI)  envelope  .1  l I  alteration outer  .5  cl-a  DA6S.a  td  DA6S.5  0.565-3D  0A65-5D  cl-n  microdiorite  DAOS-t  DA63.ID  envelope  alteration ineor  veil,  ‘  envelope  \ alteration outer  ‘‘,  S  nsicrodiorite  propylitic  clOt .10.0 eta Sd clad 00-5 .tn-a ,,n-ao cit .lt t cit-S cia-S 00-Sd clod ett-5 .io-u 00.60  Central segment of the No. 3 veits  alteration outer envelope  DAe5-4  Switch Back vein  -•—•  ,,,.,,,,,..,,...,,,.  absolute loss or gain  .e  bASS-S  95% confidence level  alteration envelope  vein  DA65.0D  0A63.6  oocecauinty at  0A65-&  absolute loss or gain  .  Si,  [:  20  St  20  Switch Back vein  .5-20  3i  ---  envelope  .5-3  eS-i  -,  cltera inner envelope  vela  0 4  54  envelope  \S\  .5-3  \.  .5-4  -‘  eS-6d  .5-7  microdiorite  propylitic  .s-ed  ‘  alteration  sericitic  eS-S  Southern segment of the No.3 vein  -  uncertainty at 95 % confidence level absolute loss or gain  cs-s  E1  alteration outer  -  alteration outer envelope  DA63.t 0A655 DA65.4 OA6S’SD 0A65.5D bASS-ID 0A63-OD DA63-4 toAet.6 bAns-S  \ \  VeIl,  .5 9  -  DA6S.8  alteration inner  --  uaceraaiutyat95%confidenceloml  absolute loss or gain  Figure 6-5o, Absolute losses and gains of Y from four alteration profiles at the Silver Queen mine, central British Columbia. The blank part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) and a range representing ± 2 standard deviations.  SI  30  .50  2,  I’  .3-S  el-n  .3-2 .3-0  ct-3d  .2  propylilic onslesile  eS-S  use No.3 veits  -  a  11  el-S  el -  el-SD  .1-3  alteaution nlabee envelope  el-C .10-2  envelope  aiteration outer envelope  a  propylitic usicrodiorite  em-3d o- tn- to- em-nb dO-Sd .33-4 dO-S dO-u .15-eD  nb-C  alteration inner  veill  rIO-I  Cenlral segment of the No. 3 vein  0.2  OS  bA63-3r DAOS-5  alteratIon moor envelope  DAut-e  DAe3-a  envelope  ‘\  e$-2  \‘a-.  eS-I  alteration inner  Vein  as-In  as-C  absolute loss or gain  bAnS-3D  bA6t-nl  eS-4 as-S  alteration outer envelope  es-a  ‘S  aS-S .5-6  eS-nd  .5-S  niicrodioeite  propylitic  e$.Od  alteration  aerieltic  .5-8  ——  propylitic nticrodionite  DA6S-1  Southern segment of the No. 3 vein  \  0A65-ID  Switch Back vein 0A62-3  ‘alletntlon outer envelope  DA03-4  uncertainty at 95 99 confidence level  eS-9  fl  DA63 8  obsolute loss or gain  once rlnioly at 95 99 coulisle ore love I  Figure 6-5p. Absolute losses and gains of P 5 from four alteration profiles at the Silver Queen mine, central British Columbia. The 0 2 blank part of each bar includes the mean estimate (a horizontal imaginary line through the centre of the blank bar) and a range representing ± 2 standard deviations.  t  0  ‘  .5-I  tIle ration C uvelope  -  00111  eS-4  of  _..  --  0  el-fl  eS-S  Northern segment  .  9  propylitic andesite  eat  absolute loss or gain  lilrlertaiLily 0195 99 confide floe level  9  0 a.  I  02  Ii  Appendix E. Tables of Alteration Evaluation, Silver Queen Mine  268  -  -  -  -2.5 2.66  -2.5  163 12 172 231  220 32 96 23  188 28 123 567  192 30 108 607  4.9 0.9 0.5 1.9 15.0 25.0 Distance 2.84 2.76 2.76 2.62 2.68 2.80 Density silicic and and silicification pyritization. argillization: prop propylitization: scr-arg sericitization distance from the vein in metres, + in hangingwall side and in footwall side.  57.25 17.45 0.67 1.25 5.82 1.57 1.09 0.73 0.29 2.77 0.20 3.9 5.75 0.073 98.81  198.22 27.31 122.91 376.45  191 28 100 5’)3  0.40 2.18 2.34 0.016 100.05  3.04  56.67 17.27 0.57 1.26 5.78 1.65 1.15 0.73 0.44 4.12 0.19 2.69 5.9 0.127 98.55  58.45 18.11 0.87 1.26 3.69 1.34 0.90 2.69 0.31 2.34 0.27 4.39 5.2 0.029 99.85  57.97 15.87 0,65 2.86 3.05 0.20 2.64 5.66 4.09 2.92 0.38 1.27 2.14 0.018 99.72 198 27 123 376  57.86 15.61 0.65 3.09 2.89 0.34 2.94 6.07 3.65 3.09 0.38 0.97 2.03 0.013 99.58 188 23 114 630  Si02 Al203 Ti02 Fe203 FeO MnO MgO CaO Na20 K20 P205 H20 C02 S Total ppm ZR Y Rh Sr  60.21 18.35 0.72 2.33 3.65 0.60 0.99 1.73 0.34 3.41 0.26 3.93 4.3 0.050 100.87  57.20 16.03 0.66 3.12 2.70 0.23 2.61 5.97 3.55  -16.0 2.74  180.19 23.62 117.16 605.75  57.59 15.80 0.65 2.81 3.08 0.35 3.07 5.61 3.69 3.13 0.39 1.84 1.65 0.025 99.69  -8.0 2.66  185.22 31.91 103.70 597.0k  3.02 0.39 1.14 1.92 0.018 99.52  57.75 15.85 0.66 3.02 2.86 0.31 2.87 5.75 3.96  Lithogeochemical data of altered rocks at the Silver Queen mine, central British Columbia x3-3d x3-3 x3-2 x3-2 x3-4 x3-1 x3-6 x3-5 x3-7 x4-4 prop. ser-arg prop. ser-arg ser-arg arg ser-arg prop. prop. prop. andesite andesite andesite andesite andesite andesite andesite andesite andesite andesite segmen segmen North segmen segmen North North North segmen segmen North North North segmen North segmen North segmen North segmen of No.3 vein of No.3 vein of No.3 vein of No.3 vein of No.3 vein of No.3 vein of No.3 vein of No.3 vein of No.3 vein of No.3 vein 59.94 18.30 0.71 2.18 3.65 0.59 0.97 1.70 0.35 3.37 0.26 3.93 4.3 0.056 100.31  wt %  Alterations Rock type Location  Table 6-5. Sample  C  -  57.29 Si02 15.70 A1203 0.66 Ti02 3.08 Fe203 2.92 FeO 0.25 MnO 3.33 MgO 5.67 CaO 3.39 Na20 3.15 K20 0.37 P205 1.04 1-120 2.75 C02 0.003 S 99.60 Total ppm 178.64 ZR 3105 Y 121.40 Rh 573.45 Sr -26.0 Distance Density microdiorite * m.diorite  wt %  Table 6-5 (continued-i) x2-5 Sample prop. Alteration andesite Rock type North segmen Location of No.3 vein  128.98 25.39 166.47 260.16 2.0 2.85  91.49 21.35 123.33 73.83 1.0  98.78 20.10 120.07 86.99  -1.0 2.89  1.0  100.64 16.39 118.44 225.10 -1.0 2.95  104.20 23.18 175.61 160.12  0.0825 99.20  54.59 14.95 0.46 2.02 9.13 0.63 0.87 1.04 0.02 3.29 0.29 2.88 7.05 0.3815 97.60  53.00 16.59 0.50 1.15 9.94 0.81 0.69 0.89 0.02 148 0.28 2.93 7.45 0.3849 98.11  49.14 17.09 0.53 1.48 9.83 2.46 0.90 1.64 0.01 4.11 0.21 2.83 8.04 0.2673 98.54  54.41 15.34 0.45 2.15 9.14 0.69 0.80 1.24 0.04 3.34 0.31 2.88 7.25 0.3815 98.42  48.40 18.16 0.59 0.86 12.79 0.90 1.21 1.02 0.06 4.04 0.29 3.01 7.79  112.23 23.69 178.76 142.96  128.98 25.39 166.47 260.16 2.0  4.0  51.36 16.29 0.57 0.59 11.24 0.98 1.36 1.24 0.05 4.26 0.26 2.14 7.85 0.0566 98.25  DA63-3D ser-arg m. diorite Switch back Vein  48.43 18.07 0.59 1.01 12.68 0.90 1.21 1.02 0.06 4.05 0.29 3.01 7.79 0.0825 99.19  Lithogeochemical data of altered rocks at Silver Queen mine, central British Columbia DA63-4 DA63-4 DA63-5 DA63-5D DA63-6 DA63-8 ser-arg silicic ser-arg silicic s-alt s-alt ni. diorite m. diorite ni. diorite m. diorite ni. diorite m. diorite’ Switch back Switch back Switch back Switch back Switch back Switch back Vein Vein Vein Vein Vein Vein  4.0  112.23 23.69 178.76 142.96  51.68 16.20 0.56 0.41 11.24 0.98 1.34 1.24 0.03 4.24 0.25 2.14 7.85 0.0566 98.22  DA63.3D ser-arg m. diorite Switch back Vein  114.43 24.75 173.06 141.19 4,0 2.78  51.19 16.24 0.58 0.66 11.24 0.98 1.35 1.25 0.25 4.27 0.28 2.14 7.85 0.0566 98.34  DA63-3 ser-arg m. diorite Switch back Vein  Distance Density  6.0  Table 6-5 (continued-2) DA63-1D Sample w-alt Alteration m. di. Rock type Switch back Location Vein wt % 57.72 Si02 16.63 A1203 0.72 Ti02 2.32 Fe203 3.76 FeO 0.16 MnO 2.62 MgO 6.45 CaO 3.28 Na20 3.26 K20 0.43 P205 0.93 1-120 1.34 C02 0.0122 S 99,63 Total ppm 164.70 ZR 25.23 Y 103.70 Rb 636.30 Sr -1.6 2.72  -2.4  -3.2 -14.0 2.68  -27.0 2.7  6.0 2.7  161.90 25.59 168.89 209.32 161.74 29.89 214.85 90.54 156.04 23.94 176.68 111.36  166.25 32.94 217.03 132.04 -7.0 165.87 32.51 223.70 157.42  171.40 25.86 187.90 137.58  158.38 25.75 92.65 608.28  64.23 15.50 0.39 1.30 4.70 0.81 0.92 0.95 0.14 4.02 0.15 2.14 3.65 0.091 98.97 64.18 15.65 0.42 1.43 3.26 1.10 1.04 1.69 0.16 4.37 0.16 2.43 3.30 0.080 99.25 61.11 17.60 0.45 1.61 3.07 0.65 1.36 2.11 0.37 5.73 0.15 2.51 3.24 0.041 99.99  59.43 16.44 0.43 1.51 3.36 0.81 1.54 3.01 0.79 5.61 0.15 2.25 4.66 0.019 100.01  60.43 16.90 0.43 1.58 3.53 0.42 1.52 2.61 0.99 4.69 0.16 2.03 5.16 0.028 100.45  57.99 16.53 0.71 2.22 3.76 0.16 2.63 6.25 3.43 3.16 0.43 0.93 1.34 0.0122 99.55  57.46 15.93 0.38 1.23 8.05 0.98 1.38 0.74 0.32 4.98 0.11 1.63 5.80 0.062 99.03  -0.8  165.81 219.70  158.67 21.74  0.09 4.04 0.16 1.90 3.26 0.073 99.50  68.44 15.38 0.38 0.76 2.93 0.68 0.93 0.47  -0.6 2.65  134.75 17.61 147.60 201.17  3.