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Mass changes during hydrothermal alteration, Silver Queen epithermal deposit, Owen Lake, central British… Cheng, Xiaolin 1995

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MASS CHANGES DURING HYDROTJIERMAL ALTERATIONSILVER QUEEN EPITHERMAL DEPOSIT,OWEN LAKE, CENTRAL BRITISH COLUMBIAbyXIAOLIN CUENGB.Eng., The China University of Geosciences (Wuhan), 1982M.Sc., The China University of Geosciences (Wuhan), 1985A THESIS SUBMITFED IN PARTIAL FULFILLMENT OFTUE REQUIREMENTS FOR TUE DEGREE OFDOCTOR OF PHILOSOPHYinTIlE FACULTY OF GRADUATE STUDIES(Department of Geological Sciences)We accept this thesis as conformingTHE UNIVERSITY OF BRITISH COLUMBIAOctober 1995© Xiaolin Cheng, 1995In presenting this thesis in partial fulfilment of the requirements for an advanceddegree at the University of British Columbia, I agree that the Library shall make itfreely available for reference and study. I further agree that permission for extensivecopying of this thesis for scholarly purposes may be granted by the head of mydepartment or by his or her representatives. It is understood that copying orpublication of this thesis for financial gain shall not be allowed without my writtenpermission.(Signature)______________________________Department of óe.iic.cA Sc4’v2-iThe University of British ColumbiaVancouver, CanadaDate Oct- 9 ,DE-6 (2/88)ABSTRACTA procedure for determining metasomatic norms is developed in this thesis toquantitatively and objectively estimate mineral abundances from lithogeochemical data,The norm calculations use the same principles as do other norms such as CIPW, but thedifferent mineral phases present in alteration systems are used as the normative standardminerals. Another distinctive difference between a metasomatic and a conventional norm isthat the calculation procedure proposed for a metasomatic norm does not proceed alongsuch a fixed hierarchical path as in the case of an igneous norm. A particular usefulapproach to the application of the norm concept to metasomatic rocks is to constrain thecalculated normative mineralogy by apriori knowledge of existing minerals (i.e. toapproximate the mode as closely as possible).Where an immobile component can be recognized the metasomatic norms forprotoliths and altered rocks, as well as the chemical constituents lost or gained, can befurther recast into the absolute amounts ofminerals and chemical constituents relative to agiven mass of parent rock. Known errors within lithogeochemical data studied can bepropagated to the final results of all norm calculations. As a result, a chemicomineralogical model for material exchange, including absolute losses and gains of chemicalconstituents, normative minerals in extensive units, as well as the correspondingpropagated 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 initialand final rocks, absolute gains and losses of specific chemical constituents as well as theuncertainties on each estimate at a specified confidence level.11The methodology for this approach is a natural extension of the use ofPearceelement ratio (PER) diagrams for the study ofmetasomatic rocks. The metasomatic normrecovers the same quantitative information as do Pearce element ratio diagrams. Thecommon principles are (i) correction for closure, that provides true relativelithogeochemical and mineralogical variations between parent and daughter rocks, and (ii)an effort to explain chemical variability in terms ofmineralogical variability. The strategyof a PER diagram is to test whether chemical changes in different rocks can be explainedpurely by the variation(s) of certain mineral(s), as demonstrated by disposition of thebinary plotted points along predefined trends (slopes). Metasomatic norms are displayedmore effectively as equations or profiles showing the spatial distributions of normativemineral assemblage, as well as the absolute losses and gains of chemical constituents basedon comprehensive mass balance relationships.The approach described in the first part of this thesis is applied to a hydrothermalalteration study of the Silver Queen mine in central British Columbia. Hydrothermalalteration at the Silver Queen mine was derived from a multiple precursor system.However, local, individual alteration profiles exhibit the attributes of a single precursorsystem. Six types of hydrothermal alteration at Silver Queen mine have been described:viz. propylitization, sericitization, argillization, silicification, pyritization andcarbonatization. In general, the wall rock alteration in the study area is composed of awidespread regional propylitic alteration with superimposed carbonatization. Regionalalteration gives way, as the vein is approached, to an outer envelope of sericitic andargillic alteration + carbonatization and an inner envelope of silicification and pyritization+ sericitic or argillic alteration + carbonatization. Thus, the sequence of alterationdevelopment is (i) widespread regional propylitic alteration, (ii) sericitic and argillic outerenvelope, and (iii) silicification and pyritization inner envelope.Most of the hydrothermally altered samples in alteration envelopes at the SilverQueen mine have gained mass during hydrothermal alteration. In contrast, samples from111the profile of the northern segment of the No. 3 vein have lost mass. Other spatialvariations of hydrothermal alteration from the southern segment to the northern segmentof the No. 3 vein and from different levels (from 2600-foot level to 2880-foot level) havebeen recognized. In brief, the wall rock alteration is most intense in the alteration envelopeat the central segment of the No. 3 vein and mildest at the northern segment of the No. 3vein. The total mass change of each altered sample is largely the result of depletion of CaOandNa20, and addition of Si02,K2O,H20 and CO2.ivTABLE OF CONTENTSAbstract IITable of Contents VList of Tables xliiAcknowledgement XChapter 1. Background and Objectives 11. 1. Introduction 11. 2. Current Quantitative Approaches to the StudyofHydrothermal Alteration 41.2.1 The Closure Effect 51.2.2 Comparison ofVarious Techniques Used toRemove the Closure Effect 71.3. Two Requirements for Loss and Gain Calculation 101.4. Pearce Element Ratios (PER) and Their Applicationto Hydrothermal Alteration 161.5. Additional Problems 23Chapter 2. Metasomatic Norms: AMethod ofNorm CalculationAdapted to Hydrothermally Altered Rocks 262.1. Introduction 262.2. The Principle ofMetasomatic Norms 282.3. A Set of Standard Normative Minerals for Metasomatic Systems 322.4. A Manual Procedure for Metasomatic Norm Calculation 332.5. A Quantitative Model ofMetasomatic Systems 412,6. Case Histories: Application ofMetasomatic Norms 432.6.1. Sigma Mine, Abitibi, Quebec 432.6.2. Erickson Gold Mine, Northern British Columbia 472.7. Conclusions 55VChapter 3. Quality Control/Assessment ofLithogeochemical Data 573.1. Introduction 573.2. Strategies of Sampling and Sample Preparation 583.3. Quality Assessment ofAnalytical MeasurementsBased on a Small Set ofDuplicates 643.4. Propagation ofErrors in Lithogeochemical Calculations 71Chapter 4. Geology of the Silver Queen mine, Owen Lake area,Central British Columbia 764.1. Introduction 764.2. Regional Geological Setting 774.3. Geology of the Study Area 804.4. Lithogeochemical Characters and Two Series ofIgneous and Volcanic Rocks 924.5. Veins: Character and Correlation 964.6. Structures and the Interpretations 994.7. Summary 106Chapter 5. Hydrothermal Alteration Associated with Epithermal, Base- andPrecious-Metal Veins at Silver Queen Mine: Petrographic Variations 1085.1. Introduction 1085.2. Petrography ofHydrothermal Alteration Types 1095.3. The Spatial Zonation ofHydrothermal Alteration 1155.4. Paragenetic Sequence ofHydrothermal Alteration 1255.5. Discussion and Conclusions 130Chapter 6. A Quantitative Evaluation ofHydrothermal Alterationat Silver Queen Mine, Central British Columbia 1336.1. Introduction 1336.2. Sampling and Sample Preparation 134vi6.3. Errors inherent in Lithogeochemical Data 1406.4. Lithogeochemical Data ofAltered Rock andDetermination of immobile components 1426.5. Calculation ofAbsolute Losses and Gains of ChemicalConstituents and their Spatial Variations 1446.6. Application ofPER Diagram to the InterpretationofHydrothermal Alteration 1496.7, Application ofMetasomatic NormMethodology 1586.8. Propagated Error Analysis and Confidence Level ofthe Quantitative Evaluations 1676.9. A Comprehensive Model ofHydrothermal Alteration 169Chapter 7. Conclusions and Recommendations 172Bibliography 183Appendix A. Megascopic Description ofAltered Sample, Silver Queen Mine 196Appendix B. Lithogeochemical Duplicate Analyses, Silver Queen Mine 201Appendix C. Use of “Quattro Pro for DOS 5.0” to Calculate Metasomatic Norms 205Appendix D. Diagrams of Alteration Evaluation, Silver Queen Mine 246Appendix E. Tables ofAlteration Evaluation, Silver Queen Mine 268viiLIST OF TABLESTable 1-1. A Summary of Quantitative Techniques Devised to Removethe Closure Effect and Evaluate Mass Transfer Process 8Table 1-2. Eight Possible Cases ofPERDiagram 13Table 2-1. A List of Standard Normative Minerals for MetasomaticVolcanic Rocks Associated with Epithermal Ore Deposits 34Table 2-2. Variations in Major Element Oxide Concentration(in wt%) in the Profile 2103 across Alteration EnvelopeAround Tension Vein, Sigma Mine, Quebec 44Table 2-3. The Calculation Results ofMetasomatic Norms (in wt%) in the Profile2103 across Alteration envelope around Tension Vein, Sigma Mine, Quebec 44Table 2-4. Summary of Characteristics ofAlteration Zones ofEnclosing Gold-BearingQuartz Veins and the McDame Dolomite Vein, Total Erickson Mine 48Table 2-5. Chemical Analyses of Jennie Vein Alteration Profile,Erickson Gold Mine 50Table 2-6. Metasomatic Norms of Jennie Vein Alteration Profile,Erickson Gold Mine 50Table 2-7. Metasomatic Norms Corrected for Closure and Absolute Lossesand Gains of Components from Profile 80-88-JH across the Jennie Vein,Erickson Mine, Northern British Columbia 52Table 3-1. The Classification ofMajor Variations ofLithogeochemical DataGenerated by Different Processes 57Table 4-1. Table ofFormations, Owen Lake Area 83Table 4-2. Lithgeochemical Data ofVarious Types ofRock at Owen Lake Area,Central British Columbia 94Table 5-1. Estimated Modes of Alteration Minerals in Hydrothermally Altered Rockaround the No. 3 Vein, Silver Queen Mine, Central British Columbia 120viiiTable 5-2. Paragenetic Sequence ofMineral Assemblages, Silver Queen Mine 129Table 6-1. Estimation of Optimal Sample Size by Using Binomial Function 136Table 6-2. Estimated Optimal Fineness of Subsample by Using Binomial Function 138Table 6-3. Error ofLithgeochemical Data Estimated by Using Sample Duplicates 141Table 6-4. Error ofLithogeochemical Data Estimatedby Using Measurement Duplicates 141Table 6-7. Metasomatic Norms Corrected for Closure and Absolute Losses andGains of Components (in Moles) around the No. 3 Vein, Silver Queen Mine,Owen Lake, Central British Columbia 160Table 6-8. Metasomatic Norms Corrected for Closure and Absolute Losses andGains of Components (in Grams) around the No. 3 Vein, Silver Queen Mine,Owen Lake, Central British Columbia 161Table 6-9. Propagated Errors ofMetasomatic Norms Corrected for Closure andAbsolute Losses and Gains of Components in Grams at the 68% ConfidenceLevel, the No. 3 Vein, Silver Queen Mine, Central British Columbia 168ixACKNOWLEDGMENTSIn the course of completing my thesis, several individuals and agencies haveprovided much appreciated assistance, without which the thesis would have been animpossibility.I am especially indebted to Dr. Alastair J. Sinclair for offering me the opportunityto work on the Owen Lake Project as a Ph. D. graduate student under his supervision, andfor his constructive criticism, insights, and extraordinary patience that allowed me tocomplete this work.Dr. Gerry Carlson, Dr. Craig Leitch and Dr. Margaret Thomson provided muchneeded assistance in deciphering the geological story behind the Silver Queen precious-and base-metal vein deposit and greatly supplemented the evolution of this thesis withtheir own work. My thanks also go out to my coworkers Christopher T. S. Hood, ZophiaRadlowski and Asger Bentzen for their suggestions, discussions and assistances.Pacific Houston Resources Inc. and New Nadina Explorations Ltd. are thanked forallowing access to the Silver Queen workings and for financial assistance in and out of thefield. J. Hutter and W. W. Cummings provided helpful discussions on the mine area duringmy stay at Silver Queen mine.Dr. L. A. Groat and K. N. Nicholson are thanked for the advice and assistancewith the X-ray diffraction operation; Dr. W.K. Fletcher and S. Horsky for the guidance onthe 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. Stanleyand Dr. Mm Sun for providing instruction and discussion.This work was supported by Pacific Houston Resources Inc., New NadinaExplorations Ltd. and by a grant from the Natural Science and Engineering ResearchCouncil of Canada to Dr. A.J. Sinclair.xChapter 1. Background and Objectives1.1. IntroductionBates and Jackson (1987) define alteration as: “ ... any change in the mineralogicalcomposition of a rock brought about by physical or chemical means, especially, by theaction of hydrothermal solutions . . .“It is one of the most important topics studied byeconomic geologists because in many hydrothermal ore deposits the changes incomposition, mineralogy and/or texture ofwall rocks, etc., that enclose the ore deposit aremore extensive and more obvious than the ore deposit itself. Hydrothermally altered wall-rock is thus a “fossil” of a hydrothermal system; many parameters of the depositionalenvironment of ore are interpretable from the assemblages of alteration minerals.Consequently, wall-rock hydrothermal alteration has been used widely as a guide duringexploration of hydrothermal ore deposits and as a clue to the properties of thehydrothermal solution from which ores precipitated.However, hydrothermally altered wall rock can be the product of the reactionbetween wall rock and ore-bearing hydrothermal solution either before, during or after theprecipitation of ore minerals from hydrothermal solutions. To understand the relationbetween ore and associated hydrothermally alteration is a challenging task. Uncertaintiescan lead to errors or complexities in using wallrock alteration as a guide to exploration ofhydrothermal ore deposits if different types of alteration are confused. Appleyard andGuha (1991) review such practical uses of hydrothermal alteration and state:Wall-rock alteration was generally accorded little signficance as an explorationfocus. Dunbar (1948), for example, notedwith reference to the ores of thePorcupine district that moderate bleaching of the chloritic host rock wasconsidered to be a conditionfavorablefor ore occurrence but such evidence canonly be utilized in a very general way. Conversely, hefound strong bleaching to bea poor indicator ofmineralization andwrote that it cannot be said that the ore1occurs where its effect (that ofhydrothermal alteration) is most intense. Since thosedays, technical improvements have been at the heart of the advancement of thestate ofknowledge we have seen rather than the appearance ofnew paradigms.Lithogeochemistry, isotope geochemistry, fluid inclusion studies, statisticalapplications, and geochemical modeling are all areas where great advances intechnique and important observations have been achieved.In recent years, research into hydrothermal alteration associated with precious-metal ore deposits has accelerated appreciably with increasing interest in understandingwater/rock interactions, mass losses and gains, the geometry of alteration zones relative tothe associated mineral deposit, and assemblages of alteration minerals. This informationleads to the development of comprehensive models of alteration systems and provides abasis for designing mineral exploration guidelines, particularly as they relate to the use oflithogeochemical data and their integration into deposit model definition as an explorationtool.The general aim of this thesis is to improve quantitative methods of evaluatinghydrothermal alteration associated with precious- and base-metal vein deposit in volcanicsequences. This goal will be approached through a particular case study of alteration at theSilver Queen mine, central British Columbia. This study is preceded by a brief review ofthe current status of the study in the field of quantitative losses/gains to wallrock duringhydrothermal alteration.The basic aims ofmany alteration studies involve such questions as:(1) What are the changes in mineralogical assemblage of the rock during the alterationprocess?(2) What variations in chemical compositions of the rock arise from the alterationprocess?(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 ofhydrothermal 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 ofmaterial exchangeduring hydrothermal alteration are: (i) determination ofmineral assemblages of altered andparent rocks, and (ii) calculations of the losses and gains of chemical components as aresult of hydrothermal alteration.The mineralogy of altered rocks has been particularly important as a means ofclassification, such mineral-dependent terms as phyllic, sericitic, argillic, propylitic, etc.,are entrenched in the literature. One reason for this is that a mineral assemblage containsinformation both about the chemical composition and the formation environment of therock. Such information contributes to answering question 1 to 3, above, and lesssignificantly to questions 4 to 6. Unfortunately, fine grain size, absence of easilyidentifiable optical features, and mixtures of non-ideal structures of alteration products canobscure mineralogy and/or make mineral abundances impractical to estimate withconfidence. Consequently, the use of a mineralogical approach to study and classificationof hydrothermally altered rocks, while essential, is limited.A lithogeochemical approach to the study of altered rock complements and hassome advantages over the mineralogical approach. The large samples commonly used forchemical analysis can be more representative than, say, small areas of a thin section; thus,more accurate and consistent quantitative data can be obtained. A lithogeochemicalapproach to the study of hydrothermal alteration commonly is directed toward quantifyingthe loss or gain of each component during the alteration process and thus provide an3objective and quantitative chemical classification scheme. Elliott-Meadows and Appleyard(1991) state:the outer limits ofalteration can be detected more sensitively by theirgeochemical signatures than by their mineralogical expression, as can alterationzone boundaries.Lithogeochemical data provide information on the chemical compositions of rock. Rockswith similar chemical composition will have different mineral assemblages under differentphysical conditions. Therefore, a simple lithogeochemical analysis can provide definitiveanswers to question 2, and partial ones to question 3, 5 and 6, above, but can not give anyanswers to questions 1 and 4.Mineralogical- and lithogeochemical-based methodologies utilize different types ofdata. However, the two are related through the compositions and amounts of individualminerals. These two approaches are complementary; many researchers have integratedthem 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 reviewof the various approaches used to quantitatively evaluate hydrothermal alteration is givenin the following sections.1. 2. Current Quantitative Approaches to the Study of hydrothermal AlterationThe quantitative evaluation ofmaterial exchange during hydrothermal alterationrelies on lithogeochemical data. With the development ofX-ray fluorescence (XRF),atomic absorption spectrometry (AA), inductively coupled plasma-atomic emissionspectrometry (ICP) and other advanced analytical techniques, the availability of highquality, sensitive, precise, and inexpensive analyses for a long list of elements has comeabout.It is probably fair to say, however, that the use of these data in exploration has todate been largely limited to empirical procedures including: (i) the identification and4distribution of pathfinder elements (e.g., Descarreaux, 1973; Boyle, 1979; Fyon andCrocket, 1982; Davies et al., 1982; Kishida and Kerrich, 1987), and (ii) the application ofa varieties of empirical indices, such as an alteration index (A.I. = 100 x (MgO +K20)/(Na +K20+ CaO + MgO)) proposed by Ishikawa et al. (1976), and many othersincludingFe3/(Fe+MgO),A1203/Na,(Fe+MgO)/(FeMgO+CaO+NaO),K20/(Na+K),K20/Na,MgO/CaO,Na20/(Na +K20+CaO),K20/(Na +K20+ CaO) and CaO/(Na20+K20+CaO) (Hashiguchi and Usui, 1975; Spitz andDarling, 1978; Saeki and Date, 1980). A thorough review of these indices has been madeby 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 positiveanomalies. In some cases, however, where subjective interpretation procedures have beenused, these depletion or enrichment anomalies have been misconstrued as to whether ornot they are absolutely depleted/enriched or relatively diluted/concentrated by theenrichment/depletions of other components. For example, silica depletion anomalies havebeen confused with Al or Mg enrichment effects (Appleyard and Guha, 1991). Thisconfusion of enrichment and/or depletion is a product of the closure effect oflithogeochemical data.1.2.1. The Closure EffectIn attempting to deal quantitatively with the material exchange during alterationusing lithogeochemical data, a common problem arises, the closure effect. In amulticomponents system closure refers to the fact that all components must total 100percent. Thus, if a single component is changed, say 5i02 is added, the relative abundanceof all other components decrease even though their absolute amounts are unchanged. Thisis the problem of the closure effect. Lithogeochemical analyses of altered rockssuperficially can provide a distorted view of losses and gains of components. The matter5can be evaluated quantitatively as follows. Assume an original, simple system S0 consistingof three components X, Y and Z.S0 = X0 + + = 100(gram) (1-1)(upper case letters are used for weights)During an alteration process, components change by the absolute amounts dx, dY and dZrespectively. The total change of the system (in grams) will be:dS=dX+dY+dZ (1-2)In practice, the values ofX0+dX,Y0+dY andZ0+dZ are not accessible directlybecause 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 thefollowing form:100(X+dX)I(SdS) (1-4)y =100(Y+dY)I(SdS) (1-5)z=100(Z+dZ)/(SdS) (1-6)Equations 1-4 to 1-6 indicate that the difference in the concentration of a particularcomponent between the unaltered parent and the altered product is affected not only bythe absolute change of individual component (dx, dY or dZ), but also by the totalabsolute change of all components (dS).With regard to the impact of the closure effect on different constituents, Stanleyand Madeisky (1993) indicate:Closure will most affect those constituents that occur in large concentrations in asystem andwhich are added to or removedfrom the system in an incomplete way.Conversely, it will least affect those elements that have been added to or removedfrom the system in more complete ways. In essence, the larger the concentration ofa constituent in a rock relative to the amount ofmaterial transfer that constituent6has undergone, the more closure will obscure our ability to understand the materialtransfers using the constituent concentrations.As a result, the closure effect should be removed before a meaningful interpretation ofgeochemical data proceeds.1.2.2. Comparison of Various Techniques Used to Remove the Closure EffectThe closure effect has long been recognized and researchers working in relatedfields have devised various techniques to deal with this problem. The earliest paper dealingwith this issue has been traced back almost a hundred years. Geochemists working withweathered rock, calculated losses and gains of constituents by assuming the amount ofalumina to have remained constant during the weathering process (e.g., Merrill, 1897;Golditch, 1938; Krauskopf, 1967). Later researchers in the field ofmetasomatic alterationand igneous fractionation developed their own techniques to remove the closure effectfrom 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 theirprincipal contributions is presented in Table 1-1. The formulae of Table 1-1 are presentedwith standardized symbols to emphasize the degree of similarity of proposals by variousauthors.Among these techniques, Gresens’ equation (Gresens, 1967) and its modification(Grant, 1986) have been widely used by economic geologists to quantify the losses andgains of constituents during hydrothermal alteration processes (e.g., Babcock, 1973;Appleyard, 1980; Morton and Nebel, 1984; Robert and Brown, 1986; MacLean andKranidiotis, 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 andMacLean, 1989; Barrett and MacLean, 1991, Barrett el al., 1993).7Table 1-1. A Summary of Quantitative Techniques Devised to Remove the ClosureEffect and Evaluate Mass Transfer ProcessStudy Year Formula Application NotesMerrill, G. P. 1897 . = (ZP)—weathering z A1203and assumed to beimmobileZdf can be assumed to be one orGresens, R. L. 1967 dK = — p metasomatismdetermined by assuming onep component is immobile sof =PpXp/j.Pearce, T.H. 1968 dX — Xd — x, igneous x can be a combination of—— fractionation several components, Z isZ, Za Zpimmobile.Winchester et al. 1977 Za Xd metabasalt Both z and x are immobile.Floyd et al. 1978 — = — classificationzp xpGrant, 3. A. 1986 P Metasomatic p / .D = Za / Z,Xa = — (x +) alterationDMacLean, W. H. 1993 . =—Metasomatic z = immobile elements-“ alteration such as Zr, Ti, Al, Nb, Y.ZaNotes: 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 parentalrock;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;2d - weight or molar fraction of immobile component z in daughter oraltered rock;p - specific gravity of parent rock;Pd - specific gravity of daughter or altered rock; and- volume factor = vd / v.8Pearce element ratio (PER) diagrams, devised by Pearce (1968) for examiningmaterial exchange during the process of fractional crystallization, recently have beenextended by Stanley and Madeisky (1994) to metasomatic rocks. PER diagrams have beenused in the past to examine chemical variations caused by igneous differentiation (Russelland 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 intomolar units, then uses a conserved/immobile element as a reference scale to remove theclosure effect, and finally, utilizes various diagrams designed in the light of thestoichiometries of the relevant minerals, to test various causes of the lithogeochemicalvariations in terms ofmineralogical variation(s).Gresen& equation and Pearce element ratio diagrams are superficially different butthey are used to solve similar problems. Cheng and Sinclair (1991), and Stanley andMadeisky (1993) show that these two techniques, although having different startingpoints, are fundamentally similar in principle — that is, they both remove the closure effectin order to decipher the true chemical variations during alteration. Even though anindependent solution exists for Gresens’ equation where the volume factor is known andthe specific gravities have been measured, in practice, the volume factor can not beestimated except through the use of either an immobile component or an assumption suchas constant volume during the hydrothermal alteration process.The concept of immobile element is defined by Stanley and Madeisky (1993) asan element that is neither signficantly added nor removedfrom a rock duringmetasomatism because of its low solubility in aqueousfluids (the stabilities ofaqeuous complexes that contain it are signflcantly lower than the stabilities ofminerals that contain it).’The procedure of removing the effect of closure by using an immobile component isillustrated as follows. Given that a component Z is immobile (i.e. dZ = 0) then we have:9z = 100ZJ(S+&) (1-7)The use of this immobile component to remove the effect of closure involves using theimmobile component as a divisor (standard reference) for other components as follows:x xo 100(Xo+dK)/(So+&) X0dX18Z Zo 100Z/(S+d ) Z0 1,The final result dX/Z0 in equation 1-8 can also be treated as the absolute change ofelement x with the reference unit of conserved or immobile component z0 because 4, = z0if the original system is assumed to be 100 gram. Rearranging equation 1-8 producesGrant’s version of Gresens’ equation:dX=—x0—X (19)In summary, these various techniques of dealing with closure are all based on thesame fundamental principle, an immobile component that allows the calculation of thetrue variations in rock compositions caused by material exchange. Applications of thesetechniques rely on a knowledge of either the change in rock volume during hydrothermalalteration (e.g. Robert and Brown, 1986), or the recognition of immobile component(s) inthe rocks (e.g. MacLean and Kranidiotis, 1987).1. 3. Two Requirements for Loss and Gain CalculationsBefore applying these quantitative techniques for estimating losses and gains in ametasomatic system, two requirements must be met. First, the available analytical datamust be shown to contain immobile components; second, a suite of samples for whichloss/gain variations are to be evaluated, must be the alteration products of either: (i) acommon parent rock characterized by chemical and mineralogical homogeneity (singleprecursor system), or (ii) a suite of rocks with determinable pre-alteration chemicalcomposition (multiple precursor system).10In order to examine whether a set of lithogeochemical data meets the firstrequirement, Nicholls (1988) summarizes three ways of recognizing a conserved elementfor the study of igneous differentiation:(1) The petrologic behavior of the element can be used to select conservedelements. 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 constructedwith a set ofconservedelement in the denominator will have a trendwith a near zero intercept.The geochemical behavior of elements is helpful to infer which elements might beconserved or immobile, particularly under certain circumstances where they areincompatible with the known mass transfer process. For example, the elements P, K and Tiare commonly thought to be incompatible with the main minerals that crystallize in abasaltic 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 ofZr, Ti and/or Al immobility hasbeen used widely because of the relative insolubilities of these components inhydrothermal solutions. An objective method is needed to test these assumptions.In practice, ratios of immobile components remain constant regardless of thenature of alteration. This is an objective criterion for the recognition of immobile orconserved elements, and it can be easily proven as follows. Given that both dX and dZequal to zero (i.e. both X and Z are immobile), then we have equation 1-4 divided byequation 1-6:x 100X(S+d )— (1-10)— 100Z/(S+d ) — ZoThus, a bivariate plot of two immobile components from altered samples with acommon parent will define a linear trend that extends through the origin. The concept ofequation 1-10 for determining whether certain elements have been immobile in11metasomatism and hydrothermal alteration has been discussed and applied by Gresens(1967), Babcock (1973), Finlow-Bates and Stumpfl (1981), Grant (1986), Kranidiotis andMacLean (1987), MacLean (1988, 1990), Elliott-Meadows and Appleyard (1991), andMacLean and Barrett (1993). For example, Al, Ti, Zr, Nb, Yb and Lu commonly areshown to be immobile in hydrothermal alteration zones formed in homogeneous volcanicrock units (single precursor systems) at the Phelps Dodge deposit (MacLean andKranidiotis, 1987), at Atik Lake (Bernier and MacLean, 1989), and at other mines in theNoranda district (Cattalani et al., 1989).Some problems arise with the application ofNicholls’ (1988) third criterion forimmobility. First, let us see theoretically how many possible patterns can be present in aPER 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 zdY—ydZ (1-12)d(x/z) dX/z—xdZ/z2 zdX—xdZthe general form of intercept will be:ydX-xdY(1-13)z z z (zdX — xdZ)z zdX — xdZIf the slope and intercept of each individual pair ofpoints in a data set are equal, then allpoints will plot as a straight line on a PER diagram. Otherwise, a data set may show ascattered distribution pattern to various extents on a PER diagram. Eight possible casesare summarized in Table 1-2.According to Table 1-2, we see that Nicholl’s third criterion for recognizingimmobility is correct only under certain constrained conditions: (i) where elements in both12numerators 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 butwith 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. TheTable 1-2. Eight possible cases of PER diagram*case dX dY dZ slope intercept distributedpatterninfinite lines or1 < >0 < >0 < >0 zdY — ydZ ydX - xdY randomlyzdX — xdZ zdX — xdZ distributed2 < >0 < >0 =0 dY ydX - xdYdX zdX3 <>0 =0 <0 —ydZ ydXzdX - xdZ zdX - xdZ4 =0 < >0 < >0 zdY - ydZ dY-xdZ dZinfinite lines5 0 0 < >0 y/x 0 through the origin6 =0 < >0 0 {x/z = xdzo} cc a line// y/z axis7 < >0 0 =0 0 {y/z y0/z} a line II x/z axis8 =0 =0 =0 undefined undefined a point* After Russell and Stanley, 1990physical meaning of this example is that components x and y are highly correlated to eachother (i.e. both of them may exist in the same mineral phase concerned and have verysimilar geochemical properties). When this mineral phase is removed from the currentsystem, either depletion by crystal fractionation or by hydrothermal alteration, the contentsof 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, an13element ratio diagram that is not constructed with a set of conserved element in thedenominator could be randomly distributed rather than having a well defined trend with anear 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 immobilecomponents on the basis ofunderstanding the behaviors of these components and thegeological processes in which they are involved. Nevertheless, it is risky to accept suchassumptions without objective tests. It is efficient and rational to demonstrate immobilityin the available data set on the basis of the theorem that the ratios of conserved orimmobile components remain constant. Moreover, a re-examination of all possiblecandidates for immobility is warranted to demonstrate that they are not mineralogically orgeochemically compatible with each other during the hydrothermal alteration process.The concepts ofmobile/immobile and compatible/incompatible are used frequentlyin the literature. These terms share many features in common, but it is necessary to clarifytheir specific implications in the context of hydrothermal alteration. The concepts ofmobile/immobile are used to indicate whether or not a component has mass loss or gainduring a hydrothermal alteration process. The terms incompatible and conserved havebeen used to describe certain elements not involved in a primary differentiation processes.Here the terms compatible/incompatible are used to describe whether or not thegeochemical relationship among a particular group of components/elements aresufficiently correlated that they may have mass loss or gain in proportion to their initialratio during a hydrothermal alteration process. Therefore, a pair of possible immobilecomponents, determined from their constant ratio or highly correlated linear trend passingthrough the origin of the binary plot, also should be incompatible with each other. Toemphasize the point, consider a pair ofmobile components such as K and Rb which arealso highly compatible with each other and which in a hydrothermal alteration system maydisplay a highly correlated linear trend passing through the origin of the binary plot.14In 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 geologicalvariation, sampling and analytical error. Theoretically, the immobile component has notbeen involved in chemical transfer processes so the mass of the immobile componentremains constant in a single precursor system. In reality, samples may not have beenabsolutely identical to each other before hydrothermal alteration in terms of immobilecomponents, 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 ahigh degree of homogeneity in the parent system prior to hydrothermal alteration.Analytical error is another major source of apparent variation of ratios of immobileconstituents. Considering the influence of analytical error, Russell and Stanley (1 990a,1990b) suggest that one could test for immobile/conserved components with a PearceElement Ratio diagram accompanied by the propagated analytical error. If the dispersionor standard deviation of the ratio of two immobile or conserved candidates is less than orequal to the propagated analytical error, the dispersion can be interpreted to result entirelyfrom analytical error. In such a case, the two candidates may be used as immobile orconserved components. This rule has been used in the study of basalt systems by Russelland Stanley (1989, 1990a, 1990b).The rule should be used cautiously. If the PER ratio is constructed with one of thecomponents having a large geological variation and the other having poor analyticalprecision, then the latter component will contribute more to the final propagated error ofthe ratio, especially where it is used as the denominator of the ratio. As a result, mobilityof the former component might be obscured and the plot might lead to the correctconclusion that both numerator and denominator are immobile. Therefore, ‘immobile’components of relatively high analytical quality should be accepted in preference to thosewith poor analytical precision.15The second requirement for the removing of closure from lithogeochemical datacan be met conventionally through the careful investigation of field and petrographicrelationships in the study area. Rock derivatives altered to various degrees from a commonhomogeneous parent rock commonly are in close spatial proximity and may showgradational contacts between each other. Primary textural and structural features mayremain identifiable in least-altered to more intensely altered derivatives. To examine thesetypes ofvariations rigorously it is recommended that samples be collected systematicallyalong alteration profiles from the strongly altered rock adjacent to or within a mineralizedzone, to the least altered rock far from the ore deposit itself. Such sampling should bedone after a careful field investigation of the profile. Even though the altered rocks are ofmain concern, careful attention should be paid to the least altered or unaltered rocks. Theyprovide important information about the parent rocks that preceded hydrothermalalteration and give insight into the occurrence of single precursor or multiple precursorsystems.For a multiple precursor system, the sequential relationships between differentvolcanic or intrusive events and their phase variations should be determined as clearly aspossible. An efficient way of defining a single precursor system versus a multiple precursorsystem is to examine lithogeochemical plots, especially those constructed with immobilecomponents such as Zr, Ti andAl203(MacLean, 1990). A single precursor system willpresent a trend that extends through the origin on the plot. The plot pattern for multipleprecursor system will be more scattered but generally convergent toward the origin. If thenumbers of least altered or unaltered samples collected and analyzed are sufficient, theirplots may present a well defined trend either going through or cutting tangentially theregion where the altered samples plot, as in the case of a sequence of volcanic precursorsrelated through fractional crystallization from a common magma.161. 4. Pearce Element Ratios (PER) and their Applicationto Hydrothermal AlterationThe PER approach to examining metasomatic systems has an advantage over otherprocedures in not only removing the closure effect of lithogeochemical data but also: (i)explaining the corrected chemical variations in terms ofmineralogical variation(s), and (ii)testing for a multiprecursor system (Stanley and Madeisky, 1993). PER diagrams havebeen widely applied to the interpretation of igneous fractionation (Russell and Nicholls,1987, Russell and Stanley, 1989, 1990a, 1990b). Commonly, igneous crystal fractionationcan be interpreted by the addition or subtraction of one or a few minerals. Thus, a specificPER diagram can be designed to illustrate this crystal fractionation trend according to theknown stoichiometries of the relevant mineral phases. For example, the compositionalvariations of a suite of samples which are subjected only to olivine fractionation must berelated to the stoichiometry of olivine [(Fe,Mg)2SiO4],e.g., one mole Si gain or lossalong with two moles ofFe and Mg; thus the appropriate combinations (e.g., axescoefficients) of numerator elements for the axes ofPER diagram are SiI(conservedelement) as x-axis and 0. 5(Fe+Mg)/(conserved element) as y-axis. Finally, the hypothesisof olivine fractionation can be tested according to whether the plots of data are consistentwith the model trend that has a predesigned slope of one on the binary plot SiI(conservedelement) versus O.5(Fe+Mg)/(conserved element).Recently, Madeisky and Stanley (1993) applied PER analysis to lithogeochemicaldata for altered rhyolites collected from the volcanic hosted massive sulfide (VHIvIS)deposit at Rio Tinto, Spain. Their work revealed that quartz, potassium-feldspar andplagioclase fractionation and crystal sorting contribute to geochemical variations of theunaltered rhyolite. The fractionation trend is clearly shown on a PER diagram constructedwith Al/Zr as abscissa and (2Ca+Na+K)/Zr as ordinate. In addition, metasomatism (alkalidepletion) disperses data on such a plot, toward the abscissa, away from the fractionationtrend on the same PER diagram. Metasomatic additions and losses of elements have been17recognized up to 3 km from the centre of the mineralization system (Cerro Colorado openpit). Madeisky and Stanley (1993) also indicate that the rhyolite directly underlying themineralization is a highly evolved melt and only the most evolved portions of this rhyoliteare metasomatized, suggesting a genetic link between these highly evolved rhyolites andthe associated VITIVIS mineralization.Recent advances in dealing with metasomatic system have not dealt quantitativelywith mineral abundances ofboth parent and altered rocks. Nor have there been enoughefforts 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 aredue to variations of particular mineral(s), but the amount of these minerals have not beendetermined explicitly.The methodology of designing such a specific PER diagram for the purpose oftesting 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 acrossthe top), A is an axes coefficient matrix (with elements down the side and axes across thetop) and P is a phase displacement matrix (with minerals down the side and axes acrossthe top). The phase composition matrix contains the formulas ofminerals whose masstransfer effects are to be considered on the diagram. The axes coefficient matrix containsthe coefficients for the linear combinations for each axis of the PER numerator. The phasedisplacement matrix depicts the displacement that mass transfer due to specific minerallosses or gains will have on each axis.A number ofPER diagrams with known axes coefficients have been designed forspecific petrological material transfer hypothesis (e.g., Russell and Stanley, 1990a; Stanleyand Madeisky, 1994). They can be used to test real data sets for particular mineralogicalvariations as explanation of chemical variations. However, in attempting to design a18diagram, without knowing the PER numerator linear combination coefficients, a moredifficult set of procedures must be followed. These rely on the fact that a number ofconstraints, both mineralogical and geometric on the PER diagram being designed, can beassigned. This information allows determination of the entries in the ‘phase displacementmatrix’. Thus, with knowledge of the mineral formulae, the ‘axes coefficient matrix’ may becalculated using the approach of Stanley and Madeisky (1993). If C is a square and non-singular 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 Acan be obtained through:A=(CT xC’xCTxP (1-16)The following example is used to illustrate the procedure of designing a specificPER diagram, given a host rock of andesite in which feldspar and clinopyroxene aredominant. Propylitic, sericitic, argillic and silicic alterations and carbonatization arethought to be major causes of secondary lithogeochemical variations. Specifically, thereplacement of primary feldspar (about 60%) by muscovite or kaolinite and quartz, andthe replacement of primary mafic minerals (mainly augite and hornblende, about 5% and3%, respectively) by epidote, chlorite and carbonates are the major contributors tolithogeochemical variations. Thus a composition matrix (C) could be composed offourteen mineral phases (anorthite, albite, orthoclase, augite, hornblende, epidote,chamosite, clinochiore, calcite, siderite, magnesite, kaolinite, muscovite and quartz) andseven constituents (Si, Al, K, Na, Ca, Fe and Mg). This composition matrix C is thenused as a simplified system to test the hypothesis. The displacement vectors of primaryminerals such as anorthite, albite, K-feldspar and augite are defined to have slopes equal toone. The displacement vectors of alteration minerals are designed to have their slopesdifferent 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 PER19diagram can be determined by using equations 1-15 and 1-16. The detailed procedure ofthis calculation is as follows.An 2 2 0 1 0 0 0 x. y 2 2 AnAb 3 1 0 0 0 1 0 x 3 3 AbOr 3 1 1 0 0 0 0AL YAK 3 OrAug 2 0 0 1 0 0.5 0.5 K YK 2 2 Aug 117Qtz 1 0 0 0 0 0 0 X Ya 1 0 Qtz -Kao22000 0 0 XNaYNa 20.5KaoMus 3 3 1 0 0 0 0 Xpe YFe 3 35 MusEp 32020 1 0 XMgYMg 3 4 EpC x A =PMultiply the right side matrix (P) of equation 1-17 by the inverse matrix C to produceX, Ysz 0 0 0.29 0 0.43 0.29 —0.29 02 1 0XAI YAL 0 0 —0.36 0 —0.29 0.14 0.36 0 0 0.25XK YK 0 0 0.36 0 —0.71 —0.14 0.64 0 0 2.75XCa YCa = 1 0 0.14 0 —0.29 —0.86 —0.14 0 x = 0 1.5 (1-18)XNa YNa 0 1 —0.5 0 —1 —1 0.5 0 o”s 0 2.75XFe YF6 —2 0 —0.43 0 —0.14 0.57 0.43 1 3 3:5 0 0.5x 0 0 —1 2 —1 0 1 —1 0 0.5Mg .1MgA = (CTxC)4xCT x P = x yThe results of this calculation show that this specific PER diagram has a SiI(immobilecomponent) as its x-axis and [1/4A1+ 1 1/4(Na+K)+3/2Ca+1/2(Fe+Mg)j/(immobilecomponent) as its y-axis. The physical implications of this PER diagram can be understoodthrough the stoichiometries of relevant minerals. For example, the decrease or increase inmolar units of augite can be decomposed into two vectors (i.e., a one mole decrease orincrease ofboth Ca and Fe and/or Mg (along the y-axis) will cause a corresponding twomole decrease or increase of Si (along the x-axis) on this specific PER diagram because ofthe stoichiometry of augite [Ca(Fe, Mg)Si206].As a result, the plots of different sampleswhose lithogeochemical variation is caused by the fractionation of augite only, will display20a trend with a slope of one on this particular PER diagram. The vector directions of otherrelevant mineral phases including hornblende, chlorite (chamosite and clinochlore) andcarbonate (calcite, siderite, magnesite) then be projected on this PER diagram by usingequation 1-14.Fe—Cl 3 2 0 0 0 5 0 1 0Mg—C13200005 33Ca 0001000 X_01.5Sd OOoOolOxX,,1_OOS -Ma 0000001 00.5Hb 7201022 00:5 ‘C x A =PThe expected mineralogical variation paths on this PER diagram are illustrated inFigure 1 for various hydrothermal products commonly associated with precious- and base-metal vein mineralization in volcanic sequences. A detailed description about this PERdiagram is given as follows:(1) If all lithogeochemical variations are restricted by mineralogical variations offeldspar, augite and chlorite, then this set of lithogeochemical data will plot along atrend of slope equal to one and an intersection of zero.(2) Where quartz exists and has not been involved in mass change, the trend abovewill be shifted toward the right.(3) If the wall rock has suffered propylitic alteration (i.e. augite is replaced bychlorite, and primary feldspars are partially replaced by sericite through the additionofvolatile components), the ‘loss’ of primary minerals can be pictured as movingfrom the precursor composition (P) to a1 down along the trend of slope equal to oneand the ‘addition’ of alteration minerals can then be viewed as moving from P to a2along the trend of slope equal to one (the replacement of primary mineral and21a2C A//d/at////!/////,I//+e,(1,,I//.-12Figure1-1.PERdiagramspecificallydesignedtodiscriminateprimaryfractionationandhydrothermalalterationtypescommonlyassociatedwithprecious-andbase-metaldepositsinvolcanicsequences.qtz.Qtz-quartz,Carb-carbonates,Kao-kaolinite,An-anorthite,Ab-albite,Or,K-feldspar,Chi-chlorite,Aug-augite,Mus-muscovite,Ep-epidote.Seetextsforcetailedexplanation.c53 + c”1 ÷ + + ‘I +LegendAlterationpatherrorEp21.81.61.4-1.2- 1-0.8-0.6-0.4-0.2- 0-CarbAb,Or,ChlKaoQtzSi/TiO6formations of alteration mineral happen in the meantime, but it is convenient toanalyze a metasomatic process as two superimposed processes on this PERdiagram). As a result, propylitically altered samples will plot roughly around theirprimary precursor’s position (P) on this diagram.(4) Where the wall rock has altered into a bleached alteration envelope around theepithermal precious- and base-metal vein, in general, all primary mafic mineralsand feldspar are completely replaced by alteration minerals (from P to b1).(5) If carbonates and pyritization are the dominante alteration products whichreplace the primary minerals (i.e. intense carbonatization plus pyritization), sampleswill plot along a vertical trend shown on the left side of the primary fractionationtrend of slope equal to one (from b to c).(6) If muscovite or sericite is the dominante alteration product (i.e. intensesericitization), samples will plot around a trend of slope equal to 7/6, which is closeto 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), sampleswill 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), sampleswill plot around a trend parallel to x-axis (from b to f).In brief, some of the alteration types commonly associated with precious- andbase-metal vein mineralization in volcanic sequences are expected to be discriminated in apreliminary fashion on the PER diagram ofFigure 1 by the relative displacements ofaltered samples from the primary feldspar and augite fractionation trend (slope = 1).1. 6. Additional ProblemsMineral assemblages commonly occurring in alteration envelopes or zones can beidentified routinely with the aid of various conventional and advanced moderninstruments. However, still lacking is an objective and efficient way to assess the23abundances of each alteration mineral with confidence. This arises because hydrothermallyaltered rock commonly is characterized by a very fine-grained nature and/or intimateintermixing ofmineral species. The technique of point counting, useful for medium tocoarse grained rocks (especially igneous and metamorphic rocks) is limited in applicationsto products of hydrothermal alteration. In addition, serious sampling problems commonlyarise in using thin sections for quantitative modal analysis.The losses and gains of chemical components during the hydrothermal alterationprocess can be calculated with the aid of immobile components. This leads to anappreciation of possible reactions between primary minerals and altered minerals.However, the results of such calculations are not linked routinely in a quantitative waywith the mineralogical changes that arise during hydrothermal alteration. To make suchquantitative links immobile constituents must be identified and the precursor must beknown; such needs are relatively difficult to provide in hydrothermally altered rocks thatare products of open systems.PER diagrams are superior to other quantitative approaches for the evaluation ofhydrothermal alteration by not only removing the closure of lithogeochemical data, butalso by linking the lithogeochemical variations to the mineralogical variations. However,the PER diagram approach still has some limitations in a quantitative evaluation ofhydrothermal alteration. As demonstrated above, the PER diagram can be used to testhypotheses that chemical variations are due to variations of particular mineral(s). But theamount of these minerals can not be determined explicitly when a complicatedmultivariable system is dealt with because the total displacement on a PER diagramcommonly is the sum of the displacements of different minerals. The length and slope of adisplacement vector on a PER diagram may be the combination of various displacementvectors (i.e., various types of alteration). Briefly, the ambiguity about the relationshipbetween lithogeochemical variations and mineralogical variations may arise where toomany variables are squeezed into a two dimensional space. It is one of the goals of this24thesis to develop the idea of linking the lithogeochemical variations to the mineralogicalvariations and overcoming this limitation ofPER diagrams. The following study consistsof two parts: (i) a theoretical documentation about a quantitative approach extended fromthe PER diagram to hydrothermal alteration systems; and (ii) a detailed, quantitative casehistory of the alteration system associated with the Silver Queen polymetallic epithermalvein deposit in central British Columbia.25Chapter 2. Metasomatic Norms: A Method of Norm Calculation Adapted toHydrothermal Altered Rocks2.1. IntroductionModeling a hydrothermal system quantitatively using either only mineralogical oronly lithogeochemical data limits our knowledge of the system. We commonly limit ourquantitative understanding of chemical losses and gains in a system if hydrothermalalteration minerals are the extent of our study. Conversely, if only chemical gains and lossesare determined from lithogeochemical data (cf. Gresens, 1967) important mineralogicalfeatures are commonly minimized. Clearly, a procedure that takes account ofbothmineralogy and chemistry of altered rocks is desirable.lVlineralogy and chemistry of rocks are intimately linked through mineral abundancesand the compositions of individual minerals. One way of combining mineralogical andlithogeochemical approaches to the study of altered rocks is to compute mineral abundancesfrom 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 additionalinformation because: (i) the minerals so-generated are idealized, or are end members ofcomplex mineral families, and (ii) certain minerals or combinations ofminerals arechemically equivalent, for example, (Fe,Mg)2SiO4+ Si02 = 2(Fe, Mg)Si03.However,where sufficient mineralogical and chemical controls are available, the norm can be made toapproximate closely or even coincide with a mode.A norm is a’ ... theoretical mineral composition of a rock expressed in terms ofstandard mineral molecules that have been determined by specific chemical analysis....’(Margaret, et al., 1972). Norms are used to standardize rock description and classificationand to provide insight into some aspects of genesis. The concept, applied widely to igneousrocks, has had limited application to other rock types. Applications to metasomatized rocks26are hindered by the wide range of chemical changes involved and the complexity ofmanymineral compositions and mineral assemblages.Various researchers have attempted to derive mineralogical information fromlithogeochemical compositions for rocks other than igneous rocks. A particularlyinformative work by Brown and Skinner (1974) and Capitani and Brown (1987) usethermodynamic constraints and mass balance relations to calculate the weights of theminerals in the equilibrium mineral assemblages. Their results compare remarkably closelywith modes. Davis and Ferry (1993) use mass balance relations to calculate the modelprotolith mineral abundances by assuming that a simple mineral assemblage (includingcalcite, 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) formetasomatic rocks for the purpose of approximating modes of altered rocks.The above techniques share the use ofmass balance relations between bulk rockcomposition and mineral abundances. They differ in the method used to select a reasonablemineral assemblage with which to partition the lithogeochemical data. Brown and Skinner(1974) and Capitani and Brown (1987) determine the mineral assemblage based on whetheror 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 observationand/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 thecorresponding estimated normative mineral abundances. In reality, such is not the case.Some norm calculations leave some chemical components unused (residuals), such residualsshould be in the range of analytical error. In general, the smaller the residuals are, the betteris the quality ofmass balance. Brown and Skinner (1974), Capitani and Brown (1987) and27Davis and Ferry (1993) explain residuals as the mass losses or gains of correspondingconstituents. The assumption of a stable equilibrium relation in a hydrothermal system isoften questionable, whereas petrographic examination can provide the actual mineralassemblage.Normative approaches originally designed principally for igneous rocks are rigid intheir application, and in general, do not accomodate important alteration minerals. Inparticular, volatile components are essential constituents ofmany metasomatic rocks butare not involved directly in determining normative minerals either by the CIPW norm orNiggli-Barth norm procedures. A different approach to the determination of norms ofhydrothermally altered rocks by combining petrographic and lithogeochemical datawarrants investigation.2.2. The Principle ofMetasomatic NormsA possible approach to the application of the norm concept to metasomatic rocksis to constrain the calculated normative mineralogy by apriori knowledge of existingminerals (i.e., to approximate the mode as closely as possible). The methodology for thisapproach is a natural extension of the use ofPER (Pearce element ratio) diagrams for thestudy of metasomatic rocks (e.g., Stanley and Madeisky, 1993, 1994).Metasomatic norm calculation uses the same principles as the calculation of CIPWnorms (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 ofmetasomatic norms that represent hydrothermal alteration systems. Moreover, thecalculation of a metasomatic norm needs to take volatile components into account.Another distinctive difference between a metasomatic and a conventional igneous norm isthat the calculation of a metasomatic norm can not proceed along as fixed a hierarchicalpath as is the case of an igneous norm. More flexibility is necessary because of the widerange in both rock and mineral compositions. In some cases, where constrained by known28mineralogy, the calculations must iterate back and forth using various abundance ofnormative minerals in order to eventually balance or best fit a calculated mineralassemblage with the fixed chemical composition of an altered rock (i.e., to make thechemical masses and the mineral masses balance). In addition, the calculation of ametasomatic norm must take into account possible incompatible mineral pairs inhydrothermal system, for example, kaolinite and feldspar are not stable in the presence ofquartz.The mathematical relationship between lithogeochemical data and metasomaticnorms is discussed by Cheng and Sinclair (1994) as follows: a rock mass, P, is comprisedof the masses of a set ofminerals (mj):(2-1)For practical purposes, this equation can be extended in terms of the measurable items (inweight units) as follows:P x = (m x f,)) (2-2)i=1 1=1 j=1for i= 1, 2,..., q; and j1, 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 ofmineralj 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 andcorresponding molar amounts can be expressed as follows:29(2-3)for i = 1, 2, ..., q, andj = 1, 2,...,p, where nij is the number ofmoles of component unmineral phase j, a is the molar weight of component i, and bJ is the molar weight ofmineralphasej.The reference weight P can be assigned any value, for example, 100 grams, andequation 2-2 can be converted into molar units as follows:100 x(w1/a)=((m/b1)xn) (2-4)1=1 1=1 j=iIn equation 2-4 the weight fraction of each chemical constituent of the rock (Wi) ismeasurable through whole rock chemical analysis; a and b hold the constant molar weightsfor each chemical constituent i and each mineral phase j; f1 and nij are either measurablethrough an analysis of mineral separates or referenced from the standard stoichiometry ofcorresponding 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.. 0.. 0o :::: oo :: o }*;qflu ... fllj ... flip 1/b1 •. 0 •. 0 rnio :::: o (2-5)flqi...flqj...flqp o::o::i ,,orAxW=NxBxM (2-6)30where A [l/ajjlpxq (for ij, lIa1 = 0), W = [wjlq, B = [l/bijlpxq (for ij, 1/b = 0), N = [njjlpxqand M = [m].Generally, there is a larger number of unknowns than equations in the linear set ofequations 2-5 or 2-6. The values q and p are related to the number of analytical items andthe number ofmineral phases considered, respectively. Usually, the composition of a rocksample 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 solvedexplicitly. Some constraints are needed to reduce the number of independent variable m3sthrough either: (i) thermodynamic calculations (e.g., Brown and Skinner, 1974) to decidewhat are the stable mineral assemblages, or (ii) observation of the assemblage comprisingthe rock in question. It is essential that p is equal to or less than q in order that a uniquesolution is possible.In some cases the matrix might be singular or overdetermined. These problemsmay be caused by analytical errors and/or discrepancies between the compositions of realmineral phases of the rock sample and standard normative mineral phases used in matrixN. Thus, such set of linear equations needs to be solved using a fitting procedure, such asminimizing the sum of squares, R2 (e.g. Wright and Doherty, 1970; Stout and Nicholls,1977). The principle of the technique is to search for the solution which produces the leastR2 value (R2),where R2 (sum of squares of residual) is given by:R2 =>(w/a->(m x))2 (2-7)The least squares technique can provide either the best fit solution or the best fitapproximations.In brief, the calculation of metasomatic norms as introduced here rests on thesuppositions that lithogeochemical data are of adequate quality, and that the principal31alteration minerals have been identified. Norms determined in the foregoing manner areobjective and quantitative. They are representative of the processes being modeled and canclosely approximate modes of the altered rocks under study if appropriate constraints areavailable.2.3. A Set of Standard Normative Mineral Components for a Metasomatic SystemThe metasomatic process ofwall rock alteration, in most cases, can be describedas the additions ofvolatile components (H20, C02, S, etc.) and ionic components (K, Si,etc.) from hydrothermal fluid to wall rock and a corresponding depletion of some ioniccomponents of the wallrock (Na, Ca, Mg etc., extracted from the wall rock andcontributed to hydrothermal fluid). This process of chemical exchange can also bedescribed partly in terms ofmineral transformations. For example, anhydrous silicates suchas 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 arean essential part of a hydrothermal alteration system and cannot be omitted as in the caseof C]PW normative calculations.The selection of a set of standard minerals for metasomatic norm calculationshould be based on geological observations. Rock-forming minerals which account formost of the chemical components clearly have priority. In most cases for hydrothermallyaltered rock systems the major components are composed of: Si02,Al203,Fe203,FeO,MgO, CaO, Na20,K20,H20 and CO2. The standard minerals for metasomatic normsmust include hydrous phases, carbonates and sulfides as well as anhydrous minerals.Ivlinerals found to be appropriate for metasomatic systems can be classed into ninecategories:(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.The minor components contained in accessory minerals such asP205 (apatite), Ti02(ilmenite or rutile), are less important to make the masses balance. The abundances of suchaccessory minerals generally do not exceed a few weight percent; however, in certain casesthese normally minor minerals or trace minerals can be relatively abundant and can havestrong impact on the norm calculation. For example, S can be dealt with as a minorcomponent in most cases, but if a sample has more than a few weight percent of pyrite thenS becomes an important component.A set of standard normative minerals based on the autho?s experience in treatingmetasomatism associated with precious- and base-metal deposits in volcanic sequences islisted in Table 2-1. This list is not exhaustive. It can be extended by the addition of newstandard normative mineral(s) or substituted by other identified mineral species in order tomeet specific requirements.2.4. A Manual Procedure ofMetasomatic Norm CalculationPractically, the calculation ofmetasomatic norms is completed using a computer,but it is essential to understand the conceptual nature of the calculations. A manualprocedure has been developed patterned after the CIPW procedure. These calculationsmust balance the available components (analytical data for an altered rock) with theamounts of a particular group ofminerals of known or assumed compositions. By usingalteration minerals presented in the altered rock as members of the starting group of33Table 2-1. A List of standard normative mineral components for metasomatic volcanicrocks associated with epithermal ore depositsNormative Symbol Formula Molecularmineral weightFayalite Fa Fe2SiO4 203.79Forsterite Fo MgSiO 140.71Ferrosilite Fs FeSiO3 131.94Enstatite En MgSiO3 100.4Wollastonite Wo CaSiO3 116.17Rhodonite Rn MnSiO3 131.03Orthoclase Or KA1SiO8 278.34Albite Ab NaAlSi3Og 262.24Anorthite An CaA12Si8 278.22Epidote Ep aFeAli12(OH) 483.24Chamosite Fe-Cl e5A1Si30(OH)g 713.48Clinochlore Mg-Cl Mgl2i1(OH)g 555.78Muscovite Mu KA1Si0(OH) 398.3Paragonite Pa NaA13i1(OH) 382.2Kaolinite Ka A12Si5(OH)4 258.14Quartz Qz Si02 60.09Calcite Ca CaCO3 100.09Magnesite Ma MgCO3 84.32Siderite Sd FeCO3 115.86Rhodochrosite Rc MnCO3 114.95Pyrite Py FeS2 119.97Ilmenite Tm TiFeO3 151.75Rutile Ru TiO2 79.9Hematite He Fe203 159.7Magnetite Mt Fe304 231.55Apatite Ap Ca5(P0)OH) 502.21standard minerals, a metasomatic norm is expected to approximate the mode of thehydrothermally altered rock. The extent to which this end can be achieved depends on howclose the true mineralogy is reflected in the norm and whether appropriate mineralcompositions have been used in the calculations. In principle, the calculation scheme isdesigned to allot cations to various normative minerals and to add in as many anions asrequired. Hence, the difference in value between calculated cations and the correspondinganalyzed cations is generally equal to zero.To illustrate the procedure ofmetasomatic norm calculation, equation 2-3 or 2-4 isexpanded by using the standard normative minerals listed in Table 3-1 and a set ofequations results as follows.wax3map/bap (2-8a)w=a5x2m,/b (2-8b)34WTj (2-9a)WMil ax(mm/b+mrc/brc) (2-9b)WNa= aNax(maIjbabt mpa “bpa) (2-9c)WK= aKx(mo/bor+ mmu/bmu) (2-9d)WMg= aMgx(2mfo/bfo+men/ben+5Mgcl/ Mgcl+ mma/bmj (2-9e)WCa= acax(mwo/bwo+mjb+2ep/ ep+mca/bca+5apf ap) (2-9f)WFe+3 aFe+3x(mep/bep+mhjbha mj (2-9g)WFe+2 aFe+2x(mfa/bfa+e’bfe+5mFeC/bFeC1+mSd/’bSd+m3/b13,+m/b) (2-9h)w1 aMx(mO/bor+mabfbab+aflfbep/ epFec1/bFec1+2mMgcl/bMgcl+3mu mu aThpa+2mkaka) (2-1Oa)asix(mf.a/bfa+mf.o/bfo+mfe/bfe+mefl/befl+mwo/bwo+n+3mo/bof+3mab/bab+2mafl/bafl+3mep/bl,+3mFec1/bFe.C1+Mgc1/bMgcIfl.u/ mu.pa/bpa2mkabka+mdb) (2-lOb)w03=acox(m/b+m.a/bma+mJbsd+ml.Jbfc) (2-11 a)WOH aoHY(meJbl,+8mMgcl/bMgcl8flIrcFeC1/bFe1+2m/b+2mp/b+4Imjbka+map/bap) (2-i ib)WTO1 = Wet.j1s (2-lie)where w represents the weight percent of the certain constituent indicated by subscript, arepresents the molar weight value of the constituent denoted by subscript, m is the weightfraction of the mineral indicated by subscript, and b is the molar weight value of the mineralindicated by subscript.A general procedure to be followed in determining a metasomatic norm has beendeveloped patterned after the procedure used in igneous norm calculation. Significantchanges arise in the “metasomatic procedure mainly due to the necessity of accounting forvolatile components. A detailed procedure for establishing a metasomatic norm follows.351. Recast the oxide weight percentage values to cation amounts, obtained by dividing theweights percent of oxides by their respective molecular weight, multiplying by thenumber of cations in the oxide formula. For example, if a sample has 12 wt% AJ203,thenA13 = (12.00x2)/(26.98x2+16x3) = 0.23542. Use all P (and necessary Ca) to make apatite [Ca5(P04)3OH)]. A unique solution existsfor equation 2-8a because apatite is the only mineral in the set of standard normativeminerals containing P.3. Use all S (and necessary Fe) to make pyrite (FeS2). There is a unique solution forequation 2-8b because pyrite is the only sulfide considered in the current set of standardnormative minerals.4. Use all Ti (and necessary Fe) to make provisional ilmenite (FeTiO3)and temporarilyassign the value Ofmrjtjle equal zero (equation 2-9a).5. Use all Mn to make provisional rhodonite (MnSiO3)and assign the value of mrhodocosjteequal zero temporarily (equation 2-9b).6. Use all Na to make provisional albite (NaA1S13O8)and let the value Of1pagomte equalzero temporarily (equation 2-9c).7. All K is provisionally allotted to K-feldspar (KAISi3O8)and the value of is setto zero temporarily (equation 2-9d).8. There are 3 independent variables in equation 2-9e. Use all Mg to make provisionalMg-end member pyroxene, enstatite (MgSiO3),and leave the values of other Mg-bearingminerals as zero temporarily.9. There are five mineral phases in equation 2-9f the value of m tite has been calculatedpreviously with equation 2-8a. If the composition of plagioclase is known (i.e., the ratioof Ca:Na in plagioclase can be set) then an appropriate amount of Ca can be allottedprovisionally to anorthite (CaA12SiO8)by assigning all Na to albite. In other words,is dependent on malbite. Finally, use the remaining Ca to make provisional Caend member of pyroxene, wollastonite (CaSiO3)and set the values of mepjdote and mcalcjte36to zero.10. There are three mineral variables in equation 2-9g; the value of mepjdote has been setprovisionally in equation 2-9f above. Use all Fe3 and corresponding amount of ferrousiron to make provisional magnetite (Fe2O3FeO) and leave the values of mhematjteto bezero temporally.11. The values ofm.te and mmagnetjte have been determined by previous equations so thereare four items unknown in equation 2-9h. Use the remaining Fe2 to make provisionalFe-end member ofpyroxene, ferrosilite (FeSiO3)and leave the values of the remainingferrous 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 determinedby previous equations. As a result, the remaining excess Al is used to make provisionalkaoliriite [A12SiO5(OH)4].However, the rock may already have a deficit ofA13 at thisstage. In this eventuality the variable mkao1te in equation 2-1 Oa disappears and equation2-lOa becomes a constraint for the previous equations. To eliminate a deficit ofAt3 theindependent variables of certain minerals containing less A13 are used to substitute forsome or all of the provisional minerals in previous equations.13. All of the items but mqu in equation 2-lOb have been determined by previousequations. As a result, any excess Si is used to make provisional quartz (5i02). Ofcourse, Si4 may already be in deficit at this step, in which case equation 2-lOb becomesa constraint for the previous equations. This deficiency can be accounted for by using asindependent variables, certain minerals containing less Si4 relative to the provisionalminerals estimated in previous equations. For example, convert pyroxene[(Fe,Mg)2SiO6]to provisional olivine [(Fe,Mg)2SiO4]to the extent necessary to rectifythe deficiency.14. All items in equation 2-1 la have been determined by previous equations. Therefore, itis a constraint equation. If the sum of the provisional values on the right side of theequation is not equal to the measured value on the left side, adjustments are required to37make the mass ofCO;2 balance. Usually, the value on the left side is greater than that onright side of the equation at this step because the provisional allotments set the values ofall carbonates to be zero. Therefore, more carbonate(s) should be allotted to balancethe equation.15. There are no unknown items in equation 2-1 lb. As a result, it is another constraintequation. If the sum of the provisional values on the right side of the equation is notequal to the measured value on the left side, adjustments are required to balance theequation. If the measured value on the left side is greater than that on the right side ofthe equation, the independent variables ofminerals containing more hydroxyls arerequired and provisional amounts of anhydrous mineral must be reduced. Conversely, inother 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 twosides of this equation are not balanced, the preceding allotments of standard mineralabundances are somewhere in error.To this point in the calculation, there are two equations with unique solutions (2-8aand 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 thanavailable 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 notcompatible with quartz. In other words, the following reactions move to the right untilone of the components on the left side of the reactions is used up.Fe2SiO4+ Si02 2FeSiO3 (2-l2a)Fa Qz FsMg2SiO4+ Si02 = 2MgSiO3 (2-12b)Fo Qz En18. The second simplification is that kaolinite is not compatible with feldspar and38pyroxene under the condition that quartz exists. In other words, the following equilibriaproceed to the right until either kaolinite or anhydrous silicates on the left side of thereactions are used up.A12SiO5(OH)4+KA1Si3O8+2CaA1SiO8+Fe304+ 2CaSiO3 (2-1 2c)Ka Or An Mt Wo=KA13SiO10(OH)2+Si02 +2CaFeA1Si3O12(OH)+ FeSiO3Mu Qz Ep FsA12SiO5(OH)4+NaA1Si3O8+2CaA1SiO8+Fe304+ 2CaSiO3 (2-12d)Ka Ab An Mt Wo=NaA13SiO10(OH)2+Si02 +2CaFeAlSi3O12(OH)+ FeSiO3Pa Qz Ep FsM(OH)+Si4/9CaA1i1/9FeFeS O (2-12e)Ka Or An Mt Fs=KA13Si30 0( H)+2/9CaFeAIi2OH)+2/9Fe5823/ SiOMu Ep Fe- Cl Qz2i(0H)+NaMSi4/9Mh FeFeSi0 (2-12f)Ka Ab An Mt Fs=NaA13Si(OH)+2/9CaFe 12OH)+2/9Fe123/ SiOPa Ep Fe-Cl QzMi5(OH)+KISi84/9CaA11/9FeMgSiO3 (2-12g)Ka Or An Mt En=KA13 0( H)+2/9CaFe I2OH)+ /9Mg23/ SiOMu Ep Mg-Cl Qz12Si(OH)+NaAlSi4/9CaAl1/9Fe3O4+MgSiO3 (2-12h)Ka Ab An Mt En=NaA13 i00(OH)+2/9CaFe 12OH)+ /9Mg3/9Si02Pa Ep Mg-Cl QzThis simplification is supported by geological observation and thermodynamic relations.For example, according to the copper porphyry model, a phyllic or sericitic zoneseparates a potassic alteration zone from an argiffic alteration zone. On log (JQ/Hjversus log(H4SiO)activity-activity diagram, the stable region ofK-feldspar is39separated from that of kaolinite by muscovite in the presence of quartz.19. Some additional practical constraints can be set on a normative calculation. Forexample, the composition of plagioclase (k) is easily measured, thus, the relationbetween 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 solutionminerals. As a result, more constraints can be established. In addition, a set ofconstraints can be established limiting the values of calculated norms as never less thanzero.In summary, there are 14 independent variables after initial allotments, threeconstraints related to the mass balance equations ofOH-, C0;2 and total, and eightconstraints derived from two simplifications. In most cases, the bulk chemical compositionof the rock studied can be explained by about a dozen minerals within this set of standardnormative minerals. The final result is that a particular sample represents a system that issimpler than that initially assumed. In other words, a realistic system generally hassubstantially less than 14 independent variables. Therefore, a satisfactory solution cancommonly be achieved by using the above approach.A complex system, such as a weakly altered rock in which significant amount ofprimary minerals coexist with secondary alteration minerals, may have even moreindependent variables. Therefore, additional constraints are needed. Modern analyticaltechniques can provide the required knowledge-based constraints.The general procedural scheme for metasomatic norm calculation has beenintroduced. The procedure, however, is grossly inefficient for manual calculation.Consequently, a computer-based procedure using Quattro Pro 5.0, a sophisticated andreadily available spread sheet program, has been devised to process norm calculations. Itcan be easily converted to other spread sheet software (Appendix C). The procedureinvolves the use of a built-in module (the ‘Optimizer’) in the software. The general40procedures of using Optimizer is to (i) decide the solution destination such asW0 - Wmineral = 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 Optimizermodule can adjust the amounts of the variables and adhere to the constraints to provide afinal best fit solution. Unlike other ‘black box’ types of software, this calculation model istransparent. Users can easily adjust and develop it according to their own purposes.2.5. A Quantitative Model ofMetasomatic SystemsThe central goal of this work is to develop the concept ofmetasomatic norms andto apply the technique. One important outcome is the likelihood that with appropriatepetrographic constraints the norm and mode can be made to coincide. With the recognitionof an immobile component and a set of lithogeochemical compositions that includes bothleast altered parent rock (Zr) and altered daughter rock (Zd), the metasomatic norms andchemical constituents of an altered rock (xd) can be fhrther recast into the absolute amountsof minerals and chemical constituents (x+dx) for a given mass of parent rock (xe) by usingthe 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):zXP+dXEXd (2-14)Consequently, the contribution of each mineral to the chemical variations of bulk rock, theabsolute loss or gain of individual chemical constituents during hydrothermal alterationprocess can be stated explicitly as follows:Mineralent rock + Constituent gained from solution= Minerala1tered rock + Constituent lost from wall rock (2-15)41where all items have extensive units (e.g. grams). Such an equation is comprehensive,quantitative, and provides an easily understood chemico-mineralogical model; it illustratesand interprets a hydrothermal alteration system in terms of initial and final normativemineral assemblages (corrected for the closure) plus absolute losses and gains of chemicalconstituents. The model can be applied without the constraints of closed system andequilibrium assemblages.The value of such a model is that it provides useful, quantitative information aboutthe hydrothermal system. If the altered rock is the product of a simple and uniquehydrothermal alteration process, the model may reveal the properties ofhydrothermalsolutions associated with metasomatic events. In reality, the reaction used may more likelyrepresent 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 modelincludes starting and ending rock mineralogies that may be evident in the field, as well asdocumenting gains and losses of specific chemical constituents.This model is quantitative in the same way as Pearce element ratio diagrams. Thecommon principle is the correction for closure that provides true relative lithogeochemicaland mineralogical variations between parent and daughter rocks. The normative approachis a useful supplement to PER analysis; the two procedures have much in common andcontain much the same information presented in different ways. The sequence ofdeveloping a PER diagram is to:(1) remove the closure effect of lithogeochemical data to calculate the absolutechemical changes of elements by using an conserved or immobile element, and(2) interpret these absolute chemical variations in terms of specific mineral ormineral assemblage on a binary plot.In contrast, the technique ofmetasomatic norm is to:(1) allot the chemical analytical data of bulk rock into an assemblage of normativeminerals (that in certain cases will approximate the mode), and42(2) remove the closure effect of the norms and use the difference between norms(modes) ofparent and metasomatized rocks and elemental losses and gains todevelop a combined chemico-mineralogical model of the metasomatic process.The strategy of a PER diagram is to test whether chemical changes between two rocks canbe explained purely by changes in amounts of one or a few minerals as demonstrated by thedistribution of points along predefined trends (slopes). Metasomatic norms are displayedmore explicitly as equations (models) or profiles showing the spatial distributions ofnormative mineral assemblage as well as the absolute losses and gains of chemicalconstituents based on the comprehensive mass balance relationships.2.6. Case Histories: Application ofMetasomatic Norms2.6.1. Sigma Mine, Abitibi, QuebecMesothermal gold-quartz veins of the Sigma mine are enveloped by well defined, ifnarrow, walirock alteration zones (Robert and Brown, 1984, 1986). An outer crypticalteration zone is succeeded by a visible alteration zone immediately adjacent to the vein.The semiquantitative mineral variations across the alteration envelope are illustrated inFigure 2-1. Unaltered rocks are composed of a greenschist mineral assemblage: albitechiorite-epidote-white mica-biotite-quartz with minor carbonate and accessory apatite,ilmenite, and pyrite. The cryptic alteration is characterized by the variable replacement ofepidote by carbonate; the zone ofvisible alteration is marked by an abrupt outer transition(2-3 mm wide) parallel to vein margins, a carbonate-white mica outer subzone and acarbonate-albite inner subzone immediately adjacent to the vein. The salient mineralogicalfeature of visible alteration is the complete destruction of chlorite and biotite originallypresent in the parent volcanic rocks.A reassessment of the overall process of hydrothermal alteration at Sigma minecan be made by applying the technique ofmetasomatic norms using the lithogeochemicaldata presented in Table 2-2. The results of such a calculation (Table 2-3 and Figure 2-2)43Table 2-2. Variations in major element oxide concentration (inwt%) in the profile2103 across alteration envelope around tension veins, Sigmamine, QuebecSample_id 2103-14 2103-13e - 2103-13d 2103-13c2103-13b 2103-13aAlteration u ch-cb-mi cb-mi cb-abcb-ab cb-abSi02 61.28 59.19 50.04 49.5940.75 33.79A1203 15.66 16.33 11.73 13.04 10.52 9.22Ti02 0.66 0.7 2.23 1.33 1.27 1.62FeO 5.39 5.16 1.96 2.89 8.63 12.8MnO 0.14 0.12 0.27 0.180.17 0.17MgO 2.65 2.56 0.66 0.630.62 0.59CaO 5.03 4.65 14.76 13.42 14.52 14.1Na20 4.34 4.12 6.56 7.355.38 4.6K20 0.67 1.57 0.02 0.030.02 0.03P205 0.23 0.23 0.54 0.49 0.65 0.78H20 1.98 2.05 0.13 00 0C02 2.1 2.94 10.43 9.6710.76 10.63S 0.12 0.86 0.8 1.816.2 10.31Total 100.25 100.48 100.13 100.4399.49 98.64Density 2.74 2.74 2.71 2.74 2.84 2.98Profile 2103 is in feldspar porphyry.Alteration facies: U=unaltered rock, CH-CB-MI=carbonate-chlorite-white mica,CB-MI = carbonate-white mica, CB-AB=carbonate-albitend = not detectedData source: Robert & Brown 1986.Table 2-3. The calculation results of metasomatic norms (inwt%) in the profile2103 across alteration envelope around tension veins, Sigma mine, QuebecSample_id 2103-14 2103-13e 2103-13d 2103-13c2103-13b 2103-13aAlteration u ch-cb-mi eb-mi cb-abcb-ab cb-abCalcite 0.000 0.133 23.118 21.69022.769 21.749Epidote 20.367 18.323 0.000 -0.000 -0.000 -0.000Ca.pyx* 0.000 0.041 2.270 0.249 0.000 0.000Anorthite 0.000 0.000 0.000 2.489 4.497 4.401Mg-carb 3.543 5.355 -0.000 0.0000.000 1.078Mg-chl 2.637 0.000 0.300 0.0000.000 0.008Mg-pyx 0.000 0.000 1.373 1.5691.544 0.178Siderite 0.730 1.611 -0.000 0.0001.621 0.956Fe-chl 3.524 0.939 -0.000 0.0000.000 0.007Fe-pyx 0.000 0.000 0.000 1.5830.738 0.000Muscovite 5.667 13.279 0.169 0.0000.000 0.003K-feldspar 0.000 0.000 0.000 0.177 0.118 0.175Na-mica 3.973 1.254 2.775 0.0160.000 0.003Albite 33.999 34.003 53.607 62.18545.526 38.924Ilmenite 0.000 0.000 2.246 0.000 0.582 1.375Rutile 0.660 0.700 1.047 1.3300.963 0.896Kaolinite -0.000 0.300 0.198 0.000 0.000 0.009Quartz 24.126 21.980 9.6183.856 6.175 4.901Mn-carb 0.227 0.194 0.438 0.292 0.275 0.275Apatite 0.543 0.543 1.274 1.1561.533 1.840Pyrite 0.225 1.609 1.497 3.387 11.600 19.290Hemtite 0.000 0.000 0.000 0.0000.000 0.000total 100.220 100.265 99.930 99.97897.943 96.067* pyx - pyroxene; carb - carbonate; chl - chlorite.44II CDCDCDII0ot-t1.0CDto0II-i C0(oCD--CDCD 0II CD-CDCD.SD CDCDb C CD CD 0C -I CDCD CD CDD-toDCD<-t cL. CDooCD 0 CD CD -t 0 C CD C CD C))00 C CDI.wt%vol.%()1agree qualitatively with the results reported by Robert and Brown (Figure 2-1), but a fewquantitative differences arise. One is that the norm profile shows no significant differencebetween unaltered rock and cryptic alteration zone in contrast to the claim that rocks inthe cryptic zone have a marked decrease in epidote (from about 10 % to zero) andcarbonate increase (from 1 % to more than 10 %) relative to unaltered rock (Robert andBrown, 1984). Moreover, in all three alteration profiles for which chemical data arepublished by Robert and Brown (1986) it is clear that the CO2 content of the cryptic zoneis indistinguishable from the CO2 content ofunaltered rock (the contents ofCO2 inunaltered samples versus cryptic altered samples in profile 2103-10, profile 2103-13 andprofile 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 thenormative calculations reported here is the existence of abundant pyrite in an innersubzone of visible alteration zone. Even though Robert and Brown (1984) describe theexistence of pyrite, they did not estimate its abundance. Up to 10.6 % of S has beenmeasured, equivalent to about 10 wt.% pyrite or other sulfides.The third difference between the profile of norms and generalized modes is in theestimation of albite abundance. The reported modes indicate no change in the abundanceof albite between the unaltered rock and the cryptic alteration zone (about 50 volume % inboth) and an obvious increase in the amount of albite in the visible alteration zone (up to55 %). 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 60wt. % in the outer subzone of the visible alteration zone and a decrease to about 40 % inthe inner subzone immediately adjacent to the vein.The differences noted above emphasize how important quantitative changes can beoverlooked where semiqualitative modes are reported. A more objective procedure,46illustrated here by the metasomatic norm calculation, clearly avoids ambiguity inmeasuring mineralogical changes.2.6.2. Erickson Gold Mine, Northern British ColumbiaThe Erickson gold-bearing deposits are quartz veins that cut Mesozoic basalts inthe Cassiar area of northern British Columbia (Sketchley and Sinclair, 1991). These veinsare surrounded by extensive alteration envelopes (Sketchley and Sinclair, 1987) that canbe divided megascopically into 6 distinctive zones (Table 2-4). A semiquantitativecumulative 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 usingGresens equation and the assumption that Zr, Ti02and A1203were immobile (Sketchleyand Sinclair, 1987, 1991).The parent rock at the Erickson mine is noncarbonated basalt that has beenregionally metamorphosed to the upper greenschist faces. Sketchley and Sinclair (1991)concluded that the major chemical changes that took place during the development of thecarbonate alteration envelope are:(i) volatile components increase progressively from unaltered rock toward the vein,(ii)K20 is added throughout an alteration envelope but is most pronounced nearthe vein,(iii) Na20 is depleted throughout an envelope,(iv) Si02 is increased throughout an envelope, particularly where a quartz vein ispresent,(v) CaO is depleted in the outer part of an envelope and added to the inner part, and(vi) MgO and Fe203are depleted throughout an envelope except where quartzveinlets are present ( depletion is greater near the vein than in the outer portionof an alteration halo).They further qualitatively interpreted these variations as follows:47variations in mineralogy as afunction ofhost-rock composition and lossesandgains ofcomponents. Minerals noted in the carbonated basalt are ankerite,siderite, quartz, muscovite, kaolinite, titanium oxides, andpyrite. The presence ofcarbonates, hydrous aluminum silicates, andpyrite implies that the volatile (LOl)include, at least, CU2,H20, and S. An increase in volatile content corresponds to avolume increase.Table 2-4. Summary of Characteristics of Alteration Zones of Enclosing GoldBearing Ouartz Veins and the McDame Dolomite Vein, Total Erickson MineZone Thickness Occurrence Color Mineralogy(m)B-Noncarbonated Host Pale to dark green p1, chl, act, epi, aug, calc(trace),basalt ti-oxides, ±py±qtz±hem±mt2C-outer < 1 very pale green to buff p1, chl, ank, sid, qtz, ser, ti-oxide,carbonate common and pale gray ±kao±dol±py±carbon±calc±epi±aug±act2B-intermediate < 10 very buff to pale gray ank, sid, qtz, ser, ti-oxides±kao±dolcarbonate common ±py±carbon2A-inner <4 common buff to pale gray ank, qtz, ser, py, ti-oxides±sid±carbonate with minor green carbon±arsenopy±plmottlinglB-outer carbon < 1 uncommon buff to black ank, qtz, ser, py, ti-oxides, carbon±sid±arsenopylA-inner carbon < 3 uncommon black ank, qtz, ser, py, ti-oxides, carbon±sid±arsenopyNote: pl-plagioclase, chl-chlorite, act-actinolite, epi-epidote, aug-augite, calc-calcite, py-pyrite, qtzquartz, hem-hematite, mt-magnetite, ank-ankerite, sid-siderite, ser-sericite, kao-kaolinite, doldolomite, arsenopy-arsenopyrite.Data source: Sketchley and Sinclair (1991)Even though the chemical data (Sketchley and Sinclair, 1991; listed in Table 2-5)contain LOT rather than measurements of F120 and C02, it is still possible to allot cationto carbonates and hydrous minerals in such a way that theH20plus CO2 comprising LOTcan be balanced. Normative calculations ofminerals comprising the alteration envelope atErickson gold mine involve such a partitioning and results are in good agreement withestimated modes (Table 2-6, and compare Figures 2-3 and 2-4). Zone B (unaltered basalt)48has a mineral assemblage consisting of primary minerals such as plagioclase, pyroxene,etc., with a significant amounts of epidote and minor amounts of carbonate, ilmenite andapatite, that is, a greensehist facies assemblage. Zone 2C is characterized by kaolinite andmore quartz. Zone 2A is composed of abundant carbonates, sericite, quartz etc.The distribution pattern of chlorite, the main difference between the normative andmodal (petrographic) estimates, may arise due to an underestimation ofLOl (particularlyC02) since there is obvious difference between 100% and the reported analytical total(about 95%). More CO2 than reported will reduce the abundances of chlorite and K-feldspar and form more carbonate, sericite and quartz according to the following reaction.(Fe,Mg)5A12Si3O10(OH8+KA1Si3O85C02CM Or= 5(Fe, Mg)C03+KAIi3SiO10(OH)23SiO2+ 3H20 (2-16)Fe-Mg carbonate Mu QzThis reaction also indicates the importance of accurate measurements of H20, CO2 and Sin 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 fromthe 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, phlogopiteand biotite, etc.Several pairs of chemical constituents (e.g. Zr, Ti02A1203,totalFe203)show alinear trend through the origin of a binary plot (Figure 2-5); these pairs of components orelements are incompatible and they are interpreted as having been immobile during thealteration process. Metasomatic normative minerals can be divided by an immobilecomponent/element, such as Zr, to correct for closure (as in the case ofPER diagrams)and produce a quantitative model ofmineralogical changes during alteration. Figure 2-6shows the result of such calculation for a ‘typical’ Erickson alteration profile, by treatingthe percentage values of components of parent rock as the mass values in grams. It49Table2-5.ChemicalAnalysesofJennieVeinAlterationProfile,EricksonGoldMineU’CSample_id80-88-311-80-88-JH-80-88-JH-80-88-ill-80-88-311-80-88-.JH-80-88-ill-80-88-1H-80-88-311-Alteration2A2A2A2A2A2C2CBB(wt%)Si0238.8438.9539.5540.0441.8248.1952.6046.8147.90A120311.4011.4612.0712.0610.0215.1513.4313.5214.14Ti021.,D.A.andSinclair,A.J.1991,Econ.Geol.vol.86,pp.570-587Table2-6.MetasomaticNormsofJennieVeinAlterationProfile,EricksonGoldMineSample_id80-88-IN-80-88-311-80-88-ill-80-88-ill-80-88-ill-80-88-JH-80-88-JH-80-88-311-80-88-ill-Alteration2A2A2A2A2A2C2CBBCarbonate34.4834.4728.7327.3723.033.404.035.593.44Epidote0.>_____a)-o02A 2A 2A 2A ZA 2C ZCInner carboante zone outer carbonate zoneY’’sericite I* kaolintie fl I pyroxenevein quartz Ti-oxide chloriteFigure 2-3 Generalized distribution ofmineral species throughout carbonate alterationenvelopes enclosing gold-bearing veins,white quartz veins and carbon veins.Simplified from Sketchley and Sinclair (1991)‘ %- % S. S. S. S- :-VeinZoneLI I lo1ate epidote sericite kaolinitepyroxcne V//j plagioclase K-feldspar r I quartzFigure 2-4. Metasomatic norms profile Jennie vein, Erickson gold mine, northernBritish Columbia:70.--.--- , , , , / / , ., / , / / — ‘- - . ----:- ‘ . ‘. ‘. . .. ‘. ‘. . ‘. ‘. ‘. ‘. ‘. ,////////.. ‘ttt’fl ‘ .‘ . ‘. ‘. ‘. ‘ ‘. ‘‘. \ ‘. ‘. ‘.. ‘ S. ‘. ‘‘S.. ‘,,,,—,/—,,,,,,,,,,,‘.S.S.S.S. S. \S.’. ‘. S. \‘.S.S.’.S.5.5.5., /,,,,/,.,/, , ,, / // /...-. S.5.S.S.\5.S.5.5.’.5.’.S.5.5.5.S.’.S.5.\S.n •--•---.. 5.5.-....‘-.-.-’.‘--:-40 ::::.:,metabasaltepidotetY/’/i plagioclase80706050403020100(2AJennie2A 2A 2AInner Carbonate Zone2A 20 2COuter carbonate Metabasalt51Table 2-7a. Metasomatic norms corrected for closure and absolutelosses and gains of componentsfrom profile 80-88-JET across the Jennie vein, Erickson mine, northern British ColumbiaSample_id 8O-88-JH-1 80-88-JH-la 80-88-JH-2 80-88-JH-2a 8O-88-JH-380—88-JH-4 80-88-JH-5 80-88-JH-6 80-88-JH-7Alteration 2A 2A 2A 2A 2A2C 2C B BmoleCalcite 0.234 0.237 0.228 0.219 0.2490.03 1 0.040 -0.000 0.000Mg-carb 0.029 0.033 0.000 0.061 0.034 0.000 0.000 0.000 0.000Fe-carb 0.128 0.126 0.108 0.052 0.0250.000 0.000 0.000 0.000Mn-carb 0.003 0.003 0.003 0.003 0.003 0.002 0.003 0.003 0.002Mg-chl 0.029 0.028 0.034 0.022 0.0330.027 0.031 0.037 0.022Fe-chi 0.000 0.000 0.006 0.017 0.0220.017 0.021 0.009 0.004Muscovite 0.052 0.055 0.049 0.047 0.0380.002 0.013 0.000 0.000Na-mica 0.011 0.011 0.011 0.011 0.004 0.000 0.000 0.001 0.007Kaolinite 0.000 0.000 -0.000 0.000 0.0000.06 1 0.050 0.000 0.000quartz 0.435 0.446 0.415 0.415 0.5650.412 0.584 0.225 0.127Epidote 0.000 0.000 -0.000 0.000 0.0000.038 0.019 0.053 0.050K-spar 0.018 0.017 0.033 0.036 0.0270.002 0.000 0.003 0.002Anorthite 0.000 0.000 0.000 0.000 0.0000.000 0.000 0.014 0.020Aibite 0.000 -0.000 0.000 0.000 0.000 0.000 0.000 0.047 0.061Ca-pyx 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.044 0.031Mg-pyx 0.000 -0.000 0.000 0.000 0.0000.000 0.000 0.000 0.035Fe-pyx 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.015 0.028ilmenite 0.001 0.001 0.002 0.000 0.0150.009 0.017 0.016 0.017rutile 0.013 0.014 0.014 0.016 0.000 0.008 0.000 0.000 0.000apatite 0.001 0.001 0.000 0.000 0.000 0.000 0.001 0.000 0.000total 0.954 0.970 0.902 0.900 1.016 0.610 0.781 0.468 0.408dSiO2* 0.031 0.020 -0.018 -0.017 -0.142 0.005 -0.145-0.024 0.000dAl+3 0.012 0.008 -0.016 -0.012 0.012 -0.016 -0.006 -0.002 0.000dTi±4 0.002 0.001 0.001 0.001 0.002 -0.001 -0.001 0.000 0.000dFe+2 0.013 0.015 0.003 0.005 -0.010 0.011 0.002 -0.002 0.000dMn+2 -0.000 -0.000 -0.000 -0.000 -0.001 0.000 -0.001 -0.000 0.000dMg+2 0.009 0.008 0.009 0.011 -0.019 0.045 0.026 -0.005 0.000dCa+2 -0.05 1 -0.054 -0.044 -0.036 -0.065 0.076 0.102 -0.025 / 0.000dNa+ 0.057 0.057 0.057 0.057 0.064 0.068 0.068 0.020 0.000dK+ -0.068 -0.069 -0.080 -0.081 -0.062 -0.001-0.011 -0.001 0.000dP+5 -0.001 -0.000 0.000 0.000 0.000 0.000 -0.000 -0.000 0.000Sum 0= -0.015 -0.025 -0.065 -0.048 -0.0720.139 0.147 -0.026 0.000dH2O -0.042 -0.041 -0.084 -0.077 -0.129 -0.182-0.194 -0.076 0.000dCO2 -0.390 -0.396 -0.336 -0.333 -0.309 -0.031 -0.041 -0.000 0.000dS 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000dTotal -0.444 -0.477 -0.571 -0.531 -0.731 0.111 -0.054 -0.141 0.000dH2O’ -0.026 -0.017 -0.019 -0.029 -0.057 -0.321 -0.341 -0.051 0.000dCO2’ -0.360 -0.347 -0.206 -0.237 -0.166 -0.308 -0.334 0.000 0.000dOH- 0.000 0.000 0.000 0.000 0.000 0.000 0.000 -0.05 1 0.000dCO3= 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000dHCO3- -0.030 -0.049 -0.129 -0.096 -0.1430.277 0.294 -0.000 0.000* prefixe d stands for the absolute difference of corresponding constituent between the least altered and altered rocks52Table 2-7h. Metasoniatjc norms corrected for closure and absolute losses and gains of componentsfrom profile 80-88-Ill across the Jennie vein, Erickson mine, northern British ColumbiaSample_id 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 80-88-111-6 80—88--IH-7Alteration 2A 2A 2A 2A 2A 2C 2C B BgramCalcite 23.38 23.69 22.77 21.92 24.89 3.10 4.01 -0.00 0.00Mg-carb 2.43 2.81 0.00 5.16 2.91 0.00 0.00 0.00 0.00Fe-carb 14.78 14.56 12.49 6.08 2.87 0.00 0.00 0.00 0.00Mn-carb 0.29 0.29 0.30 0.30 0.39 0.26 0.33 0.29 0.26Mg-chl 15.99 15.58 19.12 12.10 18.41 15.20 17.29 20.76 12.31Fe-chl 0.00 0.00 4.06 12.10 16.01 11.98 14.74 6.26 2.76Muscovite 20.54 21.80 19.39 18.78 15.09 0.71 5.28 0.00 0.00Na-mica 4.39 4.14 4.27 4.37 1.66 0.06 0.00 0.38 254Kaolinite 0.00 0.00 -0.00 0.00 0.09 15.62 13.01 0.11 0.10quartz 26.17 26.81 24.93 24.92 33.95 24.78 35.11 13.52 7.62Epidote 0.00 0.00 -0.00 0.00 0.00 18.45 9.40 25.48 24.16K-spar 5.13 4.69 9.28 10.00 7.39 0.49 0.00 0.81 0.65Anorthite 0.00 0.00 0.00 0.00 0.00 0.01 0.01 3.98 5.68Albite 0.00 -0.00 0.00 0.00 0.00 0.04 0.09 12.23 16.12Ca-pyx 0.00 0.00 0.00 0.00 0.00 0.00 0.25 10.24 7.28Mg-pyx 0.00 -0.00 0.00 0.00 0.00 0.00 0.00 0.00 7.09Fe-pyx 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4.04 7.40ilmenite 0.22 0.22 0.33 0.00 2.20 1.38 2.59 2.48 2.51rutile 1.07 1.10 1.09 1.27 0.00 0.66 0.00 0.00 0.00apatite 0.34 0.31 0.20 0.20 0.22 0.23 0.25 0.25 0.24total 114.70 115.98 118.24 117.21 126.11 92.97 102.36 100.82 96.71dSiO2* 1.86 1.18 -1.06 -1.04 -8.52 0.31 -8.69 -1.46 0.00dAl+3 0.33 0.21 -0.42 -0.32 0.33 -0.44 -0.16 -0.06 0.00dTi+4 0.08 0.07 0.03 0.03 0.10 -0.04 -0.03 0.01 0.00dFe+2 0.72 0.83 0.19 0.26 -054 0.60 0.11 -0.09 0.00dMn+2 -0.01 -0.02 -0.02 -0.02 -0.06 0.00 -0.03 -0.01 0.00dMg+2 0.21 0.19 0.23 0.27 -0.46 1.09 0.63 -0.13 0.00dCa+2 -2.06 -2.18 -1.77 -1.43 -2.62 3.04 4.08 -1.00 / 0.00dNa+ 1.30 1.32 1.31 1.30 1.47 1.56 1.56 0.47 0.00dK+ -2.64 -2.71 -3.11 -3.16 -2.43 -0.05 -0.43 -0.02 0.00dP+5 -0.02 -0.01 0.01 0.01 0.00 0.00 -0.00 -0.00 0.00dH2O -0.75 -0.74 -1.51 -1.39 -2.32 -3.28 -3.50 -1.37 0.00dCO2 -17.17 -17.42 -14.77 -14.66 -13.60 -1.36 -1.79 -0.01 0.00dS 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00dTotal -18.39 -19.68 -21.93 -20.91 -29.81 3.64 -5.90 -4.10 0.00Residual -0.40 -0.40 -0.40 -0.40 -0.40 -0.09 -0.24 0.02 0.00dH2O’ -0.48 -0.30 -0.34 -0.52 -1.03 -5.77 -6.14 -0.91 0.00dCO2’ -15.83 -15.25 -9.08 -10.42 -7.29 -13.56 -14.72 0.00 0.00dOll- 0.00 0.00 0.00 0.00 0.00 0.00 0.00 -0.87 0.00dCO3= 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00dHCO3- -1.86 -3.01 -7.90 -5.87 -8.75 16.91 17.93 -0.02 0.005315 c0caC’] LIQI—• 00.0.• Ti02 * A1203 C Fe203Figure 2-5. Immobile components scatter plot, Erickson gold mine, northerm British Columbia20)inner carbonate zone outer carbonate zone metabasaltvein11111111 carbonate sericite chlorite pyroxene I:: quartzepidote kaolinite plagioclase K-feldspar mDisFigure 2-6. Metasomatic norm profile after closure effect removed, Erickson gold mine,northern British ColumbiaZr ppm54provides a clear and quantitative appreciation ofmineralogical differences between parentand daughter rock.The metasomatic norms corrected for closure can be integrated with the results ofthe absolute loss or gain of each chemical component to illustrate the totalchemico/mineralogic effect of the hydrothermal alteration process in equation form (Table2-7a and 2-7b). For example, the hydrothermal alteration of parent rock (sample 80-8 8-JH-7) to altered rock (sample 80-88-JH- 1) at Erickson gold mine can be illustrated in asimplified balanced equation as follows:0.O02Carbonate + 0.O5Epidote + 0.026CM + O.O94Pyroxene + O.081P1 + 0.O07Sericite + 0.l27Qtz0.26 g 24.16 g 15.07 g 21.76 g 21.8 g 2.54 g 7.63 g+0.Ol7llmenite+ Apatite+ 0.05 1Ca2+0.068K++2p+5+0.0261120+ 0.36C020.03HC032.51 g 0.24 g 2.06 g 2.64 g 0.01 g 0.02 g 0.48 g 15.83 g 1.86 g= 0.394Carbonate + 0.O29Chlorite + 0.O92Sericite + 0.018K-spar + 0.435Qtz+0.Ol3Rutile40.87 g 15.99 g 24.92 g 5.13 g 26.17 g 1.07 g+0.00 lllmenite+0.OolApatite+0.03 lSiO2+0.012A1+ 0.OO2Ti +0.013Fe20.22 g 0.34 g 1.86 g 0.33 g 0.08 g 0.72 g+0.009Mg2+0.057Na (2-17)0.21 g 1.30 gThis equation explicitly indicates which minerals are destroyed, which minerals are formedand which components are gained and lost during the hydrothermal alteration process.2.7. ConclusionsA metasomatic norm, particularly if constrained to approximate a mode, provides auseful tool to quantify the combined mineralogical and lithogeochemical changes affectedduring walirock alteration associated with hydrothermal mineral deposits. Advantages ofboth mineralogical and lithogeochemical approaches to the study of such systems areinherent in the procedure, Where modes can be approximated by norms the normativeprocedure generally will provide results more efficiently and more optimally because of55the better representative of samples collected for lithogeochemical analysis relative tothose generally used for modal analysis. Moreover, lithogeochemical analytical datagenerally are more objective and reproducible than are modal data.In summary, metasomatic norms:(i) lead to high quality estimates ofmineral abundances, and thus, provide accuratemineral distribution profiles across alteration envelopes,(ii) provide an objective and quantitative basis for a mineralogical classification ofhydrothermally altered rock,(iii) give an interpretation of lithogeochemical variations in terms ofmineralogicalvariations which are more compatible with field observations than areinterpretations quantifying lithogeochemical losses and gains only,(iv) with the recognition of an immobile component, can be recast into the absolutemasses (not percentages) ofminerals relative to a specified amount of the parentrock (e.g. about 100 grams), and(v) can be combined with the results of calculated absolute losses and gains oflithogeochemical constituents to form comprehensive mass balanced equations(model) for a hydrothermal alteration system no matter whether it is closed oropen, or in equilibrium or disequilibrium.56Chapter 3 Quality Control/Assessment of Lithogeochemical Data3.1. IntroductionIn a quantitative evaluation of hydrothermal alteration, it is essential to know thequality of data so that conclusions can be derived with confidence. Thus, it is important tounderstand all sources of lithogeochemical variations and know how to separate thevariation(s) generated by geological process(es) of interest from those generatedartificially. The major causes for the variations of lithogeochemical data are listed in Table3.1.Table 3.1. The classification of variations of lithogeochemical datagenerated by different processesPrimary causes Secondary causes Artificial causesFractionation metamorphism sampling and sample preparationMixing hydrothermal alteration analytical measurementAssimilation weathering closure effectIdeally, variations generated by artificial processes should be eliminated. Inpractice, they can only be minimized through quality control, such as the estimation of theoptimum sample size and the necessary fineness of the ground particle size. Thesevariations should be evaluated by quality assessment in terms of precision, accuracy anddetection limit. Among the artificial causes, closure effect has already been discussed inthe foregoing chapter. Consequently, this chapter focuses on:(i) strategies of field sampling and sample preparation (i.e., estimation of an optimalsample 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.573.2. Strategies of sampling and sample preparationVariation caused by improper strategies of sampling and sample preparation hasbeen 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 bysampling and sample preparation may be so large that the meaning of lithogeochemicaldata can be seriously distorted or obscurred. The object of lithogeochemical sampling andsample preparation is to use a small amount of sample or subsample to represent a muchlarger geological entity. However, silicate rocks, with few exceptions, contain two ormore mineral species with various grain sizes; rock powders prepared from them areheterogeneous to some extent. Consequently, it is possible that artificial variations whichcould significantly obscure lithogeochemical variations could arise from improperprocedures of sampling and sample preparation.The concepts of homogeneity and heterogeneity of certain elements in a sample orsubsample 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 theelement of interest in different samples can change correspondingly. From the perspectiveof sampling and sample preparation, the abundance of the mineral(s) containing theelement of interest is an objective constant or nearly so. However, the sample size isadjustable at the sampling stage and the particle sizes of subsamples are definable at thestage of sample preparation to make the sample or subsample more representative.Heterogeneity between the samples from the same site or subsamples from the samesample could be reduced to a minimum degree if the size (mass) of sample is large enoughor the particle size of a subsample is fine enough. In general, the coarser the grain size of a58rock, the larger the sample size needed to be representative. The smaller the size (mass) ofa 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 particlesize prior to subsampling, the effects are the same (i.e., increasing the number of grains orparticle (n) of the sample or subsample).To estimate the optimum mass for a sample or the necessary fineness of theparticle 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 ofinterest 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 compositionthroughout the bulk specimen.In reality, a sample or subsample may consist ofmore than two minerals and thedistribution of the element of interest can be more complicated than in the simplifiedsystem above. However, the main concerns here are:(i) whether the element of interest is homogeneously distributed in the sample orsubsample, 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 isgenerally more homogeneous than in a simplified ‘two-mineral mixture ofuniform size’system. For example, to analyze a rock consisting of quartz, K-feldspar and plagioclase asphenocrysts by using ‘two-mineral mixture ofuniform size’ model, plagioclase will betreated as the only mineral phase containing sodium and calcium, K-feldspar as the onlymineral having potassium and quartz phenocryst as the main contributor to the59heterogeneity of Si02. As we know, plagioclase also can contain a minor amount ofpotassium, K-feldspar, similarly, can contain small amount of sodium and calcium too.Both feldspars contain significant amounts of silica. Therefore, the homogeneity ofvariouselements as described in the simplified system is adequate in place of the more complicatedreal system. In brief, the simplified system is adequate for our discussion; use of real, morecomplicated systems may be more complicated than necessary in most cases and toocomplicated to deal with practically, in other cases.With regard to the simplification of uniform grain size, the mineral rich in theelement of interest contributes to both the total concentration of the element of interestand the error in determining concentration. Therefore, the grain size of the mineral rich inthe element of interest is usually used as the reference ofuniform grain size. The rest ofthe grains containing a low content of the element of interest are treated as the matrix. Inreality, the grain or particle size of a sample or subsample is not commonly uniform. Theassumption of a uniform grain size is acceptable ifwe either: (i) imagine that a coarsegrain ofmineral containing a negligible content of the element of interest is the equivalentof a number of grains as fine as the mineral enriched in the element of interest, or (ii) treata few finer grains of minerals containing a negligible content of the element of interest asthe equivalent of a coarser grain of the mineral enriched in the element of interest. In briefthe concept of uniform grain size always uses the grain size of the mineral rich in theelement of interest as the reference.With the above simplifications, a binomial distribution function can be used tosimulate the distribution ofmajor and trace elements during sampling and subsamplingprocesses 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 ofinterest 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 isequal to p and remains the same from grain to grain, and the probability of gettinga 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 elementof interest among the n grains.For a binomial distribution we haveP(x)=n! pxqn_x (3-1)x’(n—x)!where n is the total number of equant grains; x is the number of equant grains rich in theelement 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 elementof interest. Thus, the expectation (p.) of the binomial distribution is,u=np (3-2)and its variance (a2) jo2 =np(l—p)=npq (3-3)and its coefficient ofvariation (Rg) is(34)Equation (3-4) given by Kleeman (1967) illustrates the relationship between the number ofgrains (n) of the sample or subsample and the coefficient of variation of the graindistribution (Rg) generated by sampling or stages of sample preparation. Engels andIngamells (1970) improved Kleeman’s equation through converting the coefficient ofvariation (Rg) generated by sampling the non-representative grain distributions to thecoefficient of variation generated by lithogeochemical inhomogeneity (RE). The reason fordoing this is to take into account the minor contribution of the grains which are poor inthe element of interest to the total concentration in the sample of the element of interest.61p+q=1 (3-5)where p and q are the weight fractions of the minerals rich and poor in the element ofinterest, respectively. The relationship between the volume proportions and the weightproportions of the two minerals in the mixture is:qqd(3-6)P PWdLwhere dH and dL are the densities of the minerals rich and poor in the element of interestrespectively.E=Hp+Lq (3-7)where E represents the concentration of the element of interest in sample; H is theconcentration of the element of interest in the grain population with p fraction; L is theconcentration of the element of interest in the grain population with q fraction. FromKleeman’s equationR=./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 componentsLRL and HRH because these are not independent: as p increases, q decreases and Eapproaches H. The exact relation is:(ERE)2=(PWHRH —qLR)2 (3-10)The physical implication of equation (3-10) is that the distribution of the element ofinterest will become more and more homogeneous if the contributions from bothpopulations of grains to the total concentration of the element of interest become closerand closer to each other; thus the error from sampling and sample preparation will become62less and less significant. Furthermore, substitution of equation (3-6) in (3-8) and (3-9), andthen substituting (3-8) and (3-9) in (3-10), givesR = I x Hdff — LdL (3-il)E1fndHdL ENext, the relationship between the weight of the sample or subsample (w) and thecoefficient of variation is derived as follows:=+ wq = w (PWdL +qd) (312)dffv dLv dHdLvwhere v is the grain or particle volume in cubic millimeters; w is the weight in gram of asample or a subsample. Substitution of equation (3-12) and (3-7) in equation (3-11) gives:(Hdff—LdL)2 (3-13)R(pWdL + qd) (Hp +Lq)2Rearranging equation (3-13) gives:= wR(p,(,d +qdff) (Hp,, +Lq)2(3-14)(HdH — LdL)2In equations (3-13) and (3-14) the value ofRE can be predefined; the values ofH, L, dHand dL are known when the ‘two minerals’ are determined, the values ofp and q, can bereasonably estimated by examining the hand specimen. Consequently, equation (3-13) canbe used to calculate the optimum weight of the sample after the value ofv is estimatedthrough examining the grain size of the mineral containing the element of interest. For thepurpose of determining the necessary fineness of the subsample, equation (3-14) can beused 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 aredescribed in Chapter 6. It is helpful to understand the significances of equation 3-13 and 3-14 by following the calculation of a realistic example.633.3. Quality assessment of analytical measurementsbased on a small set of duplicatesThe discussion in the foregoing section has been aimed at the improvement inquality of lithogeochemical data at the stages of sampling and sample preparation. Next, itis important to focus on the quality assessment of lithogeochemical data at the stage ofanalytical measurement. A similar concept, quality control, has been commonly used bychemical analysts. However, the quality of lithogeochemical data in terms of analyticalprecision is not in all cases under the control of the geologist, but the quality oflithogeochemical data can be assessed through the examination of different types ofduplicates.All analytical measurements are subject to error. There are two types of errors:(1) random errors arising from the variations inherent to any sampling ormeasurement process, and(2) non-random errors causing systematic negative or positive deviations from thetrue result. Bias can be recognized through repeated measurement of standardsand is not considered here.Errors are assessed in terms of either precision or accuracy. Precision is a measureof analytical repeatability. A precise analysis is one where a set of replicate analyses formsa tight cluster around the average. The degree of precision is normally measured by thestandard deviation of the analyses or by the relative error (coefficient ofvariation).Accuracy is a measure of how close the analyzed data lie to the ‘true’ composition of thesample. One of the difficulties in silicate rock analysis is that the true composition, even inreference material, is in some cases poorly known (Potts, 1987). From a practicalviewpoint adequate accuracy can be considered to have been achieved where differentanalytical methods give essentially identical results (Fletcher, 1981). Further discussion onthis issue is beyond the scope of this thesis. Of practical concern is the issue of how todetermine the precision by using a small set of duplicate analyses.64Thompson and Howarth (1976, 1978) demonstrate that errors in analyticaldeterminations can vary significantly and systematically over a wide range ofconcentrations. Therefore, a single value of standard deviation calculated from a set ofduplicates of one sample cannot properly describe the analytical precision of a particularset of geochemical data over a wide range of concentrations. Instead, quantification of thesystematic relation of error to concentration is desirable. This approach leads to realisticerror estimates in contrast to the usual assumption of either a constant absolute error (byusing the standard deviation), or a constant relative error (by using the coefficient ofvariation). Thompson and Howarth (1976, 1978) approximate the variation of error as astandard deviation (Se) as a linear function of the concentration (C):S=S0+kC (3-15)The parameters S0 (intercept) and k (slope) can be used to quantif,’ the precision (Pc) atthe 95% confIdence level and at concentration C, by means of:P=2SJC (3-16)Substitution for S in equation (4-16) gives:= (2S0/C + 2k) (3-17)In addition, the practical detection limit Cd (when P = 1.0) can also be estimated fromequation (3-17) as follows:Cd = 2S0 /(1-2k) (3-18)Equation (3-18) indicates that the detection limit Cdis proportional to S0 and k, but thevalue of k should not be equal to or larger than 0.5, otherwise the detection limit C will beinfinite or negative and meaningless in the present context.To calculate the precision (Pa) of a particular component in a sample at a specificconcentration (C), it is necessary to know the values ofS0 and k. There are twoprocedures utilizing duplicate analyses to estimate these values (Thompson and Howarth,1976, 1978). Procedure 1 needs 50 or more duplicates which cover the whole range ofconcentration of interest in a relatively uniform pattern. These duplicates are further65divided into five or more groups (concentration ranges) with equal number of duplicates ineach group; this is done easily with a data set ordered using average concentrations ofpairs [(X1+2)/2]. The mean of the concentration [(X1+2)/2] and the median of thedifference (1X-21)for each group is then calculated. A linear regression of these valuesof[(X1+2)/2] and (1X-21)for each group is calculated or obtained graphically. Theregression parameters (intercept and slope) are multiplied by a coefficient (e.g. 1.048 at50th percentile because median values rather than mean values as the y-coordinate) to giveS0 (intercept) and k (slope) of the error model (cf. Fletcher, 1981).Procedure 2 requires only 10 to 50 duplicates. This is normally the range oflithogeochemical duplicates for a study ofhydrothermally altered rocks. Therefore, adetailed discussion will be given herewith. The basic idea of this procedure is to test theavailable duplicate data against an empirical standard of precision to see whether theanalytical duplicates can be accepted at a specific precision. The empirical equations givenby Thompson and Howarth, (1976, 1978) are listed below:d90 = 2.326(S0+ kC) (3-19)d99 = 3.643(S0+ kC) (3-20)The equations above are derived from equation (3-15) and the specific constants (2.326and 3.643) represent specific percentiles of a one-sided normal distribution (i.e. d99 andd90 represent the 99th and 90th percentiles respectively of the absolute difference 1X-2between pairs of duplicate analyses (X1,X2)). These absolute difference are estimators ofthe standard deviation (Se) at composition C where C = (X1+2)/2. Consider an exampleto illustrate this procedure. Figure 3-1 is constructed with (X1+2)/2 as x-axis and 1X-2as y-axis; eighteen pairs ofAl203duplicate data are plotted. Then assuming S0 = 0, twopercentile lines (90th 99th respectively) are drawn on this diagram according to equation3-17 to test whether the precision ofAl203in this set of lithogeochemical data is betterthan 2 % (Pc = 0.02). If the duplicate analytical data comply with the specification, onaverage 90% of the points will fall below the A90 line and 99 % of the points below the66A99 line. If in Figure 3-lA, the precision is worse than that tested, then the value of kshould be raised, a poorer precision will result. In this example, a satisfactory result isachieved by raising the value ofprecision to 4.2%. As a result, around 90% of the plottedpoints fall below the 90th percentile line and 99 % of the plotted points below the 99thpercentile line in Figure 3-lB.For general geochemical purposes a control chart (for 10% precision, i.e. withpercentile lines drawn for the specification S=0.05C on logarithmic axes) devised byThompson and Howarth (1976,1978) has been widely used. Difficulties in the use of thiscontrol chart arise where the concentrations of some duplicates are close to the detectionlimit, that is, where the precision is near 100%. For example, an alteration profile crosscutting a propylitic alteration halo and a sericitic/argillic alteration envelope are usuallycharacterized by a high concentration ofNa20 in propylitically altered rock, but an almostcomplete depletion ofNa20occurs within the sericitic/argillic alteration envelope. Usingthe control chart, above, the precision ofNa2Omeasurement tends to be largelyoverestimated because only the k value of the linear equations 3-19 and 3-20 is adjustableto meet the plotting requirements imposed by the 99th and 90th percentile lines (i.e. thereis no point above the 99th percentile line and there are less than or equal to 10% of pointsabove the 90th percentile line). There is an obvious discrepancy between the calculatedprecision and the deviation represented by the duplicates of high concentration (Figure 3-2A). 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 fromthe detection limit.There is a substantial disparity between procedure 1 and 2. Procedure 1 defineserror 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 50pairs of duplicates, where data are sufficiently precise that both S0 and k can be estimated,even if not as rigorously as in procedure 1.67><C\4><><Figure 3.-I. Schematic illustration of Thompson and Howarth’s procedure 2 (see text) forthe precision estimation of a set of lithogeochemical data. (A) The duplicate data donotcomply with the 2% error test percentile lines. There are more than 10% and 1% ofplots fall above the 90th and 99th percentile lines respectively. This means that theprecision ofA1203in this set of data is higher than 2%. (B) After raising the precision to4.2%, only 2 out of 18 duplicates plot between the 90th and 99th percentiles. Therefore,this precision is acceptable.(Xl +X2)/20 5 10 15 2025(Xl +X2)/2680.899t0.7 thNa2050________0.6So = 0.00k = 0.8Pc = 1.6c40.4><•CD CD0--a p II I —0 0.5 1 1.5 22.5 3 3.5 4 4.5(Xl +X2)/20.80.7Na200.6So = 0.09::z—CD 50th0.1_________ _ _ _ _ __ _ ____________________ID0- I0 0.5 1 1.5 22.5 3 3.5 4 4.5(Xl +X2)/2Figure 3-2. Comparison of the methods of precision estimation of lithogeochemical databy using: (A) constant precision and variable standard deviation for whole range of theconcentration, and (B) variable precision and variable standard deviation. See text fordetailed explanation.69One 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 ofdetection limits of each analytical technique for differentconstituents are provided by the analyst. With the known value of detection limit (Cd),equation (3-18) can be rearranged as follows:S0= Cd (0.5-k) (3-2 1)substitution of equation (3-21) in (3-19) and (3-20) gives:d90 =2.326(O.5Cd+ k(C-Cd)) (3-22)d99 =3.643(O.SCd + k(C-Cd)) (3-23)Now only one variable (k) remains in equation (3-22) and (3-23). Following the sameprocedure as Thompson and Howarth (1976, 1978) one increases the value of k andmoves the 99th and the 90th percentile lines up until no plotted point lies above the 99thpercentile line and less than or equal to 10% of the plotted duplicates lie above the 90thpercentile line. The value (k) can then be estimated. Thus, the value S0 can be calculatedby using equation (3-2 1).Where the information about detection limits is not available, there is another wayto deal with this problem, that is, the estimation of S0 and k based on the analyticalduplicates. A recommended procedure is as follows:(1) Introduce one more empirical precision equation to set one more constraint for takingone more variable (S0) into account,d50 0.954(S + kC) (3-24)(2) Initially assume S 0;(3) Gradually increase the value of k starting from zero in equations (3-20) until no pointis above the d99 line (since 99% of points for a small set of duplicates 10 to 49 pair ofduplicates means that all points should be below the 99th percentile line);(4) Construct the d90 line with the current values of S0 and k derived from the previousstep and check whether 90% of the points are below the d90 line. If not, continue to70increment of k until only 10% of the points are above the d90 line;(5) Construct the d50 line with the current values of S0 and k derived from previous stepsand check whether about 50%, or the maximum amount between 10 to 50% of thepoints, are above the d50 line. If the points above the d50 line are less than 50% or themaximum amount value between 10 to 50% of the total plotting points, then reject theinitial assumption of S0;(6) Reassign the initial value of S0 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 S0 and k, no point is above the d99 line, no more than 10% of thepoints are above the d90 line and about 50% or the maximum amount between 10 to50% of the points are above the d50 line (Figure 3-2B).In brief, this approach helps obtaining reasonable estimates of S0 and k.Consequently, the precisions of a particular set of lithogeochemical data with wide rangesof concentrations can be estimated in a form consistent with the case for more abundantpaired data (i.e., duplicate pairs> 50).3.4. Propagation of Errors in Calculation ofMetasomatic NormsLithogeochemical data always incorporate some component of random error.Quantitative estimates of losses and gains of components during hydrothermal alterationare limited by the magnitude of these errors. Errors in analyses of individual componentscommonly are known. An important concern is the effect these known errors have onvarious calculated quantities, that is, the propagation of errors (Le Maitre, 1982; Chengand Sinclair, 1994).In mathematical terms, if the calculated result, z, is a ffinction of a set ofmeasuredvariables: x1, x2, . .z=f(x1,x2...x) (3-25)71The quantity z will be in error by an amount dz as a consequence of the errors in each ofthe measured quantities x1, x2, . . .x. Then the error dz (as a variable) can be estimatedusing the approximation (e.g. Kendall, 1943):=--Js. + )s (3-26)where x1 and Xj are the ith component and thejth component respectively, S is theanalytical error calculated through equation (3-15) by using corresponding S0 and kvalues; and S, is the value of covariance between the ith andjth variable. It is reasonableto treat the error of lithogeochemical data as independent since the analytical error of oneelement has no obvious link to the error of the other element. Therefore, a simplifiedequation used to calculate error propagation is as follow:2= (3-27)Substitution of equation (3-15) in (3-27) gives:2=(St,. +k1x)2 (3-28)Since the value of S)q is one standard deviation of a normal distribution, the value of errorpropagation (Si) derived from it is at the 68% confidence level. Equation 3-27 iscommonly 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, andtheir sum must be negative. This means that if the covariance terms in equation 3-27 areignored, the absence of their overall negative contribution will tend to give anoverestimate of the variance. As this is generally more acceptable than an underestimate ofthe variance, the use of equation 3-27 for closed data would, therefore, seem reasonableas a first approximation.72For the calculation of loss or gain of a specific component in a single precursorsystem the following equation is used:zdX=tXdxp(3-29)where dx is the value of absolute loss or gain of a component x during the hydrothermalalteration process, Z is immobile during the alteration process, x., and Xd are the mobileelement concentrations in the least altered parent rock and altered daughter rockrespectively. In equation (3-29) the calculation result (dx) is derived from four analyticalmeasurement values (i.e. Zd, Z,, Xd and x.). Each of these four values has its ownuncertainty. The value of dx contains the combination of the errors derived from all formerdependent variables. Thus, the error propagation can be evaluated as follows:= +kZ)2+[_)(S0 +kzZd)22 2(3-30)(S0 +kXxd)2+[._] (S +kx)2,- iZxi=(Se, +kZ)2+ ) (S0 + kzZd)2z2(3-31)(S0 + kXxd)2+(S0 +By using an error determined from equation (3-31) the calculated absolute losses andgains of chemical constituents can be evaluated at an appropriate confidence level.For the calculation of the propagated error of an specific normative mineral, it isfirst necessary to find the functional relationship between the amount of a specificnormative mineral and related chemical constituents allotted to it. A specific normativemineral can be treated as the summation of certain portions of relevant chemical73constituents from the whole rock compositions. Therefore, the functional relationshipbetween the percentage of normative mineral and concentration of different componentsused 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 ithcomponent used to make the normative mineral from the bulk rock compositions, and x1 isthe concentration value of ith component in the rock. Substituting equation (3-3 2) in (3-28), we have:S =a(S0+k1x)2 (3-33)By using equation (3-3 3) the uncertainty of a metasomatic norm calculation can beestimated through error propagation at the 68 % confidence level.There are two fundamental assumptions for the calculation of propagated errors asoutlined above:(i) the errors of lithogeochemical data are assumed to be independent of each otherbecause the error of certain chemical constituent of the whole rock sample has noobvious 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 anormative mineral in the same proportion as the chemical constituent is allotted tothe normative mineral.It is hard to prove these assumptions. Their use may lead to small overestimates of thepropagated 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 acomprehensive mass balance equation introduced in the previous chapter. We have:74M1neraI,eflt rock ±error + Constituent gained from solution±error=4ineralalted rk±0r + Constituent lost from wall rock±error (3-34)Propagated errors provide a basis for screening data for inclusion in the chemicomineralogic model. Abundances less than twice the propagated error are not significantlydifferent from zero and can be ignored.75Chapter 4. Geology of the Silver Queen Mine, Owen Lake Area,Central British Columbia4.1. IntroductionThe Silver Queen (also known as Nadina or Bradina) mine is near Owen Lake, 35kilometres southeast ofHouston, and 100 kilometres southeast of Smithers in the BulkleyValley region of central British Columbia (Figure 4-1). The deposit has had a long historyof 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 210,185short tons of ore during a brief period from 1972 to 1973. Mine closure was due tooverdesign of the mill and complex metallurgy (Cummings, 1987; Dawson, 1985).Geological reserves of the No. 3 vein at the Silver Queen mine presently stand atapproximately 500,000 short tons grading 3 g/t Au, 200 glt Ag, 0.23% Cu, 0.92% Pb and6.20% Zn (Nowak, 1991). Equity Silver mine (total reserves plus production ofapproximately 30 million tonnes of 0.4% Cu, 110 g/t Ag, and 1 g/t Au) lies 30 km to theeast-northeast.Geological mapping of the 20 square kilometre area surrounding the depositsuggests 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 correlatedwith rocks hosting the Equity Silver deposit (Wetherell et al., 1979; Cyr et al., 1984); theyare 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 bytheir distinctive lithogeochemical characters and K-Ar dating ages. The Silver Queen mineis hosted in the older series of igneous and volcanic rocks and is cut by dikes belonging tothe younger series. Therefore, mineralization at the Silver Queen mine occurred during theperiod after the older series of igneous and volcanic activity, but before the younger one.764.2. Regional Geological SettingThe study area lies within the Stikine terrane, which includes submarine calcalkaline to alkaline immature volcanic island-arc rocks of the Late Triassic Takla Group;subaerial to submarine caic-alkaline volcanic, pyroclastic and sedimentary rocks of theEarly to Middle Jurassic Hazelton Group; successor basin sedimentary rocks of the LateJurassic and Early Cretaceous Bowser Lake, Skeena and Sustut groups; and LateCretaceous to Tertiary calc-alkaline continental volcanic arc rocks of the Kasalka, OotsaLake and Endako groups (Maclntyre and Desjardins, 1988). The younger volcanic rocksoccur sporadically throughout the terrane, mainly in down-thrown fault blocks andgrabens. Plutonic rocks of Jurassic, Cretaceous and Tertiary ages form distinct intrusivebelts (Carter, 1981), with which porphyry copper, stockwork molybdenum andmesothermal and epithermal base-precious metal veins are associated.The Silver Queen mine lies on the caldera rim or perimeter of the Buck Creekbasin, which is delineated roughly by a series of rhyolite outliers and a semicircularalignment ofUpper Cretaceous and Eocene volcanic centres scattered between FrancoisLake, Houston, and Burns Lake (Figure 4-1; see also Fig. 59 of Church 1985). The BuckCreek basin has been interpreted as a resurgent caldera, with the important Equity Silvermine located within a window eroded into the central uplifted area (Church, 1985; Churchand Barakso, 1990). A prominent 30 km long lineament, trending east-northeasterly fromthe Silver Queen mine towards the central uplift hosting the Equity mine, appears to be aradial fracture coinciding with the eruptive axis of the Tip Top Hill volcanics and a line ofsyenomonzonite stocks and feeder dikes to an assemblage of Tertiary ‘moat volcanics’(Church, 1985). Block faulting is common in the basin, locally juxtaposing volcanic rocksof various ages.Within the basin, a Mesozoic volcanic assemblage is overlain by a Tertiary volcanicsuccession. The oldest rocks exposed within the basin are at the Equity Silver mine and77540 540Figure 4-1. General geology of central British Columbia, showing the regional setting ofthe study area (after Maclntyre, 1985). Tpb - Tertiary plateau basalt; Eg - Eocene granite;KTo - Ootsa Lake Group; Kg - Cretaceous granite; Kk - Kasalka Group; Ks - SkeenaGroup; Jg - Jurassic granite; Th - Ha.zelton Group.128° 126°55°5500 25 50K I 0n e t r e s78the 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 withangular unconformity by Lower Cretaceous Skeena Group sedimentary rocks.However, Wojdak and Sinclair (1984) correlate the sequence hosting the Equity minewith the Lower Cretaceous Skeena Group sediments, and Wetherell et al. (1979) andCyr et al. (1984) correlate it with the Lower to Upper Cretaceous Kasalka Group. TheKasalka Group is considered to be a late Early Cretaceous (Armstrong, 1988) or earlyLate Cretaceous (Maclntyre, 1985; Leitch et al., 1991) continental volcanic successionthat is predominantly porphyritic andesite and associated pyroclastic rocks. It is wellexposed in the Kasalka Range type section near Tahtsa Lake.Upper Cretaceous rocks with similarities to the Kasalka Group are exposedwestwards from the Equity mine to the Owen Lake area, where they host the Silver Queendeposit (Church, 1984). These rocks, which have been dated at 75 to 80 Ma by K-Arwhole rock (Church, 1973; Leitch et a!., 1991) consist of a lower felsic volcanic unitoverlain by andesites and dacites of the Tip Top Hill volcanics (Church, 1984). Thissubdivision is based on ‘rhyolitic volcanic rocks below the Tip Top Hill Formation in theOwen 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 exposednearby on Okusyelda Hill’ (Figure 4-2). Recent mapping indicates that the lower volcanicunit exposed in the drill holes may, in part, be a strongly altered equivalent of the Tip TopHill volcanics (Leitch et a!., 1991). The quartz porphyry of Okusyelda Hill could correlatewith dacitic quartz porphyry sills, dikes and laccoliths common within the type KasalkaGroup section in the Tahtsa Lake area. Late quartz-feldspar porphyry dikes are also foundat the Equity mine (Cyr et a!., 1984; Church, 1985), although these are dated at 50 Maand 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 Goosly79Lake andesitic to trachyandesitic volcanic rocks are dated at 48.8 ± 1.8 Ma by K-Ar onwhole rock, and this is supported by similar dates of 49.6 ± 3.0 to 50.2 ± 1.5 Ma forrelated syenomonzonite to gabbro stocks with distinctive bladed plagioclase crystals atGoosly and Parrot Lakes between Equity and Silver Queen (Church, 1973). Andesitic todacitic volcanic rocks of the Buck Creek formation, which directly overlie the GooslyLake Formation, are dated at 48.1 ± 1.6 Ma by K-Ar on whole rock (Church, 1973). TheGoosly Lake and Buck Creek formations correlate with Ootsa Lake Group rocks in theWhitesail 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 ofOotsa 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 ofEocene-Oligocene age. Theserocks give dates of4l.7 ± 1.5 to 31.3 ± 1.2 Ma by K-Ar on whole rock samples from theadjacent Whitesail Lake map-area (Diakow and Koyanagi, 1988; cf. the range of 45-40Ma reported by Woodsworth, 1982).The youngest rocks in the Buck Creek basin are cappings of columnar olivinebasalt ofMiocene age, called the Poplar Buttes Formation by Church (1984). These havebeen dated at 21.4 ± 1.1 Ma by K-Ar on whole rock (Church, 1973) and are correlatedwith the Chilcotin Group.4.3. Geology of the study areaThe preliminary geology of the study area immediately surrounding the SilverQueen 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 mapunits are shown diagrammatically in Figure 4-3. The succession is strikingly similar to thatobserved in the Kasalka Range (Maclntyre 1985) and on Mount Cronin (Maclntyre andDesjardins, 1988).80Okusyelda I-liltSb 45b 1’.4 76270 _••_Emil ‘42George\b3,‘ i-1&0 \.5 4 GeorgeCopper Veja \ Lake —Lake26/ BartteVebt\*1-47 i ‘k.oleVetri Systemc Sear Veki/‘ 3No. 2 Vein / 2sf \7I/ / 76 Lead VeNo.1 2Vein7\26n5George Lake0 4 •[;- CLIneament Vein0, 78 NG 6 VenS --... .. / 70 2 ci60 Mine Q-5 No. 56 -. • -.,tfll 855 . :---v NA \eo. \ CFCamp V ns . . •. ,08 £11O 2.25 Sw(tchback .-.2,,VekiNo. Ruby Vein.... 5 Vein SV — 5a NG 3 Vein3 \.5 -.-.-.- V•,,,5a60\Cttuci2.: \3:°“,>. 2holm Veins2________________________4 t,5c\0.7e1Figure 4-2. Detailed property geology of the Silver Queen mine, Owen Lake area, west-central British Columbia (from Leitch et al., 1990). Units are defined in Table 4-1.0 200 400 eoo Boo 1000 metres• .— 0 1000 2000 3000 f€et81XZflv%7<LJV 4 t—:Figure 4-3. Schematic diagram of stratigraphic and intrusive relationships, OwenLakearea, west-central British Columbia. Units are defined in Table 4-1 (after Leitch et al.,1990).I,Esv:E5E:EEEEEEEESJ7’8 7aVVVVVVK: ÷ VVVVVVVV82Table 4-1. Table of formations, Owen Lake area*Period Epoch Age Formation Symbol Unit Lithology4a)Tertiary Miocene 21 Poplar Buttes MPBV Olivine basaltEocene- 45- Endako Group EOEV 8 Basalt diabase dikeOligocene 30Eocene 56- Ootsa Lake E 7a Trachyandesite basalt47 Group 7 Bladed feldspar porphyry dikeMineralization veinsCretaceous 6 Amygdular dikes(Late) “Okusyelda” uKqp 5b Quartz-eye rhyolite stock, dikeuKp 5a Intrusive porphyry sills, stocksuKud 5 “Mine Hill” microdiorite4a Feldspar-biotite porphyry dike85- “Tip Top Hill’ uKfp 4 “Tip Top Hill” andesite75 formationuKb 3 Medium to coarse tuff-brecciauKt 2 Crystal tuff, local lapilli tuff2a Fine ash tuffuKc 1 Polymictic basal conglomerate,sandstone and shale interbeds*p.fter Leitch et al., 1990The rocks of the study area have been subdivided into five major units plus threedike types; Table 4-1 lists the map units defined to date. A basal reddish purple polymicticconglomerate (Unit 1) is overlain by fragmental rocks ranging from thick crystal tuff (Unit2) to coarse lapilli tuff and breccia (Unit 3), and this is succeeded upwards by a thickfeldspar porphyritic andesite flow unit (Unit 4), commonly grading into and locallyintruded by microdiorite sills and other small intrusions (Unit 5). The stratified rocks forma gently northwest-dipping succession, with the oldest rocks exposed near Riddeck Creekto the south and the youngest exposed in Emil Creek to the north. All the units are cut bydikes that can be divided into three groups: amygdaloidal dikes (Unit 6), bladed feldsparporphyry dikes (Unit 7), and diabase dikes (Unit 8). The succession is unconformablyoverlain by basaltic to possibly trachyandesitic volcanics that crop out in Riddeck Creekand further south. These volcanics may be correlative with the Goosly Lake Formation83(Church, 1973). The units are described below in detail, to facilitate comparison withother possibly correlative rocks.Basal Polymictic Conglomerate (Unit 1)The basal member of the succession is a reddish to purple, heterolithic, poorlysorted pebble conglomerate that contains rounded to subangular small white quartz andgray-brown to less commonly maroon tuff and porphyry clasts. Local interbeds of purplishsandstone 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. Thebest exposure is found in a roadcut at the southern tip ofOwen Lake, where the unit isabout 10 m thick and dips 25° to the northwest. The base is not exposed and the unit is inpresumed fault contact with the younger volcanic rocks of the Ootsa Lake Group (GooslyLake Formation; Unit 7) exposed at higher elevations farther south along the road. In drillholes farther north, near the centre of the property, the upper contact of the conglomeratewith overlying porphyry is sharp and appears conformable, but the porphyry may be anintrusion rather than a flow.Crystal-Lithic Tuff (Unit 2)In outcrop, the next major unit is a sequence ofmainly fragmental rocks that aremostly fine crystal tuffs with thin interbeds of laminated tuff, ash tuff, lapilli tuff and lessabundant breccia. The unit may be as much as 100 m thick. The most widespread rocktype is a massive, gray to white, strongly quartz-sericite-pyrite altered, fine crystal tuff thatgrades imperceptibly into a porphyry of similar appearance and composition; the lattermay be partly flow, intrusive sill, or even a welded tuff. Only the presence ofbrokenphenocrysts and rare interbeds of laminated or coarsely fragmental material suggest thatthe bulk of this unit is tuffaceous. In thin section, the rock is seen to be made up of 1 to 2mm broken, altered plagioclase relics and 0.5 mm anhedral quartz grains (that may be84partly to entirely secondary) in a fine matrix of secondary sericite, carbonate, pyrite andquartz. Drill core exposures show that the basal contact ofUnit 2 with the underlyingconglomerate is commonly occupied by the porphyry rather than the tuff. The bestexposures ofUnit 2 are in the area of Cole Creek and the Chisholm vein, where thin (10cm) 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 drillcore, sections of laminated tuffs with faint but discernible layering on a cm scale, may beup 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 avery fine, uniform “ash tuff’ that are up to several m thick (Unit 2a). Typically they aredark gray to medium gray-green and have a siliceous appearance. Locally they containangular fragments of either mixed origins (heterolithic clasts) or of larger blocks that areonly 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 ofUnit 2. It is composed of blocks and bombs(?) (cf. Maclntyre, 1985) offeldspar-porphyritic rock similar in appearance to both the underlying porphyry and theoverlying porphyritic andesite. The clasts are mostly angular to subangular and about 2 to5 cm in diameter, but some are much larger (up to 0.5 m); the matrix makes up a widelyvariable percentage of the rock, from almost 0 to 90 per cent. In places the rock has theappearance of an intrusive breccia with little or no rotation of fragments. In other placesthe fragments are clearly unrelated and “accidental” or unrelated clasts of chert or fine tuffare common, although still volumetrically minor; this has the appearance of a lahar.In outcrop near the Cole veins, this breccia unit forms discontinuous lensesgenerally less than 10 m thick, with a suggestion of gentle northerly dips. The lensesappear to be conformable with the underlying or enclosing tuffs. In drill core, two85distinctly different modes of occurrence are noted for this unit: in one, it appears to beconformably overlain by Unit 4 porphyritic andesites (the total thickness of the brecciaunit is up to 30 m); in the other, it appears to have subvertical contacts, implying it is anintrusive breccia. Good examples of the latter distribution are found in the Cole Lakearea, 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 andmineralized 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 alteredandesite, fine tuff and quartz or quartzofeldspathic rocks, enclosed in a fine tuffaceousmatrix. 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 ofporphyritic andesite that outcrops over much ofMine Hill and is best developed north ofWrinch 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 sparserphenocrysts than the exposures on Tip Top Hill. At exposures in Wrinch Creek canyon, adistinct flow lamination is developed by trachytic alignment of phenocrysts, best seen onweathered surfaces. This suggests that these andesites are mostly flows, with gentlenortherly to northwesterly dips. However, some of the coarsest material probably formsintrusive sills and stocks [cf. the type sections ofMaclntyre and Desjardins (1988) andMaclntyre (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 TopHill itself, may actually be crystal tuff. In these exposures, the feldspar phenocrysts aresmaller, 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 from86Tsalit Mountain on the west side of Owen Creek valley, 10 kilometres northwest of theSilver Queen mine, gives a very similar isotopic date of 77.8 ± 3.0 Ma, also by K-Ar onwhole rock. This rhyolite is correlated with the Okusye1da1’quartz porphyry by (Church,1973).In thin section, the andesite is seen to contain abundant 2 to 3 mm euhedralcrystals of andesine. Oscillatory zoning is present, but with little overall change incomposition within a given specimen, from An45 to An35.Mafic minerals include roughlyequal amounts (about 5% each) of 1-2 mm clinopyroxene and hornblende, and euhedral 1to 2 mm biotite phenocrysts. The groundmass is an aphanitic mesh of intergrown feldsparwith 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 ofunit 4, probably represent feeders to flows ofunit 4. They are distinguished by prominentscattered 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 ofCole Lake and on the highway at the north end of Owen Lake, but they could be moreextensive (they are difficult to distinguish because of their similarity to unit 4). They aredated by K-Ar on whole rock at 70.3 ± 2.5 Ma, indicating a possible 7-8 Ma span of TipTop Hill volcanic activity (Leitch et al., 1992).Microdiorite (Unit 5)Microdiorite forms subvolcanic sills, dikes, and possibly, small irregular stocks onthe Silver Queen mine property. These intrusions are centrally located in the two mainmineralized areas of the property, the No. 3 Vein and Cole vein areas. Contacts with theandesite are indistinct or gradational. Typically the microdiorite is a medium to finegrained, dark greenish gray equigranular to porphyritic rock characterized by small (1 mm,87but locally glomeratic to 4 mm) plagioclase phenocrysts and 0.5 mm mafic relics in aphaneritic pink feldspathic groundmass. Primary magnetite is found in the less alteredspecimens. It is distinguished in outcrop by its relatively fine-grained, even-weatheringtexture and lacks the flow structure of the andesite. Because of the gradationalrelationship to the andesite, distinction is difficult in places. In thin section, the plagioclaseis the same as in the andesite (oscillatory zoned andesine,An45_30), and euhedralclinopyroxene phenocrysts, partly altered to carbonate, are the most abundant mafic.Apparent hornblende relics are completely altered to chlorite. No biotite is seen, but rarescattered quartz phenocrysts, displaying late-stage overgrowths of quartz, are observableranging up to 1 mm in size (these are not visible in hand specimen). The groundmass iscomposed 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 Mareported by Leitch et al. (1992) and Church (1973), respectively. The age of themicrodiorite is indistinguishable from the age ofunit 4 andesite, in agreement with thegradational contacts between these two rocks.Porphyry (Unit 5a)Large bodies up to 1000 m across of a coarse feldspar porphyritic rock crop out inthe vicinity of Cole Creek and are also found in drill core from the south end of the No. 3vein system, where the porphyry body usually occurs between Unit 1 and Unit 3. The rockis composed of roughly 50% plagioclase phenocrysts of up to 5 mm diameter and 10 to20% smaller mafic minerals in a fine feldspathic groundmass. The porphyry isdistinguished from the andesite, Unit 4, by its coarser texture and by the absence of flowtextures. It probably represents subvolcanic or high-level intrusive bodies that wereemplaced below or postdate the extrusive andesite, but are related to the same magmaticevent that produced the andesite. Such subvolcanic intrusive bodies, with identicalmineralogy to the extrusive porphyritic andesites, have also been noted in the Kasalka88Group near Tahtsa Lake (Maclntyre, 1985). No K-Ar whole rock age data is determinedfor this rock unit because no fresh sample can be found (the outcrops of this unit of rockare always variably saussuritized or sericitized).Quartz-feldspar Porphyry (Unit Sb)Quartz-feldspar porphyry, which appears to be part of a subvolcanic intrusivestock, crops out along Emil Creek and on Okusyelda Hill to the north of the creek. Thisunit was called “Okusyeld&’ dacite (rhyolite) by Church (1970). Although its contactrelation 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 withfelsic volcanic rocks in the Tchesinkut Lake and Bulkley Lake areas, and possibly with theTsalit 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 themicrodiorite-feldspar porphyry in the Owen Lake area; the 84.6 ± 0.2 Ma U-Pb date onzircon shows that it is the same age or older. It is cut by thick calcite veins and quartzsericite-pyrite alteration on the extension of the George Lake vein and so is probably premineralization.Thin sections show the quartz porphyry consists of 10 to 15% 2 mm quartzphenocrysts and slightly smaller euhedral andesine plagioclase crystals, plus smaller relicmafic grains, in a microgranular groundmass of roughly equal amounts of quartz,plagioclase and potash feldspar. Quartz, and to a lesser extent, plagioclase also occur asangular fragments.89Amygdaloidal Dikes (Unit 6)Units 1 to 5 are cut by a series ofvariably amygdaloidal dikes that areconcentrated in the two main areas ofmineralization (No. 3 vein and Cole vein areas).They generally trend northwesterly parallel to the mineralized veins, but north, east andnortheast-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 arecommonly 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 andEquity, but this is an inappropriate term, implying an alkali-rich mineralogy including sodaorthoclase, alkali pyroxene or amphibole, and feldspathoids.In underground exposures the dikes range from dark gray-green where fresh, topale green or creamy-buffwhere strongly altered in underground exposures; they arepurplish in weathered surface outcrops. They are typically fine grained and arecharacterized by amygdules filled by calcite, or less commonly, iron oxides, particularly attheir chilled margins (dikes less than 1-2 m wide commonly lack amygdules), Floworientations, generally parallel to the walls, provide an indication of attitude in surfaceoutcrops.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 tocarbonate and sericite is extensive, but the texture is generally preserved. This dike has anEocene K-Ar whole rock age ofSl± 1.8 Ma that almost certainly reflects alteration, thusestablishing a maximum but likely age ofmineralization.Bladed Feldspar Porphyry Dikes (Unit 7)A set of trachytic-textured porphyry dikes, 1 to 5 m wide and characterized bycoarse (up to 1 cm long) bladed plagioclase phenocrysts, cut and slightly offset the90amygdaloidal 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 ofthese dikes is 51.9 ± 1.8 Ma, indistinguishable from the K-Ar whole rock isotopic age ofthe amygdular dikes (Unit 6). Their spatial distribution is also similar to that of theamygdaloidal dikes, with concentrations in the two main mineralized areas; orientationsare similar too, but with subvertical dips only. The similarity of these post-mineral bladedfeldspar porphyries to the Goosly and Parrot Lake syenomonzonite stocks, and bladedfeldspar andesite dikes at Equity dated at 50.7 ± 1.8 Ma by K-Ar on whole rock, suggeststhat there is a genetic relation among them.In thin section, the bladed feldspar porphyry dikes are composed of large (4-10mm) plagioclase phenocrysts and rare to locally abundant clinopyroxene crystals up to 5mm across, set in a dark purplish groundmass of feathery interlocking plagioclasemicrolites with interstitial quartz, alkali feldspar, opaque and skeletal rutile. Theplagioclase forms strongly zoned, oscillatory crystals that range from cores of andesine(An50) to rims of oligoclase (An15). The pyroxene has a strong green color and is probablyiron-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 andnorthwest or east-west strikes. In thin section, they lack olivine and are composed ofdiabasic-textured plagioclase set in clinopyroxene, with accessory opaque.mineralsThe K-Ar whole rock isotopic age of these dikes is 50.4 ± 1.8 Ma, only slightlyyounger than the dikes ofUnit 6 and Unit 7. It is likely that Unit 8 dikes are related to thebasaltic Buck Creek Formation (48.1 ± 1.6 Ma; Church, 1973).914.4 Lithogeochemical characters and two series of igneous and volcanic rocksThe various types of igneous and volcanic rocks at Owen Lake area and itsperipheral region can be classified into two series according to lithogeochemical featuresand K-Ar ages. The first series consists of igneous and volcanic units from intermediate tofelsic composition, and is characterized by having relatively low contents ofTi02 (from0.36 to 0.8 wt%), MgO (from 0.65 to 4.18 wt%), total iron (from 1.73 to 6.5 wt%) andP205 (from 0.09 to 0.42 wt%) as well as the older K-Ar ages (from 78.8 to 57.2 Ma). Incontrast, the second series consists of the igneous and volcanic units from intermediate tomafic composition, and has higher contents of TiO2 (from 0.95 to 1.27 wt%), MgO (from2.11 to 7.81 wt%), total iron (from 5.14 to 8.98 wt%) andP205 (from 0.49 to 0.67 wt%)as well as younger K-Ar ages (from 48.7 to 21.4 Ma; Table 4-2). The former seriespredates and hosts the mineralization; the latter is post-mineralization. These two series ofigneous and volcanic rocks can be distinguished by using a Zr-Ti02binary plot (Figure 4-4).In Figure 4-4, the amygdaloidal dike composition plots in the middle of the olderseries of igneous and volcanic rock but has a young age (51.3 Ma). The tentativeexplanation 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 alsoarise because of the effects ofhydrothermal alteration; dated samples of both of these rockunits were not as fresh as the others plotted in Figure 4-4.Lithogeochemical data used to construct Figure 4-4 are selected from relativelyunaltered rocks and listed in Table 4-2. Two lithogeochemical analyses with thecorresponding K-Ar age known from Church and Barasko (1990) are listed in Table 4-2to complete the illustration of the relation between the lithogeochemical compositions andthe timing of igneous and volcanic activities.920 0 V1.50[.00-0.50LegendDiabasedikeAndesiticflowSynerrnzoniteRhyoliteGraniteArnygdalOidaldikeAshtuftMicrodioriteAndesitePorphyry•1 SeriesIesIISeriesI0.00—I0100.00200300.00ZrppmFigure4-4.AZr-Ti02binaryplotdistinguishstwoseriesofigneousandvolcanicrocksinOwenLakeareaanditsperipheralregion.SeriesIhasK-Aragefrom78-51MaandhoststheSilverQueenveinmineralization.SeriesIIhasK-Arageof50Maoryoungerandoverliesorcutstheveins.XLC29/09/96Table4-2.LithochemicaldataofvarioustypesofrockatOwenLakearea,centralBritishColumbiaSampleIDChurch-v18S91-9SQ-SOS91-4SQ-113S91-1AS91-3S91-10Church-i4DA48-13xll-lbx4-4Syen-AmygdaRockNameBasaltNadinadikeDiabasedikeAndesiteAndesitemonzoniteRhyoliteGraniteGraniteloidaldikeMicrodioriteAndesiteLocationPoplarNadinaMt.WretchE.RidgeofRiddichN.EquityNEquityNadinaMt.EquitymineColeLakeJackveinN.segmentButtesCreekOwenLakeCreekofNo.3veinwt%Si02440049.6455.2057.2660.3961.3872.1168.0367.0056.0557.0557.86Ti023011.,07Y26.4720.8027.7429.1925.7126.5132.6912.8430.7527.95Rb99.1054.17100.6179.5492.02137.16201.25122.2092.04100.28Sr733.87922.481187.571148.24901.97313.80423.86409.23630.05592.72Age(Ma)*21.450.448.848.757.251.378.778.3*K-Ardatingagewithabout2Maerroronaverage.XLC29/09/95Table5-2.LithochemicaldataofvarioustypesofrockatOwenLakearea,centralBritishColumbia(Continuous)SampleIDxlO-6xlO-6DDA63-1SQ-119x5-6x2-5x33x3-6x3-7SQ-77S91-15RockNameMicrodioriteMicrodioriteMicrodioriteAndesiteAndesiteAndesiteAndesiteAndesiteAndesiteAshtuft’porphyryLocationC.segmentC.segmentSwitchBackN.OwenSouthsegmentN.segmentN.segmentN.segmentN.segmentSWColehillDuckLakeofNo.3veinofNo.3veinveinLakeofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinwt%SiO261.2559.0057.9956.0556.5857.2957.7557.2057.9761.1663.22Ti020.580.590.710.800.670.660.660.660.650.610.55A120315.1115.9816.5316.0916.0415.7015.8516.0315.8715.5314.81Fe2032.302.522.224.452.363.,200.150.12MgO2.782.182.632.782.503.332.872.612.642.713.40CaO4.925.166.257.455.115.675.755.975.665.293.03Na203.933.633.433.223.053.393.963.554.093.814.20K203.,38124.27168.02178.64185.22188.35192.04140.62126.03Y24.2924.8925.7518.0229.6533.0531.9128.4930.3624.5818.36Rb119.76118.7792.6577,94108.22121.40103.70122.52108.4575.7477.13Sr620.61472.32608.28587.771071.44573.45597.08566.67607.36524.71562.36Age(Ma)*4.5. Veins: Character and CorrelationMineralization on the property is mainly restricted to 0.1 to 2 m thick quartzcarbonate-barite-specular hematite veins that contain disseminated to locally massivepyrite, sphalerite, galena, chalcopyrite, tennantite and argentian tetrahedrite. Locally, inchalcopyrite-rich samples, there is a diverse suite ofCu-Pb-Bi-Ag sulfosalts such asaikinite, matildite (in myrmekitic intergrowth with galena), pearcite-arsenopolybasite, andpossibly schirmerite (Hood, 1991). Berryite (Harris and Owens, 1973), guettardite andmeneghinite (Weir, 1973), boulangerite (Marsden, 1985) and seligmannite and pyrargyrite(Bernstein, 1987) have also been reported but not yet confirmed. All the Au and much ofthe Ag are in the form of 60-70 fine electrum, as grains generally less than 50 microns indiameter 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 centralsegment of the No. 3 vein. Barite, svanbergite, and binsdalite become abundanttowards the south end of the No. 3 vein, with marcasite more abundant towards thenorth.Stage II is dominated by the presence ofmassive sphalerite and layeredcarbonate (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 inthe 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), andare cut by the series of dikes with bladed plagioclase crystals (Unit 7). Both these diketypes are possibly correlative with the Ootsa Lake Group Goosiy Lake volcanics of96Eocene (approximately 50 Ma) age, although chemically the amygdaloidal dikes appearolder. The bladed feldspar porphyry dikes cut the amygdaloidal dikes, and both are cut bythe diabase dikes that may correlate with Endako Group volcanism ofEocene-Oligocene(approximately 40 to 30 Ma) age.The major veins are concentrated into two main areas on the property centered onthe Mine Hill and Cole Lake areas, with an apparently less mineralized area between inwhich only the George Lake vein has been found to date. However, this intervening area isheavily covered by overburden and more veins may remain to be discovered here (therelatively minor Jack and Axel veins, not shown on Figure 4-2, are located west of theGeorge Lake vein). The most important known vein on the property, both in terms oflength 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 existon faulted extensions to the south where exploration has been hampered by heavyoverburden cover. South ofRiddeck Creek post-mineralization volcanic cover maypreclude further exploration.The predominant strike direction for the main veins is northwesterly, withmoderate to steep northeasterly dips. The relatively minor Church, Chisholm and Owlveins 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, althoughone major difference is the presence of gently west-dipping dikes; no veins of thisorientation are seen.The veins are highly variable in character, ranging from simple massive or bandedgangue-rich veins with well-defined walls through irregular massive sulfide veins to illdefined 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, makingcorrelation difficult even between closely spaced drill holes. In places, the vein pinches97out, with the zone of pinching (which correlates with flattening of the vein) rakingmoderately 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 mineralizedsection. A strong bleaching alteration envelope (quartz-sericite/kaolinite-carbonate-pyritealteration) generally accompanies the veining. True thickness of the mineralized structureis also an aid to correlation if the total thickness (e.g. of all the vein strands) is comparedfrom hole to hole. However, the strong lateral and vertical variations make this a lessuseful tool over longer distances between sections. In general, the tenor ofmineralization,as measured by assay composites, is the most reliable correlation tool. Although the assaysare necessarily a reflection ofvein mineralogy, and mineralogy is useful for correlation, thesilver and gold values that have proved to be the most important correlations, cannot beseen visually.Correlation is made more difficult by the presence of one or more hangingwall orfootwall veins that are found discontinuously along the length of the major vein structures.The presence of these subsidiary structures has been well established during undergrounddevelopment for exploration of the No. 3 vein; however, in drill core it is difficult to besure if a given intersection is of a hanging/footwall structure or an en echelon shift of themain vein. In fact, some of the ‘hangingwall’ and ‘footwalP veins are probably en echelonportions 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 echeloncharacter ofmany of the veins, both along strike and down dip. Resolution of this problemis important because of the implications it has for physical continuity of the vein, andconsequently, for tonnage and grade estimations. For example, intersections ofveins in theNo. 3 vein, George Lake, Camp and Cole Lake areas can be interpreted either as simpletabular bodies or as en echelon lenses (see sections in Fig. 4-5 to 4-9); there may be novein, or an attenuated vein, in the locations predicted by the simple tabular model.98Potential 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 InterpretationsThe structure of the Silver Queen mine area is dominated by a gently west tonorthwest-dipping homocline. There is no folding apparent at the scale mapped; thesequence appears to have been tilted 200 to 300 from the horizontal by block faulting. Theaverage 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 aseries 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 thelatter is mainly post-mineral (a few veins trend east-northeast). The NW faults dip 60° to80° to the northeast (average 315/75°NE), and the ‘cross’ or NE set appears to besubvertical (070/90°). There are subsidiary trends indicated at 295/85°NE and085/90°, 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 placesveins are cut off and displaced by the northeast set.The sense of motion on the northwest faults is such that each successive panel tothe 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), thereis considerably more of the lower fragmental rocks (Unit 2 and Unit 3) exposed than inthe next panel to the west, between the Owen Lake and the George Lake faults. Theredoes not seem to be much displacement across the No. 3 vein fault; slickensides seenunderground on this structure suggest a reverse sense of last movement withindeterminable horizontal component.9925002400CC0 2300220021002000Figure 4-5. Cross-section of Camp vein shows gently dipping dike approximatelyperpendicular 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 - drillsite.SW260000wz0000OCC.,1%q \ONE//b100260025002400z0>w 2300-JUi22002100Figure 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 verticalscale. Numbers represent the geological units which are defined in Table 4-1. Thick solidline - vein, thin solid line - geological contact, dash line - drill, circle - drill site.5EEJUT2.8U116541013000 22500NSW29002800 -270026002500240023002200200Figure 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 verticalscale. Numbers represent the geological units which are defined in Table 4-1. Thick solidline - vein, thin solid line - geological contact, dash line - drill, circle - drill site.2NE244b.i3U88-06 I4U88-075102NEz 0 > Ui -J UiSW32003100300029002800200Figure4-8.Cross-sectionofColeveinshowsgentlydippingdikeofunit6cutbylaterdikesofUnits7andUnit8.Horizontalscaleequalsverticalscale.NumbersrepresentthegeologicalunitswhicharedefinedinTable4-1.Thicksolidline-vein,thinsolidline-geologicalcontact,dashline-drill,circle-drillsite.C0z0I>LU-JLUSWFigure 4-9. Cross-section of George vein at the 2600 foot level of the Bulkley cross-cut,with the available intersections interpreted as part of an en echelon system. Horizontalscale equals vertical scale. Numbers represent the geological units which are defined inTable 4-1. Thick solid line - vein, thin solid line - geological contact, dash line - drill, circle— drill site.NE442900280027002600250024002600 Lev&X-Cut44104The sense of motion on the northeast faults appears to be south side down, witha small component of sinistral shear. Offsets of No. 1 and 2 veins across the fault alongWrinch Creek (Fig. 4-2) suggest a few m of left-lateral displacement, but thedisplacement of an amygdaloidal dike near the portals of the 2880 level suggests thesouth 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 defmedzone up to 10 m wide, with segments that have possible shallow southerly to moderatenortherly dips. The Cole Creek fault is not well exposed at surface; a splay from it maycause the change in orientation of the No. 3 vein to the Ruby vein (Fig. 4-2). Aconsiderable left-lateral offset of as much as 200 m is suggested by drill-holeintersections of the NG3 vein, which may be a faulted extension of the No. 3 veinsouth of the Cole Creek fault. Underground, this fault is exposed at the southernmostextent of drifting as a northeast-trending gouge zone 1 to 2 m thick. Other examples ofminor 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 theveins. Along the No. 3 vein, one such major dike causes significant dilution problemsdue to the incompetent nature of some of these soft, strongly clay-altered dikes near theveins. There is one major exception to this northwest trend: a prominent gently west-dipping (323/33°SW) set of Unit 6 (pre-mineralization amygdaloidal dikes) is welldeveloped in both the No. 3 vein, Camp and Cole Lake areas (Fig. 4-5, 4-7, 4-8 and 4-9). This gently-dipping set is roughly orthogonal to the main, steeply northeast dippingdikes and veins, and also roughly parallel to the general gentle westerly dip of the hoststratigraphy. A similar orthogonal fracture pattern, with steeply dipping fractures bettermineralized and with stronger alteration surrounding them than the gently dippingfractures, is also observed in outcrops in Wrinch Creek.1054.7. SUMMARYThe sequence of rocks exposed in the Silver Queen mine area, mapped as Tip TopHill Formation (Church, 1984) is petrographically and stratigraphically similar to theKasalka Group as defined in the Tahtsa Lake area by Maclntyre (1985) and the MountCronin area by Maclntyre and Desjardins (1988). The section in all three areas comprisesa sequence from a basal, reddish purple heterolithic conglomerate upwards through asequence of fragmental volcanic rocks, to a widespread, partly intrusive porphyriticandesite, all intruded by a distinctive microdiorite. However, K-Ar dating suggests that therocks in the Silver Queen mine area are ofLate Cretaceous age; both porphyritic andesitevolcanics and microdiorite are about 78 Ma. This is younger than the Kasalka Grouprocks in the type section near Tahtsa Lake, which give dates of 108 to 107 Ma near thebase, and are cut by intrusions dated at 87 to 84 Ma (Maclntyre, 1985). These datesactually straddle the Early to Late Cretaceous boundary (Harland et al., 1989). Thus, theremay be two episodes, with the later one as young as 78 Ma (Leitch et al., 1991). Possiblythe magmatic front associated with mid- to Late Cretaceous volcanic activity took longerto arrive further inland (i.e. 65 kilometres in 30 Ma gives a rate of advance of 0.22 cm peryear, 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 timeof deposition of the Late Cretaceous Kasalka Group and before the intrusion ofEarlyTertiary post-mineral dikes dated at about 50 Ma. Some of these dikes may correlate tothe Goosly Lake trachyandesite volcanics (49 Ma) of the Ootsa Lake Group andsyenomonzonite 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 theBuck Creek basaltic volcanics, dated at 48 Ma (Church, 1973). Although the mainoutcrop areas ofKasalka anclesite and microdiorite correlate with the main areas ofmineralization, and a genetic link has been postulated between two (Church, 1970), the106Late Cretaceous Kasalka andesite and microdiorite must have preceded mineralization byat least 25 Ma. So far there is no evidence at Silver Queen that the Early Tertiary dikeshave remobilized older mineralization. Recognition of the fact that significantmineralization at Equity and Silver Queen is Early Tertiary in age, but is found inregionally correlative Upper Cretaceous rocks has important implications for metallogenyof the area. Since no significant mineralization has been found to date in the Early Tertiaryrocks, it may be postulated that the Upper Cretaceous rocks represent a regionalmetallotect for base- and precious-metal mineralization. More significantly, it is possiblethat only the older (Cretaceous) rocks were sufficiently structurally prepared for oredeposition during a period ofwidespread magmatism during the Early Tertiary (Leitch etal,, 1991).107Chapter 5. Hydrothermal Alteration at the Silver Queen mine:Field and Petrographic Characters5.1. IntroductionThe aim of this chapter is to describe petrographically the various hydrothermalalteration types, the spatial zonation of alteration associated with precious- and base-metalveins in volcanic sequences and the paragenetic sequences of the alteration mineralassemblage at the Silver Queen mine. Hydrothermal alteration at the Silver Queen minehas been examined in a preliminarily way by other workers. Most of the previous workfocused mainly on the alteration types and only briefly discussed the spatial zonation ofalteration. Fyles (1984) stated that clay with or without sericite is common at the SilverQueen 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-Agsulfide-rich veins at the Silver Queen mine are characterized by silicification and argillicalteration. Church and Pettipas (1990) noted that the veins at the Silver Queen mine arecommonly in an argillic envelope within a broader aureole of propylitic alteration. Chenget al. (1991) presented field descriptions and a preliminary petrographic study of thehydrothermal alteration envelopes.Emphasis in the present chapter is given to the qualitative identification of thealteration 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 arebased on 20 km2 field mapping, drill core logging, 72 whole rock sampling, 140 thinsection examination and X-ray diffraction analysis. These investigations have defined aspecific succession of related alteration and mineralization events at the Silver Queen mineand contribute to the development of a genetic model for this type ofmineralizationsystem.1085.2. Petrography ofHydrothermal Alteration TypesSix types of hydrothermal alteration have been recognized at the Silver Queenmine, viz. (i) propylitization, (ii) carbonatization, (iii) sericitization, (iv) argillization, (v)silicification and (vi) pyritization. They are fhrther classified into three zones on whichcarbonatization is superimposed to various degrees: propylitic alteration halo, sericiticargillic alteration outer envelope, and silicic-pyritic alteration inner envelope. Detaileddescriptions of these hydrothermal alteration types at the Silver Queen mine are givenbelow.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 strongmagnetic character that can be tested easily in the field with a hand magnet indicates thepresence of relatively abundant magnetite.The propylitically altered andesite is typical of those with porphyritic texture. Acommon mineral assemblage for the propylitically altered andesite is: aphaniticgroundmass (about 40%), plagioclase (3 5-40%), clinopyroxene (0-6%), hornblende (0-4%), biotite (0-2%), epidote (0-4%), chlorite (4-8%), carbonates (1-15%), sericite (1-8%), and accessory magnetite and ilmenite (about 5%) and apatite and zircon (trace). Ofthese, plagioclase, biotite, augite and hornblende are replaced by epidote, chlorite,carbonate and sericite to various degrees. Pseudomorphs of epidote, chlorite andcarbonate after clinopyroxene and hornblende are commonly well preserved. Theremaining minerals are not obviously affected by hydrothermal alteration (Figure 5-1).Propylitically altered microdiorite has features roughly equivalent to those ofpropylitically altered andesite, except that it is paler in color and ofgranular or porphyroidtexture. 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%), chlorite109Figure 5-1. Photomicrograph (crossed nicols) of propylitically altered andesite withsuperimposed carbonatization (SQ-44: surface outcrop sample from the southern segmentof the No. 3 vein). Plagioclase (P1) phenocrysts are partially replaced by sericite (Ser) andcarbonate (Carb). Augite phenocrysts are completely replaced by epidote (Ep), chlorite(Chi), carbonate and magnetite (mt).I •“$- *I$fr4WI-r.. ‘—‘--:iV -0.2 mmroui d -n j S SC).2 mm110(3-10%), carbonate (5-15%), sericite (2-8%), and accessory magnetite and ilmenite (about5%) and apatite and zircon (trace). The grain sizes of plagioclase, augite and hornblendeare relatively coarser. They are commonly replaced by: epidote, chlorite, carbonate andsericite to various degrees (Figure 5-2).Sericitic-argillic alteration commonly appears as a bleached outer envelopearound a vein. This type of alteration is called as ‘moderate’ and is more intense thanpropylitic alteration. Microdiorite and andesite having this type of alteration are softerand paler than their propylitic alteration equivalent. Magnetite is altered to hematite orpyrite. Biotite is unstable in this type of alteration and is progressively replaced bymuscovite. Pseudomorphs of primary minerals, especially plagioclase, are remarkablywell preserved. Recrystallization, especially of quartz, is obvious in the groundmass.Sericite, kaolinite and carbonates are the major dominant mineral phases and arecommonly present with very fine grain size (Figure 5-3). An approximate mode of thistype 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 anddolomite (4-10%) as well as trace amount of apatite, rutile and zircon.Silicic and pyritic alteration is the most intense alteration type at the SilverQueen mine in terms of the variations ofmineral composition and rock texture. It candevelop particularly intensely altered zones of hard, pale apple green rock where fresh andorange-yellow on weathered surfaces. No magnetite is present. A distinctive feature of thistype of alteration zone is that pseudomorphs of primary minerals are not preserved as wellas they are in sericitic and argillic alteration zones. The texture of the silicification andpyritization alteration zone is mosaic or polygonal (Figure 5-4). The rock is characterizedby having a simple mineral assemblage. For example, unidentified fine grain minerals(about 20%), quartz (26-30%), sericite (10-28%), kaolinite (0-24%), carbonates (10-15%) and pyrite (10-15%) as well as trace amount of apatite, rutile and zircon.111Figure 5-2. Photomicrograph (crossed nicols) of propylitically altered microdiorite withsuperimposed intense carbonatization (SQ-85: surface outcrop sample from the Cole lakesegment). Note rock has an unequal-granular texture. Pseudomorph of carbonate afteraugite 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 iscompletely replaced by carbonate instead of by epidote, chlorite and carbonate.• 4-kI0.5 mm112Figure 5-3. Photomicrograph (crossed nicols) of sericitized-argillized andesite (X5-3:underground sample from the southern segment of the No. 3 vein). Note pseudomorph ofsericite (Ser), kaolinite (Kao) and quartz (Qtz) after plagioclase; pseudomorph of sericiteand carbonate (Carb) after mafic phenocryst.0.2 mmSer— KaoCO LI fl d massQtzCia LI n d rn ass113Figure 5-4. Photomicrograph (crossed nicols) of silicified-pyritized microdiorite (X5-1O:underground sample from the southern segment of the No. 3 vein). Note the replacementof sericite (Ser) by abundant quartz (Qtz) and the formation of abundant pyrite (Py). Thepseudomorph of sericite and kaolinite (Kao) after plagioclase is not preserved as well asthose in the outer sericitic-argillic alteration envelope.0.2 mm114Carbonatization superposed on propylitically altered rock is characterized by thefurther replacements of epidote, chlorite and plagioclase by carbonates. Where the rock isintensively carbonatized, epidote and chlorite are completely replaced by carbonates whichbecome pervasive in the rock (Figure 5-2). Of the carbonates calcite is an abundantspecies characterized by reacting with diluted acid fiercely. Carbonatization is alsoobserved in the visible alteration envelope (sericitic and argillic alteration, andsilicification and pyritization envelope as described below) as replacements of calciteand chlorite by Fe- and Mg-carbonates such as siderite and dolomite.5.3. The Spatial Distribution ofHydrothermal AlterationIn general, the zonation of hydrothermally altered rocks in the Silver Queen minedistrict consists of a broad propylitic alteration halo which gives way as the polymetallicvein is approached to a broad bleached outer sericitic-argillic alteration envelope, which inturn gradates into a narrow inner silicic-pyritic alteration envelope (Figure 5-5).All rocks within the study area, that are older than mineralization, have affectedsome degree of propylitic alteration. That is, an early stage of propylitic alteration appearsto be regional in extent (>20 km2). The least propylitized andesite and microdiorite arecharacterized by only slight alteration of plagioclase by sericite and partial replacement ofmafic minerals (clinopyroxene and hornblende) by epidote and chlorite with very minorcarbonate. A propylitically altered rock with superimposed carbonatization has beenrecognized at the Silver Queen mine through the examination of a total of 140 thinsections from various successive profiles cross-cutting the No. 3 vein throughout its lengthand rock samples altered to various degrees from different parts of the Owen Lake area.The spatial distribution of propylitically altered rocks with superimposed carbonatization iscontrolled by a complicated structure system, rather than by being restricted to the veinand associated mineralized structures. Samples collected a few hundred metres away froma vein commonly have intense propylitic alteration with superimposed carbonatization,11518000E19000E20000E21000E126°44---IIIo++++++\4--I-+.++++-I-—‘‘,,/‘/,////,//////////+++++++\+++-J--+++++0+++++++++++++-2+++++÷++++++++++++++++++++++4-++++Propyliticandesite++++++\++÷.++—+÷÷++\÷Propyliticmicrodiorite÷÷++\+÷+—++\+\+÷÷÷++++\+PyroclasticrockZ+++\++\++S—,,/,,/////++/+Gradationalcontact++‘-f\++4-++(5)++-4-+‘++—+++++\+...+Sharpcontact++++++-“‘I,,++++++‘‘I,,++++++\—vein(Northern4-+•/++\/\+‘\+\÷++++(ISilicic/pyriticinner-////‘++_—-÷i÷+-+++[jalterationenvelope//“//+-4+÷‘-+++C•._///////____/.-4-+++++N-÷±Undergroundworking++++\++“+++//,‘i,•1-+++\++++4-++÷4-+‘777999•+++\÷\777797V,VV7777V/777777VV.’VV9VV77‘7,,,,,,,,,,,,iii,,,,,V99VV7V7_///////////////////,•••.z•••///////////////////1/SZV‘79‘7‘7V‘779—-.-,.r)777Vv-c’i////////////////////////A.m_-N-.,k?<4\,8///VV/I\I////////////////////////7/,-.--Figure5-5.Schematicplanofhydrothermalalterationonthe2600-footlevel,SilverQueenmine(modifiedfromChengCtal,,1991).similar to or even stronger than those collected only a few metres from the bleachedalteration envelope around the vein. In contrast, there is a tendency for the intensity ofcarbonatization in propylitically altered rocks at the southern segment of the No. 3 vein tobe 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 zonationsboth parallel and perpendicular to the vein. Three representative alteration profiles crosscutting the No. 3 vein at the 2600 foot level of the southern, the central, and the northernsegments are illustrated in Figures 5-8a, 5-8b and 5-8c. In general, all alteration profileshave the following zonation parallel to the vein:(1) An outer sericitic and argillic alteration envelope commonly has a relative ‘sharpcontact’ that grades from a bleached envelope into a dark colored propylitic wallrock within a few centimetres (Figure 5-9).(2) An inner silicification and pyritization envelope immediately adjacent to the veinhas 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. Indetail, the silicic and pyritic inner envelope is almost absent at the northern segment of theNo. 3 vein. Also, the alteration envelope is more argillic at the northern segmentcompared with the southern segment of the No. 3 vein which has more sericite thankaolinite. Silicification and pyritization are more intense at both the central and southernsegments than at the northern segment of the No. 3 vein. In addition, the width of thealteration envelope is narrower along the northern segment ofNo. 3 vein (total widthabout 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. Forexample, the widths of the alteration envelopes at the northern and central cross-cuts of117Figure 5-6. Photomicrograph (crossed nicols) of least propylitically altered andesite in thenorthern segment of the No. 3 vein (X3-7: underground sample from the northernsegment of the No. 3 vein). Note primary phenocrysts (augite and plagioclase) are slightlyaltered along their margin and cleavages. Aug - augite; P1 - plagioclase, Mt - magnetite.-:\ ;;:;:F‘118-4Figure 5-7. Photomicrograph (crossed nicols) of propylitically altered andesite withsuperimposed carbonatization in the southern segment of the No. 3 vein (SQ-44: surfaceoutcrop sample from the southern segment fo the No. 3 vein). Note pseudomorph ofchlorite (Chi) and carbonate (carb) after augite, partial replacement of plagioclase (P1) bycarbonate and sericite (ser). Ap - apatite Crossed nicols.I.0.2 mmC ra u n d rn assGroUnd in assC roUnd in ass119Tabel 5-la. Estimated modes of alteration minerals in hydrothermally altered wall rock at the northernsegment of the No. 3 vein, Silver Queen mine, central British ColumbiaMode Propylitically altered andesite Sericitic and argillic alteration envelope(Volume %) with superimposed carbonatizationDistance(m) 10 9 8 7 6 5 4 3 21 0.5 0unknown* 40 40 40 40 40 25 25 25 25 25 20 20augite&Hb 7 9 10 7 5 0 0 0 00 0 0Epidote 1 2 2 1 0 0 0 00 0 0 0Chlorite 5 4 2 7 7 0 0 0 00 0 0Carbonate 4 3 1 3 6 4 4 44 5 5 6Magnetite 5 5 5 4 4 0 0 00 0 0 0Pyrite 0 0 0 0 0 4 4 3’ 33 4 5feldspar 35 36 39 35 35 0 0 00 0 0 0Muscovite 3 1 1 3 3 27 27 22 2218 18 16Kaolinite 0 0 0 0 0 25 25- 26 26 27 28 28Quartz 0 0 0 0 0 15 15 20 2022 25 25Total 100 100 100 100 100 100 100 100 100100 100 100Figure 5-8a. Estimated mode of alteration minerals in hydrothermal alteration profile at northernsegment of the No. 3 vein at the Silver Queen mine. Unknown - unidentifiable material includinggroundmass and extremely fme-grain mineral aggregates.10090807060- 50403020100i:i QuartzI KaoliniteMuscovitetill FeldsparMagnetiteCaibonateChloiite /EpidoteP3’X & FibD unknownDistance from the vei:(m)_____________________________propylitic alteration halo . . .sencitic & argillicwith superimposed alteration envelopecarbonatization120C0’qCDCDC0gECDi-z-000$--t<a00CDCDCDI4)LfCDHi qcoCDCDDCDo_B..CD0--::::CD flH CD - CD II ECD CD— CD 0. Ir!f1—;.INccv -1 0 c,— CDCDt’J.0.C0UC0tJCLl-at’3u0000000J1V._))CCCCCOO00 CDCC000_ -)CI—‘.)CDcCCOOCC0 CD000CCL’.0000000. CDl(•)CD——000QCC‘C,00.CDCDCDCDT1CDCD0CD(g0 F’CpDCD CDCDIn 0CD CD 0 CD0 E;.H CD CD rn I 0 CD 0 IModevol.%—.)WU.C00C’Cococ0000 00)CD—i.CDNNQ0O0CD1CD CD 0=0t)00U)0\00.0U)C’C’U)0000000U)C.0U)00U)000C’U)U.U.0 00 U.L)U)0 CD“CDU)0 U)0ifru00U)CU)0000U)0U)000J000000J000000J000C) I.000000U)C’C’00000Figure 5-9. The relatively sharp contact between propylitic alteration and ableached alteration envelope (Bulkley cross-cut, 2600 foot level undergroundworking).123Figure 5-10. Outcrop of the southern segment of the No. 3 vein and its bleachedalteration envelope.124the No. 3 vein are greater on the footwall than on the hanging-wall. At the cross cuts ofthe Jack and George veins the situation is reversed (Figure 5-5). These asymmetricalfeatures can be explained by en echelon geometry of individual veins within mineralizedzones (Leitch et a!., 1991). The reason for these is that the alteration envelope isdeveloped around the structure zone centering the en echelon veins. Therefore, thealteration envelope may appear in different asymmetrical patterns depending uponwhere the cross-section cuts the upper or lower part of an individual vein (see Figure 5-11). This explanation may help exploration for hydrothermal veins developed in enechelon structural patterns.5.4. Paragenetic Sequence ofHydrothermal AlterationPropylitization, carbonatization, sericitization, argillization and silicification as wellas 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 observedin the host rocks. Many other textures and features in vein-wall-rock profiles stronglysupport the concept of a consistent sequence in the development of the hydrothermalmineral assemblages at the Silver Queen mine.The distribution of broad propylitic alteration halos suggests that this type ofalteration is the product of regional, pre-mineralization hydrothermal activity.Carbonatization controlled by the complicated fracture system developed subsequent toregional propylitic alteration and was superimposed on the propylitically altered rocks.The distribution of bleached alteration envelopes around mineralized structures suggeststhat the bleached alteration envelopes developed subsequent to, and superimposed on, thebroad propylitic alterations referred to above. A series of schematic profiles areconstructed to illustrate the spatial distribution pattern and timing sequences of thesealteration types (Figure 5-12).125SWNELevelILevelIIFigure5-1ISchematicprofileillustratestheasymmetricalrelationshipbetweenenechelonveinsandhydrothermalalterationenvelopes,SilverQueenmine.SWNEFigure 5-12. A series of schematic profiles illustrate the spatial zonation and sequenceof development of various types of alteration at Silver Queen mine.Propylitic alterationStage I: A regional broadpre-mineralizationpropylitic alterationCkrbonatizationStage H: Carbonatizationsuperposed on thepropylitically alteredrocks is controlled byfracturesStage III: Bleached alterationenvelopes (sericitic-argillicouter envelopes and silicicpyritic inner envelopes)VCIfl around the main vein (a NWmineralized fracture zone).127The general sequences of formation of alteration minerals has been established bythe replacement relationship between mineral pairs. Microscopic observations indicate thefollowing alteration sequences. Propylitically altered samples show that mafic minerals suchas augite and hornblende and plagioclase are initially altered to epidote, chlorite, calcite andsericite along margins and cleavages (Figures 5-1, 5-2, 5-3, 5-6 and 5-7). Thesereplacements are completed where propylitic alteration is intense with superimposedcarbonatization; in such cases pseuclomorphs of carbonate, mainly calcite, after primarymafic 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, primaryminerals are completely altered. In particular, plagioclase is completely replaced bysericite and kaolinite along with quartz. Clinopyroxene and hornblende are totallyaltered to carbonate. No epidote or chlorite pseudomorphs after primary minerals arepresent in the bleached alteration envelope. Therefore, it appears that epidote, chloriteand calcite pseudomorphs after primary mafic mineral, as well as biotite, are furtheraltered 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 thedecomposition of plagioclase (Figure 5-3). Silicification in the inner envelope ischaracterized by the progressive replacement of sericite by quartz; eventually sericiteoccurs as inclusions in pervasive quartz (up to about 30 wt%). Siderite and othercarbonates are abundant (up to 10 wt%). Pyrite is disseminated and locally, denselydisseminated (content up to about 15 wt%) in the inner alteration envelope.Recrystallization and silicification of the matrix are intense in the inner alterationenvelope (Figure 5-4).128Table5-2.ParageneticSequenceofMineralAssemblages,SilverQueenmine,OwenLakeAreaMineralsMagnetite/ilmeniteApatiteZirconAugiteHornblendePlagioclaseK-feldsparBiotiteQuartzEpidoteChloriteCalciteSiderite/dolomiteKaoliniteMuscovitePyriteHematiteRutileSericitizationNote:Thesolidlineanditsthicknessrepresenttheformationofamineralanditssemiquantitativeabundance.Thedashlinemeansthatthemineralsremainstableatcertainalterationstages.Combining all the relationships described above leads to a general parageneticsequence for the alteration around veins at the Silver Queen mine. This sequence issummarized and illustrated in Table 5-2.5.5 Discussion and ConclusionsHydrothermal alteration patterns, similar to those described above, have beenreported in many other deposits [e.g., Waite Amulet (Price and Bancroft, 1948), Creedand Summitville (Hayba Ct al., 1985), Sigma (Robert and Brown, 1984, 1986), RoundMountain (Sander and Einaudi, 1990), Erickson (Sketchley and Sinclair, 1991), PorgeraRichards 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 superimposedcarbonatization at the Silver Queen mine shares many similar features with the crypticalteration at Sigma mine and the carbonate envelope at Erickson mine in terms ofalteration mineral assemblages and the mineral paragenetic sequence. For example,primary mafic minerals initially replaced by epidote and chlorite are subsequently replacedby carbonate. However, there are significant differences in the spatial distribution patternsbetween the propylitic alteration with superimposed carbonatization at the Silver Queenmine and the cryptic alteration reported at the Sigma mine. The width of the crypticalteration zone is up to 2 m into the walls of the veins at the Sigma mine (Robert andBrown, 1984). The spatial distribution of propylitically altered rock with superimposedcarbonatization at the Silver Queen mine is much more widespread than the Sigmaexample (Figure 5-5). Propylitic rocks with intense carbonatization have also been foundat Goose Lake, about 10 kilometres southwest of the Silver Queen mine, but no veinmineralization was found nearby. In short, the distribution pattern of the propyliticalteration with superimposed carbonatization at the Silver Queen mine is a wide irregularhalo, unlike a restricted envelope that locally parallels the veins. In contrast, the intensity130of carbonatization, more precisely the completeness of the replacement of epidote andchlorite by carbonate, is weak in the northern segment of the No. 3 vein and stronger tothe south.In brief, the distribution pattern of propylitic alteration with superimposedcarbonatization at the Silver Queen mine is likely controlled by a complicated fracturesystem rather than by the mineralized structure zone only. It is suggested that thepropylitic alteration at the Silver Queen mine might be related to the hydrothermalactivities that immediately followed the volcanic eruption and intrusion of the early LateCretaceous Kasalka Group equivalent rocks. Carbonatization superimposed on the earlypropylitic alteration halo may be the product of a CO2 degassing process. This might berelated to the hydrothermal activity associated with mineralization and controlled by acomplicated fracture system. Even though the propylitic alteration with superimposedcarbonatization at the Silver Queen mine is not an alteration envelope, the distributionpattern of propylitic alteration with superimposed carbonatization does indicate a broadCO2 degassing halo that may be used to delineate the hydrothermal alteration anomalyassociated with mineralization.In summary, the following conclusions about hydrothermal alteration at the SilverQueen mine can be deduced based on observations above:(1) Regional propylitic alteration is characterized by replacement ofmainly primarymafic minerals initially by epidote and chlorite as well as minor amount ofcarbonate and the partial replacement of plagioclase replaced by carbonate andsericite. This type of alteration is interpreted to be the product of hydrothermalactivity followed by the initial stage ofvolcanism, which predates themineralization.(2) Carbonatization superimposed on the early propylitic alteration halo may be theproduct of a CO2 degassing process, which might be related to the hydrothermalactivity associated with mineralization; it is controlled by a complicated fracture131system. With increasing intensity of superimposed carbonatization on propyliticalteration at Silver Queen, more complete replacement of epidote and chlorite byabundant carbonates occurs.(3) Hydrothermal activity associated with mineralization forms the outer alterationenvelopes marked by complete replacement of plagioclase by sericite andkaolinite, chlorite by siderite and magnetite by pyrite or hematite.(4) Inner alteration envelopes are interpreted as maximum stage hydrothermalalteration superimposed on the sericitic and argillic outer alteration envelope; itis marked by the replacement of sericite by quartz and direct precipitation ofquartz, sulfide and carbonate. The close association between mineralization andthe inner silicification envelope indicates that the ore-forming metals aretransported as Si, S and C complexes, and that the precipitation of quartz, sulfideand carbonate through reaction with wall rock and hydrothermal solution mighttrigger ore deposition.132Chapter 6. Quantitative Model of lEydrothermal Alteration,Silver Queen Mine, Central British Columbia6.1 IntroductionThe Silver Queen mine is an ideal locality to study hydrothermal alteration for thefollowing reasons:(1) The major types of the rocks that host the vein at the Silver Queen mine areandesite and diorite; these are typical wall rocks in many other ore deposits ofsimilar type.(2) The petrographic and timing relations among various rock types andmineralization at the Silver Queen mine are well understood through contactrelations, thin section study and isotopic dating.(3) The young ages and short interval between the formation ofwall rock andmineralization event (about 78 Ma for the wall rock and 50 Ma formineralization, respectively) as well as the simple deformation history in thestudy area exclude the complexities caused by other processes superimposed, butunrelated to, deposit genesis.(4) The uniformity of composition of both the andesite flows and the microdioritedome, the two host units for veins, is favorable in terms of having a singleprecursor.(5) Abundant trenches, drill cores and underground workings provide goodaccess for the study of alteration and its spatial relationship to veins.Silver Queen mine, thus, provides an excellent opportunity to evaluate thequantitative effects of hydrothermal alteration spatially associated with precious- and basemetal vein mineralization in volcanic sequences.This chapter discusses a quantitative evaluation of the hydrothermal alteration atthe Silver Queen mine, Owen Lake area, central British Columbia by applying theapproaches 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 lossesand gains of chemical constituents during the hydrothermal alteration,(iv) interpretation of the lithogeochemical variations in terms ofmineral variationsthrough the use ofPER diagrams,(v) calculation ofmetasomatic norms,(vi) calculation of the propagated errors for the quantitative evaluations oflithogeochemical data, and(vii) integration of the mineralogical variations corrected for closure with theabsolute losses and gains of chemical components and the errors at specificconfidence levels to provide a quantitative chemico-mineralogic model ofhydrothermal alteration.6.2 Sampling and Sample PreparationThe collection and preparation of samples is an often overlooked aspect of datagathering that impacts strongly on the quantitative interpretation of losses/gains inhydrothermal systems. Many published papers related to lithogeochemistry do notdocument sampling and sample preparation methods in detail. For example, small chipscollected from limited drill core may not be of sufficient size to represent the geologicalunit being sampled; a small sample may not be representative of coarse grained units. Asshown in Chapter 3, the larger the sample mass and the finer the sample is ground, themore 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 asubsample finer than needed. In order to minimize the artificial sampling and samplepreparation errors, equations 3-13 and 3-14 have been applied to samples used to studyhydrothermal alteration at the Silver Queen mine.134Rock types in study area are massive and porphyritic volcanic flows and high levelintrusive 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 mineralssuch as rutile (rich in Ti02)and zircon (rich in Zr). The results of calculated optimalsample sizes based on equations in Chapter 3 are presented in Table 6-1. Thesecalculations indicate that the optimal sample size depends on the coarseness ofphenocrysts and inhomogeneities of the constituents of interest among the minerals. Forinstance, plagioclase and augite phenocrysts are the important minerals which determinethe size of a field sample because they are the coarsest minerals (v (mm3)= 8 and 1.73respectively); albite and enstatite, as end members of these two mineral series, are rich inNa20 and MgO relative to the rest of the rock (the values OfHNa2O and HM of these twoend member mineral phases are 0.24 and 0.40 respectively, whereas the value ofLN2oandLMgO for the rest of rock are 0.00 and 0.01, respectively). Therefore, they are the biggestcontributors to inhomogeneity of the sample, and nearly 500 grams of sample is needed toreduce the sampling error to about one percent at the 68% confidence level. In contrast,another relatively coarse mineral, quartz (v (nun3)= 3.38), has a high value ofH502 ( 1)but also a high value ofL502(0.4) for the rest of the rock. This means that Si02 isdistributed more homogeneously in the rock thanNa20orMgO. According to thecalculation using equation 3-13 and by treating the rest ofbulk rock as the equivalent ofultramafic rock or mafic rock, only 15 grams of sample are necessary to provide anadequately homogeneous sample for analysis of Si02. Accessory minerals, such as apatite,may have a high value ofH (=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. 0.0005mm3). So if the sample size is just a few grams the homogeneity ofP205 in the sample willbe adequate. Therefore, 500 grams is considered the optimal sample size to provideadequate homogeneity for all components of the samples. This size results in a samplingerror of less than or equal to 1% (RE) at the 68% confidence level.135Table 6-1. Estimation of Optimal Sample Size by Using Binomial FunctionComponent Si02 TiO’, FeO MgO Na20 P205 ZrMineral Quartz Rutile Pyrite Enstatite Albite Apatite Zirconv (nun3) 3.375 0.064 0.125 1.728 8.000 0.0005 0.0003H 1.000 1.000 0.470 0.402 0.240 0.424 0.498L 0.400 0.001 0.010 0.010 0.000 0.000 0.000d(gIcm3) 2.648 4.245 5.011 3.210 2.620 3.180 4.669dL (g/cm3) 2.87 2.87 2.87 2.87 2.87 2.87 2.87Pw 0.150 0.005 0.050 0.050 0.300 0.005 0.0003qw 0.850 0.995 0.950 0.950 0.700 0.995 0.9997RE 0.01 0.01 0.01 0.01 0.01 0.01 0.01(HdH-LdL)2 2.250 17.996 5.413 1.588 0.395 1.818 5.4061p+Lq2 2.40x10’ 3.59x10 1.09x103 8.75x104 5.18x103 4.49x106 2,28x108w (g) 15.0 376.2 60.2 466.7 475.5 3.2 38.9Note: the notations used are defined in Chapter 3.The detailed descriptions of sampling strategy including: sampling locations, thelength of the profile that sample represented, rock and alteration type, as well as samplesize are listed in Appendix A. An example of sampling strategy along a typical profile isillustrated in Figure 6-1. The samples are collected continuously in the intensely alteredzone adjacent to the vein, and discontinuously in the broad moderately and weakly alteredzones away from the vein.Using equation 3-14, the optimal fineness of subsamples have been calculated andare listed in Table 6-2. This table shows various components, their principal minerals and136Q)‘ii-dSampleIDdc’cocou)cc)CONCDOIIIIIIIIIIIIIIII•Q0000000-—-1—,—1—-r-.10—I—-—><>>‘<<>M>><><<Samplesite/f+++Geological++++++++++++++++\_/+\+++++++\-+++f++-++++++profileouterenvelopeinnerenvelopeveininnerenvelopeouterenvelopemicrodioritesericitic/argiliicsilicic/pyriticNo3silicic/pyriticsericitic/argillicpropyliticpropyliticsericitic/argillicLegend[\vein[+microdiorite.1outerenvelope0510msilicic/pyriticDiscontinouscontinuousIinnerenvelopeVchipsampleIchipsampleFigure6-1.AtypicalsamplingprofileacrossthealterationenvelopeinthecentralsegmentoftheNo.3vein,SilverQueenmine.Table 6.2. Estimated Optimal Fineness of Subsample by Using Binomial Functionthe proportional abundance of each component in the principal mineral (H) and theremainder of the rock (L), as well as the weight proportion of the mineral rich in theconstituent of interest (P). These are the key factors in determination of the optimalfineness of a subsample. For instance, the fineness of passing through 80 mesh (i.e. thediameter of grain 177 microns) can provide adequate homogeneity of the majorcomponents: FeO, MgO andNa20. It gives a subsampling error of less than or equal to1% (RE) at the 68% confidence level. In contrast, the homogeneities ofminor constituentsComponent Si02 TiO, FeO MgO Na20 P205 ZrMineral Quartz Rutile Pyrite Enstatite Albite Apatite ZirconH 1.000 1.000 0.470 0.402 0.240 0.424 0.498L 0.400 0.001 0.010 0.010 0.000 0.000 0.000dH (g/cm3) 2.648 4.245 5.011 3.210 2.620 3.180 4.669dL (g/cm3) 2.87 2.87 2.87 2.87 2.87 2.87 2.87Pw 0.150 0.005 0.050 0.050 0.300 0.005 0.0003qw 0.850 0.995 0.950 0.950 0.700 0.995 0.9997RE 0.01 0.01 0.01 0.01 0.01 0.01 0.04(HdH-LdL)2 2.250 17.996 5.413 1.588 0.395 1.818 5.406(Hp+Lq)2 2.40x10 3.59x10 1.09x103 8.75x104 5.18x103 4.49x106 2.28x108w (g) 4.00 4.00 4.00 4.00 4.00 4.00 4.00v (mm3) 0.89765 0.00068 0.00831 0.01481 0.06730 0.00063 0.00041d (micron) 964.65 87.96 202.54 245.58 406.77 85.81 74.37Sieve Size (mesh) < 12 < 140 < 60 < 60 < 40 < 140 < 200Note: Common sieve size Micron Conimon sieve size Micron12 1680 80 17720 841 140 10540 420 200 7460 250 400 37138such as Ti02 andP205 require the fineness ofmaterial to be subsampled to pass through200 mesh (i.e. the diameter of the grains are 74 microns). This provides a subsamplingerror of less than 1% (RE) at the 68% confidence level. Zircon has the lowestconcentration (about 0.0003 wt%) among the minerals listed in Table 6.2. It is the onlycommon mineral containing Zr (i.e. L = 0), so even a subsample that has been ground topass through 200 mesh will have a subsampling error four time larger than those of otherconstituents at the same confidence level. The detailed procedure of subsamplepreparation 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 ajawcrusher;(5) homogenize sample thoroughly on rag paper and randomly scoop out a 300grams 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 passingit through a nylon sieve (200 mesh); if not fine enough, randomly scoop outabout100 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 errorarising from improper sampling and sample preparation. It is of a special significance forthe determination of immobile components of interest in this study. As indicated in Table6.1., if the size of a field sample is less than 200 grams (equivalent of a sample from a halfdrill core with diameter of 4 cm and length of 12 cm), the sampling error for Ti02 couldbe doubled relative to the current sample size (equal to or greater than 500 g). Similarly,139if the weight of subsample is reduced from 4 gram to 2 gram, the subsampling error for Zrwill increase by (i.e. from RE = 4% to RE 4%xl.414 = 5.7%). Consequently, thedifficulty of recognizing and using these potentially immobile components correspondingwould be increased significantly.6.3. Errors in Lithogeochemical DataThe lithogeochemical determinations of: Si02,Ti02,A1203,TotalFe203,MgO,MnO, CaO, Na20,K20,P205, S, Rb, Sr, Y and Zr reported here were obtained by X-rayfluorescence (XRF) using 4 gram pressed rock powder pellets. This technique is suitablefor the purpose here because there is neither the sample dilution problem inherent inborate bead preparation, not the problem of incomplete solution in acid digestion methods(MacLean and Barrett, 1993). In the analytical scheme ofXRF the oxidation state of iron(i.e. ferrous and ferric) cannot be distinguished. Thus, the XRF data have beensupplemented by determinations for ferrous iron based on titrimetry (Potts, 1987). Thedeterminations of structural water and carbon dioxide were conducted separately by theignition method (Shapiro and Brannock, 1955, 1962).The quality of lithogeochemical data is a function ofvarious factors including thestrategy of the sampling and sample preparation scheme, the skill and experience of theresearcher and instrument operator, the operating condition of the instrument, thestandards used to calibrate the counting values, the method of converting the countingvalues to meaningful lithogeochemical data and the concentrations ofcomponents/elements. Therefore, the quality of each set of lithogeochemical data shouldbe assessed individually through the use of duplicates that are representative of the rangeof composition.The duplicates selected for this study were obtained at two different stages. Onewas at the field sampling stage and other was at the analytical measurement stage. Thereare 18 sample duplicates and 20 measurement duplicates for major components analyzed140by XRF, 10 duplicates for ferrous iron, 10 duplicates for structural water, 10 duplicatesfor carbon dioxide, 20 duplicates for sulfur and 22 duplicates for trace elements analyzedby methods previously mentioned. The general procedure for assessing errors is presentedin Appendix D (Figures 6-2a, 6-2b, 6-2c, 6-2d, 6-3a and 6-3b). The final results of erroranalysis of lithogeochemical data are listed in Tables 6-3 and 6-4. With the determinationof the values of S0 and k for each component or element, the standard deviation (Se) andthe precision (Pc) for each component or element at specific concentration can becalculated by using equation 3-15 and 3-16 introduced in Chapter 3.Table 6-3. Error of lithoeochemical data estimated by usina sample duplicatesSi09 TiO, A1,O Fe,O FeO MgO MnO CaO Na,OSo 0.01 0.006 0.01 0.06 0.045 0.074 0.022 0.08 0.09k 0.012 0.008 0.021 0.018 0.018 0.03 0.007 0.011 0.013Cd 0.02 0.012 0.021 0.124 0.093 0.157 0.045 0.164 0.185K,O P,Oç CO, 11,0 S Zr Y Rb SrSo 0.02 0.02 0.01 0.04 18 0.01 0.3 2.00 5.00k 0.018 0.015 0.12 0.13 0.07 0.032 0.09 0.035 0.019Cd 0.041 0.041 0.026 0.108 41.86 0.021 0.732 4.301 10.395Table 6-4. Error of lithogeochemical data estimated by using measurement duplicatesSiO, TiO, A1,O. The MgO MnO CaO Na,O K,O P,OçSo 0.001 0.006 0.001 0.042 0.07 0.007 0.028 0.02 0.005 0.001k 0.002 0.008 0.007 0.025 0.008 0.01 0.012 0.003 0.009 0.04Cd 0.002 0.012 0.002 0.088 0.142 0.014 0.057 0.04 0.01 0.002Analytical precision for all components can be seen to be much less than fieldsampling precision. The reason for this is that the duplicates at the field sampling stage141contain more sources of variability, including the artificial errors caused by insufficientsample size, inhomogeneity of subsamples and inconsistent analytical measurements. Onthe other hand, measurement duplicates reveal only the error caused by inconsistentanalytical measurements. The purpose of lithogeochemical data is to reveallithogeochemical variations at scales larger than sample size. Therefore, the sum of allsources ofvariability of the samples should be known for interpretation purposes.6.4. Lithogeochemical Data of Altered Rock andDetermination of Immobile ComponentsThe analytical results of the whole rock samples collected from four representativealteration profiles at the Silver Queen mine are listed in Appendix E (Table 6-5). A Ti02versus Zr binary plot (Figure 6-4) is constructed with these data and the lithogeochemicaldata are listed in Table 4-2. The two distinctive series ofvolcanic and intrusive rocksaround Owen Lake area (Chapter 4) are evident in Figure 6-4. Compositions of alteredrocks from four alteration profiles form linear patterns which converge toward the origin.These patterns indicate that the hydrothermally altered samples were derived from amultiple precursor system along the fractionation trend of the older series of igneous rocksat Owen Lake area. Therefore, Ti02and Zr are likely immobile in the hydrothermalalteration system at the Silver Queen mine.The lithogeochemical data indicate that hydrothermally altered rocks are related toa multiple precursor system on the scale of the entire property. However, samples fromeach local hydrothermal alteration profile exhibit the attribute of a single precursor systemthat is a linear trend going through the origin of the Ti02-Zr binary plot. This linearpattern results from dilution or concentration ofTi02 and Zr in proportion to the gain orloss of the total mass of the sample during the hydrothermal alteration (Figure 6-4). Inother words, before wall-rock hydrothermal alteration at the Silver Queen mine, rocks thatare hundreds ofmetres apart from each other have significant differences in their1421.50HLegendZrppmPostmineralizationigneousseriesPremineralizationigneousseries3001.00—UnalteredrocknorthNo.3veincentralNo.3veinsouthNo.3vein0SwitchBackveinerror0.50—0.000100200400Figure6-4.Immobilecomponent/e1ementscatterplot,SilverQueenmine,centralBritishColumbia.lithogeochemical compositions, but those within a few tens ofmetres from each other arenot significantly different in composition. Therefore, each individual hydrothermalalteration profile can be treated as a single precursor system. Furthermore, Ti02 and Zrare mineralogically and geochemically incompatible, hence both are used as immobileconstituents with which to quantifj the mobilities of other components.Theoretically, there should be no significant difference in the recognition ofmobilecomponents using both immobile components (Ti02 and Zr). In reality, this is not so.Thus, the question is, which should be used to correct for closure to provide the mostaccurate quantification of losses and gains? The sampling (+analytical) variability for Ti02ranges from 3 to 5.6% at 95% confidence level in the abundance range of interest (0,3 to0.9 wt% Ti02). Comparable variability for Zr is 6.4% or more at 95% confidence level inthe abundance range of interest (120 to 220 ppm Zr). It therefore is reasonable to deducethat Zr has contributed more to the dispersion of the immobile linear trend for each profilethan has Ti02. This conclusion is also consistent with what is expected based on thecalculations of the optimal sample size and the optimal fineness of subsample (Tables 6-1and 6-2). As a result, Ti02 is chosen to be the preferred immobile component. It is used toremove the closure of lithogeochemical data in this study.6.5. Calculation ofAbsolute Losses and Gains of Chemical Constituentsand Their Spatial VariationsThe total mass change of each sample can be visually and qualitatively evaluatedfrom the Ti02-Zr plot (Figure 6-4) after knowing the composition of the precursor. Mostof the hydrothermally altered samples at the Silver Queen mine plot between the primaryLate Cretaceous fractionation trend and the origin of the plot. This means that thesehydrothermally altered rocks have gained mass during alteration, so that the immobileconstituents Ti02 and Zr are diluted proportionally. For example, most of thehydrothermally altered samples from the southern and central profiles of the No. 3 vein,144and Switch Back vein plot in this fashion. In contrast, the samples that plot further fromthe origin reflect loss of the mass and thereby proportional concentration of the immobileconstituents Ti02 and Zr. The specific amounts lost and gained remain to be determined.Equation 1-9 is used to calculate the absolute losses and gains of individual chemicalconstituents. The mass ofprecursor is assumed to be around 100 grams and the mass lossor gain is also presented in an extensive unit (grams), which are the absolute mass changerelative 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 whatvariation is caused by error propagation, equation 3-31 is applied to calculate thepropagated error. If the variation of a constituent between two samples is obviously largerthan its propagated error, then this variation is thought to be significant; otherwise, it isnot significant. A selected example of these calculations are combined with the previouscalculation result are present in Figure 6-5a and rest of the results in Appendix D (Figures6-5b, -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 samplesfrom different hydrothermal alteration profiles at the Silver Queen mine have manyfeatures in common and show some systematic variations from the southern segment tothe northern segment of the No. 3 vein and from different levels (from 2600-foot level to2880-foot level). The general feature shared by all profiles may represent the commonattributes of ore-forming hydrothermal solutions in this district. Whereas the differencesfrom place to place may illustrate the spatial variations of the properties of ore-forminghydrothermal solutions. Both are important in the study of ore deposits, but the latter is ofspecific significance to exploration. The systematic variation in fluid/rock interaction mayhelp to interpret the migration direction of ore-bearing hydrothermal fluid. Therefore, boththe general features and the spatial variation of absolute losses and gains of each chemicalconstituents in various hydrothermal alteration profiles at the Silver Queen mine aredescribed below.145-60x4-4x3-6x3-4x3-2x3-3dx2-5x3-7x3-5x3-1x3-2x3-3propyliticandesite\\alterationenvelope\propyliticandesiteveinbc80_—.--—.—60—-—-----———........—_-.::...j.::z::zzzhtyficeTvF—4(•...*CentralsegmentoftheNo.3vein-60xi-8sl-6xl-4xl-2c1al-ixlO-lxll-3x10-3dxiO-4dO-SclO-6x10-6Dxi-7al-SDxi-3xi-2xbO-lxlO-2,clO-3x10-3dxlO-4xlO-5xlO-6x10-6Dalterationouter\\0alterationouter’.propyliticenvelopesalteraioninnerenvelope“nsicrodioriteenvelopeiouuncertaintyat95%confidencelevel80—absolutelossorgain60....*zSwitchBackvem-60DA63-8DA63-5DDM34DA63-3DDA63-3DA63-1DA63-6DM3-SDM34DA63-3DDA63.IDalterationouterenvelope”\propylitic-niicrodioriteFigure6-5a.AbsolutelossesandgainsofSi02fromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia.Theblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations.uncertaintyat95%confidencelevelabsolutelossorgain4o).*20 -2:.......!..L40*-NorthernsegmentoftheNo.3vein0 Ialterationinner”\envelopedic-i 0xS-1x5-3x54x5-10xS-2xS-4xS-5x5-6x5-6dx5-8\vein\‘\alterationouteralterationinnerenvelopeenvelope‘\propylitic”\sericiticmicrodioritealterationSi02: In general, this constituent is added from hydrothermal solution to wall rocksin all alteration envelopes discussed here, except in the alteration envelope of the northernsegment of the No. 3 vein and in the outmost subzone of the alteration envelope at thecentral and southern segment of the No. 3 vein. The greatest addition of Si02 is at the2600-foot level of central segment of the No. 3 vein, and the 2600-foot level of southernsegment of the No. 3 vein. In turn, mildly intensive addition of Si02 occurs at the SwitchBack vein. In contrast, a loss of Si02 occurs at the northern segment of the No. 3 vein andin the outmost subzone of the alteration envelope at the central and southern segments ofthe No. 3 vein (Figure 6-5a).A1203.In general, A1203 has a loss-gain pattern similar to that of Si02 but thechanges are less obvious than are those of 5i02 (Appendix D, Figure 6-5b).Fe203:Ferric oxide is depleted or reduced to various extents in most portions ofthe alteration envelopes. A moderate increase in Fe203commonly occurs immediatelyadjacent 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 inall alteration envelopes. This ‘addition’ is strongly intensified at the Switch Back vein andin the central segment of the No. 3 vein (Appendix D, Figure 6-5d).MnO: Manganese addition and depletion patterns are two-fold. Type one ischaracterized by a pervasive addition ofMnO to the wall rocks in the alteration envelopesat the northern segment of the No. 3 vein and the Switch Back vein. Type two involvesthe addition ofMnO to most portions of the alteration envelopes, but there is a narrowdepletion ‘valley’ adjacent to the vein at the 2600-foot level of central segment andsouthern segment of the No. 3 vein (Appendix D, Figure 6-5e).MgO: Magnesium is moderately depleted in the alteration envelopes. There is nosignificant systematic addition and depletion pattern in the profiles (Appendix D, Figure 6-5f).147Na20and CaO: Sodium and calcium depletions from the wall rocks are prominentand intense in all alteration envelopes. In particular, the depletion ofNa20 is almostcomplete in all alteration envelopes (Appendix D, Figures 6-5g, 6-5h).K20 and Rb: Potassium and rubidium additions to the wall rocks are prominentbut variable in intensities from the southern segment to the northern segment of the No. 3vein. Additions ofK20 and Rb are most intense in parts of the alteration envelopes at the2600-foot level of the central and southern segment of the No. 3 vein, and moderatelyintense in the alteration envelope at the Switch Back vein. In contrast, only one sampleshows a slight addition ofK20 and Rb, the rest indicate depletion or no significant masschange, ofK20 and Rb in the alteration envelope at the northern segment of the No. 3vein. K20 and Rb depletions occur at the outmost parts of the alteration envelopes at thecentral and southern segments of the No. 3 vein (Appendix D, Figures 6-5i, 6-5j).H20, CO2and S: Volatile constituents are prominently added from hydrothermalsolution to wall rocks in all alteration envelopes discussed here except the southernsegment of the No. 3 vein. The spatial variation of addition ofH20, CO2and S aredescribed as follows. The additions ofH20 and CO2are the most intense in the alterationenvelopes at the Switch Back vein and the central segment of the No. 3 vein, the secondmost intense in the alteration envelope at the northern segment of the No. 3 vein. There isalmost no significant addition ofH20 and CO2in the alteration envelope at the southernsegment of the No. 3 vein. In contrast to the addition ofH20 and C02, the addition ofsulfur reaches its peak in the alteration envelope about the southern segment of the No. 3vein, as well as at the central segment of the No. 3 vein. The addition of sulfur is minoralong the Switch Back vein profile. There is very little addition of sulfur in the alterationenvelope at the northern segment of the No. 3 vein (Appendix D, Figures 6-5k, 6-51 and6-5m).Sr: Strontium is depleted in the alteration envelopes in a pattern similar to those ofNa20 and CaO but the intensity of depletions vary from profile to profile. It appears to be148more intense at the southern segment of the No. 3 vein than at the northern segment of theNo. 3 vein. In addition, the subzone adjacent to the vein in the alteration envelope at thecentral 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 ofmass from thehydrothermal solution, but lost its mass in part of the alteration inner envelope in thecentral and southern segment of the No. 3 vein. These changes may not be significantsince yttrium has a large analytical error (Appendix D, Figure 6-5o).P205:Phosphorous is probably a locally immobile component during thehydrothermal alteration process because it has no significant loss or gain in the sericiticand argillic outer alteration envelope; its depletion is mild in the silicic and pyritic inneralteration 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 centralsegment ofNo. 3 vein and least intense at the northern segment ofNo. 3 vein in terms ofabsolute losses and gains of chemical constituents according to the lithogeochemical datafrom the current four profiles. The total mass change of each altered sample is largely theresult of the depletions of CaO andNa20, and the addition of 5i02,K20, 1120 and CO2.6.6. Application of PER Diagram to the Interpretation of Hydrothermal AlterationKnowing the absolute losses and gains of chemical constituents during thehydrothermal alteration process, we can infer corresponding mineralogical changes. Forexample, an addition ofK20 along with the depletion of CaO andNa20ofandesiticvolcanic rock samples might be intuitively interpreted as the replacement of plagioclase orK-feldspar by muscovite. This can be illustrated by the following equations:3CaA12SiO8+2K + 4H =2KA13SiO10(OH)+ 3Ca (6-1)Anorthite Muscovite3NaAlSiO8+K+2W =KA13SiO10(OH)2+ 3Na + 6SiO2 (6-2)Albite Muscovite1493KAISiO8+2H =KA13SiO10(OH)2+2K + 6SiO2 (6-3)K-feldspar MuscoviteIn another case, the depletions ofK20, CaO andNa20along with no mass changes ofSi02 might indicate the occurrence of argillic alteration. This can be represented as follows:CaAl2SiO8+ 2W +H20=A12Si05(OH4+Ca (6-4)Anorthite Kaolinite2NaA1Si3O8+2W + 1120 =Al2Si5(0H4+ 2Na + 4Si02 (6-5)Albite Kaolimte2KA1Si3O8+2W +1120 =A12Si5(OH)4+2K + 4Si02 (6-6)K-feldspar KaolimteA previous petrographic examination documents the existences of propylitization,carbonatization, argillization, sericitization and silicification in the study area. Thesealteration processes lead to the replacement ofprimary minerals such as plagioclase, augiteand hornblende by epidote, chlorite, carbonates, kaolinite and sericite, with the addition ofquartz.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 aretwo preconditions that must be satisfied before applying this PER diagram to theinterpretation of the lithogeochemical data. The first is that the chemical composition andmineral assemblage of parent rock or precursor of alteration derivatives must be known orpredictedable. This has already been demonstrated in Figure 6-4 and the relateddiscussion. The lithogeochemical composition and mineral assemblage of a propylitic rockcan be treated as the precursor of the altered rocks in the superimposed alterationenvelope. The second precondition is that the proportion ofprimary minerals convertedinto alteration product must be reasonably estimated. The microscope observationsindicate that primary minerals are completely replaced by altered minerals including mainlysericite, kaolinite, quartz, carbonate and pyrite within the alteration envelope, and partiallyreplaced by epidote, chlorite, carbonate and sericite in propylitic alteration halo.150The PER diagram designed previously (Figure 1) is used to test (i) whetherfeldspar and augite fractionations are still the main contributors to lithgeochemicalvariation among the propylitically altered rocks; (ii) whether either carbonatization,sericitization, argillization or siicification is the dominant alteration type at the SilverQueen mine.The propylitically altered samples on the PER diagram are characterized by ascattered 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 constituentsused to construct this PER diagram have had no significant changes during the propyliticalteration process. In other words, primary feldspar and augite crystal fractionations maybe still the major causes for the lithogeochemical variations of the corresponding chemicalconstituents among the propylitically altered samples (Figure 6-6a). However, it is notcertain whether the unchanged mass means that the mass of each constituent is unchangeor that the masses of corresponding constituents do change but the total mass remainunchange by compensation.In general, all the samples from the alteration envelope (not including propyliticalteration) plot far from the primary fractionation trends on this PER diagram. This impliesthat there are significant mass changes of the corresponding chemical constituents amongthese samples relative to the propylitically altered samples. Also, all the samples from thealteration envelope spread between sericitic trend and argillic trend rather thanconcentrating around one alteration trend, indicating that the lithogeochemical variation ofaltered rocks is not entirely controlled by either carbonates, sericite, kaolinite or quartz atthe Silver Queen mine. Instead, the lithogeochemical variations among these samples haveto 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 andquartz. According to petrographic observations one of the possible alteration paths isdeduced as follows (Figure 6-6b): all primary minerals and propylitical minerals in the least151Figure6-6a.PERplottodiscriminatethealterationtypesassociatedwithprecious-andbase-metalveinmineralizationinvolcanicsequencesattheSilverQueenmine.Qtz-quartz,Carb-carbonates,Kao-kaolinite,An-anorthite,Ab-albite,Or,K-feldspar,Chl-chlorite,Aug-augite,Mus-muscovite,Ep-epidote,N.No.3v.-thenorthernsegmentoftheNo.3vein,SWBKv.-SwitchBackvein,C.No.3v.-centralsegmentoftheNo.3vein,SNo.3v.-southernsegmentoftheNo.3vein,seetextfordetaileddiscussion. C0.8errorunaltered0.60.40.2+N.No.3v.*SWBKv.xC.No.3v.A S.No.3v.Si!TiO22r3 C1.81.41.2 10.8a2,/P//b4LegendAlterationpatherrorEpb5b3I— I——I0.4b2,//1,/,/tAb,Or,ChlCarbKao1234Si/Ti02Figure6-6b.OneofthepossiblealterationpathsonPERdiagramdesignedtodiscriminatethealterationtypesassociatedwithprecious-andbase-metalveinmineralizationinvolcanicsequencesattheSilverQueenmine.Qtz-quartz,Carb-carbonates,Kao-kaolinite,An-anorthite,Ab-albite,Or,K-feldspar,Chi-chlorite,Aug-augite,Mus-muscovite,Ep-epidote.or propylitically altered wall rocks are completely replaced (from P to b 1) bycarbonatization (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 Queenmine. This PER diagram has a A1/Ti02 as x-axis and (2Ca+Na+K)/Ti0 as y axis (Stanleyand Madeisky, 1993). The displacement vectors of primary minerals (feldspar andhornblende) are defined to have slopes equal to one, the displacement vectors ofcarbonates are vertical, that of kaolinite horizontal, that ofmuscovite has a slope equal to1/3, 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 thatleast or propylitically altered samples plot along the fractionation trend of slope equal toone within the error range (at the 95% confidence level). This means that lithgeochemicalvariation of least or propylitically altered wall rock is caused mainly by feldspar. Thedisplacement vector of augite is vertical on this PER diagram (Figure 6-6d).Compared to the previous PER diagram, this PER diagram shows a moreunderstandable dispersion of plotted points; the alteration patterns are moredistinguishable because the effect of quartz has been removed and only carbonates,muscovite and kaolinite alteration are presented on this PER diagram. In addition, abubble plot superimposed on this PER diagram is used to investigate the effect ofsilicification (Figure 6-6e). With regard to the alteration intensity relative to the spatialdistribution, the plots of the samples from the alteration envelopes of the northern segmentof the No. 3 vein, the Switch Back vein, the southern segment of the No. 3 vein and thecentral segment of the No. 3 vein are presented in turn from the lowest left portion to thehighest right portion of this PER diagram. This plotting pattern indicates that samplesfrom the alteration envelope of the central segment of the No. 3 vein are affected by themost intense alteration including sericitization, carbonatization, pyritization andsilicification. In contrast, the alteration intensity of the samples from alteration envelope of154Figure6-6c.PERdiagramdesignedtodiscriminatethealterationtypeswithoutconsideringtheeffectofquartz.Qtz-quartz,Carb-carbonates,Kao-kaolinite,An-anorthite,Ab-albite,Or,K-feldspar,Chi-chlorite,Aug-augite,Mus-muscovite,Ep-epidote.P-protolith;augitereplaced(al)bycarbonates(a2);primarymineralsarecompletelyreplaced(b)bycarbonates(c),muscovite(d)orkaolinite(e).0.90.8-Legend +C + z + Ce0II00. z + L)Legenderrorunaltered+N.No.3V.SWBKV.xC.No.3v.A S.No,3v.,Carb-carbonates,Kao-kaolinite,An-anorthite,Ab-albite,Or,K-feldspar,Chl-chlorite,Aug-augite,Mus-muscovite,Ep-epidote,N.No.3v.-thenorthernsegmentoftheNo.3vein,SWBKv.-SwitchBackvein,C.No.3v.-centralsegmentoftheNo.3vein,SNo.3v.-southernsegmentoftheNo.3vein,seetextfordetaileddiscussion.+ z + L)Figure6-6e.PERdiagramsuperimposedbySi/(immobileelement)bubbleplot.ThesizeofbubblerepresentstherelativemolaramountofSicorrectedforclosure.A1/TiO2LIthe northern segment of the No. 3 vein is the mildest relative to others. Its alteration typesare mainly carbonatization and argillization plus sericitization. All these are consistent withthe conclusions drawn from the calculations of absolute losses and gains of chemicalconstituents in the previous section.6.7. Application ofMetasomatic Norm MethodologyFor the purpose of a general examination of the types and intensities ofhydrothermal alteration associated with precious- and base-metal vein deposit in volcanicsequence by using the lithogeochemical data, the PER diagram, described above, is auseful tool. However, projections ofmulticomponents systems can be ambiguous and maynot involve all variables, partly because of its 2-dimensional limitation. For example, analtered sample plotted on the PER diagram, above, could be interpreted as either thecombined product of argillization, carbonatization, sericitization and silicification or simplythe product of carbonatization plus intense silicification. A more complicated system hasto be taken into account to reduce the ambiguities or to test other hypotheses. In theexample mentioned above, the product of carbonatization plus intense silicification willlead to the content of CO2 in the bulk rock composition being more abundant than in thecase of silicification, argillization and sericitization. In contrast, the combined product ofsilicification, argillization, carbonatization and sericitization will contain more 1120 in thebulk rock composition than in the product of carbonatization plus intense siliciflcation.One means of reducing these ambiguities is through use of the methodology described byCheng and Sinclair (1994) and in Chapter 2.The lithogeochemical data of four hydrothermal alteration profiles at the SilverQueen mine have been processed by applying the approach ofmetasomatic normcalculation. The minerals listed in Table 2-1 are chosen to be the standard normativeminerals for the metasomatic norm calculation. These mineral occurrences are based onthe petrographic observations and XRD examination of the samples (Cheng et al., 1991).158Finally, all the calculated metasomatic norm values have been corrected for closure byusing Ti02as an immobile component and equation 1-9. The metasomatic normscorrected for the closure and the absolute loss and gain values of chemical constituents ofthe northern segment of the No. 3 vein profiles as the selected examples are presented inunits ofmole and gram in Tables 6-7a and 6-8a, respectively. The calculations of otherprofiles are listed in Appendix E, Table 6-7b, 6-7c and 6-7d and Tables 6-8b, 6-8c and 6-8d, respectively.Residuals have been used to monitor how closely the masses of parent-daughterlosses and gains balance. A residual is defined as metasomatic normftered rock - (metasomatic normprecsor rock + zMass change). The residuals ofmetasomatic normcalculation after the correction for the closure range from 0.16 to -0.49 gram relative tothe mass of precursor rock (about 100 gram). This indicates that the mineral assemblageschosen 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 ofy-axes are uniform inFigures 6-7a, 6-7b, 6-7c and 6-7d. Thus, the type and intensity ofwall-rock hydrothermalalteration in different profiles can be quantitatively evaluated and objectively compared.The propylitic altered rock is characterized by a metasomatic normative mineralassemblage composed mainly of plagioclase, K-feldspar, pyroxene, quartz, epidote,chlorite and carbonate. There is no systematic spatial variation of the abundances of theseminerals relative to the vein. This attribute is convincing evidence that propylitic alterationis related to pre-mineralization volcanic activity rather than the ore-fluid.The carbonatization is relatively intense in hydrothermal alteration envelopes and isindicated by the increase in the content of carbonate from 5.6 gram on average in thepropylitic 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 strongly159Table 6-7a. Metasornatjc norms corrected for closure and absolute lossesand gains of components (in moles)at northern segment of the No. 3 vein, Silver Queen mine, Owen Lake, central BCSmpIeJd x4-4 x3-7 x3-6 x3-5 x3-4 x3-1 x3-2x3-2 x3-3d x3-3 x2-5Afteration w-alt w-alt w-alt rn-alt ms-alt ms-alt rn-altrn-alt w-alt w-alt w-altmolePyroxene 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.02 0.02Plagioclas 0.14 0.16 0.10 0.00 0.00 0.00 0.00 0.00 0.11 0.15 0.15K-feldspar 0.07 0.06 0.06 0.00 0.00 0.000.00 0.00 0.07 0.06 0.07Quartz 0.20 0.22 0.26 0.46 0.68 0.59 0.580.58 0.23 0.19 0.24Carbonate 0.05 0.05 0.05 0.09 0.16 0.13 0.10 0.10 0.04 0.05 0.06Epidote 0.04 0.02 0.02 0.00 0.00 0.000.00 0.00 0.03 0.03 0.01Chlorite 0.00 0.01 0.02 0.00 0.00 0.00 0.00 ,‘O.OO 0.02 0.01 0.01Sericite 0.00 0.00 0.02 0.04 0.11 0.06 0.07 0.07 0.01 0.00 0.00Kaolinite 0.00 -0.00 0.01 0.06 0.02 0.070.05 0.05 -0.00 0.00 0.00Pyrite 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 0.00Hematite 0.00 0.01 0.01 0.00 0.01 0.010.01 0.01 0.00 0.00 0.01Magnetite 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 0.00Ilinenite 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00Rutile 0.01 0.00 0.01 0.01 0.01 0.010.01 0.01 0.01 0.01 0.01Apatite 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00Total 0.53 0.55 0.56 0.67 1.00 0.870.83 0.82 0.52 0.52 0.58dSiO2 0.00 0.00 -0.03 -0.24 0.11 -0.04-0.05 -0.06 -0.00 -0.02 -0.02dAl+3 0.00 0.01 0.00 -0.04 0.08 0.030.02 0.02 0.00 -0.00 -0.00dTi+4 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 0.00dEe +3 0.00 -0.00 -0.00 -0.03 -0.02 -0.02-0.01 -0.01 -0.00 -0.00 -0.00dFe+2 0.00 0.00 -0.00 -0.00 0.05 0.040.01 0.01 0.00 -0.00 -0.00dMn+2 0.00 -0.00 -0.00 0.01 0.02 0.020.00 0.00 0.00 -0.00 -0.00dMg+2 0.00 -0.01 -0.01 -0.06 -0.04 -0.05-0.05 -0.05 0.00 -0.00 0.01dCa+2 0.00 -0.01 -0.00 -0.07 -0.09 -0.10-0.08 -0.08 -0.01 -0.01 / -0.01dNa+ 0.00 0.01 -0.00 -0.11 -0.10 -0.11-0.11 -0.11 0.00 0.01 -0.01dK+ 0.00 -0.00 -0.00 -0.03 0.03 -0.01-0.00 -0.00 0.00 -0.00 0.00dP+5 0.00 0.00 0.00 -0.00 -0.00 -0.00-0.00 -0.00 0.00 0.00 -0.00Sum 0= 0.00 -0.01 -0.02 -0.30 -0.01 -0.15-0.17 -0.17 -0.00 -0.01 -0.01dH2O 0.00 0.02 0.07 0.13 0.12 0.16 0.15 0.14 0.05 0.01 0.00dCO2 0.00 0.00 0.01 0.04 0.11 0.080.04 0.04 -0.01 -0.00 0.02dS 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 -0.00dTotal 0.00 0.01 0.01 -0.69 0.26 -0.15-0.25 -0.27 0.04 -0.03 -0.03160Table 6-8a. Metasomatic norms corrected for closure and absolute losses and gains of components (in grams)at northern segment of the No. 3 vein, Silver Queen mine, OwenLake, central BCSample Id x4-4 x3-7 x3-6 x3-5 x3-4 x3-1. x3-2 x3-2x3-3d x3-3 x2-5AIteraon w-alt w-alt w-alt rn-alt ms-alt ms-altrn-alt rn-alt w-alt w-alt w-altgramPyroxene 5.11 1.22 0.90 0.00 0.00 0.000.00 0.00 1.80 4.33 33Plagioclase 36.01 41.63 26.19 0.25 1.12 0.530.89 0.08 28.51 39.58 40.72K-feldspar 18.26 17.26 16.00 0.00 0.00 0.00 0.00 0.08 18.50 17.58 18.34Quartz 12.02 13.40 15.88 27.38 40.9035.35 34.72 34.76 13.87 11.17 14.21Carbonate 4.86 5.85 5.35 9.81 17.14 14.1410.25 10.21 3.98 5.10 5.53Epidote 18.70 9.79 11.07 1.78 0.00 0.000.00 0.00 15.49 13.55 3.89Chlorite 3.05 7.28 11.35 0.00 0.00 0.000.00 ,.0.00 11.71 4.16 7.65Sericite 0.00 0.02 7.39 17.28 44.29 25.4328.75 29.59 3.96 0.00 0.00Kaolinite 0.00 -0.00 1.56 16.28 6.06 17.7713.92 12.95 -0.00 0.17 0.01Pyrite 0.02 0.03 0.03 0.04 0.27 0.130.10 0.09 0.05 0.03 0.01Hematite 0.00 1.24 1.24 0.65 1.44 1.212.00 2.10 0.25 0.74 2.39Magnetite 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 0.00Ilmenite 0.00 1.20 0.00 0.00 0.00 0.430.00 0.00 0.00 0.08 0.01Rutile 0.65 0.02 0.65 0.65 0.65 0.420.65 0.65 0.65 0.61 0.64Apatite 0.90 0.90 0.93 0.48 0.51 0.460.56 0.55 0.92 0.91 0.86Total 99.58 99.83 98.53 74.60 112.38 95.8691.83 91.06 99.69 98.01 98.09dSiO2 0.00 0.11 -1.53 -14.19 6.76 -2.32-2.99 -3.50 -0.27 -0.99 -1.44dAI+3 0.00 0.14 0.09 -1.10 2.16 0.700.61 0.51 0.10 -0.00 -0.08dTi+4 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 0.00dFe+3 0.00 -0.16 -0.01 -1.50 -1.16 -1.31-0.77 -0.69 -0.20 -0.08 -0.04dFe+2 0.00 0.12 -0.18 -0.10 2.88 2.140.35 0.31 0.15 -0.06 -0.01dMn+2 0.00 -0.11 -0.09 0.51 1.19 0.920.16 0.16 0.01 -0.03 -0.07dMg+2 0.00 -0.18 -0.22 -1.37 -0.98 -1.14-1.24 -1.23 0.08 -0.07 0.20dCa+2 0.00 -0.29 -0.14 -2.90 -3.74 -3.83-3.23 -3.22 -0.33 -0.29.-0.35dNa+ 0.00 0.33 -0.11 -2.54 -2.34 -2.50-2.47 -2.48 0.03 0.19 -0.23dK+ 0,00 -0.14 -0.08 -1.11 1.34 -0.33-0.00 -0.01 0.03 -0.10 0.01dP+5 0.00 0.00 0.01 -0.08 -0.07 -0.08-0.06 -0.06 0.00 0.00 -0.01Sum 0= 0.00 -0.10 -0.25 -4.78 -0.21 -2.40-2.70 -2.76 -0.01 -0.17 -0.20dH2O 0.00 0.30 1.18 2.31 2.10 2.822.63 2.58 0.87 0.16 0.05dCQ2 0.00 0.11 0.27 1.86 4.70 3.551.91 1.85 -0.38 -0.14 0.68dS 0.00 0.00 0.00 0.01 0.13 0.060.04 0.03 0.01 0.00 -0.01dTotal 0.00 0.14 -1.05 -24.98 12.76 -3.73-7.76 -8.52 0.10 1.57 -1.49Residual 0.00 0.11 -0.00 0.00 0.03 0.010.01 0.01 0.00 0.00 -0.00161•0-. 0 —,cC co 0.0C) C)C)C) 1•c9.C)-tgramgramS PtSQ’j’B PtB PtB00-i -0—CD ,0(-tCD II. 00<CD CDCD CDgramliIgramCtijcjfi1B B Pti1oos0:t.00.00-tCDCD 0CDCD .<CDLCD••0CD —Pt-t =0CDCD BoCD0iigramgramwjii .IB Pt B Pt (I, Pt Pt Pt B S 5’ B Pt B 5’ Pt Pt1ii jfl1B PtC’, 5’ Pt 5’ Pt 5’ B Pt B 5’ B Pt B 5’ 5’ 5’(1COIjC-CC—00pJCC0—jo0-C0- 0CD0CDCM-t CD CD —CMoCM CDOCDCD•0, II IgramgramCM (CCM Io1!CM (C C-carbonatized. The carbonatization of the alteration envelope at the southern segment ofthe No. 3 vein is the mildest.Argillization is extensively developed in the narrow alteration envelope at thenorthern segment of the No. 3 vein. The alteration envelope of the Switch Back vein ischaracterized by an inner extensive argillic subzone. The broad alteration envelope at thecentral segment of the No. 3 vein has an inner argillic subzone similar to that of the SwitchBack vein but much narrower than that of the Switch Back vein. There is also an argillicalteration outer subzone adjacent to the boundary between the alteration envelope andpropylitic halo at the central segment of the No. 3 vein. A similar outermost argillicsubzone is present in the alteration envelope of the southern segment of the No. 3 veintoo.Sericitization is extensive in all four alteration envelopes but is strongest in thealteration envelope of the southern segment of the No. 3 vein (the content of sericite is upto about 61 gram relative to 48 gram on average). In contrast, the content of sericite in thealteration envelope of the northern segment of the No. 3 vein is relatively low (up to 44gram and 29 gram on average, respectively).Potassic alteration is indicated by the presence of normative K-feldspar in thealteration 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 Backvein and the northern segment of the No. 3 vein.Silicification is strong in the alteration envelopes of the central and southernsegments of the No. 3 vein. It is weakest in the alteration envelopes of the northernsegment of the No. 3 vein and the Switch Back vein.In brief, the results of the metasomatic norm calculations of four alteration profilesprovide a comprehensive, quantitative view ofmass and mineralogical changes that areassociated with hydrothermal alteration at the Silver Queen mine. The ambiguities of theinterpretation have been largely reduced by considering all constituents of the geochemical166system, and by using mass balance and known minerals as constraints. The metasomaticnorm profiles documented in this section link the lithogeochemical variations with themineralogical variations. They present the hydrothermal alteration associated withprecious- and base-metal vein mineralization in an easily understood way.6.8. Propagated Error Analysis and Confidence Level of the QuantitativeEvaluationsTo decide which chemical and mineralogical variations discussed in the previoussections are significant, the propagated errors are calculated using equations 3-31 and 3-33 and the values of S0 and k of each chemical constituent (derived from the duplicateanalyses, cf. Table 6-3). The propagated error calculation of the northern profile of theNo. 3 vein are listed in Tables 6-9a as a selected example. The calculation results of otherthree profiles are listed in Appendix E, Table 6-9b, 6-9c and 6-9d. Only the chemical ormineralogical variations that are larger than the corresponding propagated errors can besafely considered as significant. Smaller apparent variations may be caused entirely byartificial factors. By using this technique the words ‘significant’ and ‘insignificant’ are usedto describe the variations according to an objective criterion.Based on the calculation of propagated error, the four alteration profiles can beinterpreted with respect to significant chemical variations. For example, the propyliticaltered samples from the alteration profile at the northern segment of the No. 3 vein haveabsolute losses and gains of Si02 ranging from -0.11 to 1.53 gram, and the propagatederrors of Si02 for these samples range from ± 1.76 to ±1.80 gram at 68% confidencelevel. Thus, Si02 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 gainsof Si02 equal to -14.19 and 6.76 gram respectively. These changes in Si02 contents aremuch greater than their propagated errors (±1.38 and ±2.03 gram at the 68% confidencelevel, respectively). The other three samples (x3 -1, x3 -2 and x3 -3d) in the alteration167Table 6-9a. Propagated errors of metasomatic norms correctedfor closure and absolute losses/gains of componentsin grams at the 68% confidence level, the northern segment ofthe No. 3 vein, Silver Queen mine, central BCSan,pleid x4-4 x3-7 x3-6 x3-5 x3-4x3-1 x3-2 x3-2 x3-3d x3-3 x2-5AlteTation w-alt w-alt w-alt rn-alt ms-alt ms-alt rn-alt rn-alt w-alt w-alt w-altgramPyroxene 0.17 0.04 0.03 0.00 0.000.00 0.00 0.00 0.16 0.19 0.28Plagioclase 0.95 1.10 0.69 0.01 0.040.02 0.04 0.00 0.75 1.04 1.08K-feldspar 0.48 0.45 0.42 0.00 0.00 0.000.00 0.00 0.49 0.46 0.48Quartz 0.33 0.36 0.43 0.71 1.150.96 0.93 0.93 0.38 0.30 0.39Carbonate 0.40 0.36 0.34 0.60 1.050.86 0.65 0.65 0.24 0.34 0.40Epidote 0.50 0.26 0.29 0.05 0.00 0.000.00 0.00 0.41 0.36 0.10Chlorite 0.11 0.28 0.41 0.00 0.00 0.000.00 0.00 0.42 0.15 0.27Serjcite 0.00 0.00 0.20 0.47 1.26 0.710.79 0.82 0.11 0.00 0.00Kaolinite 0.00 0.00 0.05 0.51 0.21 0.580.45 0.42 0.00 0.01 0.00Pyrite 0.00 0.00 0.00 0.00 0.01 0.010.01 0.01 0.00 0.00 0.00Hematite 0.00 0.06 0.06 0.04 0.10 0.090.10 0.10 0.01 0.03 0.11Magnetite 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 0.00Ilmenite 0.00 0.04 0.00 0.00 0.000.01 0.00 0.00 0.00 0.00 0.00Rutile 0.02 0.00 0,02 0.02 0.02 0.010.02 0.02 0.02 0.02 0.02Apatite 0.04 0.04 0.04 0.02 0.05 0.040.03 0.03 0.04 0.04 0.03Total 2.99 2.99 2.98 2.44 3.89 3.293.01 2.98 3.04 2.94 3.16dSiO2* 1.73 1.73 1.68 1.33 1.95 1.66 1.63 1.61 1.72 1.70 1.69ciAl+3 0.32 0.32 0.32 0.28 0.38 0.330.33 0.32 0.32 0.31 0.31dTi+4 0.01 0.01 0.01 0.01 0.01 0.010.01 0.01 0.01 0.01 0.01dFe+3 0.13 0.12 0.13 0.09 0.11 0.100.11 0.11 0.12 0.12 0.12dFe+2 0.12 0.12 0.12 0.11 0.20 0.170.13 0.12 0.12 0.12 0.12dMn+2 0.03 0.03 0.03 0.03 0.05 0.040.03 0.03 0.03 0.03 0.03dMg+2 0.14 0.14 0.14 0.11 0.12 - 0.120.11 0.11 0.15 0.14 0.15dCa+2 0.18 0.18 0.18 0.12 0.13 0.120.13 0.13 0.18 0.18 0.17dNa+ 0.16 0.16 0.16 0.11 0.13 0.120.12 0.12 0.16 0.16 0.15dK+ 0.11 0.11 0.11 0.08 0.15 0.100.11 0.11 0.11 0.11 0.11dP+5 0.02 0.02 0.02 0.01 0.02 0.010.01 0.01 0.02 0.02/0.02Sum 0= 0.65 0.65 0.65 0.53 0.70 0.620.60 0.60 0.65 0.65 0.65dH2O 0.24 0.27 0.36 0.49 0.48 0.560.54 0.53 0.33 0.25 0.24dCO2 0.36 0.37 0.39 0.54 0.87 0.740.55 0.55 0.33 0.35 0.43dS 0.00 0.00 0.00 0.00 0.01 0.010.01 0.01 0.00 0.00 0.00dTotal 4.19 4.23 4.28 3.87 5.31 4.724.41 4.37 4.25 4.15 4.20* prefixe d stands for the absolute difference of corresponding constituent between the least altered and altered rocks.168envelope have gained Si02 ranging from 2.32 to 3.5 gram, respectively. This is close totheir propagated errors of Si02 ranging from ±1.68 to ± 1.73 gram at the 68% confidencelevel and is almost equal to the propagated error at the 95% confidence level (from ±3.36to ± 3.46 gram). Therefore, the gains of Si02at the sites where these three sample werecollected are very small. Similar examination of the other chemical and mineralogicalvariations can be carried on by comparing the data listed in Tables 6-8a, with thecorresponding propagated errors listed in Tables 6-9a.6.9. A Comprehensive Model ofHydrothermal AlterationA comprehensive model is suggested here to illustrate the process of hydrothermalalteration at the Silver Queen mine. A set of comprehensive, mass balanced reactionequations 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 hydrothermalalteration of sample x3-5 can be interpreted as follows. The primary minerals such aspyroxene (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 alteredminerals including chlorite (0.004 mole or 3.05±0.11 gram) and epidote (0.039 mole or18.7±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±0.34gram to 0.093 mole or 9.81±0.6 gram) and quartz (increased from 0.2 mole or 12.02±0.3 3gram to 0.456 mole or 27.3 8±0.71 gram). These replacements are accompanied by themass losses of Si02 (-0.236 mole or -14.19±1.38 gram),A13(-0.041 mole or -1.1±0.22gram),Fe3(-0.027 mole or -1.5±0.04 gram), Mg2 (-0.056 mole or -1.37±0.03 gram),Ca2(-0.072 mole or 2.9±0.07 gram), Na (-0.110 mole or -2.54±0.04 gram), K(-0.029mole or -1.11±0.06 gram) from wall rock to hydrothermal solution and the mass gains ofH20 (0.129 mole or 2.31±0.1 gram) andC02(0.042 mole or 1.86±0.12 gram). All theseexchanges can be presented as a comprehensive reaction equation as follows:169Primary 0.O23pyroxene +0. l36plagioclase + 0.066K-feldspar + 0.2quartzminerals 5.11±0.17 g 36.01± 0.95 g 18.26±0.48 g 12.02±0.33 gPropylitic + 0.O04chlorite + 0.O39epidote + 0.O53carbonatealteration 3.05±0.11 g 18.7±0.5 g 4.86±0.34 gmass - 0.236SiO - 0.04 1A13 - 0.027Fe3 - 0.056Mg2 - 0.072Ca2- 0.11Na - 0.029Klosses -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 gmass + 0. 129H + 0.042C02gains 2.31±0.1 g 1.86±0.12 gsericitic, argillic, = 0.O44sericite + 0.O63kaolimte + 0.O93carbonate + 0.456quartzcarbonatized, 17.28±0.47 g 16.28±0.51 g 9.81±0.6 g 27.38±0.71 gsilicified alterationThe 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 onthe value of the total weight of the sample. Analytical measurements provide the results ofmost 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, Fe2 may notcombine with oxygen anion entirely as an oxide but may combines partly with sulfur anionas a sulfide, such as FeS2. As a result, the total weight of the sample may be exaggeratedwhen abundant sulfides exist in the sample and their cations are analytically reported asoxides. In contrast, calculations of a metasomatic norm allot cations to critical minerals andtake corresponding required amounts of necessary anions to form each normative mineralaccording to the stoichiometries of the mineral. Consequently, the total value of normativeminerals will not be balanced with the total value of analytical constituents when sulfur ispresent in an analysis. The extra oxygen will be easily taken out during the conversion ofoxides to ionic species.The other reason for converting oxides to ionic species except Si02 is that a massbalanced equation is commonly presented in the forms of solid mineral phases and solubleionic species or complexes rather than oxides. Si02 is an exception because it exists both ina solid form as quartz and as an aqueous species. It is also possible that these species can170be further converted to any probable form of aqueous complex such as HC02,Al(OH)2,etc., if there is sufficient evidence to support the existences of these complexes in thehydrothermal fluid.171Chapter 7 Conclusions and RecommendationsThe aim of this thesis is to extend quantitative methods in the evaluation ofmaterial exchanges during hydrothermal alteration associated with precious- and base-metal 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 arefundamentally similar in principle. That is, they both remove the closure effect in order todecipher the true chemical variations during alteration. Gresens’ procedure emphasizeschemistry. Pearce element ratios provide the ability to discuss losses and gainsmineralogically.The first requirement of applying these quantitative techniques to the estimation ofabsolute losses and gains in a metasomatic system is to determine immobile componentsfrom lithogeochemical data. The determination of immobile components is recommendedthrough a two-fold consideration of:(i) the ratio of two immobile components remains constant in a single precursorsystem regardless of the nature of the alteration, and(ii) two immobile components must not be mineralogically or geochemicallycompatible 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 preparationprocedure as well as analytical error. Analytical error can be quantified to provide a basisfor recognizing significant variation, such as ratio variability that is too large to beattributed to analytical error (thus, too large to accept the two components of the ratio asbeing immobile). This rule is to be used cautiously. If a PER ratio is constructed with oneof the components being mobile and the other having poor analytical precision, then thelatter component will contribute more to the final propagated error of the ratio, especially172where it is used as the denominator of the ratio. As a result, mobility of the formercomponent might be obscured and the plot might lead to the incorrect conclusion thatboth numerator and denominator are immobile. Therefore, ‘immobil& components ofrelatively high analytical quality should be accepted in preference to those with pooranalytical precision.The second requirement of applying these quantitative techniques for estimatinglosses and gains in metasomatic system is that a suite of samples for which loss/gainvariations are to be evaluated, must be the alteration products of either: (i) a single parentrock characterized by chemical and mineralogical homogeneity (single precursor system),or (ii) a suite of rocks with determinable pre-alteration chemical compositions (multipleprecursor system). This requirement can be met conventionally through the carefulinvestigation of the field and petrographic relationships in the study area. Rock derivativesaltered to various degrees from a common homogeneous parent rock commonly are inclose spatial proximity and may show gradational contacts between each other. Primarytextural and structural features may remain identifiable in least-altered to more intensivelyaltered derivatives. To examine these types ofvariations rigorously it is recommended thatsamples be collected systematically along alteration profiles from the strongly altered rockadjacent to, or within, a mineralized zone, to the least altered rock far from the ore deposititself. Such sampling should be done after a careful field investigation of the profile. Eventhough the altered rocks are our main concern, equal attention should be paid to the leastaltered or unaltered rocks because they provide important information about the parentrocks before hydrothermal alteration. This gives insight into the possibilities of a singleprecursor system versus a multiple precursor system.The PER approach to examining a metasomatic system has an advantage overother procedures in not only removing the closure effect of lithogeochemical data by usingimmobile components, but also by explaining the corrected chemical variations in terms ofmineralogical variation. Two specific PER diagrams have been designed to discriminate173the hydrothermal alteration types commonly associated with epithermal vein deposits involcanic sequences. The first one is constructed with Si/(immobile component) as its xaxis 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 K-feldspar, and alteration mineral chlorite are defined to have slopes equal to one, thedisplacement vectors of carbonates and pyrite are parallel to the y-axis, the slope ofmuscovite is 7/6, the slope of kaolinite is 1/4 and the slope of quartz is zero. Thereforelithogeochemical variations cuased by either primary feldspar and augite fractionation,intense carbonatization, argillization, sericitization or silicification can be discriminated ifeither of them is the dominant contributor to the lithogeochemical variation. The secondPER diagram is designed to deal with more complicated types of alteration. It hasA1/(immobile component) as its x-axis and (2Ca+Na+K)/(immobile component) as its yaxis. The displacement vector of quartz is designed to be perpendicular to the diagram. Asa result, the discriminations of carbonatization, argillization and sericitization from primarycrystal fractionations are relatively easier on this PER diagramThese specifically designed PER diagrams can be used to test the hypotheses thatchemical variations are due to variations in amounts of a particular set ofminerals, but theamount of each mineral can not be determined explicitly because the total displacement ona PER diagram commonly is the sum of the displacements of different minerals when acomplicated multiple variable system is considered. In other words, ambiguity arises wheretoo many variables are summarized in two dimensional space.A metasomatic norm approach has been developed in this thesis to quantitativelyand objectively evaluate material exchange in complicated hydrothermal alteration systemsassociated with precious- and base-metal vein deposits in volcanic sequences. Ametasomatic norm is a quantitative and objective approach to estimating mineralabundances from the lithogeochemical data since the mineralogy and chemistry of a rockare intimately linked through mineral abundances and the compositions of individual174minerals. The normative approaches, originally designed principally for igneous rocks, arerigid in their application and in general, do not utilize important alteration minerals. Thedifferent approach here, to the determination of norms of hydrothermally altered rockscombines petrographic and lithogeochemical data. Metasomatic norm calculation uses thesame principles as the calculation of CIPW norms, but different mineral phases includingvolatile component-bearing minerals are used as the normative standard minerals thatrepresent hydrothermal alteration systems. Another distinctive difference between ametasomatic and a conventional igneous norm is that the calculation of a metasomaticnorm does not proceed along as fixed a hierarchical path as in the case of an igneousnorm. More flexibility is necessary because of the wide range in both rock and mineralcompositions. In some cases, where constrained by known mineralogy, the calculationsmust alternate back and forth following a loosely defined sequence in order to eventuallybalance or best fit a calculated mineral assemblage with the fixed chemical composition ofan altered rock (i.e., to make the chemical masses and the mineral masses balance). Inaddition, the calculation of a metasomatic norm take into account possible incompatiblemineral pairs in a hydrothermal system. A possible approach to the application of the normconcept to metasomatic rocks is to constrain the calculated normative mineralogy by apriori knowledge of existing minerals (i.e. to approximate the mode as closely aspossible).The selection of a set of standard minerals for metasomatic norm calculation isbased on geological observations. A set of standard normative minerals based on theauthor’s experience are given in this thesis. This set of normative minerals should not beconsidered exhaustive. It can be extended by the addition of new standard normativemineral(s). Other identified mineral species can be substituted to meet specificrequirements.The general procedural scheme for metasomatic norm calculation is inefficient formanual calculation. Consequently, a computer-based procedure using Quattro Pro 5.0, a175sophisticated and readily available spread sheet program, has been devised to processnorm 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. Thegeneral procedure ofusing Optimizer is to decide on the solution destination, choose thevariables (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 theconstraints 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 totheir own purposes.With the recognition of an immobile component, the metasomatic norms forprecursor and altered rocks, and the constituents lost or gained, can be further recast intothe absolute amounts of minerals and chemical constituents relative to a given mass ofparent rock by using Gresens’ equation. Consequently, the calculated results can be usedto construct a comprehensive mass balanced and easily understood chemico-mineralogicalmodel to interpret a hydrothermal alteration system in terms of initial and final normativemineral assemblages (corrected for closure) plus absolute losses and gains of chemicalconstituents. It does not matter whether the system is closed or open, or whether itrepresent equilibrium or disequilibrium assemblages.All lithogeochemical data contain errors. Therefore, errors have been propagatedin this thesis to the final results of all calculations of absolute losses and gains, includingmetasomatic norm in intensive units (percentage) and metasomatic norm in extensive units(grams relative to a specific amount of precursor rock) after correction for closure. Suchpropagated errors also have been integrated with the results of the chemico-mineralogicmodel for material exchange (including absolute losses and gains of chemical constituentsas well as the normative minerals) formulated in this work as follows:Mineralparent rocic ± error + Constituent gained from so1uon± errorMineralaiterk± error + Constituent lost from wall rock± error (7-1)176The value of such an equation is that it provides useful, quantitative informationabout the hydrothermal system and limits the properties of the hydrothermal solution thateffected the metasomatism, provided the equation represents a simple and uniquealteration process. In reality, this type of reaction equation may more likely represent thefinal result of a series of sequential and/or superimposed processes. Nevertheless, the formof the equation is particularly useful because it is both quantitative and easilycomprehensible. Specifically, the equation includes starting and ending rock mineralogiesthat may be partly evident in the field. It documents gains and losses of specific chemicalconstituents in space. Also it includes the uncertainties of each item at certain confidencelevel, which indicate what variations are significant.In brief, this chemico-mineralogical model:(i) provides an objective and quantitative basis for a mineralogical classificationof hydrothermally altered rock;(ii) maps spatial distribution of normative minerals from lithogeochemical data;(iii) interprets lithogeochemical variations in terms ofmineralogical 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 lithogeochemicalconstituents 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 ofPearceelement ratio (PER) diagrams for the study ofmetasomatic rocks. The metasomatic normapproach is quantitative in the same way as Pearce element ratio diagrams. The commonprinciple is the correction for closure that provides true relative lithogeochemical andmineralogical variations between parent and daughter rocks. The normative approach is auseful supplement to PER analysis; the two procedures have much in common and containmuch the same information presented in different ways. The strategy of a PER diagram is177to test whether chemical changes between two rocks can be explained purely by thevariation(s) of certain mineral(s) as demonstrated by disposition of plotted points alongpredefined trends (slopes) according to the partial mass balance relationship. Metasomaticnorms are displayed more explicitly as equations or profiles showing the spatialdistributions of normative mineral assemblages, as well as the absolute losses and gains ofchemical constituents based on comprehensive mass balance relationships. In brief,metasomatic norms solve the problems ofmultiple variables in multiple dimensional space.In a quantitative evaluation of hydrothermal alteration, it is essential to know thequality of data so that conclusions can be derived with confidence. The major causes forthe variations of lithogeochemical data are classified as primary causes (such as crystalfractionation, 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 byartificial processes should be eliminated. In practice, however, they can only be minimizedthrough quality control, such as the estimation of the optimum sample size, the necessaryfineness of the ground grain size, and quality assessment of analytical results in terms ofprecision, accuracy and detection limit.To estimate the optimum size for a sample or the necessary fineness of the particlesize for a subsample, the model of’two-mineral mixture ofuniform grain size’ and binomialdistribution function are used in this thesis to simulate the distribution ofmajor andcompatible trace elements during sampling and subsampling processes. Because the rocktypes in the study area (Silver Queen mine) are massive and porphyritic volcanic flows andhigh level intrusive rocks, the inhomogeneities ofvarious constituents at the samplingstage are mainly caused by phenocrysts, such as plagioclase and augite. Calculationsindicate that the optimal sample size depends on the coarseness of phenocryst andhomogeneities of the constituents of interest in the rock; 500 grams of sample are neededto reduce the sampling error to around one percent at the 68% confidence level. The178optimal particle fineness of the subsample depends on the variable being considered: boththe abundance of an element in a mineral of interest and the amount of the mineral areimportant parameters.The quality of lithogeochemical data is a function ofvarious factors including: (i)strategy of sampling, (ii) the sample preparation scheme, (iii) the skill and experience ofthe 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 convertingthe counting values to meaningful lithogeochemical data as well as (vii) the concentrationsof components/elements. Therefore, the quality of each set of lithogeochemical data mustbe assessed individually through the use of duplicates.To assess the quality of lithogeochemical data the method ofThompson andHowarth (1976, 1978) has been used to treat precision as a function of concentration; themethod has been modified slightly to deal with small sets of duplicate lithogeochemicaldata. 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 reasonfor this is that the duplicates arranged at the field sampling stage contain more sources oferrors and include the artificial errors caused by insufficient sample size, inhomogeneity ofsubsample and inconsistent analytical measurements. Because the purpose of usinglithogeochemical data is to reveal real geochemical variations it is essential to includesampling variability (i.e. using duplicates samples) as a basis for recognizing meaningfulvariation.The application of the approach described in the first part of this thesis to the studyof the Silver Queen mine reveals that there are two distinctive series ofvolcanic andintrusive rocks in Owen Lake area. The first series consists of igneous and volcanic unitsfrom intermediate to felsic composition. They are characterized by having the lowercontent ofTi02,MgO, total iron andP205as well as the older K-Ar dating ages (range179from 78.8 to 57.2 Ma). The second series consist of igneous and volcanic units fromintermediate to mafic composition. They have higher contents ofTi02,MgO, total ironandP205 as well as the younger K-Ar dating ages (range from 48.7 to 21.4 Ma). Theformer predates and hosts the mineralization. The latter is post-mineralization.The hydrothermally altered samples at the Silver Queen mine derive from amultiple precursor system defined by the fractionation trend of the older series of igneousrocks of the Owen Lake area. However, each local, individual hydrothermal alterationprofile exhibits the attributes of a single precursor system. These are characterized by alinear trend going through the origin of a Ti02-Zr binary plot. Furthermore, themineralogical and geochemical incompatibility of these two potentially immobileconstituents are examined to eliminate any possibility that Ti02 and Zr could be mobile. Ofthese two immobile components, Ti02 is used to remove the closure of lithogeochemicaldata because its lithgeochemical error is smaller than that ofZr.Six types of hydrothermal alteration at the Silver Queen mine have been described.They are propylitic alteration, sericitic and argillic alteration, silicification, pyritization andcarbonatization. In general, the wall rock alteration in the study area is composed of awidespread regional propylitic alteration which gives way as the vein is approached to anouter envelope of sericitic and argillic alteration + carbonatization and an inner envelopeof silicification and pyritization + sericitic or argillic alteration + carbonatization.Widespread regional propylitic and carbonatic alteration, sericitic and argillic outerenvelope and silicification and pyritization inner envelope developed sequentially in thatorder.Most of the hydrothermally altered samples in alteration envelopes at the SilverQueen mine have gained mass during the hydrothermal alteration. In contrast, samplesfrom the profile of the northern segment of the No. 3 vein have lost mass. Other spatialvariations of hydrothermal alteration from the southern segment to the northern segmentof the No. 3 vein and from different levels (from 2600-foot level to 2880-foot level) have180been recognized. In brief, the wall rock alteration is most intense in the alteration envelopeat the central segment of the No. 3 vein and mildest at the northern segment of the No. 3vein. The total mass change of each altered sample is largely the result of depletions ofCaO andNa20, and additions of Si02,K20, 1120 and CO2.In addition, the width of the alteration envelope is very much narrower along thenorthern segment of the No. 3 vein (total width about 7 m wide) compared to the centraland 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 thepresence 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 summarizedas follows:(1) The regional propylitic alteration is characterized by the replacement ofmainlyprimary mafic mineral initially by epidote and chlorite as well as minor amount ofcarbonate and the partial replacement of plagioclase replaced by carbonate andsericite. This type of alteration is interpreted to be the product of hydrothermalactivity that followed the initial stage of volcanism and predates the mineralization.(2) Carbonatization superimposed on the early propylitic alteration may be theproduct of a CO2 degassing process, which might be related to the hydrothermalactivity associated with mineralization, and is controlled by complicated fracturesystems. With increasing intensity of superimposed carbonatization on propyliticalteration, more complete replacements of epidote and chlorite by abundantcarbonates occur.(3) The hydrothermal activity associated with mineralization leads to the completereplacement ofplagioclase by sericite and kaolinite, chlorite by siderite andmagnetite by pyrite or hematite to form the outer alteration envelope.(4) The inner alteration envelope is interpreted as the product of the processsuperimposed on sericitic and argillic alteration outer envelope at a maximum stage181of ore-forming hydrothermal activity. This is marked by the replacement of sericiteby quartz and by the direct precipitation of quartz, sulfide and carbonate from thehydrothermal solution. The close association between mineralization and the innersilicification envelope is clear. This implies that ore-forming metals are transportedas Si, 5, C complexes, and that the precipitation of quartz, sulfide and carbonate bythe reaction between wall rock and hydrothermal solutions might trigger oredeposition.Many questions dealing with material exchange in hydrothermal systems remainunanswered. A great deal ofwork is required to adapt what is known to a workablesystem that can be used by explorationists. Further insight is required into optimizingsampling procedure. Methods such as Pearce element ratio diagrams and metasomaticnorms need to be extended to a wide range ofgeological environments so that themethodologies can be extended and their advantages and limitations more fullyappreciated.182BibliographyAlbarede, F., and Provost, A. (1977): Petrological and geochemical mass-balanceequations; an algorithm for least-square fitting and general error analysis,Computers & Geoscience, 3, pp. 309-326.Appleyard, B.C. (1980) Mass balance computations in metasomatism; metagabbro/nepheline syenite pegmatite interacton in northern Norway. Contributions toMineralogy and Petrology, 73, (2), pp.13 1-144.Appleyard, E.C. and J. Guha (1991) A special issue on application of hydrothermalalteration studies to mineral exploration, Preface. Economic Geology, 86, (3),pp. 461-465.Armstrong, R.L. (1988): Mesozoic and Early Cenozoic Magmatic Evolution of theCanadian Cordillera; Geological Society ofAmerica, Special Paper 218, pp. 55-91.Babcock, R.S. (1973) Computational Models ofMstasomatic Processes. Lithos, 6,pp. 279-290.Barrett, T.J., MacLean, W.H. (1994) Chemostratigraphy and hydrothermal alteration inexploration for VIIMS deposits in Greenstones and younger volcanic rocks. inLentz, D.R., ed., Alteration and alteration processes associated with ore-formingsystems: Geological Association ofCanada, Short Course Notes, 11, pp. 433-467.Barrett, T.J. and MacLean, W.H. (1991): Chemical, mass, and oxygen isotope changesduring extreme hydrothermal alteration of an Archean rhyolite, Noranda, Quebec.Economic Geology, 86, (2), pp. 406-414.Barrett, T. J., MacLean, W. H. and Cattalani, S. (1993) Massive sulfide deposits of theNoranda area, Quebec. V. The Corbet mine: Canadian Journal ofEarth Sciences,30, pp. 1934-1954.Barth, T.F.W., (1959) Principles of classification and norm calculations ofmetamorphicrocks. Journal of Geology, 67: pp.135-52.Barth, T. F. W. (1962) Theoretical Petrology. Wiley, New York, 416 p.Bates, R. L. and Jackson, J. A, editors (1987): Glossary of Geology. American GeologicalInstitute, 749 p.Bernier, L. R. and MacLean, W. H. (1989): Auriferous chert, banded iron formation, andrelated volcanogenic hydrothermal alteration, Atik Lake, Manitoba. CanadianJournal ofEarth Sciences, 26, (12), pp. 2676-2690.Bernstein, L.R. (1987) Mineralogy and petrography of some ore samples from the SilverQueen mine, near Houston, British Columbia. Unpub. report to Pacific Houston183Resources Inc. by Mineral Search, 380 Willow Road, Menlo Park, California94025, Aug. 1, 1987, 13 p.Billings, M. P. and C. J. Roy (1933) Weathering of the Medford Diabase - Pre- orPostglacial? A discussion. Journal of Geology, XII, pp. 654-666.Boyle, R. W., (1979) The geochemistry of gold and its deposits (together with a chapteron geochemical prospecting for the element): Geological Survey Canada Bull. 280,584 p.Bodnar, R. J., Reynolds, T. 3. and Kuehn, C. A. (1985) Fluid-inclusion systematics inepithermal systems; in Berger, B. R., and Bethke, P. M. (ed.), Geology andGeochemistry ofEpithermal Systems: Society ofEconomic Geologists, Reviews inEconomic Geology, 2, pp. 73-98.Brown, T.H. and Skinner, B.J., (1974) Theoretical prediction of equilibrium phaseassemblages in multicomponent systems, American Journal of Science, 274,pp. 961-986.Capitani, C. and Brown, T.H. (1987) The computation of chemical equilibrium in complexsystems containing non-ideal solutions. Geochimica et Cosmochimica Acta, 51,pp. 263 9-2652.Carter, N.C. (1981): Porphyry Copper and Molybdenum Deposits West-central BritishColumbia; B. C. Ministry ofEnergy, Mines and Petroleum Resources, Bulletin64, iSO p.Cattalani, S., Barrett, T. J., MacLean, W.H., Hoy, L. Hubert, C. and Fox, J.S. (1989): TheHome massive sulfide deposit, Noranda, Quebec. Steam, Cohn W. GeologicalAssociation of Canada, Mineralogical Association of Canada; annual meeting;program with abstracts, 14. p. 33-34Cheng, X. and Sinclair, A.J. (1994) Optimizing norm calculations ofmetasomatic rocks. inChung, C. F. (ed.) Proceedings, 1994 International Association for MathematicalGeology Annual Conference, pp. 8 1-86.Cheng, X. and Sinclair, A.J. (1991) Recognition of immobile/conserved components and itsapplication to hydrothermal altered rocks. Exploration Geochemistry, 1990, ed. F.Mrna, Prague, 1991, pp. 137-143.Cheng, X., Sinclair, A.J., Thomson, M.L., and Zhang, Y. (1991) Hydrothermal alterationassociated with Silver Queen polymetallic veins at Owen Lake, central B.C. (93L/2).B.C. Ministry ofEnergy, Mines and Petroleum Resources, Geological Fieldwork1990, Paper 1991-1, pp. 179-183.Church, B.N. (1970): Nadina (Silver Queen). B. C. Ministry ofMines, Energy andPetroleum Resources, Geology, Exploration and Mining 1969, pp. 126-13 9.184Church, B.N. (1971) Geology of the Owen Lake, Parrot Lakes, and Goosly Lake Area. B.C. lVlinistry ofEnergy, Mines and Petroleum Resources, Geology, Explorationand Mining 1970, pp. 119-127.Church, B.N. (1973): Geology of the Buck Creek Area; B. C. Ministry ofEnergy, Minesand Petroleum Resources, Geology, Exploration and Mining, 1972, pp. 353-363.Church, B.N. (1984): Geology of the Buck Creek Tertiary Outlier; B.C. Ministry ofEnergy, Mines and Petroleum Resources, unpublished 1:100 000 scale map.Church, B.N. (1985): Update on the Geology and Mineralization in the Buck Creek Area -the Equity Silver Mine Revisited (93L/1W); B.C. Ministry ofEnergy, Mines andPetroleum Resources, Geological Fieldwork, 1984, Paper, 198 5-1, pp. 175-187.Church, B.N. and Barakso, J.J. (1990): Geology, lithogeochemistry and mineralization inthe Buck Creek area, British Columbia. Paper Ministry ofEnergy, Mines andPetroleum Resources. 95 p.Church, B.N. and Pettipas, A.R. (1990) Interpretation of second derivative aeromagneticmaps at the Silver Queen and Equity Silver mines, Houston, BC. Canadian MiningMetallurgy Bull., 83, no. 934, pp.69-76.Cox, K.G., Bell, J. D. and Pankhurst, R. J., (1979) The interpretation of igneous rocks.George Allen & Unwin Ltd. London, 450 p.Cross, W., Iddings, J.P., Pirsson, L. V. and Washington, H.S., (1903) Quantitativeclassification of igneous rocks. University of Chicago Press.Cross, W., Iddings, J.P., Pirsson, L. V. and Washington, H.S., (1902) A quantitativechemico-mineralogical classification and nomenclature of igneous rocks. Journal ofGeology, 10: pp. 555-690.Cummings, W.W. (1987) Report on the Silver Queen Mine, Omineca Mining Division,British Columbia. Unpub. report for Houston Metals Corporation, March, 1987,17 p.Cyr, J.B., Pease, R.B., and Schroeter, T.G. (1984) Geology and mineralization at theEquity Silver Mine. Economic Geology, 79, pp. 947-968.Davies, J. F., Whitehead, R. E. S., Cameron, R. A., and Duff, D. (1982) Regional andlocal patterns ofC02-K-Rb-As alteration: A guide to gold in the Timmins area:Canadian Inst. Mining Metallurgy Spec., 24, pp. 130-143.Davis, S.R. and Ferry, J.M. (1993): Fluid infiltration during contact metamorphism ofinterbedded marble and calc-silicate hornfels, Twin Lakes area, central SierraNevada, California. Journal ofMetamorphic Geology, 11. (1). pp. 7 1-88.185Dawson, J.M. (1985) Report on the Owen Lake Property, Omineca IVlining Division,British Columbia, for Bulkley Silver Resources Ltd. Unpub. report by DawsonGeological Consultants Ltd., Kamloops, B.C., August 1985, 30 p.Descarreaux, J. (1973) A petrochemical study of the Abitibi volcanic belt and its bearingon the occurrence ofmassive suiphide ores: Canadian Mining Metallurgy Bull.,66, (730), pp. 61-69.Diakow, L.J. and Koyanagi, V. (1988) Stratigraphy and mineral occurrences of ChikaminMountain and Whitesail Reach Map areas (93E/06, 10). B.C. Ministry ofEnergy,Mines and Petroleum Resources, Geological Fieldwork 1987, Paper 1988-1, pp.155-168.Dipple, G. M., Winstch, R.P., Andrews, M.S. (1990) Identification of the scales ofdifferential element mobility in a ductile fault zone. Journal ofMetamorphicGeology, 8, pp. 646-661.Dunbar, W.R. (1948) Structural relations of the Porcupine ore deposits, in Structuralgeology of Canadian ore deposits: Montreal, Canadian Inst. Mining Metallurgy,Geology Div. Spec. Pub., pp. 442-456.Duffell, S. (1959): Whitesail Lake Map-area, British Columbia. Geological Survey ofCanada, Memoir 299.Elliott-Meadows, S.R. and Appleyard, E. C. (1991): The alteration geochemistry andpetrology of the Lar Cu-Zn deposit, Lynn Lake area, Manitoba, Canada. EconomicGeology, 86. (3). pp. 486-505.Engels, J. C. and Ingamells, C. 0. (1970) Effect of sample inhomogeneity in K-Ar dating.Geochimica et Cosmochimica Acta, 34, pp. 1007-1017.Ferry, J.M.(1985a): Hydrothermal alteration ofTertiary igneous rocks from the Isle ofSkye, Northwest Scotland; 1, Gabbros. Contributions to Mineralogy andPetrology, 91. (3). pp. 264-282.Ferry, J.M. (1985b): Hydrothermal alteration of Tertiary igneous rocks from the Isle ofSkye, Northwest Scotland; 2, Granites. Contributions to Mineralogy andPetrology, 91. (3). pp. 283-304.Finlow-Bates and Stumpfl (1981) The behavior of so-called immobile elements inhydrothermally altered rocks associated with volcanogenic submarine-exhalativeore deposits. Mineralium Deposita, 16, pp. 319-328.Field, C. W., and Fifarek, R. H. (1985) Light stable-isotope systematics in the epithermalenvironment; in Berger, B. R., and Bethke, P. M. (ed.), Geology andGeochemistry ofEpithermal Systems: Society ofEconomic Geologists, Reviews inEconomic Geology, 2, pp. 99-128.186Fletcher, W.K. (1981) Analytical methods in geochemical prospecting. handbook ofexploration geochemistry, editor: Govett, G. J. S. Handbook of explorationgeochemistry. 1. 262 p.Floyd, P. A. and Winchester, J.A. (1978) Identification and discrimination of altered andmetamorphosed volcanic rocks using immobile elements. Chemical Geology,21, pp. 29 1-306.Fyles, J.T., (1984) Report on notes on thin sections ofNew Nadina DDH 84-15.unpublished report to Mr. G. Stewart. 2 p.Fyon, J. A., and Crocket, J. H., (1982) Gold exploration in the Timmins district using fieldand lithogeochemical characteristics of carbonate alteration zones: Canada Inst.Mining Metallurgy Spec., 24, pp. 113-129.Giggenbach, W. F. (1984) Mass transfer in hydrothermal alteration systems—Aconceptual approach. Geochimica et Cosmochimica Acta, 48. pp. 2693-2711.Godwin, CI. (1975): Imbricate Subduction Zones and their Relationship with UpperCretaceous to Tertiary Porphyry Deposits in the Canadian Cordillera; CanadianJournal ofEarth Sciences, 12, pp. 1362-1378.Golditch, S.S. (1938) A study in rock weathering, Journal of Geology, 46, pp. 17-58.Grant, I. A. (1986) The isocon diagram - A simple solution to Gresen& equation formetasomatic alteration. Economic Geology, 81, pp. 1976-1982.Gresens, R. L. (1967) Composition-volume relationships ofmetasomatism: ChemicalGeology, 2, pp. 47-65.Guilbert, J. M. and Park, C. F. Jr. (1986): The geology of ore deposits. W.H. Freemanand Company I New York, 985 p.Hanor, J.S., and K. C. Duchac (1990): Isovolumetric silicification of early Archeankomatiites; geochemical mass balances and constraints on origin, Journal ofGeology, 98, pp. 863-877.Harland, W.B., Armstrong, R.L., Cox, A.V., Craig, L.E., Smith, A.G. and Smith, D.G.(1989): A Geologic Time Scale, 1989; Cambridge University Press, 1st EditionJuly, 1989.Harris, D.C., and Owens, D.R. (1973). Berryite, a Canadian occurrence. CanadianMineralogist, 11, (5), pp. 1016-1018.Hashiguchi, H. and Usui, H. (1975) An approach to delimiting targets for prospecting ofthe Kuroko ore deposits: on the sulphur and magnetic susceptibility haloes: MiningGeology, 25, pp. 293-301.187Hayba, D. 0. (1983) A compilation of fluid-inclusion and stable-isotope data on selectedprecious- and base-metal epithermal deposits: U.S. Geological Survey, Open-FileReport 83-450, 24 p.Hayba, D. 0., Bethke, P. M. Heald, P. and Foley, N. K. (1985) Geologic, mineralogic,and geochemical characteristics ofvolcanic-hosted epithermal precious-metaldeposits; in Berger, B. R., and Bethke, P. M. (ed.), Geology and Geochemistry ofEpithermal Systems: Society ofEconomic Geologists, Reviews in EconomicGeology, 2, pp. 129-168.Helgeson, H. C. (1979) Mass transfer among minerals and hydrothermal solutions, InGeochemistry of hydrothermal ore deposits. edited by H. L. Barnes, John Wiley &Sons, Inc., New York, NY, pp. 568-610.Hood, C.H.B. (1991) Mineralogy, paragensis, and mineralogic zonation fo the SilverQueen vein system Owen Lake, central British Columbia, Unpublished M. Sc.thesis, The University ofBritish Columbia, 273 p.Hughes, C. 3., (1982) Developments in petrology 7, Igneous petrology, Elsevier ScientificPublishing Company, 551 p.Ingamells, C.O. and Switzer, P. (1973) A proposed sampling constant for use ingeochemical analysis. Talanta, 20, pp. 547-568.Ingamells, C.O. (1974a) New approaches to geochemical analysis and sampling. Talanta,21, pp.141-55.Ingamells, CO. (1974b) Control of geochemical error through sampling and subsamplingdiagrams. Geochmica et Cosmochimca Acta, 38, pp. 1225-1237.Ingamells, C.O. (1981) Evaluation of skewed exploration data— the nugget effect.Geochimica et Cosmochimica Acta, 45, pp. 1209-1216.Ishikawa Y., Sawaguchi, T., Iwaya, S. and Horiuchi, M. (1976) Delineation ofprospecting targets for Kuroko deposits based on modes of volcanism ofunderlying dacite and alteration haloes. Mining Geology, 26, pp. 105-117.Kamilli, R. 3., and Ohmoto, H. (1977) Paragensis, zoning, fluid-inclusion, and isotopicstudy of the Finlandia vein, Colqui district, Central Peru: Economic Geology,72, pp. 950-982.Ke, Peiwen (1992): A new approach to mass balance modeling: Applications to igneouspetrology, M. Sc. thesis, University ofBritish Columbia, 153 p.Kendall, M.G. (1943) The advanced theory of statistics. vol. 1, Griffin & Co., London,457 p.188Kishida, A., and Kerrich, R. (1987) Hydrothermal alteration zoning and goldconcentration at the Kerr-Addison Archean lode gold deposit, Kirkland Lake,Ontario: Economic Geology, 82, pp. 649-690.Kleeman, A.W. (1967) Sampling error in the chemical analysis of rocks. Journal ofGeological Society ofAustralia, 14, pp. 43-47.Kranidiotis, P. and MacLean, W. H. (1987): Systematics of chlorite alteration at the PhelpsDodge massive sulfide deposit, Matagami, Quebec. Economic Geology, 82. (7).pp. 1898-1911.Krauskof, K. B. (1967) Chemical weathering, chapter 4, Introduction to Geochemistry,McGraw-Hill, Inc. 721 p.Kwong, Y. T. J., Brown, T. H. and Greenwood, H. J. (1982) A thermodynamic approachto the understanding of the supergene alteration at the Afton copper mine, south-central British Columbia: Canadian Journal ofEarth Sciences, 19, pp. 2378-2386.Le Maitre, P. W. (1982) Numerical Petrology - Statistical Interpretation of GeochemicalData. Developements in Petrology 8, Elsevier Scientific Publishing Company Inc.281 p.Leitch, C.H.B. (1989): Geology, Walirock Alteration, and Characteristics of the OreFluids at the Bralorne Mesothermal Gold Quartz Vein Deposit, SouthwesternBritish Columbia; unpublished Ph.D. thesis, The University ofBritish Columbia,Vancouver, 483 p.Leitch, C.H.B. and Day, S.J. (1990) Newgres: a Turbo Pascal program to solve a modifiedversion ofGresens’ hydrothermal alteration equation: Computers & Geoscience,16, pp. 925-932.Leitch, C.H.B. and Lentz, D. R. (1994) The Gresens approach to mass balance constriantsof alteration systems: Methods, Pitfalls, Examples. in Lentz, D.R., ed., Alterationand alteration processes associated with ore-forming systems: GeologicalAssociation of Canada, Short Course Notes, 11, pp. 161-192.Leitch, C.H.B., Hood, C.T., Cheng, X. and Sinclair, A.J. (1990) Geology of the SilverQueen mine area, Owen Lake, central British Columbia. B.C. IVlinistry ofEnergy,lVlines and Petroleum Resources, Geological Fieldwork 1989, Paper 1990-1, pp.287-295.Leitch, C. H. B., Cheng, X., Hood, C. T., Sinclair, A.J. (1991) Structural character of enechelon polymetallic veins at the Silver Queen mine, British Columbia. CIMBulletin, 84, (955), pp. 57-66.Leitch, C.H.B., Hood, C.T., Cheng, X. and Sinclair, A.J. (1992) Tip Top Hill unit: UpperCretaceous volcanic rocks hosting Eocene epithermal base- and precious-metal veins189at Owen Lake, central British Columbia.Canadian Journal ofEarth Sciences, 29,pp. 854-864.Lindgren, W., (1933): Mineral Deposits. 4th ed. New York: McGraw-Hill, 930 p.Maclntyre, D.G. (1985): Geology and Mineral Deposits of the Tahtsa Lake District,West-central British Columbia; B.C. Ministry ofEnergy, Mines and PetroleumResources, Bulletin 75, 82 p.Maclntyre, D.G. and Desjardins, P. (1988): Babine Project (93L/15); B.C. Ministry ofEnergy, Mines and Petroleum Resources, Geological Fieldwork, 1987, Paper,1988-1, pp. 181-193.MacLean, W.H. (1988) Rare earth elements mobility at constant inter-REE ratios in thealteration zone at the Phelps Dodge massive suiphide deposit, Matagami, Quebec.Mineralium Deposita, 23, pp. 231-238.MacLean, W.H. (1990): Mass change calculations in altered rock series. MineraliumDeposita. 25. (1). pp. 44-49.MacLean, W.H. and Barrett, T.J., (1993) Lithochemical techniques using immobileelements, Journal of Geochemical Exploration, 48, pp. 109-133.MacLean, W.H. and Kranidiotis, P. (1987): Immobile elements as monitors ofmasstransfer in hydrothermal alteration; Phelps Dodge massive sulfide deposit,Matagami, Quebec. Economic Geology, 82. (4). pp. 951-962.Madeisky, H. E. and Stanley, C. R. (1993): Tdentifjing metasomatic zones associated withvolcanic-hosted massive sulfide deposits using Pearce Element Ratio analysis,Lithogeochemical exploration for VMS deposits. The Gangue, GAC- MineralDeposits Division Newsletter, issue 41, Jan. 1993, pp. 5-7.Margaret, G., McAfee, Jr., R., and Wolf, C. L.,(1972) (eds.) Glossary of Geology; Amer.Geol. Inst., Washington, D. C., 805 p. plus appendix.Marquis, P., A. C. Brown, C. Hubert and D. M. Rigg (1990) Progressive alterationassociated with auriferous massive sulfide bodies at the Dumagami mine, Abitibigreenstone belt, Quebec. Economic Geology, 85, pp. 746-764.Marsden, H.W. (1985): Some Aspects of the Geology, Mineralization and WallrockAlteration of the Nadina Zn-Cu-Pb-Ag-Au Vein Deposit, North-central B.C.;Unpublished B.Sc. thesis, The University ofBritish Columbia, 90 p.Maxwell, J.A. (1968) Rock and mineral analysis. Wiley-Interscience, new York.Merrill, G.P. (1897) Rock, Rock-Weathering, and Soil. New York, Macmillan Co., 218 p.Meyer, C., and Hemley, J.J. (1967) Wall rock alteration, in Geochemistry of hydrothermalore deposits, ed. Barnes, H. L. : New York, Holt, Rinehart and Winston, Inc., pp.166-23 5.190Myers, J. D., and C. L. Angevine (1986): Mass balance calculations with end membercompositional variability: application to petrologic problems, EOS Trans. AGU,67, p. 404.Myers, J. D., C. D. Frost and C. L. Angevine (1986): A test of a quartz eclogite sourcefor parental Aleutian magmas: a mass balance approach, Journal of Geology, 94,pp. 811-828.Myers, J. D., and C. L. Angevine and C. D. Frost (1987): Mass balance calculations withend member compositional variability: application to petrologic problems, EarthPlanet. Sci. Lett., 81, pp.212-20.Morton, R.L. and Nebel, M.L. (1984): Hydrothermal alteration of felsic volcanic rocks atthe Helen siderite deposit, Wawa, Ontario. Economic Geology, 79, pp. 1319-1333.Nicholls, J. (1988) The statistics ofPearce element diagrams and the Chayes closureproblem. Contributions to Mineralogy and Petrology. 99, pp. 11-24.Niggli, P., (1954) Rocks and mineral deposits. San Francisco: W. H. Freeman.Nowak, M. (1991) Ore reserve estimation, Silver Queen vein, Owen Lake, BritishColumbia; Unpubl. M.A.Sc. thesis, The University ofBritish Columbia, 204 p.Ondrick, C. W. and Suhr, N. H. (1969) Error and the spectrographic analysis ofgreywacke samples. Chemical Geology, 4, pp. 429-437.Pearce, T. H, (1968) A contribution to the theory of variation diagrams. Contributions toMineralogy and Petrology, 19, pp. 142-157.Pearce, T.H. (1987): The identification and assessment of spurious trends in Pearce-typeratio variation diagrams; a discussion of some statistical arguments. Contributionsto Mineralogy and Petrology, 97, (4), pp. 529-534.Philpotts, A. R. (1990) Principles of igneous and metamorphic petrology. Prentice Hall,Englewood Cliffs, New Jersey, 498 p.Potts, P.J.(1987) A handbook of silicate rock analysis, Blackie & Son Limited.Press, W. H., B. P. Flattery, S. A. Teukolsky, and W. T. Vetterling (1987): NumericalRecipes in C, Cambridge University Press, 818 p.Price, P., and Bancroft, W. L. (1948) Waite Amulet mine—Waite section, in Structuralgeology of Canadian ore deposits: Montreal, Canadian Inst. Mining metallurgy,Geology Div., Spec. Pub., pp. 748-756.Ribbe, P.H. (1983) Chemistry, structure and nomenclature of feldspars, FeldsparMineralogy, ed. Ribbe, P. H., Reviews in Mineralogy, 2, Mineralogical Society ofAmerica. pp. 1-20.191Rice, AR. (1977): Solute banding; a possible indicator of turbulent thermal convection inmagmas and a possible precursor to rollover in stratified magmas with attendentexplosive volcanism. EOS (Am. Geophys. Union, Trans.). 58. (12). p. 1249Richards, J. P. McCulloch, M. T. Bruce, W. C. and Kerrich, R. (1991) Sources ofmetalsin the Porgera gold deposit, Papua new Guinea: Evidence from alteration, isotope,and noble metal geochemistry. Geochimica et Cosmochimica Acta, 55, pp. 565-580.Rittmann, A., (1973) Stable mineral assemblages of igneous rocks, A method ofcalculation, Springer-Verlag, 262 p.Robert, F. and Brown, A. C. (1984): Progressive alteration associated with gold-quartztourmaline veins at the Sigma mine, Abitibi greenstone belt, Quebec; EconomicGeology, 79, pp. 393-399.Robert, F. and Brown, A. C. (1986): Archean gold-bearing quartz veins at the Sigmamine, Abitibi Greenstone belt, Quebec: Part II. vein paragenesis and hydrothermalalteration, Economic Geology, 81. pp. 593-616.Rose, A. W. and Burt, D. M. (1979) Hydrothermal alteration, in Geochemistry ofhydrothermal ore deposits, 2ed., ed. Barnes, H.L. New York, John Wiley andSons, pp. 173-235Russell, J. K. (1986) A Fortran-77 computer program for the least squares analysis ofchemical data in Pearce variation diagrams. Computers & Geosciences, 12, pp.327-338.Russell, J. K. and Nicholls, J. (1987) Early crystallization history of alkali olivine basalts,Diamond Craters, Oregon. Geochimica et Cosmochimica. Acta. 51, pp. 143-154.Russell, J. K. and Stanley, C.R. (1989) Differentiation of the 1954-1960 lavas ofKilaueavolcano. Pacific N.W. Amer. Geoph. Union, program with abstr., 1, p. 10.Russell, 3. K. and C. R. Stanley (1990a) Theory and application ofPearce Element Ratiosto geochemical data analysis. Geological Association of Canada Short Course#8, 1989, 315 p.Russell, 3. K. and Stanley, C. R.(1990b): Origins of the 1954-1960 lavas ofKilaueaVolcano; constraints on shallow reservoir magmatic processes. Continentalmagmatism; abstracts. Bulletin New Mexico Bureau ofMines and MineralResources. 131. p. 230Saeki, Y. and Date, J. (1980) Computer application of the alteration data for the footwalldacite lava at the Ezuri Kuroko deposits, Akita Prefectrue, Mining Geology,30, pp. 241-250.192Sander, M. V. and Einaudi, M. T. (1990) Epithermal deposition ofgold during transitionfrom propylitic to potassic alteration at Round Mountain, Nevada. EconomicGeology, 85, pp. 285-3 11.Shapiro, L. and W.W. Brannock (1955) Rapid determination ofwater in silicate rocks.Analytical Chemistry. 27, pp. 560-562.Shapiro, L. and W.W. Brannock (1962) Rapid analysis of silicate, carbonate andphosphate rocks. US Geological Survey Bull. 1144-A.Shaw, D. M. (1961) Manipulative errors in geochemistry: a preliminary study. Trans. Roy.Soc. Can. LV, pp. 4 1-55.Sketchley, D.A. and Sinclair, A. J., (1987) Gains and losses of elements resulting fromwall-rock alteration— a quantitative basis for evaluating lithogeochemicalsamples: British Columbia Ministry Energy Mines Petroleum Resources Rept.1987-1, pp.57-63.Sketchley, D. A. and A. J. Sinclair (1991) Carbonate alteration in basalt, Total EricksonGold Mine, Cassiar, Northern British Columbia, Canada, Economic Geology,86, pp. 570-587.Spitz, G. and Darling, R. (1978) Major and minor element lithogeochemical anomoliessurrounding the Louvem copper deposit, Val d’Or, Quebec. Canadian Journal ofEarth Science, 15, pp. 1161-1169.Stanley, C.R. and H. E. Madeisky (1993) Pearce element ratio analysis: Applications inlithochemical exploration, MDRU short course notes: SC-13, Dept. ofGeological Sciences, University ofBritish Columbia, 542 p.Stanley, C.R. and H. E. Madeisky (1994) Lithogeochemical exploration for hydrothermalore deposits using Pearce element ratio analysis. in Lentz, D.R., ed., Alteration andalteration processes associated with ore-forming systems: Geological AssociationofCanada, Short Course Notes, 11, pp. 193-211.Stanley, C. R. and Russell, J.K. (1989a)PEARCE,PLOT: Interactive Graphics-SupportedSoftware for testing petrologic hypotheses with Pearce Element Ratios. AmericanMineraloist, 74, pp. 317-320.Stanley, C. R. and Russell, J.K. (1989b) PEARCE.PLOT: A Turbo-Pascal Program forthe analysis of rock compositions with Pearce Element Ratios. Computers &Geosciences, 15, pp. 950-926.Stanley, C. R. and Russell, J.K. (1989c): Petrologic hypothesis testing with Pearceelement ratio diagrams; derivation of diagram axes. Contributions to Mineralogyand Petrology. 103. (1). pp. 78-89.193Stanley, C. R. and Russell, J.K. (1990): Derivation of axis coefficients for Pearce elementratio diagrams. Continental magmatism; abstracts. Bulletin New Mexico BureauofMines and Mineral Resources, 131. p. 252Stormer, J.C., and J. Nicholls (1978): XLFRAC: a program for the interactive testing ofmagmatic differentiation models, Computers & Geosciences, 4, pp. 143-159.Stout, M.Z and Nicholls, J. (1977): Mineralogy and petrology ofQuaternary lavas fromthe Snake River plain, Idaho. Canadian Journal ofEarth Science, 14. (9). pp.2 140-2156.Streckeisen, A.L. (1967): Classification and Nomenclature of Igneous Rocks; NeuesJahrbuch Mineralogie, Abhandlung, 107, pp. 144-214.Sutherland Brown, A. (1960): Geology of the Rocher Deboule Range; B.C. Ministry ofEnergy, Mines and Petroleum Resources, Bulletin 43, 78 p.Thompson, M. and Howarth, R.J., (1976) Duplicate analysis in geochemical practice, 1.Theoretical approach and estimation of analytical reproducibility. Analyst, 101:pp. 690-698.Thompson, M. and Howarth, R.J., (1978) A new approach to the estimation of analyticalprecision. Journal of Geochemical Exploration, 9: pp. 23-30.Tipper, H.,W. and Richards, T.A. (1976): Jurassic Stratigraphy and History ofNorth-central British Columbia; Geological Survey of Canada, Bulletin 270, 73 p.Weir, B. (1973). A mineralogical and milling study of the Nadina mine. Unpub. termreport for Geology 409, Univ. ofBritish Columbia, April 1973, 31 p.Wetherell, D.G., (1979), Geology and ore genesis of the Sam Goosly copper-silver-antimony deposit, British Columbia. Unpub. M.Sc. thesis, Univ. ofBritishColumbia, Vancouver, 208 p.Wetherell, D.G., Sinclair, A.J. and Schroeter, T.G. (1979): Preliminary Report on the SamGoosly copper-silver Deposit; B.C. Ministry ofEnergy, Mines, and PetroleumResources, Geological Fieldwork, 1978, pp. 132-137.Wickman, F. E. (1962) The amount ofmaterial needed for a trace element analysis. Ark.Mineral. Geol. 3, (6), pp. 131-139.Wilson, A.D. (1964) The sampling of silicate rock powders for chemical analysis.Analyst, 89, pp. 18-30.Wisser, E. (1951) Tectonic analysis of a mining district —Pachuca, Hidalgo: EconomicGeology, 46, pp. 459-477.Winchester, T.A. and Floyd, P.A. (1977) Geochemical discrimination of different magmaseries and their differentiation products using immobile elements. ChemicalGeology, 20, pp. 325-347.194Wojdak, P.J. and Sinclair, A.J. (1984): Equity Ag-Cu-Au Deposit: Alteration and FluidInclusion Study; Economic Geology, 79, pp. 969-990.Woods, T. L, Bethke, P. M., and Roedder, E. (1982) Fluid-inclusion data at Creede,Colorado in relation to mineral paragenesis: U. S. Geological Survey, Open-FileReport 82-3 13, 61 p.Woodsworth, G.J. (1982): Age Determinations and Geological Studies, K-Ar IsotopicAges, Report 15; Geological Survey ofCanada, Paper 81-2, pp. 8-9.Wright, T.L. and P.C. Doherty (1970) A linear programming and least square computermethod for solving petrologic mixing problems, Geol. Soc. America. Bull., 81,pp. 1995-2008.195Appendix A.Megascopic Description of Altered Samples, Silver Queen Mine196Table A-i. Megascopic Description of Altered Samples, Silver Queen MineSample Description Weight*No. (g)X1-1 the main cross-cut (also named Bulkley cross-cut) of 2600 foot level of 610underground 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; paleapple green, not magnetic, fine grain porphyroid texture, quartz, clay mineralsand abundant disseminated pyrite.X1-2 same location as above; 0.3-0.6 m from the footwall of the No. 3 vein to wallrock; 1260strongly silicified and pyritized microdkrite; petrographic features are same asabove 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; 645moderately 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; 1196sericitic-argillic altered nricrodiorite, it is getting away from the vein, the intensityof alteration seems weaker than above samples; the color of the rock looks palewhite to grey white or yellowish grey, the rock has more clay (can be tasted) andless_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 1085walirock; sericitic-argillic altered microdiorite; its petrographic features aresimilar 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; 1522sericitic-argillic altered microdiorite; its petrographic features are similar to theabove 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; 2216sericitic-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; 3051moderate sericitic-argillic microdiorite; the alteration intensity looks obviouslyweaker than the samples above; ther is a post-mineralization structure zone at theplace of 27 m.197X2-1 the northern cross-cut of 2600 foot level underground working; 6.4-8.9 m from 880the hanging-wall of the No. 1 vein to wall-rock (at the footwall side of the No. 2vein), propylitic andesite, black or dark grey, massive and dense, detectablemagnetism, reacting with diluted acid, porphyritic and flow texture, feldspar,hornblende and augite are identifiable phenocrysts, their sizes range from 0.5 to 2mm,_there are about 40% of aphanitic grounchnass.X3 -1 the northern cross-cut of 2600 foot level underground working; 1 m of horse rock 920between two veins (belong to No. 2 vein system), strong sericitic-argillic andesite;pale green, no magnetic, not reacts with diluted acide, alteration is relativelystrong characterized by intensed fracture and poorly preserved primary texture;disseminated pyrite and other sphalerite are oberserved; all primary minerals arealtered 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; 580moderate sericitic-argillic andesite; petrographic features are similar to the abovesample.X3-2d same location as above; 2.5-6 m from the footwall of the No. 2 vein to wall rock; 840moderate sericitic-argillic andesite; .pale white or grey white, no magnetic, noreaction with diluted acide, primary porphyritic and flow texture is wellpreserved, primary minerals such as feldspar, hornblende and augite are allaltered to clay minerals.X3-3 same location as above; 6-8 m from the footwall of the No. 2 vein to wallrock; 1380propylitic 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; 995propylitic 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 990wallrock; strong sericitic-argillic andesite; its petrographic features are similar tosample X3-l.X3-5. same location as above; 0.4-1.4 m from the hanging-wall of the No. 2 vein to 770wallrock; moderate sericitic-argillic andesite. Its petrographic features are similarto X3-2d.X3-6. same location as above; 1.4 - 4.4 m from the hanging-wall of the No. 2 vein to 860wallrock; 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 967wallrock; propylitic andesite. Its petrographic features are similar to X2-1.198X4-4 same location as above; 3-12 m from the footwall of the No. 3 vein to wall rock, 980propylitica 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 1350hanging-wall of the No. 3 vein to walirock, silicic and pyritic andesite. It isintensely 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 1320rock, moderate silicic and pyritic andesite, similar to the sample above but lessintensely fractrued.X5-3. same location as above; 1.1-1.6 m from the hanging-wall of the No. 3 vein to 1110walirock, sericitic and argillic andesite, pale brown, massive, primary texture wellpreserved, 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 1615wallrock, sericitic and argillic andesite,X5-5. same location as above; 3.1-14 m from the hanging-wall of the No. 3 vein to 1058wallrock, sericitic and argillic andesite.X5-5d same location as above; 14-33 m from the hanging-wall of the No. 3 vein to 908wallrock, sericitic and argillic andesite.X5-6. same location as above; 33-36 m.from the hanging-wall of the No. 3 vein to 893wallrock, propylitic andesite.X5-6d. same location as above; 36-38 m.from the hanging-wall of the No. 3 vein to 860walirock,_propylitic_andesite.X5-7. same location as above; 38-56 m from the hanging-wall of the No. 3 vein to wall- 956rock, sericitic and argillic andesite. This alteration envelope may be related to anon-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- 1512rock, sericitic and argillic andesite. The rock at the working face (70 m) isintensely fractured_(breccia_zone).X5-9 same location as above; 0-0.5 m from the hanging-wall of the Footwall vein to 1528wall-rock, silicic and pyritic andesite, pale apple green, abundant disseminatedpyrite.X5-10 same location as above; 0.5-6.5 m from the hanging-wall of the Footwall vein to 1715the footwall of the No. 3 vein, silicic and pyritic andesite, similar to the sampleabove but less abundant disseminated pyrite.199X10-1 the main cross-cut (also named Bulkley cross cut) of 2600 foot level of 487underground working; 0-1.2 m from the hanging-wall of the No. 3 vein to wallrock, silicic and pyritic niicrodiorite, pale apple green, abundant hematite veinletscut pyrite veinlets and altered wallrock with abundant disseminated pyrite. It isalso intensely fractured.X10-2 same location as above; 1.2-4 m from the hanging-wall of the No. 3 vein to wall- 950rock, moderate silicic and argillic microdiorite. Its petrographic features aresimilar to the above but less adundent of veinlets, disseminated pyrite and notintensely fractured.X10-3 same location as above; 4-5.5 m from the hanging-wall of the No. 3 vein to wall- 830rock, sericitic and argillic microdiorite. Its petrographic features are similar toabove 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 815wall-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- 803rock, 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- 847rock, 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- 651rock, 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- 545rock, 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 488post-mineralization dike (DA63-2).DA63-3 same location as above, 460-469 ft of drill 87-S-04, sericitic and argillic andesite 720DA63 -4 same location as above, 472-496 ft of drill 87-S-04, sencitic and argillic andesite, 610DA63 -5 same location as above, 497-499 ft of drill 87-S-)4, silicic andesite 620DA63-6 same location as above, 500-504 ft of drill 87-S-04, silicic andesite. There is 720hanging-wall sphalerite-galena-pyrite-barite vein (DA63-7) between sampleDA63-6 and DA63-8.DA63-8 same location as above, 506-514 ft of drill 87-S-04, silicic andesite contacs the 770hanging-wall of the main vein at 514 ft.* sample weight after sawing out the weathering surface and veinlets.200Appendix B.Lithogeochemical Duplicate Analyses,Silver Queen Mine201TableB-iSampleDuplicatesofMajorComponentsatSilverQueenmine,centralBritishColumbiaSAMPLEIDROCKTYPEALTERATIONLOCATIONS102A1203Fe203FeOMgOCaONa20K20T102MnOP205xlO-6drn.di.*w-altmainx-cut59.0515.432.642.892.695.103.703.150.590.180.28DA63-3rn.di.rn-altSwtchbkV.87-S-451.1916.240.6611.241.351.,000.033.570.544.090.30DA63-5mdi.s-altSwtchbkv.87-S-454.4115.342.159.140.801.240.043.340.450.690.31DA63-1m.di.w-altSwtchbkv.87-S-457.9916.532.223,762.636,253.433.160.710.160.43DA48-2mdi.rn-altColelkv.88-S-552.6818,880.816.431.,160.32S91-15Dporphyrywm-altDucklake60.0515.342.592.422.765,023.832.370.590.410.29DA48-5m.dl.wm-altCole1kv.88-S-554,7116.812,463.202.145.672.664.340.580.210.41DA48-4m.dl.rn-altCole1kv.88-S-552,7721.942.023.600.924.950.133.050.510.310.31x3-3and.w-altNNo3v.x-cut57.7515.853,022.862.875.753.963.020.660.310.39xll-1mdi.w-altFWJackv,57.0115.702.693.774.295.803.762.980.660.210,42S91-9Naciiandkw-altNadlnaMt.E.slo49.6415.153.345.647.816.582.961.531.270.310.56S91-10Ndgranltew-altNadlnaMt.E.slo68,0314,201.041.871.762.453.754.680.500.080.22xlO-6rn.di.w-altmalnx-cut61.2015.062.362.862.814.903.963.150.580.140.27xlO-3dm.di.rn-altmainx-cut63.2717.760.993.111.051.600.324.980.400.490.13xl-1m.di.s-altmaInx-cut59.1014.670.519.110.850.660.052.750.341.080.17xl-90m.dl.w-altmalnx-cut61.8915.331.992.442.254.093.523.690.430.160.23xl-5m.dl.rn-altmainx-cut63.8516.151.333.331.221.560.314,550,411.060.12xlO-6Dm.di.w-altmalnx-cut59.0015.982.522.852.185.163633.090.560,180,34DA63-3Dm.dl.rn-altSwtchbkv.87-S-451.6816.200.4111.241.341.240,034.240.560.980,25DA8-3Dand,s-altCarnpv.88-S-2955.6916.432.813.490.391.550.053.780.554.270.30DA63-5Dm.di.s-altSwtchbkv.87-S-454.5914.952.029.130.871.,w-altSwtchbkv.87-S-457.7216.632.323.762.626.453.283.260.720.160.43DA48-2Dm.dl.rn-altColelkv.88-S-552.6318.950.816.431.,32S91-l5Ddporphyrywrn-altDucklake60.6415,242.542.422.624.983.902.360,590.360.29DA4B-5Dmdl.wrn-altColelkv.88-S-554.2017.052.413,202.155.682.594.420.570.210.41DA48-4Dm.dl.rn-altCole1kv.88-S-553.8220.752.023,600.844.650.163.050.530.310.33x3-3dand,w-altNNo3v.x-cut57.5915.802.813.083,075.613.693.130.650.350.39xll-lbmdl.w-altFWJackv.57.0515.772.733.774.185.783.762.970.690.220.42S91-9DNadiandkw-altNadlnaMt.E.slo49.8215.033.235,647.646.502.981.511.260.310.56S91-1ODNdgranitew-altNadinaMt.E.sb67.4614.281.051.871.862.443.834.690.510.080.21xlO-6dm.dl.w-altmainx-cut59.0015.982.522.852.185.163.633.090.560.180.34xlO-3Dmdl.rn-altrnalnx-cut63.5217,991.,832.612.473.973,543.720,430.190.22X1-5Dm.dl.rn-altmainx-cut64.5115.151.523.190.861.810.004.190.441.140.20mdi.-microdiorite;and.-andesite;w-alt.-weaklyaltered;rn-alt.-moderatelyaltered;s-alt.-stronglyaltered;x-cut-CrOSScut;1K-laKe;V.-vein.CTableB-2.MeasurementDuplicatesofMajorComponentsatSilverQueenmine,centralBritishColumbiaSAMPLEIDROCKTYPEALTERATIONLOCATION-S102A1203Fe203FeOMgOCaONa20K20Ti02MnOP205x5-9and.s-altSNo3v.x-cut64.1016.002.233,351.100.350.334.730.450.080.19S91-15porphyrywm-altDucklake63.2214.813.001.823.403.034.202.620.550.120.28xIO-3m.di.rn-altmainx-cut63.2717.410.883.521.010.660.315.670.390.950.12xlO-2mdi.s-altmalnx-cut60.4315.712.455.401.280.630.294.450.391.410.10xlO-5m,di.rn-altmainx-cut59.7118.161.433.431.482.710.313.340580.310.19xlO-4mdi,rn-altmainx-cut64,1917.081.222.751,251.600.284.360.460.360.15xl-3m.di.s-altmainx-cut64.2315.501.354.700.920.950.144.020.390,810.15DA48-5m.di.wm-altCole1kv.88-5-554,6116.772.413.202.125.732.694.310.580.210.42DA48-4Dm.di.rn-altCole1kv.88-S-S53.8220.752.023.600.844.650.163.050.530.310.33DA63-4mdi.rn-altSwtchbkv.87-S-48.4018.160.8612.791.,241.341.,rn-altSNo3v.x-cut53.5316.581.813.601.936,420.813.930.690.470.28xS-5and.rn-altSNo3v.x-cut55.2417.511.574.261.714.340.333.580,780,670.26x5-6dand.w-altS.No3v.x-cut56.6815.342.223.583.424.564.192,700,640.190.26x5-6and.w-altSNo3vx-cut56.5415.942.403.382.495.313,003.150.670.220.25x5-4and.rn-altSNo3v.x-cut66,3015.901.482.621.260.660.334.560.510.370.20x2-5and.w-altNNo3v.x-cut57.1815.763.092.923.235.913.363.090.660.260.37xlO-6mdi.w-altmainx-cut61.2515.112.302.862.784.923.933.140.580.140.26x3-7and.w-alt.NNo3V.x-cut57.9115.822.893.052.575.854.102.830.650.200.38x3-2and.rn-altNNo3V.x-cut59.9418.302.183.650.971.700.353.370.710,590.26x5-9and.s-altSNo3v.x-cut64.3116.092,203.351.140.350.354.690.440.080.19S91-15porphyrywm-altDucklake63.0014.893.011.823.403.074.262.640.560.120.28xlO-3mdi.rn-altmainx-cut63.3917.370.853.521.000.670.315.610.390.960.11xlO-2m.di.s-altmainx-cut59,1916.352.934.200.930.700.031.290.411.660,19xlO-5m.dl.rn-altmalnx-cut59.9017.871.443,431.472.720.293.380.580.300.19xlO-4m.di.rn-altmalnx-cut64.2717.071.192.751.251.600.274.370.450.370.14xl-3m.di.s-altmainx-cut64.1415.681.244.680,781.000.203.960.4G0,830.19DA48-5m.dl.wm-altCole1kv.88-S-S54.7116.812.463.202.145.672.664.340.580.210,41DA48-4Dm.di.rn-altCole1kV.88-S-S53.4420.812.093.600.854.690.153.060.540.310.34DA63-4m.di.rn-altSwtchbkv.87-S-48.4318.071.0112.681.,136.230.823.940,690.480.28x5-5and.rn-altSNo3v.x-cut55.4017.501.864.001.864.380.333.620.780.690.26x5-6dand.w-altSNo3V.x-cut56.6415.422.233.583.434.444.222750.640.190.30x5-6and.w-altSNo3v.x-cut56.5816.042.363.382.505.,492.621.240.660.344.690.510.360,20x2-5and.w-altNNo3V.x-cut57.2915.703.082,923.335.673.393.150.660.250.37xlO-6m.di.w-altmalnx-cut61,2015.062.362.862.814.903.963.150.580.140,27x3-7.and.w-altNNo3v.x-cut57.9715.872.863.052.645.664.092.920.650200.38x3-2and.rn-altNNo3V.x-cut60.2118.352.333.650.991.730.343.410.720.600.26CTable 8-3. Duplicates of C02, H20 & S atSilver Queen mine, central British ColumbiaSAMPLE ID C02 H20 S(ppm) SAMPLE ID C02H20 S (ppm)xlO-2 3.64898 x10-2 4.69867xl-2 3.75 1.95800 xl-2d 3.26 ‘1.90 732xl-90 2.35128 xl-90d 2.40124xlO-3 4.15 1.86458 xlO-3d 4.04 2.27659xlO-6 1.85 1.39127 xlO-6d 2.40 1.22154xlO-4421 x10-4423xlO-5357 xlO-5349x5-4 3.30 2.121635 x5-4 3,40 2.021610x5-5 751 x5-5720xll-1 0.90970 xll-lb 0.91865x3-3 1.92 1.14181 x3-3d 1.85 1.64250xS-6 4.35 2.16711 x5-6d 4.15 1.281056S91-10 0.25 0.36S91-1OD 0.35 0.58391-9 2.88S91-9D 3.19SQ-119 2.9321 SQ119D 3.195xl-2 800 xl-2768x3-2 559 x3-2504Table 8-4. Duplicates of Trace Elements at Silver Queen mine, central British ColumbiaSAMPLE ID ZR V RBSR SAMPLE ID ZR VRB SRDA48-4D 127 29 116 217 DA48-4D 145 30116 220xl-1 133 20 11035 xl-1 131 20105 42xl-2 135 18 148 201 xl-2d 159 21165 219xl-20 159 22 166 220 xl-2d 159 21165 216xl-3 158 21 172 208 xl-3 162 26169 209xlO-2 150 19 199 69xlO-2 155 21 204 79xlO-3 177 26 206 179 xlO-3d 178 27177 172xlO-3D 178 26 206 179xlO-3d 178 27 177 172xlO-6 172 24 120 511xlO-6d 172 27 121 462xlO-6D 170 25 119 472 xlO-6d 172 27‘121 462x3-2 198 27 123 376x3-2 198 27 123 376S91-l5Dd 125 17 82 397S91-15D 116 17 77 398DA48-2D 135 30 260 196DA48-2 142 31 265 200DA48-4D 127 30 116 220DA48-4 127 30 116 220DA48-5D 124 28 179 446 DA48-5 138 28188 454DA63-ID 165 25 104 636DA63-1 158 26 93 608DA63-3D 112 24 179 143DA63-3 114 25 173 141DA63-5D 99 20 120 87DA63-5 91 21 123 74DA8-2D 152 31 177 23DA8-2 152 31 177 23DAB-3D 163 31 127 182 DA8-3 164 30121 176X1-1D 133 18 113 32xl-1 132 19 110 32xl-2D 159 22 166 220 xl-2 135 18148 201X1-5D 156 24 177 111 xl-5 160 25179 114xl-9Oci 167 21 136 421 xl-90 165 24135 422xll-lb 166 31 92630 xll-1 166 28 90 595x3-3d 180 24 117606 x3-3 185 32 104 597S91-9D 182 25 99732 S91-9 184 26 99 734SQ119D 124 18 71557 SQ-119 14518 78 588204Appendix CMetasomatic Norm CalculationUsing Quattro Pro for DOS 5.0205Instruction of using Quattro Pro for DOS 5.0 to calculate metasomatic normPage A.This is the title page ofmetasomatic norm calculation using Quattro Pro for DOS5.0Page B.The first block of this page contains lithogeochemical raw data. For example, theblock B: B3..126 contains the raw data in following page.The second block of page B converts the lithogeochemical raw data into theircorresponding molar amounts. For example, the content of Si02 of sample x4-4 in cell C7,57.86, divided by the molar weight of Si02, 60.09 g/mole in cell A32 gives its molaramount of 0.962889 in cell C32.Page C.Absolute losses and gains of lithogeochemical constituents are calculated in thefirst notebook block of this page using Ti02 as immobile component and sample x4-4 asequivalent of least altered parent rock. For example, the value in cell C :D6 is calculated byGresen& equation (cf. equation 1-9. in chapter 1):dXX0 (C1)In detail, dX is the value of absolute loss or gain of Si02 of sample x3-5, z0 is theimmobile component Ti02 of sample x3-5 (B:E9), z the immobile component Ti02 ofsample x4-4 (B:C9), x0 (B:E7) and x (B:C7) are Si02wt.% of the altered sample x3-5 andthe least altered sample x4-4 respectively.206The second block ofpage C presents lithogeochemical data corrected for closureusing the equation as follows:X=--x0 (C-2)Clearly, the equation above is derived from equation (C-i). It converts the intensive valueofx0 (wt.%) to X with an extensive unit (such as gram).Page D and EPage D and E contain the formulas to calculate metasomatic norms usingOptimizer, 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 nonlinearequations and inequalities; (iii) find a minimum or maximum solution instead of an exacttarget; (iv) find values that satisfy limits.To use Optimizer, a notebook model is created. It contains the realistic estimatesand define the elements ofmetasomatic norm calculation as follows:1. The results of calculated metasomatic norms, which are given on page E. Theformulas 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 islisted in the block ofAdjust Factor Matrix on page D; and3. The constraints, or limitations, the solution must accommodate, which are listedin 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 inChapter 2 and attached on the pages following page D and E. After the problem isproperly 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 meetsthe requirements.207Page FThis page contains the notebook blocks calculating propagated error. The formulasin each notebook blocks on this page are based on the equations introduced in Chapter 3and attached on the pages following page F for reference.Page GThis is the last notebook page of this program. It presents the final results ofmetasomatic norm calculation in units ofmole and gram respectively. A set ofcomprehensive, mass balanced reaction equations can be constructed by combining theresults listed on page F and G. For example, sample x4-4 is the least altered precursor rockof altered sample x3 -5, the hydrothermal alteration of sample x3 -5 can be presented asfollows:Primary 0.O23pyroxene + 0. l36plagioclase + 0.066K-feldspar + 0.2quartzminerals 5.11±0.17 g 36.01± 0.95 g 18.26±0.48 g 12.02±0.33 gPropylitic + 0.O04chlorite + 0.03 9epidote + 0.O53carbonatealteration 3.05±0.11 g 18.7±0.5 g 4.86±0.34 gmass - 0.236SiO - 0.041Al3 - 0.027Fe3 - 0.056Mg2 - 0.072Ca2- O.11Na - 0.029Klosses -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 gmass + 0. 129H + 0.042C02gains 2.31±0.1 g 1.86±0.12 gsericitic, argillic, = 0.O44sericite + 0.O63kaolinite + 0.O93carbonate + 0.456quartzcarbonatized, 17.28±0.47 g 16.28±0.5 1 g 9.8 1±0.6 g 27.38±0.7 1 gsilicified alterationUnlike 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 replacesome standard norm minerals, set different constrains. In addition, user should keep inmind when using Optimizer that calculations ofmetasomatic norms are complex nonlinearproblems and could have many different solutions. Depending on the values user start208with, Optimizer’s recommended solutions vary. User should use his knowledge to wellconstrain the problem and treat his negative results as a case that his hypothesis is rejectedand his positive results as the case that his hypothesis is not rejected rather than approved.209Notebook page A.METASOMATIC NORMByXiaolin Cheng and A. J. SinclairDept. of Geological SciencesUniversity of British Columbia1995210Notebook page B.Al B CI DIEt Fl G 1 H ILithogeochemical Raw Data 2Sample_id x4-4 x3-7 x3-5 x3-4 x3-1 x3.3d x2-53Alteration w-alt w-alt ni-alt nis-alt ms-alt w-alt w-alt 4rock and. and. and. and. and, and. and. 5location N No3 v. x N No3 v. x N No3 v. x N No3 V. x N No3 v. x N No3 v. x N No3 v. x 6Si02 57.86 57.97 58.45 56.67 57.25 57.59 57.29 7A1203 15.61 15.87 18.11 17.27 17.45 15.80 15.70 8Ti02 0.65 0.65 0.87 0.57 0.67 0.65 0.66 9Fe203 3.09 2.86 1.26 1.26 1.25 2.81 3.08 10FeO 2.89 3.05 3.69 5.78 5.82 3.08 2.92 11MnO 0.34 0.20 1.34 1.65 1.57 0.35 0.25 12MgO 2.94 2.64 0.90 1.15 1.09 3.07 3.33 13CaO 6.07 5.66 2.69 0.73 0.73 5.61 5.6714Na20 3.65 4.09 0.31 0.44 0.29 3.693.39 151(20 3.09 2.92 2.34 4.12 2.77 3.13 3.15 16P205 0.38 0.38 0.27 0.19 0.20 0.39 0.3717H20 0.97 1.27 4.39 2.69 3.9 1.84 1.0418C02 2.03 2.14 5.2 5.9 5.75 1.65 2.7519S 0.013 0.018 0.029 0.127 0.073 0.025 0.003 20LOl 3.01 3.43 9.62 8.72 9.72 3.52 3.7921Total 99.58 99.72 99.85 98.55 98.81 99.69 99.60 22Zr 191 192 220 163 188 180.19 178.64 23Y 28 30 32 12 23 23.62 33.0524Rb 100 108 96 172 114 117.16 121.4025Sr 593 607 238 231 630 605.75 573.45 262728Conversion of wt% to molar amountSample_id x4-4 x3-7 x3-5 x3-4 x3-1 x3-3d x2-530Molar wt Alteration w-alt w.alt rn-alt ms-alt ms-alt w-altw-alt 3160.09 Si 0.962889 0.96472 0.972708 0.943085 0.952738 0.9583960.953403 32101.96 Al 0.306199 0.311299 0.355237 0.33876 0.342291 0.309925 0.307964 3379.90 Ti 0.008135 0.008135 0.010889 0.007134 0.008385 0.008135 0.00826 34159.70 Fe+3 0.038698 0.035817 0.01578 0.01578 0.015654 0.0351910.038572 3571.85 Fe+2 0.040223 0.04245 0.051357 0.080445 0.081002 0.0428670.04064 3670.94 Mn 0.004793 0.002819 0.018889 0.023259 0.022131 0.004934 0.003524 3740.31 Mg 0.072935 0.065492 0.022327 0.028529 0.02704 0.07616 0.08261 3856.08 Ca 0.108238 0.100927 0.047967 0.013017 0.013017 0.1000360.101106 3961.98 Na 0.11778 0.131978 0.010003 0.014198 0.009358 0.119071 0.10939 4094.18 K 0.065619 0.062009 0.049692 0.087492 0.058824 0.0664680.066893 41141 .94 P 0.005354 0.005354 0.003804 0.002677 0.002818 0.005495 0.005213 4218.00 OH- 0.107411 0.141111 0.487778 0.298889 0.4.33333 0.2044440.115211 4344.01 C03= 0.046126 0.048625 0.118155 0.13406 0.130652 0.037491 0.062486 4432.06 S 0.000415 0.000549 0.000895 0.003949 0.002283 0.000780 0.000097 4590.03 Zr 2.122293 2.133067 2.445851 1.813284 2.086082 2.0014441.984227 46211Notebook page C.AIBICDIEI FIGIHAbsolute loss or gain calculation 2(by using Gresens’s/MacLean’s Equation)3Sample_id x4-4 x3-7 x3-5 x3-4x3-1 x3-3d x2-5 4Alteration w-alt w-alt rn-alt ms-altms-alt w-alt w-alt 5dSiO2 0.00 0.11 -14.19 6.76-2.32 -0.27 -1.44 6dA12O3 0.00 0.26 -2.08 4.08 1.32 0.19 -0.15 7dTiO2 0.00 0.00 0.00 0.000.00 0.00 0.00 8dFe2O3 0.00 -0.23 -2.15 -1.65-1.88 -0.28 -0.06 9dFeO 0.00 0.16 .0.13 3.702.76 0.19 -0.01 10dMnO 0.00 -0.14 0.66 1.541.18 0.01 -0.09 11dMgO 0.00 -0.30 -2.27 -1.63-1.88 0.13 0.34 12dCaO 0.00 -0.41 -4.06 -5.24-5.36 -0.46 -0.49 13dNa2O 0.00 0.44 -3.42 -3.15-3.37 0.04 -0.31 14dK2O 0.00 -0.17 -1.34 1.61-0.40 0.04 0.01 15dP2O5 0.00 0.00 -0.18 -0.16-0.19 0.01 -0.02 16dH2O 0.00 0.30 2.31 2.102.82 0.87 0.05 17dCO2 0.00 0.11 1.86 4.703.55 -0.38 0.68 18dS 0.00 0.00 0.01 0.130.06 0.01 -0.01 19dLOI 0.00 0.42 4.18 6.936.42 0.51 0.72 20dTotal 0.00 0.14 -24.98 12.80-3.72 0.11 -1.49 21dZr 0.00 0.97 -26.55 -4.91-8.87 -10.88 -15.14 22dY 0.00 2.41 -3.88 -14.29 -5.69 -4.33 4.60 23dRb 0.00 8.17 -28.33 95.5910.33 16.88 19.28 24dSr 0.00 14.64 -414.58 -328.9318.37 13.03 -27.96 2526Lithogeochemical Data Corrected for ClosureSample_id x4-4 c3-7 x3-5 x3-4x3-1 x3-3d x2-5 28Alteration w-alt w-alt rn-alt ms-alt ms-alt w-alt w-alt 29dSiO2 57.86 57.97 43.67 64.6255.54 57.59 56.42 30dAl2O3 15.61 15.87 13.53 19.69 16.93 15.80 15.46 31dTiO2 0.65 0.65 0.65 0.65 0.65 0.65 0.65 32dFe2O3 3.09 2.86 0.94 1.441.21 2.81 3.03 33dFeO 2.89 3.05 2.76 6.595.65 3.08 2.88 34dMnO 0.34 0.20 1.00 1.881.52 0.35 0.25 35dMgO 2.94 2.64 0.67 1.311.06 3.07 3.28 36dCaO 6.07 5.66 2.01 0.830.71 5.61 5.58 37dNa2O 3.65 4.09 0.23 0.500.28 3.69 3.34 38dK2O 3.09 2.92 1.75 4.702.69 3.13 3.10 39dP2O5 0.38 0.38 0.20 0.220.19 0.39 0.36 40dH2O 0.97 1.27 3.28 3.073.78 1.84 1.02 41dCO2 2.03 2.14 3.89 6.735.58 1.65 2.71 42dS 0.01 0.02 0.02 0.140.07 0.03 0.00 43dLOI 3.01 3.43 7.19 9.949.43 3.52 3.73 44dTotal 99.58 99.72 74.60 112.3895.86 99.69 98.09 45dZr 191.07 192.04 164.52 186.16182.20 180.19 175.93 46dY 27.95 30.36 24.07 13.6622.26 23.62 32.55 47dRb 100.28 108.45 71.95 195.87110.61 117.16 119.56 48dSr 592.72 607.36 178.14 263.79611.09 605.75 564.76 49212Notebook page D.Al 81 ci Dl El Fl Gi H—2x3-1 x3-3d x2-S 3ms-alt w-ak w-alt 41.000 0.149 0.271 50.000 1.000 0.339 60.000 0.000 0.0000.000 0.535 0.805 80.000 0.000 0.195 90.000 1.000 1.000 100.000 0.000 0.416 110.221 0.913 1.000 120.349 0.000 0.011 130.000 0.171 0.522 140.000 0.000 0.000 150 / 1 0.339311 160 0.535345 1 171819x3-1 x3-3d x2-5 20ms-alt w-ait w-alt 210.00000 0.00000 0.00000 220.00000 0.00000 0.00000 230.00000 0.00000 0.00000 240.00000 0.00000 0.00000 250.00000 0.00000 0.00000 260.00000 0.00000 0.00000 270.00000 0.00000 0.00000 280.00000 0.00000 0.00000 290.00000 0.00000 0.00000 300.00000 0.00000 0.00000 310.00000 0.00000 0.00000 3233340.148 -0.076 0.073 35-0.166 0.069 -0.075 360.000 0.000 0.0000.018 0.007 0.001 380.000 0.000 0.000 3914.570 3.981 5.615 400.000 15.489 3.952 4126.216 3.961 0.000 4218.313 -0.000 0.008 430.000 11.711 7.771 440.000 1.802 3.884 450.000 18.501 18.619 460.542 28.508 41.346 - 470.137 0.047 0.006 4836.433 13.867 14.434 49Adjust factor matrixSample_id x4-4 x3-7 x3-5 x3-4Alteration w-alt w-alt rn-alt ms-altCalcite 0.043 0.393 0.763 1.000Mg-chl 0.000 1.000 0.000 0.000Mg-pyx 0.472 0.000 0.000 0.000Fe-chl 0.535 0.000 0.000 0.000Fe-pyx 0.312 0.270 0.000 0.000Or 1.000 1.000 0.000 0.000An 0.156 0.191 0.000 0.000Ab 1.000 1.000 0.127 0.265ilmenite 0.000 0.969 0.000 0.000Ca-pyx 0.000 0.000 0.000 0.000magnetite 0.000 0.000 0.000 0.000Mg-chI4-p 0.472389 1 0.000479 0Fe-chl+py 0.846492 0.270079 0 0Residual MatrixSample_id x4-4 x3-7 3.5 x3-4Alteration w-alt w-alt rn-alt ms-altdSiO2 0.00000 0.00000 0.00000 0.00000dAl2O3 0.00000 0.00000 0.00000 0.00000dTiO2 0.00000 0.00000 0.00000 0.00000dFe2O3 0.00000 0.00000 0.00000 0.00000dFeO 0.00000 0.00000 0.00000 0.00000dMnO 0.00000 0.00000 0.00000 0.00000dMgO 0.00000 0.00000 0.00000 0.00000dCaO 0.00000 0.00000 0.00000 0.00000dNa2O 0.00000 0.00000 0.00000 0.00000dK2O 0.00000 0.00000 0.00000 0.00000dP2O5 0.00000 0.00000 0.00000 0.00000Constraint matrixdH2O 0.294 0.128 0.244 0.178dCO2 -0.299 -0.240 -0.251 -0.209dS 0.000 0.000 0.000 0.000dLOI 0.004 0.112 0.007 0.032dTotal 0.001 0.108 0.000 0.000Carbnate 4.857 5.850 13.129 15.027Epidote 18.700 9.787 2.388 0.000Sericite 0.000 0.016 23.128 38.839KaoI 0.000 -0.000 21.789 5.318ChI 3.052 7.280 0.001 0.000Pyx 5.106 1.222 0.000 0.000Or 18.264 17.260 0.000 0.000P1 36.013 41.628 0.334 0.985Pyrite 0.025 0.033 0.054 0.237Qtz 12.017 13.395 36.654 35.863213Notebook page E.A B I CJ DIE I FIG I HillMetasomatic Norms (closed)Sample_id x4-4 x3-7 x3-5 x3-4x3-1 x3-3d x2-5Molar wt Alteration w-alt w-alt rn-alt ms-alt ms-alt w-alt w-alt100.09 Calcite 0.350 2.626 3.1770.856 0.833 1.127 0.608483.24 Epidote 18.700 9.787 2.3880.000 0.000 15.489 3.952232.34 Ca-pyx 0.000 0.000 0.0000.000 0.000 1.802 2.844278.22 An 5.126 7.029 0.0000.000 0.000 0.000 12.65984.32 Mg-carb 3.245 0.000 1.8822.406 2.280 0.000 4.602555.78 Mg-chl 0.000 7.280 0.0010.000 0.000 8.466 3.116200.80 Mg-pyx 3.459 0.000 0.0000.000 0.000 0.000 0.000115.86 Fe-carb 0.712 2.900 5.8989.092 8.913 2.287 -0.000713.48 Fe-chl 3.052 0.000 0.0000.000 0.000 3.245 4.656263.88 Fe-pyx 1.647 1.222 0.0000.000 0.000 0.000 1.039398.30 Muscovite 0.000 0.000 19.79234.848 23.429 0.000 0.000278.34 Or 18.264 17.260 0.0000.000 0.000 18.501 18.619382.20 Na-mica 0.000 0.016 3.3363.991 2.786 3.961 0.000262.24 Ab 30.887 34.599 0.3340.985 0.542 28.508 28.686151.75 ilmenite 0.000 1.196 0.0000.000 0.444 0.000 0.01379.90 rutile 0.650 0.020 0.8700.570 0.436 0.650 0.653258.14 Kaol 0.000 -0.000 21.7895318 18.313 -0.000 0.00860.09 qtz 12.017 13.395 36.65435.863 36.433 13.867 14.434114.95 Mn-carb 0.551 0.324 2.171 2.674 2.544 0.567 0.405502.21 apatite 0.896 0.896 0.6370.448 0.472 0.920 0.873119.97 pyrite 0.025 0.033 0.0540.237 0.137 0.047 0.006159.70 hemtite 0.000 1.243 0.865 1.260 1.250 0.251 2.427231.55 magnetite 0.000 0.000 0.000 0.000 0.000 0.000 0.000total 99.581 99.825 99.849 98.547 98.813 99.685 99.600Final Metasomatic Norms (Closed)Sample_id x4-4 x3-7 x3-5 x3-4x3-1 x3-3d x2-5Alteration w-alt w-alt rn-alt ms-altms-alt w-alt w-altapatite 0.896 0.896 0.637 0.4480.472 0.920 0.873ilmenite 0.000 1.196 0.000 0.0000.444 0.000 0.013magnetite 0.000 0.000 0.000 0.000 0.000 0.000 0.000pyroxene 5.106 1.222 0.000 0.000 0.000 1.802 3.884plagioclase 36.013 41 .628 0.334 0.985 0.542 28.508 41 .346orthoclase 18.264 17.260 0.000 0.000 0.000 18.501 18.619quart 12.017 13.395 36.65435.863 36.433 13.867 14434epidote 18.700 9.787 2.3880.000 0.000 15.489 3.952chlorite 3.052 7.280 0.0010.000 0.000 11.711 7.771sericite 0.000 0.016 23.12838.839 26.216 3.961 0.000kaolinite 0.000 -0.000 21.7895.318 18.313 -0.000 0.008carbonate 4.857 5.850 13.12915.027 14.570 3.981 5.615rutile 0.650 0.020 0.8700.570 0.436 0.650 0.653hemtite 0.000 1.243 0.8651.260 1.250 0.251 2.427pyrite 0.025 0.033 0.0540.237 0.137 0.047 0.006total 99.581 99.825 99.84998.547 98.813 99.685 99.60023456789101112131415161718192021222324252627282930313233343536373839404142434445464748214A lB I C DI El F G I HI —Error Propagation 2So k Cd So k Cd 3S102 0.010 0.012 0.020 K20 0.020 0.018 0.041 4AL203 0.012 0.020 0.025 P205 0.020 0.015 0.041 5T102 0.006 0.008 0.012 H20 0.040 0.130 0.108 6FE203 0.060 0.018 0.124 C02 0.010 0.120 0.026 7FEO 0.045 0.018 0.093 S 0.002 0.070 0.004 8MNO 0.022 0.007 0.045 Zr(ppm) 0.010 0.032 0.021 9MGO 0.074 0.030 0.157 Y(ppm) 0.300 0.090 0.732 10CAO 0.080 0.011 0.164 Rb(ppm) 2.000 0.035 4.301 11NA2O 0.090 0.013 0.185 Sr(ppm) 5.000 0.019 1.395 12Standard Deviation at 68% confidence level 13Sample_id x4-4 x3-7 x3-5 x3-4 x3-1 x3-3d x2-5 14Calcite 0.0000 0.1706 0.2657 0.1037 0.1008 0.0784 0.0416 15Epidote 0.0025 0.2544 0.0358 0.0000 0.0000 0.3735 0.0952 16Ca-pyx 0.0937 0.0000 0.0061 0.0000 0.0000 0.0333 0.0524 17An 0.2666 0.1186 0.0013 0.0000 0.0000 0.0000 0.2270 15Mg-carb 0.4208 0.0000 0.2144 0.2613 0.2516 0.0000 0.4119 19Mg-chl 0.1024 0.3620 0.0000 0.0000 0.0000 0.3982 0.1512 20Mg-pyx 0.0000 0.0000 0.0034 0.0000 0.0000 0.0000 0.0000 21Fe-carb 0.0039 0.1864 0.3591 0.5657 0.5544 0.1557 -0.0000 22Fe-chi 0.0000 0.0000 0.0000 0.0000 0.0000 0.1226 0.1857 23Fe-pyx 0.0821 0.0323 0.0094 0.0000 0.0000 0.0000 0.0247 24Muscovite 0.0000 0.0000 0.3479 0.6067 0.4095 0.0000 0.0000 25Or 0.2891 0.2742 0.0000 0.0000 0.0000 0.2926 0.2943 26Na-mica 0.0174 0.0003 0.1516 0.1316 0.1152 0.0740 0.0000 27Ab 0.5104 0.5722 0.0000 0.0375 0.0274 0.4796 0.4899 28ilmenite 0.0153 0.0296 0.0000 0.0000 0.0094 0.0000 0.0003 29rutile 0.0057 0.0003 0.0130 0.0106 0.0074 0.0112 0.0112 30Kaol 0.0113 -0.0000 0.7336 0.1811 0.6116 -0.0000 0.0003 31qtz 0.1607 0.1611 0.4456 0.4367 0.4436 0.1688 0.1757 32Mn-carb 0.0507 0.0389 0.1327 0.1581 0.1516 0.0518 0.0429 33apatite 0.0406 0.0409 0.0401 0.0542 0.0559 0.0413 0.0404 34pyrite 0.0005 0.0006 0.0010 0.0037 0.0021 0.0009 0.0001 35hemtite 0.0589 0.0438 0.0704 0.0827 0.0825 0.0099 0.0910 36magnetite 0.0788 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 37Sc_SiO2 0.704 0.706 0.711 0.690 0.697 0.701 0.697 38Sc_A1203 0.324 0.329 0.374 0.357 0.361 0.328 0.326 39Sc_Ti02 0.011 0.011 0.013 0.011 0.011 0.011 0.011 40Sc_Fe2O3 0.116 0.111 0.083 0.083 0.083 0.111 0.115 41Sc_FeO 0.097 0.100 0.111 0.149 0.150 0.100 0.098 42Sc_MnO 0.024 0.023 0.031 0.034 0.033 0.024 0.024 43Sc_MgO 0.162 0.153 0.101 0.109 0.107 0.166 0.174 44Sc_CaO 0.147 0.142 0.110 0.088 0.088 0.142 0.142 45Sc_Na20 0.137 0.143 0.094 0.096 0.094 0.138 0.134 46Sc_K2O 0.076 0.073 0.062 0.094 0.070 0.076 0.077 47Sc_P205 0.026 0.026 0.024 0.023 0.023 0.026 0.026 45Sc_H20 0.166 0.205 0.611 0.390 0.547 0.279 0.175 49Sc_C02 0.254 0.267 0.634 0.718 0.700 0.208 0.340 50Sc_S 0.003 0.003 0.004 0.011 0.007 0.004 0.002 51Sc_Zr 6.124 6.155 7.056 5.234 6.020 5.776 5.726 52215Notebook page F.Al B jc I DIE I FjG I HITable 7- Error propagation of norms corrected for closure in grani(SD at 68% confidence level) 54at northern segment of No.3 vein, Silver Queen mine, Owen Lake, central BC55Samplejd x4-4 x3-7 x3-5x3-4 x3-1 x3-3d x2-556Calcite 0.025 0.192 0.1890.121 0.100 0.083 0.04357Epidote 0.638 0.336 0.070 0.000 0.000 0.5310.133 58Ca-pyx 0000 0.000 0.000 0.000 0.000 0.0550.085 59An 0.155 0.213 0.000 0.000 0.000 0.0000.376 60Mg-carb 0.307 0.000 0.168 0.306 0.250 0.0000.420 61Mg.chl 0.000 0.403 0.000 0.000 0.000 0.4480.167 62Mg-pyx 0.132 0.0000.000 0.000 0.000 0.0000.000 63Fe-carb 0.052 0.209 0.304 0.696 0.577 0.1650.000 64Fe-chl 0.144 0.0000.000 0.000 0.000 0.1460.214 65Fe-pyx 0.056 0.041 0.000 0.000 0.000 0.0000.035 66Muscovite 0.000 0.000 0.425 1.220 0.678 0.0000.000 67Or 0.531 0.502 0.0000.000 0.000 0.537 0.53168Na-mica 0.000 0.000 0.114 0.189 0.129 0.1220.000 69Ab 0.915 1.019 0.013 0.051 0.029 0.844 0.838 70ilmenite 0.000 0.041 0.0000.000 0.014 0.000 0.00071rutile 0.019 0.001 0.0180.020 0.012 0.019 0.01972Kaol 0.000 0.000 0.6560.257 0.732 0.000 0.00073qtz 0.327 0.365 0.7071.148 0.957 0.378 0.38674Mn-carb 0.052 0.040 0.1060.196 0.159 0.054 0.04375apatite 0.046 0.046 0.0320.063 0.055 0.047 0.04576pyrite 0.001 0.001 0.0010.008 0.004 0.001 0.00077bemtite 0.000 0.057 0.0450.101 0.085 0.012 0.10778magnetite 0.000 0.000 0.0000.000 0.000 0.000 0.00079Total 3.4013 3.4662 2.84804.3782 3.7823 3.4430 3.44438081Table 7- . Error propagation of absolute losses & gains in gram (SD at 68% confidence level) 82at northern segment of No.3 vein, Silver Queenmine. Owen Lake, central BC 83Sample_id x4-4 x3-7 x3-5x3.4 x3.1 x3-3d x2-584dSiO2 1.726 1.729 1.3301.946 1.660 1.720 1.6861.000 85dAl+3 0.315 0.319 0.2790.381 0.333 0.318 0.3130.529 86dTi+2 0.013 0.013 0.0130.014 0.013 0.013 0.0130.599 87dFe+3 0.126 0.122 0.093 0.107 0.100 0.122 0.125 0.699 88dFe+2 0.120 0.123 0.1110.200 0.172 0.123 0.1190.777 89dMn+2 0.027 0.026 0.032 0.051 0.042 0.0280.027 0.774 90dMg+2 0.145 0.140 0.108 0.125 0.117 0.1470.150 0.603 91dCa+2 0.182 0.176 0.124 0.128 0.122 0.176 0.174 0.715 92dNa+ 0.159 0.165 0.115 0.131 0.122 0.1590.154 0.742 93dK+ 0.109 0.105 0.081 0.147 0.100 0.1090.109 0.830 94dP+5 0.016 0.016 0.0140.016 0.015 0.016 0.0160.436 95dH2O 0.235 0.265 0.49 10.481 0.563 0.328 0.2401.000 96dCO2 0.362 0.372 0.5450.874 0.737 0.330 0.4251.000 97dS 0.004 0.004 0.004 0.013 0.007 0.0050.003 1.000 98dO= 0.652 0.650 0.533 0.696 0.618 0.6530.647 1.000 99216Notebook page G.AIBICIDIEIFIG1HTable 7a. Metasomatic norms corrected for closure& absolute losses and gains 2at northern segment of No. 3 vein, Silver Queen mine. Owen Lake, central BC 3S.nip4ld x4.4 x3-7 x3-S x3-4x3-l x3-3d x2-5 4øjwiaion w-alt w-alt rn-alt ms-alt ms-alt w-alt w-alt 5mole6Calcite 0.0035 0.0262 0.02370.0098 0.0081 0.0113 0.0060 7Epidote 0.0387 0.0203 0.0037 0.0000 0.0000 0.0321 0.0081 8Ca-pyi 0.0000 0.0000 0.00000.0000 0.0000 0.0078 0.01 21 9Au 0.0184 0.0253 0.00000.0000 0.0000 0.0000 0.0448 10Mg-carb 0.0385 0.0000 0.01 670.0325 0.0262 0.0000 0.0538 11Mg-chl 0.0000 0.0131 0.00000.0000 0.0000 0.0152 0.0055 12Mg-pyx 0.01 72 0.0000 0.0000 0.00000.0000 0.0000 0.0000 13Fe-carl, 0.0061 0.0250 0.03800.0895 0.0746 0.0197 -0.0000 14Fe-cht 0.0043 0.0000 0.00000.0000 0.0000 0.0045’ 0.0064 15Fe-pyx 0.0062 0.0046 0.0000 0.0000 0.0000 0.0000 0.0039 16Muscovite 0.0000 0.0000 0.0371 0.0998 0.0571 0.0000 0.0000 17Or 0.0656 0.0620 0.00000.0000 0.0000 0.0665 0.0659 18Na-mica 0.0000 0.0000 0.00650.0119 0.0071 0.0104 0.0000 19Ab 0.1178 0.1319 0.00100.0043 0.0020 0.1087 0.1077 20ilmenite 0.0000 0.0079 0.00000.0000 0.0026 0.0000 0.0001 21nitile 0.0081 0.0003 0.0081 0.0081 0.0053 0.0081 0.0080 22KaoL 0.0000 -0.0000 0.06310.0235 0.0688 -0.0000 0.0000 23qtz 0.2000 0.2229 0.45570.6806 0.5882 0.2308 0.2366 24Mn-carb 0.0048 0.0028 0.01410.0265 0.0215 0.0049 0.0035 25apatite 0.0018 0.0018 0.00090.0010 0.0009 0.0018 0.0017 26pyrite 0.0002 0.0003 0.0003 0.0023 0.0011 0.0004 0.0000 27bemtite 0.0000 0.0078 0.0040 0.00900.0076 0.0016 0.01 50 28magnetite 0.0000 0.0000 0.0000 0.00000.0000 0.0000 0.0000 29Total 0.5313 0.5522 0.6731 0.9987 0.8713 0.5238 0.5790 30dSiO2 0.0000 0.0018 -0.23620.1126 -0.0386 -0.0045 -0.0239 31dAI+3 0.0000 0.0051 -0.0408 0.0801 0.0259 0.0037 -0.0029 32dTi+4 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 33dFe+3 0.0000 -0.0029 -0.0269 -0.0207 -0.0235 -0.0035 -0.0007 34dFe+2 0.0000 0.0022 -0.00190.0515 0.0384 0.0026 -0.0002 35dMn+2 0.0000 -0.0020 0.00930.0217 0.0167 0.0001 -0.0013 36dMg+2 0.0000 -0.0074 -0.0563-0.0404 -0.0467 0.0032 0.0084 37dCa+2 0.0000 -0.0073 -0.0724-0.0934 -0.0956 -0.0082 -0.0087 38dNa+ 0.0000 0.0142 -0.1103-0.1016 -0.1087 0.0013 -0.0100 39dK+ 0.0000 -0.0036 -0.02850.0342 -0.0086 0.0008 0.0003 40dP+5 0.0000 0.0000 -0.0025-0.0023 -0.0026 0.0001 -0.0002 41Sum 0= 0.000 -0.006 -0.299 -0.013 -0.150 -0.001 -0.01242dH2O 0.000 0.017 0.1290.117 0.156 0.049 0.003 43dCO2 0.000 0.002 0.0420.107 0.081 -0.009 0.01544dS 0.000 0.000 0.000 0.004 0.002 0.000 -0.000 45dTotal 0.000 0.014 -0.6940.256 -0.154 0.035 -0.034 46474849217Notebook page G.AB)CIDJEIFGIH 50Table 7b. Metasomatic norms corrected for closure &absolute losses and gains 51at northern segment of No. 3 vein, Silver Queen mine.Owen Lake. central BC 52sarnp4.W x4-4 x3-7 y3-5 x3-4x3-1 x3-3d x2-5 53Ajt.ratton w-alt w-alt rn-alt ms-alt ms-alt w-alt w-alL 54gram55Calcite 0.3499 2.6257 2.37380.9765 0.8079 1.1 268 0.5989 56Epidote 18.6998 9.7869 1.78400.0000 0.0000 15.4890 3.8918 57Ca-pyx 0.0000 0.0000 0.00000.0000 0.0000 1.8023 2.8013 58Au 5.1 260 7.0290 0.00000.0000 0.0000 0.0000 1 2.4674 59Mg-carb 3.2447 0.0000 1.40592.7432 2.2120 0.0000 4.5324 60Mg.chl 0.0000 7.2799 0.00090.0000 0.0000 8.4656 3.0685 61Mg-pyx 3.4591 0.0000 0.00000.0000 0.0000 0.0000 0.0000 62Fe-carb 0.7117 2.9001 4.406810.3677 8.6472 2.2868 .0.0000 63Fe-chl 3.0522 0.0000 0.00000.0000 0.0000 3.2449 4.5852 64Fe-pyx 1.6470 1.2220 0.00000.0000 0.0000 0.0000 1.0237 65Muscovite 0.0000 0.0000 14.7874 39.7390 22.7300 0.0000 0.0000 66Or 18.2644 17.2596 0.0000 0.0000 0.0000 18.5008 18.3369 67Na-mica 0.0000 0.0156 2.4924 4.5513 2.7033 3.9605 0.0000 68Ab 30.8866 34.5992 0.2498 1.1231 0.5259 28.5076 28.2518 69ilmenite 0.0000 1.1961 0.0000 0.0000 0.4312 0.0000 0.0130 70rutile 0.6500 0.0202 0.6500 0.6500 0.4230 0.6500 0.6432 71Kaol 0.0002 -0.0001 16.2790 6.0642 17.7660 -0.0004 0.0078 72qtz 12.0169 13.3950 27.3848 40.8959 35.3457 13.8670 14.2150 73Mn-carb 0.5509 0.3241 1.6222 3.0489 2.4681 0.5671 0.3990 74apatite 0.8963 0.8963 0.4758 0.5111 0.4577 0.9199 0.8595 75pynce 0.0249 0.0329 0.0401 0.2701 0.1329 0.0468 0.0057 76hemtite 0.0001 1.2428 0.6466 1.4368 1.2127 0.2506 2.3903 77magnetite 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 78total 99.5809 99.8254 74.5996 112.3777 95.8636 99.6854 98.0914 79dSiO2 0.0000 0.1100 -14.1905 6.7637 -2.3190 -0.2700 -1.4380 80dAl+3 0.0000 0.1376 -1.1005 2.1613 0.6981 0.1006 -0.0783 81dTi+4 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 82dFe+3 0.0000 -0.1609 -1.5028 -1.1563 -1.3131 -0.1958 -0.0396 83dFe+2 0.0000 0.1244 -0.1035 2.8770 2.1425 0.1477 .0.0111 84dMn+2 0.0000 -0.1084 0.5120 1.1939 0.9163 0.0077 -0.0726 85dMg+2 0.0000 .0.1809 -1.3675 -0.9822 -1.1353 0.0784 0.2048 86dCa+2 0.0000 -0.2930 -2.9018-3.7432 -3.8320 -0.3288 -0.3473 87dNa+ 0.0000 0.3264 -2.5359 -2.3355 -2.4990 0.0297 -0.2310 88dK+ 0.0000 -0.1411 -1.11381.3350 -0.3343 0.0332 0.0102 89dP+5 0.0000 0.0000 -0.0778-0.0713 -0.0812 0.0044 -0.0068 90Sum 0= 0.000 -0.095 -4.777-0.207 -2.397 -0.010 -0.199 91dH2O 0.000 0.303 2.3132.101 2.817 0.873 0.054 92dCO2 0.000 0.110 1.8554.698 3.548 -0.380 0.678 93dS 0.000 0.004 0.0080.131 0.058 0.012 -0.010 94dTotal 0.000 0.137 -24.98212.765 -3.731 0.102 -1.487 95Residual 0.000 0.108 0.001 0.032 0.014 0.002 -0.003969798218D:B4:ConstraintmatrixD:A35:“dH2OQ:B35:(F3)@AOUND(B:Cl8-B:$A$18(E:C6/E:$A$6+E;C1O’8/E;$A$1O+E:C13t8/E;$A$13+E:G15t2/E:$A$15+E:C17’2/E:$A$17+E:C21’4/E:$A$21÷E:024/E:$A$24)/2S)D:C35:(F3)+E:D241E:$A$24)125)DD35:(F3)@RUND(B:E1B:$A$18(E:E6/E:$A$6+E:E1O*8/E$A$1O÷E:E138/E:$A$13+E:E152/E:$A$15+E;Ej7’2/E:$A$17+E:E21t4/E:$A$21+E:E24)E:$A$24)/26)D:E35:(F3)÷EF24IE:$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$13+E:G15e2/E:$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$1O+E:Il3*81E:$A$13+E:115*2/E;$A$l5+E:I172/E:$A$17+E:I2lt4/E:$A$21+E;I41E:$A$24)125)D:A36:“dCO2D:B36:(F3)@ROUND(B:C9B:$A$19*(E:C5/E:$A$5+E:C9/E:$A$9+E:C12/E:$A$12+E:C23/E:$A$23),5)D:C36:(F3)@ROUND(B:D19-B;$A$19(E:DS/E:$A$5+E:D9/E:$A$S+E:D12/E:$A$l2-t-E:D23/E:$A$23)5)D:D36:(F3)@ROUND(9’:E19-S$A$9’(E:E5/E:$A$5-i-E:E9/E;$A$9+E:E12/E:$A$t2+EE23)E$A23)5)D:E36:(F3)D:F36:(F3)@ROUND(B:G19-B:$A$19(E:G5/E:$A$5+E:G9/E:$A$9+E:G12/E$A$l2÷E:G23/E:$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$23)S)D:H36:(F3)@ROUND(B:II9-B:$A$19(E:I5/E:$A$5+E:I9/E:$A$94-E:I12/E:$A$12+E:I23/E:$A$23),5)D:A37;“dSD:B37:(F3)@ROUND(B:C20-B:$A$20E:C25’2/E:$A$256)D:C37:(F3)@ROUND(B: 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E20-B:$A$20’E:E25*2/E;$A$255)D:E37:(P3)@ROUND(B:F2OB:$A$2O*E:F252/E:$A$255)D:F37:(F3)0ROUND(B:G20.B:$A$20*E:G25’2/E:SA$265)D:G37:(P3)ROUND(B:IOB:$A$2O*E:F-5’2/E:$A$255)D:H37(F3)0AOUND(B:120=B:$A$20*E:125t2/E:$A$255)D:A39:“dLOID;B38:(P3)+B:C21-SUM(BC1BC2O)-@SUM(B35.B37)D:C38:(F3)÷B:D21-@SUM(B:D18.D20)-@SUM(C35,,C37)D:D38:(F3)+B:E21-@SU(B:E18..E2O)-@SUM(D35,,D37)D:E38:(F3)+B:F21-@SUM(B:F18..F20)-@SUM(E35..E37)D:F3:(F3)+B:G21-@SUM(B:G18.G20)-@SUM(F35F37)D:G38:(F3)-i-9:H21-gSUM(B:H18.i-O)-@SUM(G35.,G37)D:H38:(F3)+B:I21..@SUM(8:18,i2O)-@SUM(H35.H37)D:A39:“dTolaID: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:“CarbnatD:B40:(F3)+E:C5+E:C9+E:C12+E:C23D:040:(F3)+E:D5+E:D9+E:D12+E:D23D:D-4O:(F3)+E:E5+E:E9+E:E12+E:E23D:E40:(F3)+E:F5+E:F9+E:F12+EF23D:F40:(F3)+E:GS+E:G9+E:G12+E:G23D:G40:(F3)+E:-+E:H9+E:H12+E:H23D:H40:(F3)+E:15+E:19+E:112+E:123D:A41:“EpIc1otD:B41:(F3)+E:C6D:C41:(F3)+E:D6D:D41:(F3)+E:E6D:E4:(F3)+E:F6D:F41:(F3)+E:G60:641:(F3)+E:H6D:H41:(F3)+E:16D:A42:(F3)“SrlcIte0:842:(F3)+E:C15+E:C17D:C42:(F3)+E:D15+E:D17D:D42(F3)+E:E15+E:E17D:E42:(F3)+E:F16+E:F17D:F42:(F3)+E:G1S+E:G170:642:(F3)+E:H15+E:H17D:H42:(F3)+E:115+E:117D:A43:KaoID:B43:(F3)+E:C21D:C43:(F3)+E:D21D:D43:(F3)+E:E21D:E43:(F3)+E:F21D:F43:(F3)+E:621D:G43:(F3)+E:-10:1-443:(F3)+E:121D:A44:‘ChID:844:(F3)+E:C1O÷E:C130:C44:(F3)+E:D1O+E:013D:D44:(F3)+E:E1O+E:E13D:E44:(F3)÷E:F1O+E:F13D:F44:(F3)+E:G1O+E:G130:644:(F3)-t-E:H1O+E:H13D:H44:(F3)+E:IlO+E:113D:A45:‘Pyx0:845:(F3)+E:C7+E:C11+E:C14D:C45:(F3)+E:D7+E:D11+E:D140:045:(F3)+E:E7+E:E11+E:E14D:E45:(F3)+E:F7+E:F1I+E:F14D:F45:F3)+E:G7+E:G11+E:G14D:G45:(F3)÷E:H7+E:Hl1+E:H14D:H45:(F3)+5:17+5:111+E:114D:A46:“OrD:848:(F3)+E:C16D:C46:(F3)+E:D16D:046:(F3)+5:5160:E46:(F3)+E:F16D:F46:(F3)+5:616D:G46:(F3)+E:H16D:H46:(F3)+5:116D:A47:“P1D:847:(F3)+E:C8+E:C18D:C47:(F3)+E:D8+E:D18D:D47:(F3)+E:E8+E:E18D:E47:(F3)+E:F8+E:F18D:F47:(F3)+E:G8+E:G18D:G47:(F3)+E:H8+E:H18D:H47:(F3)+E:18+E:118D:A48:“PyriteD:B48:(F3)+E:C25D:C48:(F3)+5:0250:048:(F3)+E:E25D:E48:(F3)+E:F25D:F48:(F3)+5:625D:G48:(R3)+E:H260:1-148:(F3)+5:125D:A49:“Qtz0:849:(F3)+5:022D:C49:(F3)+E:D220:049:(F3)+5:522D:E49:(F3)+E:F22D:F49:(F3)+5:622D:G49:(F3)÷E:I-2D:H49:(F3)+E:122k)CE:C2:MelasornaticNcms(dosed)0:93.[Wl0]“Sample_Id0:03:(P0)U“x4-4003:(F0)U“x3-70:03:(P0)14“x3-SE:F3:(F0)U“x3-40:33:(P0)14“x3-lE:H3:(P0)Ux3-3d0:13:(P0)Ux2-5E:A4:Molarwt%E:B4:[WI0)“Alteration0:04.(P0)U“w-aIl0:04(P0)U“w-alt004(P0)UmallE:F4(F0)U“ms-all0:04(P0)U“ms-allE.H4.(P0)U“w-alt0.14:(P0)Uw-all0:A5:(F2)40.08+1201+16*3E:85:(W10]“Catdte0:05:(F3)+0:85(B:C39C7*2/$A$7.C8)$A$8.C24*5/SA$24)*$A$50:05:(P3)+D:C5*(B:D39D7*2)$A$7.09/A$8.024*5f$A$24)*$A$50:05:(P3)+D:D5*(B:E39.E7*2/$A$7.E8/$A$8E24*5/$A$24)*$A$SE:F5:(P3)+0:ES*(8:P39.F7*2f$A$7P8/A$8.F24*S/$A$24)**A$SE:GS:(P3)+0:F5*(8:039.07*21$AL7.G8/$A$e.024*6/$AS24)*$A$50:1-IS:(P3)+0:35*(8:H39.H7*2/$A$7il8I$A$8H24*5f$A$24)*SA$5E:15:(F3)+0:H5*(B:l39l7*2/$A$7le,$AS8.l24*S/SAS24)*SA$5E:A6:(P2)40.08*2+55.85+26.98*2+28.09*3+16*12+170:86:IW1O)“Epidote0:06:(P3)(10:B5)*(B:C39.C7*2/$A$7.C8f$A$8.C24*5/SA$24)*$A6/2E:06:(P3)(1.0C5)*(8039.07*21$A$7.D9/$A$8.024*54A$24)*$A$6/20:06:(F3)(10:D5)*(B:E39.E7*2fAS7E8J$AS8.E24*5/A$24)*$A$6/2E:P6:(F3)(I.D:E5)*(G:F39F7*2/$A$7.F8f$AS8F24*5/$A$24)*AS6/2E:06:(P3)(1.0:F5)*(B:339.07*2/$A$7.G8/$A$8.024*5/$A$24)*$AS6/2E:H6:(P3)(1.0.05)*(8:H39.H7*2/SAS7t18/t,AL8.H24*5/$AS24)*$A$6/20:16:(P3)(l.D:H5)*(9:l39l7*2/SA$7t8f$A$8.t24*5/$A$24)*SA$6/2E:A7:(F2)40.08*2+28.09*2+16*60:87:W10]“Ca-pyxE:C7:(P3)+0:814*(B:039C8f$A$8C24*5f$A$24)*SA$7/20:07:(P3)+0:C14*(B:039D8/$A$8024*S/$A$24)*$A$7/20:07(P3)+0:014*(B:E39.E8/SA$8.E24*54AS24)*SA$7)2E:F7:(P3)+0:014*(B.F39.PB,$AS8.F24*5/A$24)*A$7,20:37:(P3)+D:F14(8:G39.G8/$A$8G24*5/$A$24)*$A$7/2E:H7(P3)+0314*(8:H39H8f$A$8.H24*5f$A$24)*$AS7/20.17:(P3)+D:H14*(8l39I8/SA8l24*5/$A$24)*SA$7)2E:A8:(P2)4008+26.98*2+28.09*2+16*80:98.(WI0)“An0:08:(P3)+0:8i*G.C40*$A$8E:08:(P3)+0:C11*8:040*$A68E:E8:(P3)+0:0l1*8:E40*$A$8E:F8:(P3)÷0:Ell*B:F40*SA$80:38(P3)+0:Fll*B:040*SA$8E:H8:(P3)+0:31l*B.ll40*SA$8E:18:(P3)+D:Hll*8140*$A$8E:A9:(P2)24.31+60.010:89:(Wl0)“Mq-carb0:09:(F3)(t.0.86.0:87)*B.C30*$A$90:09:(P3)(1.D:C6D:C7)*B:088*$A$90:09:(P3)(1.D:060:D7)*8E38*SAS9E:P9:(P3)(10:E60:E7)*B:F38*$A$9E:39:(P3)(l.0:P60:P7)*9:Q38*SAS9E:H9:(P3)(1.036.037)*BH38*$A$9I—’)-40:19:(P3)(I.D:H6.D:H7)*9:138*$A$9E:AI0:(P2)24.31*5+26.98*2+28,09*3+16*lO+17*80:810:[WiG)Mg.chI0:010:(P3)+0:B6*0:C38/s*$A$IO0:010:(P3)+D:C6*8:038/S*$A$iOE:Ei0:(F3)+D:D6*B:E3815*$A$10E:Pi0:(P3)+0:E6*8:F38/6*$A$lO0:010:(P3)+D:F6*0:038/5*$Af.iO0:HI0:(P3)÷D:06*8:H38/S*$A$iO0:110:(P3)+0:H6*8:138/5*$A$lOE:Ail:(P2)24.31*2+28.09*2+16*6E:8l1:Wi0]“Mg.pyx0:011:(F3)+0:87*8:C3812*$A$1i0:011:(P3)+0.C7*8:038/2*$A$li0:011:(P3)+D;D7*B:03812*SA$iiE:FI1’(P3)+D:E7*8:P38/2*SA$ii0:011:(P3)+D:F7*9:G38/2*SA$ilE:H11:(P3)+D:07*8:H38/2*$A$ii0:111:(P3)+D:H7*9:138/2*$A$11E:A12:(P2)55.85+60.010:812:Wl0)Fe-carb0:012:(P3)(1.D:98.0:99)*(B:C36.Ci9/SASI9.C25/$A$25.027/$A$27)*$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D.Diagrams ofAlteration Evaluation, Silver Queen Mine246(Xl+X2)/2(Xl÷X2)/2xxxFigure6-2a.ErrorofmajorcomponentsestimatedbysampleduplicatesofXRFanalyses.(Xl+X2)/2(Xl+X2)12c’J >$0.7 0.5 0.3 0.20,13,5><(Xl+X2)/2N*ZOSo=0.0999thk=0013Cd=0i8480.490th 50thPCCCI1III0.511.521.534(Xl+X2)/24.50.03(XI+X2)/2(Xl+X2)/2Figure6-2b.Errorofmajorcomponentsestimatedbysampleduplicatesof XRFanalyses.xx(Xl+X2)/2(Xl+X2)12x(Xli•X2)/2(Xl÷X2)/2Figure6-2cErrorofferrousironandvoJatilecomponentsestimatedbymeasurementdupIicates.xC” xFigure6-2d.ErroroftraceelementsestimatedbyduplicatesofXRFanalyses,(Xl4-X2)12(Xl+X2)/2(Xl+X2)/2(Xl+X2)12[Ft203So0.042k=0.023[Cd=0.088490th60th00.511.522.533.5(Xl+X2)/20.511.522.533.5(Xl+X2)12Figure6-3a.ErrorofmajorcomponentsestimatedbymeasurementduplicatesofXRF(Xl+X2)/2> ><0.45 0.40,250.250.15 Di0.05(Xl+X2)!2c’J>0.5><xFigure6-3b.FriorofmaorcomponentsestimatedbymeasurementduplicatesofXRFo.is0160.140.12 01 0,,2- \propyliticalterationenvelope.1.80,i4I3dil-I0,l035.3d,l64.10506.10613.1.7.1-SD.13xli.10abStill.10-Id.104.10.5xml0060uncertaintyat95%confidencelevelabsolutelossorgainSwitchBackvein.1513.561-8DA63-SD0A63-4DAIS3D0.563-3DAIS-I0A656DAIS-SOAIS-4DA63-tDDA63-IDveilsuncertaintyat95%confidencelevelabsolutelossorgain.NorthernsegmentoftheNo.3vein15.68 0 08 0 tpropyliticandesite\0 t8 0 t20 1: s——Cabsolutelossorgain——CentralsegmentoftheNo.3veinpropyliticalterationinner‘alteratIonouterenvelopemicrodioriteenvelope50Eluncertaintyat95%confidencelevelabsolutelossorgain: :zjjjjzz..zz:z.zzzzSouthernsegmentoftheNo.3vein-20.3-9.5-I.,34.5II.52.59x354569SIdx54veinveinalterationoute-.\‘alterationouter\propytiticenvelope‘alterationinnerenvelope‘microdioriteenvelope\\..alterationinnerenvelopeFigure6-5b.AbsolutelossesandgainsofA1203fromfouralterationprofilesattheSilverQueenmine,centralBritishblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangealterationouterenvelope\propylitic’s.sericitiemicrodioritealterationColumbia.Therepresenting±2standarddeviations.propyiiticalterationinner—alterationouterenvelopeniicrodioriteenvelope2uncertaintyat95%contidcricilevelabsolutelossorgainPNortltcinscgmcnloftheNo.3vein0.125-0xs-2xJ.2xi-)232.0-Iz32x3-5VetisV C a.S 0 a.uttcertaistyat95%confideneclevelEabsolutelossorgain I....SwitchBackvein0.5658DA6O-$DDA63-4bA6i-sDAIS-)0.563-i0.563-60.563522.563-10.563-SDDA6Sincciiipropyliticandesitealterationenvelope-.t0tiytiii1131220.52C a.S 05 C ii.1103d00400500.6xI06Dxi)21-3Dxi-)xi-)230.3210200-3xio-3d00-42105x10-6xi0-Oi)veinalterationouter\envelopeSouthernsegmentoftheNo.3vein\‘—.alterationouter’propylitic\\alterationouterpropylitic’sericiticalterationinner—envelope—noicrodioritealteratiossinner--envelope-microdioritealterationenvelopeenvelopex3.0-x5-ix3-3--x5-4-xS-$-x3-6d-2$-)03-i)xS-2x5-425-0xS-6x3-6dx3-8veil)Figure65c.AbsolutelossesandgainsofFe203fromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia.Theblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations.C 0-isNorthernsegmentoftheNo.3vein£44.3-,3.34,2.3131.15xii.12.3.1llrOPYtiiiCaiiolesiln.pro1,ylilicandositoalieralionenvelope1:uncertaiittyat95%confidencelevelcabsolutelossorgainCentralsegmentoftheNo.3vein.1.3.0-4.1-24l.,I0.£32£10.1£10.2.103£10.34.304.10-5.30-6.1060veinalterationoute-3\alterationouter-...propyliticenvelope-alterattoninnerenvelopemicrodioriteenvelope:11Juncertarntyat5%conridenceleveiLJabsolutetossorgainSwitchBackveinDA65-01*61-3D0A634DA63.330*62.1DA63-lIiAs163*63-30*03-0*63-3DDAli.II)veilpropyliticalterationinnera.alterationouterenvelopea..microdiortteenvelopeEuncertaintyat95%confidenceleveltbsolutelossorgainSoutlternsegmentoftlteNo.3veinaS-P.5-I.5-3n5-4.3.3aS64aS-i.5-10.5-2aS-a.3-5.5-6.5-64.3-6veinL.Juncertaintya195%coafideocetenetabsotuletoolorpolo0 a.a 0 a.a 0 31.\\.alteratiotiinneraenvelopealterationouterenvelopeFigure6-5d.AbsolutelossesandgainsofFeOfromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia.Theblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations.propylitic\sericiticmicrodioritealteration.1-8vi-6,i.40.2d.11.10-i.10.5.iO.3d.10.4.10-5.10641000al-S.1-50.1-3*1.2*101.10-2.10.3hOld.10.4.105*106.1060alterationoutor\.peopyltticalterationlinerenvelopenticroclioriieenveloper, !I0,603-8ttAO3-5i)DAO3-4DAOS-OD0A03-30A01-lDAOt60A63-5ttA6l.40,66330DA63-ID-vsS 0 ‘ai••iirjnncerlainly6195%confidencelevelabsolalelossorgaiuwitchBackveinS 0, 0S 0 ‘V0: 06—oncortainlyal9t%coofidencelovelabsolutelossorgain..-I-NorthernsegmentoftheNo.3vein4.4.10x3.4x3.tes.Sdan-Se31..‘.propytitieunilvoitealterationenvelope:..:izJaecertaiotyat95%confidencelevelcjabsolutelossorgalaCentralsegmentoftheNo3veittveinS 0 ‘V\.\...alteralioatoner-..alterationoulerenvelopenecrodioriteenvelope:unteeltoinly0195%coufidettcebudatnotatetossorgale-.SouthernsegmentoftheNo.3vein53.9.5-i.5-355-4.5-5*5-edel-S.51043.2454.5-553-643.5345.8veinalterationOilierenvelope\\:.alterationalterolivelopealterationouterenvelopeFigure6-5e.AbsolutelossesandgainsofMnOfromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia.Theblankpartofeachbarincludesthemeanestimate(ahorizontalirnagii]uylinethroughthecentreoftheblankbar)andarangepropylitic\\sericilicmkrediorilealterationrepresenting±2standarddeviations.propyliticalterationtotter-..alterationouterenvelopeoticrodioriteetivelopeLIuueoriainayat95%confidencelevelIjhSonlhernsegmentoftheNo.3veineS.9aOlcOteO.4aSScO-ednO.?asiaattOaS-CaS-SaS-6aS-edCS-Sonii \\elternilenouterpropyliticsericiticalterationinnerenvelopeuticrodioritealterationenvelopeFigure6-5fAbsolutelossesandgainsof MgOfromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia.Theblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations.,t7atIat2Cititropyliticaedesite\.•.propyitlicaiidnnjteolinraiivlieiivelolioVtIllCl-Sal-Cet-2d,tiait-lOO.telt-tdatii.4i0-S00-6atll.6t7at.?at-tocital-2cit-ici0-tait-talt-Idalt4alt-Sat0.6alt-Or)alterationouter--Ualterationootorpropylitieenvelopealterationinnerenvelopeniicrodiotiieenvelopei”.06.34,02,00d.2-5vS1.3-5.3IIIvi->propyliticatidesiteirsIltylilicsuclassloalterationcttvelo1,e.5-8vt-6vi.4.1.22vil00.004.103d0040.5itO-S.1061).1.0.1-SD.1.0.1-,I0.Sd.10.4t0.3.506.1061)alterationouter\.0\i...alteratloisouter‘-.proltyliticenvelopealterationinner-envelopemicrodiorileenvelopeIlIl005lilililyat95%cotttidv,icolavaabvolusvlossor91150fl..9 0 ‘01Iiifl[9I!lI’IItiI°INorthernvegmentoftheNo9vt_in0 L) ‘0uiscvrsliily6195cairliltriacIcclabslutelc,siOrsin HHSilchB5sckveintAO>BtiA6iSDDAISat)A632)DA6J3DAebB0A6362)0635DA6O40A613150A63ID‘N6.propyliiicalitraisonlolleralterationouterenvelope-rnicrodiouteenvelope2uncertaintyat95%confidencelevelvb,olulelossorgalsIpjPSoulhcnoscgerctslofhoeNI)3vein.04’.60.566.55.56.366.38Eluncertnintyat95%confidooceleveljobsolutelossorgalls-—..IPiIHflIE*H(‘enlralsegroc61ofItoNo.3vei itlviLit cc.0-Iis-S.3-In.52.5-4Yeit, \\\.alterationouteralterationinnerenvelopeenvelopeFigure6-5g.AbsolutelossesandgainsofCaOfromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia.Theblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations.\.propylisirsericitic-nsiriodiorise‘alterationFigure65h.AbsolutelossesandgainsofNa20fromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia,Theblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations.noesrlviutyat95%confidencelevelbsolutolossorgainE 0 zLJE-0EunceIinintyutOS%confidencelevelabsolutelossorgainIHIIHiIHIz:SwitchBackvein-uhfINorthernsegmentoftheNo.3veinc4.4aSsat-4at-Sattdc2.$a3-Sat-S.at-Iat2at-Sveinpropylitieundesitepropylitieaudesitoalterationenvelopecjuecertatnty0195%confidencelevelJabsolutetossorgain‘I UHi11IUI1OHiEzCentralsegmentoftheNo.3veinat-at-n0-4xl2d0-I’00xIstala-Sd00-4xIS-S00-6als-6Dat-Sat-SDal-Sal-SclOtala-SclOtate-3d,tO-4ate-ScIO-Ocm-el)alterationouter-..alwratiaoouter\\propyliticenvelope-.alterationinnerSenvelopetnicraelinriteDA6t-SbA6t-srit)AOO-4DA6O-.tttDAO5-3DA6S-lDM5-nDAuntDA63-4tsMt-toDA6t-IDvein.\propyliticalterattotitoner-alterastosouterenvelopeNn,icrodioriteenvelopefluncertaintyat95%confidencelevelabsolute 1 ILl]SouthernsegmenloftheNo.3veinaS-Sat-Iat-saS-4cS-Set-6dat-Sat-tOct-Sa$-4cS-ScS-6aS-6dcs-nveineovelope\\\alterationinnerenvelopeallerntioeouterenvelope‘vpropylilic\sericitic-nmicrodiorite-alteration\propyliticsericiticnilerodioritealterationP 0P 0uncertaintYat95confidencelevel3absoluterossoigarnH_NorthernsegmentoftheNo.3vein4.4e3.6t.43.Ze3.3di2.53t32Cciiipropyliticandesitn..,peopyliticandenitealterationenvelopeiiiiIhDAO3.nDA63-5DA634DAna-3DDA63-1Dveinalterationouterenvelopealterationinnerenvelope\peopyliticnaicrodioriteP 0 00•UUuncertaintyat95%confidencelevelabsolutoloanorpainCentralsegmentoftheNo.3vein-Si-6rt-40-3dri-ii3-ta-on-3d00-4,in-$in-eo.ebcitst-SOci.3st-iclOteta-iitO-Sate-3d033-4riO-Sat0-nsin-unveinalterationoateeenvelopealterationouterpropyliticalterationinnerenvelopenaicrodioeiteenvelopeeS-SeS-ie$-3eO-4eS-SeS-edaSSeS-tOaS-ia3-455-5eS-65S-Oit55-Svein \\alterationletterenvelopealterationOuterenvelopeFigure6-5i.AbsolutelossesandgainsofK20fromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia.Theblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations..01tE]1111CCliiiicyat1)5%confidencelevelS -oubsolutelossorguiitInn. .5(1NorthernsegmentoftheNo.3vein.101e4.4(1165. :[DODDuncertaintyat95%confidencelevel.55_._—__—CabsolutetossorgainCentralsegmentoftheNo.3vein.10020 1áiiiJfluneurtaiitryat95%confideorelevelvolutelossorguiltSwitchBackvein.1000A638DAst.$tt0A634DAOOtD0A60.30A53tDA6O.6OtA6t.50A52.4DM320DA6O.tDvein.\.propytitiealterationtuner\nlteruttouOuterenvelopemierodioriteenvelopezooi1111uueeronitetyus95%confidencelee.et50absolutetossorgumSouthernsegmentoftheNo.3veintoonS5ett.53nO4eS-S,.c.udaSSsOtO.00a4s5.5n.%.655.ud.5-Sveil’.t.edOst.4.2ndet.ttOt,tO.3stOOdto.4uet.ts.e.io.ODet.5at.50sItnI2.10-iduO.10-0ntt.0d.104sinS,lOu.20.60veinuttetationouteralterationouterI500pylitic000010100alterationtonerenvelopenticrodiorioeenvelope1alterationouteralterationinnerenvelopeenyeto1wFigure6-5j.AbsolutelossesandgainsofRbfromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia,Theblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations,-prupyliticsericitictnicrodiorilealteration:PIIIIIIEEuncertaintyat95%confidencelevelI-J;bstiUt;io5;;io-SwltchflackveinDA6S-8b.56a.SDDAuntDA6S3DDAO3-DA6i-lctAai-6OASiSDAeS-4DAdi-tDbAet-IDveinpropyliticalterationinner‘alterationouterenvelopeenvelopeJuncertaintyat95%confidencelevel4absoluteloss—n5.9nt-iciicS-Cciici-6deS-Ici-Itel-nci-4cii56-6si-edcS-Cvein:i..1...._Jabsolutelostorgaul0 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zUNorthernsegmentoftheNo.3vein-t-tdosi-ic64el-idciSct-iel-icitciicitpropyliticandesitnpropyliticandesliralterationenvelope——1-uncertaintyat95%confidencelevelabsolutelotsorgainCentralsegmentoftheNo.3veincl-Cel-6et.4ci.2dcl-I5le-tlt-sIn-3d00.4On-I05-nctO-6t)51.1cl-SDclicl.ncit-I,l-iclvisin-3d51n-4sinSsin-nclouDveinaitniation001cralterationoutersproPYliiiCenvelope—alterationinnerenvelopensjcrodiotileenvelopeSoulhernsegnsentoftheNo.3vein\\-.alierariollinnerC1yeInltCalterationouterenvelopeFigure6-5k.AbsolutelossesandgainsofH20fromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia.Theblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations.propyliticsericiticmicrodiorite‘alterationa).St.e0.4l.2d0100.200.3dO-3d,tO.400-S00.6ett:6t)et.7al-3DxiSl:2ate-I00-200-0alOudalt-4aIS-Sat0-6stOODveil’alterationouter‘...“-.niterationouterpropylilicenvelopealterationinner‘envelope“uticeodioriteIIIE1uncertaintyat95%confidencelevelSwllchBackveinabsolutelossorgait)Ca 0 U ‘0DAOO-DAO3-SDDA6I-4DAOS-SDDA6S-3DAd3-tDAns-6tAilS-StAOS-atAnS-tODAOS-lDvein allerattontuner-alterationouterenvelopenticrodioeitnenvelopel2Southernsegment oftheNo.3veintOuncoeointyut95coufialcttmlevel0 U ‘0eS7eS-tveinpropyliticaudeultenlterntiottenvelopepropyliticundetiteuucertuitttyat95%cottfideucelevel‘°Thsolutofoosorgaie—o-.——---—19-——......gi iiCentralncgnhenloftheNo.3veioet-tet-taS-SnO.4aS-SsS.6daS.tO0- \\uiteratiouOuteralterationinnerenvelopeelitelopeenvelopeFigure6-51.AbsolutelossesandgainsofCO2fromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia.Theblankhartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations.propyjitic\..sericitic-nticrodioritealteration.34l-621-4.1-3d.3-I.10-I.20-3.30-3d210-4.30-3.tn-e.10-61).3-7nI-SD.2-\\.alterationOuterpropylilicenvelopealterationinner‘envelop.usicrodioriteenvelopealIeeaainnerNalterationouterenvelopeNenvelopemivrodioriteuilcvr(ain%NorfhcrnsegmeittoftheNo.3vciitconfidencelevelal,0oIotrtoororolt.—In—-------.-84-4.3-6.5-4,3-2.3-3d.2-0.3-7-3.03-I.3-2t-3propylisicaodositepropylilieandovitealterationenvelopeI!25uncertainty0395%confidencelevol-absolutelossorgainIn—----.——-—---—-.--—.—:SwitchBackveinDM3-S0A62-3t5DM3.4DAO3-30DM33DA63-IDM1-nDM3-SDA63-4DAO3-3DDM3-IDveinI! 0Znuncertaioty0395%confidencelevelabsolnlelosser0iIIIt•-....---...-------..-----------.--.-.—.--...--....---------.-........-.-.--....--------.-.-—e—CentralsegmentoftheNo.3veinI1,v-9.3-I.5-383-4.3-In45-2.5-4.5-3vein \\\.nllernlionOuterulteealioninnerenvelopee,IvelopeFigure6-5m.AbsolutelossesandgainsofSfromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia.Theblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations.\ \\propylilicNsericiticmicrodiorite-alterationDAO3.8DA63-$DDM34DA63-SDDM33DM33DM36DA63-5DA6O-4DM3-3DDM3-IDveillollrt,Iin,neralterationouterenvelopeSeetivelope‘$00uncertaintyat9S%confidencelevel1000--—--•--“•--•--—.....,-.---....-—.....absolute1035069Ollt500—.1000—--.—SouthernsegmentoftheNo.3vein-‘$00eS-9aS-IeS-te$-453-3aS-6da3-7aS-IS5$-n15-4eS-Sas-neS-6da3-4-uncertaitlly0195%confidencelevelabsolutelossorgall,9 50 (IS 0Sn:.*..!1.1!.!I.If-Iso.-.—------—-.----—..SwitchBackveinI500noccrtaioty0395%confidencelevel1000absoluLelossorgain503-—-:.Ers....r.:Err-3000—NorthernsegmentoftheNo.3vein-1500U-4a3-l,3-4a3-213-3dan-sat-Sa3-5.aS-I,3-l13-3veInpropylilicandesite\\\propyliticaudesitealteratioiieIlvOtOpeI306loon Ste—..-——IHWUL1wH-500——...—-.-*.....—,.....———......—..——..——.Duncertaintyat95%confidencelevel1000CabsoluteJotsorgain-CentralsegmentoftheNo.3veilstal-n13-613-411.2013-3130-I110-3aIO-3dItO-IsIn-SsIn6alO-0Det-SsI-SDIl-SIl-nsin-IdO-IsIC-SsIC-3dale-4ate-SaIO-6adO60alteralionOuterenvelopeulteraliollouter\.peopyliticalieratine11111cr.envelopeS.-nlicendiocieeenvelope\\alterationDateralierationinnerenvelopeenvelopeFigure6-5n.AbsolutelossesandgainsofSrfromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia.Theblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations.propylitic“..sericilicmicrodiorite-alterationI’2,-•—•uaceraaiutyat95%confidencelomlabsolutelossorgainSwitchBackveinabsolutelossorgainSwitchBackvein.50200A65-&DA65.0DDA6S.a0A65-5DDA6S.5DAOS-tDA6S.80A65.5DDA65.4OA6S’SD0A655DA63.t0A63.6bASS-SDAe5-40.565-3DDA63.IDtoAet.6bAns-SDA63-40A63-ODbASS-IDveinvelaalterationloneralterationouterenvelopemicrodioriteclterainneralterationouterenvelope\S\envelopeenvelope30StE1uncertaintyat95%confidencelevel20-------,-absolutelossorgain-______[:oocecauintyat95%confidencelevelLZJabsolutelossorgain.SouthernsegmentoftheNo.3veinCentralsegmentoftheNo.3veitsSI,,,.,,,,,..,,...,,,.Si,.ecl-aI4.1tdcitclOt.10.0etaSdclad00-5.tn-a,,n-ao.593ieS-i54.5-3.s-ed.5-7.5ci-SI)lIcl-n.lttcit-Scia-S00-Sdclodett-5.io-u00.60.5-20.5-304cs-s.5-4eS-6deS-Sveil,VeIl,alterationouter\alterationouter‘‘,propylitic\\alterationouter\.propyliticsericiticenvelopealterationineor‘envelopeSnsicrodioritealterationinnerenvelope-‘microdiorite‘alterationenvelopeenvelopeFigure6-5o,AbsolutelossesandgainsofYfromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia.Theblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations.\propyliticalteratIonmoor‘alletntlonouterenvelope‘Snticrodioniteenvelopefluncertaintyat9599confidencelevelOSabsolutelossorgain0.2——SouthernsegmentoftheNo.3veineS-9eS-Ias-CeS-4aS-Se$.Od.5-Sas-Ine$-2es-aas-S.5-6eS-nd.5-8VeinIiIlilrlertaiLily019599.--confidefloelevel02_..-absolutelossorgainF.NorthernsegmentofuseNo.3veits11 aoncerlniolyat9599coulisleoreloveIobsolutelossorgainSwitchBackvein0 a.9 0 teatel-neS-4.3-SeS-S-.5-I00111.3-2propyliticandesitetIlerationCuvelopepropyliliconslesilect-3d.2DA638bA63-3rDA03-4bA6t-nl0A62-3DA6S-1.3-0eS-SDAut-eDAOS-5DAe3-abAnS-3D0A65-ID9 0CenlralsegmentoftheNo.3veinel-Cel-em-3do-tn-to-em-nbel-Sel-SD.1-3el-flrIO-I.10-2nb-CdO-Sd.33-4dO-SdO-u.15-eDveillalteautionnlabeeaiterationouterapropyliticenvelope‘alterationinnerenvelopeusicrodioriteenvelope‘\\‘a-.alterationinnerenvelopealterationouterenvelopeFigure6-5p.AbsolutelossesandgainsofP205fromfouralterationprofilesattheSilverQueenmine,centralBritishColumbia.Theblankpartofeachbarincludesthemeanestimate(ahorizontalimaginarylinethroughthecentreoftheblankbar)andarangerepresenting±2standarddeviations.propyliticaerielticniicrodioeitealterationAppendix E.Tables of Alteration Evaluation, Silver Queen Mine268Table6-5.LithogeochemicaldataofalteredrocksattheSilverQueenmine,centralBritishColumbiaSamplex4-4x3-7x3-6x3-5x3-4x3-1x3-2x3-2x3-3dx3-3Alterationsprop.prop.prop.ser-argser-argargser-argser-argprop.prop.RocktypeandesiteandesiteandesiteandesiteandesiteandesiteandesiteandesiteandesiteandesiteLocationNorthsegmenNorthsegmenNorthsegmenNorthsegmenNorthsegmenNorthsegmenNorthsegmenNorthsegmenNorthsegmenNorthsegmenofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinwt%Si0257.8657.9757.2058.4556.6757.2559.9460.2157.5957.75Al20315.6115.8716.0318.1117.2717.4518.3018.3515.8015.85Ti020.650,650.660.870.570.670.710.720.650.66Fe2033.092.863.’)360756723231630376376.45605.75597.0kDistance25.,+inhangingwallsideand-infootwallside.Table6-5(continued-i)LithogeochemicaldataofalteredrocksatSilverQueenmine,centralBritishColumbiaSamplex2-5DA63-8DA63-6DA63-5DDA63-5DA63-4DA63-4DA63-3DDA63.3DDA63-3Alterationprop.s-alts-altsilicicsilicicser-argser-argser-argser-argser-argRocktypeandesitem.diorite’ni.dioritem.dioriteni.dioriteni.dioritem.dioritem.dioritem.dioritem.dioriteLocationNorthsegmenSwitchbackSwitchbackSwitchbackSwitchbackSwitchbackSwitchbackSwitchbackSwitchbackSwitchbackofNo.3veinVeinVeinVeinVeinVeinVeinVeinVeinVeinwt%Si0257.2949.1453.0054.5954.4148.4048.4351.3651.6851.19A120315.7017.0916.5914.9515.3418.1618.0716.2916.2016.24Ti020.660.530.500.460.450.590.590.570.560.58Fe2033.081.481.,0Density2.892.952.852.78*m.diorite-microdioriteCTable6-5(continued-2)LithogeochemicaldataofalteredrocksattheSilverQueenmine,centralBritishColumbiaSampleDA63-1DDA63-1xl-8xl-7xl-6xl-5Dxl-4xl-3xl-2dxl-2Alterationw-altprop.ser-argser-argser-argser-argser-argsilicicsilicicsilicicRocktypem.di.m.dioritem.dioritem.dioritem.dioritem.dioritem.dioritem.dioritem.dioritentdioriteLocationSwitchbackSwitchbackCentralsegmeCentralsegnieCentralsegmeCentralsegmeCentralsegmeCentralsegmeCentralsegmeCentralsegnieVeinVeinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinwt%Si0257.7257.9960.4359.4361.1164.1857.4664.2368.4467.14A120316.6316.5316.9016.4417.6015.6515.9315.5015.3814.51Ti020.720.710.430.430.450.420.380.390.380.32Fe2032.322.221.581.511.611.431.231.300.760.87FeO3.763.763.533.363.,6399.55100.45100.0199.9999.2599.0398.9799.5099.01ppmZR164.70158.38171.40165.87166.25156.04161.74161.90158.67134.75Y25.2325.7525.8632.5132.9423.9429.8925.5921.7417.61Rb103.7092.65187.90223.70217.03176.68214.85168.89165.81147.60Sr636.30608.28137.58157.42132.04111.3690.54209.32219.70201.17Distance6.06.0-27.0-14.0-7.0-3.2-2.4-1.6-0.8-0.6Density2.72.72.682.722.65Table6-5(continued-3)LithogeochemicaldataofaleredrocksattheSilverQueenmine,centralBritishColumbiaSamplexl-1xlO-1xlO-1xlO-2xlO’3xlO-3xlO-3dxlO-3dxlO-4xlO-4Alterationsilicicsilicicsilicicsilicicser-argser-argser-argser-argser-argser-argRocktypem.dioritem.dioritem.dioritem.dioritem.dioritem.dioritem.dioritem.dioritem.dioritern.dioriteLocationCentralsegmeCentralsegrneCentralsegmeCentralsegmeCentralsegmeCentralsegmeCentralsegmeCentralsegmeCentralsegmeCentralsegmeofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinwt%Si0259.0571.1171.2159.1963.2763.3963.2763.2464.1964.27A!20314.3214.0913.8716.3517.4117.3717.7617.8817.0817.07Ti020.330.250.260.410.390.390.400.400.460.45Fe2030.760.150.142.930.880.850.990.951.221.19FeO9.143,863.864.203.523.523.113.112.752.75MnO1.,)Table6-5(continued-4)LithogeochemicaldataofalteredrocksattheSilverQueenmine,centralBritishColumbiaSamplexlO-5xlO-5xlO-6xlO-6xlO-6Dxll-lbx5-9x5-10x5-1x5-2Alterationser-argser-argprop.proppropw-altsilicicsilicicsilicicser-argRocktypem.dioritern.dioritem.dioritem.dioritem.dioritem.di.andesiteandesiteandesiteandesiteLocationCentralsegmeCentralsegmeCentralsegmeCentralsegmeCentralsegmeBulkleycrossSouthsegmenSouthsegmenSouthsegmenSouthsegmenofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veincutofNo.3veiofNo.3veinofNo.3veinofNo.3veinofNo.3veinwt%Si0259.7159.9061.2561.2059.0057.0564.3165.9169.7262.02A120318.1617.8715.1115.0615.9815.7716.0916.0614.0015.83Ti020.580.580.580.580.560.690.440.470.400.55Fe2031.431.442.302.362.522.732.201.180.710.73FeO3.433.432.862.862.853.773.353.033.603.42MnO0.310.300.,5999.02100.2699.7998.37ppmZR211.06211.06172.67172.67169.80166.44115.13118.6992.72115.54Y25.6625.6624.2924.2924.8930.7512.8031.635.0038.76Rb126.72126.72119.76119.76118.7792.04162.75204.09122.29187.75Sr1322.731322.73510.61510.61472.32630.05590.4798.0675.5529.55Distance38.,centralBritishColumbiaSamplex5-3x5-4x5-4x5-5x5-5x5-6x5-6dx5-6dxS-7Alterationser-argser-argser-argser-argser-argpropproppropser-argRocktypeandesiteandesiteandesiteandesileandesiteandesiteanclesiteandesiteandesiteLocationSouthsegmenSouthsegmenSouthsegmenSouthsegmenSouthsegmenSouthsegmenSouthsegmenSouthsegmenSouthsegrnenofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinofNo.3veinwt%Si0262.1866.4366.3055.4055.2456.5856.6856.6455.21A120316.1116.0515.9017.5017.5116.0415.3415.4216.16Ti020.580.510.510.780.780.670.640.640.59Fe2031.891.491.481.861.572.362.222.231,30Fe02.822.622.624.004.263.383.583.583.80MnO1.310,360.370.690.670.,752.92P2050.,,27-0.99-1.449.04dA12O30.000.260.18-2.084.081,321,140.960.19-0.00-0.156.59dTiO20.,46-0.41-0.49-4.22dNa2O0.000.44-,32dP2OS0.000.000.01-0.18-0.16-0.19-0.14-’Table6-6.(continued-i)AbsolutelossorgainoflithochemicalconstituentscausedbyhydrothermalalterationSample_idDA63-6DA63-5DDA63-5DA63-4DAo3-4DA63-3DDA63-3DDA63-3DA63-1DDA63-1xl-8xl-?gramdSiO2186027.7329.341.341.387.168.735.830.001.0911.2710.10dAl2O37.266.777.915.535,423.954.203.530.000.133.673.14dTiO20.,06dFe2O3-0.660.841.12-1.27-1.09-1.57-1.79-1.500.00.0.07-0.69-0.76dFeO10.5510.5310.8611.8511.7110.4410.6910.,020.07-0.08-0.08-0.10-0.11-*dS5420.565849.305982.00884.78884.78592.95605.71580.620.001.72177.2362.12dZr-19.78-10.09-18.32-7.30-7.30-22.94-20.40-22.650.00-4.0929.5023.07dY-1.636.238.935.755.754.695.235.490.000.885.1812.91dRb66.8584.2493.6399.4599.45122.10126.13111.130.00-9.7599.72141.35dSr-312.16-500.14.518.17-318.82-318.82-455.72-452.49-461.030.00-19.45-312.34-289.27ONTable6-6.(continued-2)AbsolutelossorgainoflithochemicalconstituentscausedbyhydrothermalalterationSampleidxl-6xt-SDxl-4xl-3xl-2dxl-2xl-1xlO-1xlO-1xlO-2xlO-3xlO-3gramdSiO288918.3316.6124.4231.0545.9129.5783.2277.9413.1822.1222.27dAI2O33.582.884.974.144.256.695.5012.2010.693.966.346.29dTiO2-0.06-0.06-0.06-0.06-0.06-0.06-0.06-,151.110.870.721.951.38-0.02-0.011.841.041.05dMgO-0.67-0.93-0.37-0.99-0.95-0.52-0.73-1.30-1.30-1.05-0.89-0.90dCaO-2.82-3.13-4.19-3.93-4.55-4.10-4.20-4.90-4.91-4.31-4.31-4.30dNa2O-3.22-3.44-,19-0.20dH2O1.571.710.921.561.281.832.345.064.822.151.161.16dCO21.20L585.232.341.893.468.482.762.563.322.922.92dTotal11.9820.4531.1729.4031.7955.5849.4398.5290.8120.8929.3929.38gram/10000dS300.33815.67668.051034,01810.161099.081827.0011147.001071238904.32434d8434.18dZr14.9218.1943.0240.4538.9840.7528.7267.3458.2213.5257.9957.99dY11.713.9514.448.343.712.634.33-[63.93100.5799.41111.8546.3513.978.86123.86145.41145.41dSr-325.61-338.15-353.19-200.48-183.24-158.00-419.261464.921390.41-388.09-242.70-242.70t-)Table6-6.(continued-3)AbsolutelossorgainoflithochemicalconstituentscausedbyhydrothermalalterationSarnpleidxlO-3dxlO-3dxlO-4xlO-4xlO-5xlO-5xlO-6xlO-6xlO-6DxlO-6Dx5-9x5-10gram’dSO220.0920.0510.7712.41-7.53-7.362.,652.651.241.320.920.92-0.55-0.550.000.00-0.31-0.06dTotal26.4726.489.1411.58-13.16-13.231.401.420.000.0050.3842.83gram/10000’dS670,75670.75304.61317.00154.76147.86-26.00-“* dSiO260.2018.9715.2530.6930.52-8.99-,40-0.42-0.76-1.010.00-0.04-,29-4.32-4.24-4.24-1.35-1.380.00-0.34-0,461.89-0.30dNa2O-2.31-2.66-2.70-2.60-2.62-2.77-2.770.001.341.37-0.65-2.66dK2O3.242.612.372.842.80-0.08-0.110.00-0.36-0.310.132.24dP2OS-0.01-0.04-0.04-0.02-0.02-0.06-0.060.00-,000.003.994.0513.9118.65gram/10000dS6846.603536.802380.241404.101436.94-92.54-65.910.00394.50390.31-37.593372.41dZr-12.71.2727-31.16-17.57-17.57-49.36-49.360.00N-19.11-19.111.63-36.33dY-21.2817.575.84-7.32-7.32-3.20- —aTable 6-7h. Metasomatic norms corrected for closureand absolute losses and gains of components (in moles)at Switch Back vein, Silver Queen mine, Owen Lake. central BCSample id DA63-8 DA63-6 DA63-5D 0A63-5 DA63-4DA63-4 DA63-3D DA63-30 0A63-3 DA63•lD DA63-1Mtr&jon s-alt s-alt s-alt s-alt rn-alt rn-alt rn-alt rn-alt rn-alt w-alt w-ajtmolePyroxenc 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.03 0.03Piagioclase 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.15 0.16K-feldspar 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 0.07 0.07Quartz 0.65 0.79 0.95 0.96 0.530.53 0.66 0.68 0.64 0.19 0.21Carbonate 0.24 0.23 0.25 0.26 0.200.20 0.22 0.22 0.22 0.03 0.02Epidote 0.00 0.00 0.00 0.00 0.00 0.000.01 0.01 0.01 0.02 0.01Chlorite 0.01 0.00 0.00 0.00 0.02 0.020.01 0.01 0.01 0.01 0.02Sericite 0.12 0.10 0.11 0.11 0.110.11 0.12 0.12 0.12 0.00 0.00Kaolinite 0.04 0.07 0.07 0.07 0.040.04 0.01 ‘0.01 0.00 -0.00 -0.00Pyrite 0.01 0.00 0.00 0.00 0.000.00 0.00 -0.00 0.00 0.00 0.00Hematite 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 0.00Magnetite 0.01 0.01 0.01 0.01 0.00 0.000.00 0.00 0.00 0.00 0.00Ilmenite 0.01 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 0.00Rutile 0.00 0.01 0.01 0.01 0.01 0.010.01 0.01 0.01 0.01 0.01Apatite 0.00 0.01 0.02 0.02 0.01 0.01 0.00 -0.00 0.00 0.00 0.01Total 1.09 1.24 1.43 1.45 0.91 0.921.03 1.06 1.01 0.52 0.54dSiO2 0.15 0.31 0.46 0.49 0.02 0.02 0.12 0.15 0.10 0.00 0.02dAl+3 0.13 0.14 0.13 0.16 0.11 0.11 0.08 0.08 0.07 0.00 0.00dTi+4 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00dFe+3 -0.00 -0.01 0.01 0.01 -0.02 -0.01 -0.02 -0.02 -0.02 0.00 -0.00dFe+2 0.13 0.15 0.15 0.15 0.16 0.16 0.150.15 0.14 0.00 0.00dMn+2 0.04 0.01 0.01 0.01 0.01 0.010.02 0.02 0.01 0.00 0.00dMg±2 -0.03 -0.04 -0.03 -0.03 -0.03 -0.03 -0.02-0.02 -0.02 0.00 0.00dCa+2 -0.08 -0.09 -0.09 -0.08 -0.09 -0.09-0.09 -0.09 -0.09 0.00 -0.00dNa+ -0.11 -0.10 -0.10 -0.10 -0.10 -0.10-0.10 -0.10 -0.10 0.00 0.01dK+ 0.05 0.04 0.04 0.04 0.04 0.040.05 0.05 0.04 0.00 -0.00dP+5 -0.00 -0.00 0.00 0.00 -0.00 -0.00 -0.00 -0.00 -0.00 0.00 0.00Sum 0= 0.22 0.19 0.22 0.27 0.16 0.160.10 0.11 0.09 0.00 0.01dH2O 0.16 0.18 0.20 0.20 0.15 0.150.10 0.10 0.10 0.00 0.00dCO2 0.22 0.21 0.22 0.23 0.19 0.190.19 0.20 0.19 0.00 0.00dS 0.01 0.02 0.02 0.02 0.00 0.000.00 0.00 0.00 0.00 0.00dTotal 0.89 1.00 1.23 1.38 0.60 0.600.57 0.61 0.52 0.00 0.03280Table 6-7c. Metasomatjc norms corrected for closure and absolute losses andgains of components (in moles)at the central segment of the No. 3 vein, Silver Queen mine,central BCSample_ed xl-8 xl-7 xl-6 xl-50 xl-4xl-3 xl-2d xl-2Putere.tjon rn-aft rn-alt rn-alt rn-aft rn-alt s-aft s-alt s-alt —molePyroxene -0.00 0.00 0.00 0.000.00 0.00 0.00 0.00Plagioclase 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00K-feldspar 0.04 0.07 0.04 0.000.03 0.00 0.00 0.00Quartz 0.71 0.62 0.67 0.910.78 0.98 1.10 1.29Carbonate 0.14 0.13 0.09 0.100.16 0.10 0.09 0.12Epidote 0.00 0.00 0.00 -0.000.00 0.00 0.00 0.00Chlorite 0.00 0.01 0.00 0.010.01 0.01 0.00 0.00Sericite 0.12 0.09 0.11 0.120.12 0.12 0.12 0.13Kaolinite -0.00 0.00 -0.00 0.00 -0.000.01 0.02 0.03Pyrite 0.01 0.01 0.01 0.00 0.020.00 0.00 0.00Hematite 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00Magnetite 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00Ilmenite 0.00 0.00 0.01 0.00 0.010.00 0.00 0.00Rutile 0.00 0.00 -0.00 0.01 -0.000.01 0.01 0.00Apatite 0.00 0.00 -0.00 0.01 -0.010.01 0.01 0.01Total 1.03 0.95 0.93 1.15 1.121.24 1.34 1.59dSiO2 0.19 0.17 0.15 0.30 0.280.41 0.52 0.76dAl +3 0.07 0.06 0.07 0.06 0.10 0.08 0.08 0.13dTi+4 -0.00 -0.00 -0.00 -0.00 -0.00 -0.00 -0.00 -0.00dFe+3 -0.01 -0.01 -0.01 -0.01 -0.01 -0.01 -0.02 -0.01dFe+2 0.02 0.01 0.01 0.01 0.11 0.050.01 0.04dMn÷2 0.00 0.01 0.01 0.02 0.02 0.010.01 0.03dMg±2 -0.01 -0.01 -0.02 -0.02 -0.01-0.02 -0.02 -0.01dCa+2 -0.04 -0.03 -0.05 -0.06 -0.07-0.07 -0.08 -0.07dNa+ -0.08 -0.09 -0.10 -0.11 -0.10 -0.11-0.11 -0.11dK+ 0.05 0.07 0.07 0.05 0.070.05 0.05 0.05dP+5 -0.00 -0.00 -0.00 -0.00 -0.00-0.00 -0.00 -0.00Sum 0= 0.05 0.05 0.01 -0.02 0.140.03 -0.02 0.1 1dH2O 0.06 0.08 0.09 0.09 0.050.09 0.07 0.10dCO2 0.08 0.07 0.03 0.04 0.120.05 0.04 0.08dS 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00dTotal 0.38 0.38 0.25 0.35 0.680.54 0.52 1.10281Table 6-7c. (continued-i) Metasomatic norms corrected for closure and absolute losses andgains of components(in moles) at the central segment of the No. 3vein, Silver Queen mine, central BCS8mpleld xl-1 xlO-1 xlO-1 xlO-2 xlO-3 xlO-3xlO-3d x10-3dAlteration s-alt s-alt s-alts-alt rn-alt rn-alt rn-alt rn-altmolePyroxene 0.00 0.000.00 0.00 0.00 0.000.00 0.00Plagioclase 0.00 0.000.00 0.00 0.00 0.000.00 o.ooK-feldspar -0.00 0.010.01 0.00 0.03 0.03 0.00 0.00Quartz 1.04 1.801.74 0.80 0.85 0.85 0.88 0.87Carbonate 0.23 0.110.11 0.14 0.12 0.12 0.12 0.12Epidote 0.00 0.000.00 0.00 0.00 0.00 0.00 0.00Chlorite 0.00 0.000.00 0.00 0.00 0.00 0.00 0.00Sericite 0.09 0.100.10 0.11 0.14 0.14 0.14 0.14Kaolinite 0.06 0.120.11 0.03 0.00 0.00 0.000.00Pyritè 0.00 0.00 0.000.00 0.00 0.00 0.00 0.00Hematite 0.00 0.000.00 0.00 0.00 0.00 0.000.00Magnetite 0.00 0.02 0.020.00 0.00 0.00 0.00 0.00Ilmenite 0.00 0.00 0.00 0.00 0.00 0.00 0.000.00Rutile 0.00 0.01 0.010.01 0.01 0.01 0.00 0.00Apatite 0.01 0.00 0.00 0.02 0.00 0.01 0.000.00Total 1.46 2.17 2.101.11 1.15 1.15 1.16 1.16dSiO2 0.49 1.38 1.300.22 0.37 037 0.330.33dAl÷3 0.11 0.24 0.210.08 0.12 0.12 0.12 0.12dTi+4 -0.00 -0.00 -0.00-0.00 -0.00 -0.00 -0.00 -0.00dFe+3 -0.02 -0.03 -0.030.01 -0.02 -0.02 -0.02 -0.02dFe+2 0.15 0.07 0.060.03 0.02 0.02 0.01 0.01dMn+2 0.02 -0.00 -0.000.03 0.01 0.01 0.01 0.01dMg+2 -0.02 -0.03 -0.03 -0.03 -0.02 -0.02 -0.02 -0.02dCa+2 -0.07 -0.09 -0.09 -0.08 -0.08 -0.08 -0.06 -0.06dNa+ -0.11 -0.10 -0.10-0.12 -0.10 -0.10 -0.10 -0.10dK+ 0.02 0.02 0.020.05 0.09 0.09 0.07 0.07dP÷5 -0.00 -0.00 -0.00-0.00 -0.00 -0.00 -0.00 -0.00Sum 0= 0.16 0.200.15 0.05 0.08 0.08 0.07 0.08dH2O 0.13 028 0.270.12 0.06 0.06 0.09 0.09dCO2 0.19 0.060.06 0.08 0.07 0.070.06 0.06dS 0.01 0.030.03 0.00 0.00 0.00 0.00 0.00dTotai 1.06 2.041.85 0.44 0.61 0.610.57 0.57282Table 6-7c.(continued-2) Metasomatic norms corrected for closure and absolute losses and gains of components(in moles) at the central segment of the No.3 vein, Silver Queenmine, central BCSmpIe_id xlO-4 xlO-4 xlO-5 xlO-5xlO-6 xlO-6 xlO-6D xlO-6DMteratjon rn-alt rn-alt rn-alt rn-alt w-alt w-alt w-alt w-altmolePyroxene 0.00 0.00 0.00 0.000.01 0.01 0.00 0.00Plagioclase 0.00 0.00 0.00 0.000.13 0.13 0.10 0.10K-feldspar 0.00 0.00 0.00 0.000.07 0.07 0.06 0.06Quartz 0.79 0.81 0.54 0.550.27 0.27 0.28 0.28Carbonate 0.08 0.08 0.08 0.090.05 0.05 0.05 0.05Epidote 0.00 0.00 0.00 0.000.04 0.04 0.04 0.04Chlorite 0.01 0.01 0.00 0.000.01 / 0.01 0.01 0.01Sericite 0.11 0.11 0.07 0.070.00 0.00 0.02 0.02Kaolmite 0.01 0.01 0.05 0.040.00 -0.00 -0.00 -0.00Pyrite 0.00 0.00 0.00 0.00-0.00 -0.00 -0.00 -0.00Hematite 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00Magnetite 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00Ilmenite 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00Rutile 0.01 0.01 0.00 0.01 0.010.01 0.01 0.01Apatite 0.01 0.01 0.00 0.01 -0.01 -0.01 -0.01 -0.01Total 1.01 1.04 0.76 0.77 0.570.57 0.57 0.57dSiO2 0.18 0.21 -0.13 -0.12 0.040.04 0.00 0.00dAl+3 0.05 0.06 -0.01 -0.01 -0.02-0.02 0.00 0.00dTi÷4 -0.00 -0.00 -0.00 -0.00 0.000.00 0.00 0.00dFe+3 -0.01 -0.02 -0.02 -0.02 -0.00 -0.000.00 0.00dFe+2 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00dMn-i-2 0.00 0.00 0.00 0.00 -0.00 -0.000.00 0.00dMg±2 -0.02 -0.02 -0.02 -0.02 0.010.02 0.00 0.00dCa±2 -0.06 -0.06 -0.05 -0.05 -0.00-0.00 0.00 0.00dNa+ -0.11 -0.11 -0.11 -0.11 0.010.01 0.00 0.00dK+ 0.04 0.04 -0.00 -0.00 0.000.00 0.00 0.00dP±5 •0.00 - -0.00 -0.00 -0.00 -0.00 -0.00 0.00 0.00Sum 0= -0.07 -0.05 -0.17 -0.18 -0.02 -0.02 0.00 0.00dH2O 0.08 0.09 0.13 0.13 0.010.01 0.00 0.00dCO2 0.03 0.03 0.02 0.02 -0.01 -0.01 0.00 0.00dS 0.00 0.00 0.00 0.00 -0.00-0.00 0.00 0.00dTotal 0.11 0.17 -0.35 -0.36 0.020.02 0.00 0.00283Table 6-7d. Metasomatic norms corrected for closureand absolute losses and gains of components (in moles)at the southern segment of the No. 3 vein. Silver Queen mine, central BCSample_id x5-9 x5-10 x5-1x5-2 x5-3 x5-4 x5-4 —Alteration s-alt s-alt s-altrn-alt rn-alt rn-alt rn-altmolePyroxene 0.00 0.00 0.00-0.00 -0.00 -0.00 0.00Plagioclase 0.00 0.00 0.000.00 0.00 0.00 0.00K-feldspar 0.02 0.02 0.010.02 0.01 0.01 0.01Quartz 1.12 1.06 1.45 0.85 0.80 1.02 1.02Carbonate 0.09 0.11 0.120.13 0.11 0.10 0.10Epidote 0.00 0.00 -0.000.00 0.00 0.00 0.00Chlorite 0.00 0.00 0.00-0.00 0.00 0.00 0.00Sericite 0.15 0.14 0.150.12 0.12 0.13 0.13Kaolinite 0.00 -0.00 0.000.00 0.00 0.00 0.00Pyrite 0.00 0.00 0.000.00 0.00 0.00 0.00Hematite 0.00 0.00 0.000.00 0.00 0.00 0.00Magnetite 0.03 0.01 0.010.01 0.00 0.00 0.00Ilmenite 0.00 0.00 0.000.00 0.00 0.00 0.00Rutile 0.01 0.01 0.010.01 0.01 0.01 0.01Apatite 0.02 0.01 0.010.01 0.01 0.01 0.01Total 1.44 1.37 1.761.13 1.07 1.29 1.29dSiO2 0.69 0.62 1.000.32 0.25 0.51 0.51dAl+3 0.17 0.13 0.150.06 0.05 0.10 0.10dTi+4 -0.00 0.00 0.000.00 0.00 0.00 0.00dFe+3 0.01 -0.01 -0.01-0.02 -0.00 -0.01 -0.01dFe+2 0.02 0.01 0.040.01 -0.00 0.00 0.00dMn+2 -0.00 0.01 0.000.02 0.02 0.00 0.00dMg+2 -0.02 -0.02 -0.02 -0.02 -0.02 •0.02 -0.02dCa+2 -0.08 -0.08 -0.08 -0.08 -0.08 -0.08 -0.08dNa+ -0.08 -0.09 -0.07-0.09 -0.09 -0.08 -0.08dK÷ 0.08 0.08 0.070.06 0.05 0.06 0.06ciP+5 0.00 -0.00 -0.00-0.00 -0.00 -0.00 -0.00Sum 0= 0.17 0.11 0.12-0.02 -0.03 0.03 0.03dH2O 0.05 0.06 0.050.01 0.02 0.03 0.03dCO2 -0.01 -0.00 0.020.03 0.01 -0.00 0.00dS 0.05 0.02 0.020.01 0.01 0.00 0.00cjTotal 1.05 0.86 1.280.30 0.19 0.56 0.54284Table 6-7d. (continued) Metasomatic norms corrected for closure and absolute losses and gains of components(in moles) at the southern segment of the No. 3 vein. Silver Queen mine,central BCSample_ia x5-5 x5-5 x5-6 x5-6d x5-6dx5-7 x5-8Alteration rn-alt rn-alt w-alt w-alt w-alt rn-alt s-altmolePyroxene 0.00 0.00 0.00 0.020.01 0.00 0.00Plagioclase 0.00 0.00 0.06 0.120.12 0.03 0.02K-feldspar 0.00 0.00 0.05 0.060.06 0.03 0.01Quartz 0.49 0.49 0.37 0.260.25 0.56 0.76Carbonate 0.13 0.13 0.10 0.100.11 0.19 0.11Epidote 0.00 0.00 0.01 0.020.03 0.00 0.00Chlorite 0.00 0.00 0.02 0.010.01 0.01 0.01Sericite 0.08 0.07 0.05 0.03 0.02 0.09 0.10Kaolinite 0.03 0.03 -0.00 -0.00 0.00 -0.00 -0.00Pyrite 0.00 0.00 0.00 0.000.00 0.00 0.00Hematite 0.00 0.00 0.00 0.00 0.00 0.00 0.00Magnetite 0.00 0.00 0.00 0.00 0.000.00 0.01Ilmenite 0.01 0.00 0.00 0.00 0.000.00 0.00Rutile 0.00 0.01 0.01 0.01 0.010.01 0.01Apatite 0.01 0.01 0.01 0.00 0.000.01 0.01Total 0.75 0.74 0.68 0.62 0.610.94 1.05dSiO2 -0.15 -0.15 0.00 0.05 0.050.10 0.26dAl÷3 -0.02 -0.02 0.00 0.00 0.000.05 0.06dT+4 0.00 0.00 0.00 0.00 0.000.00 0.00dFe+3 -0.01 -0.01 0.00 -0.00 -0.00-0.01 -0.01dFe+2 0.00 0.00 0.00 0.01 0.010.01 0.00dMn+2 0.01 0.01 -0.00 -0.00 -0.000.00 0.00dMg+2 -0.02 -0.03 0.00 0.03 0.03 -0.01 -0.01dCa±2 -0.02 -0.02 0.00 -0.01 -0.010.03 -0.01dNa+ -0.09 -0.09 0.00 0.04 0.04-0.02 -0.09dK+ -0.00 -0.00 0.00 -0.01 -0.010.00 0.05dP+5 -0.00 -0.00 0.00 -0.000.00 0.00 -0.00Sum 0= -0.13 -0.14 0.00 0.04 0.05 0.08 0.04dH2O 0.03 0.03 0.00 -0.05-0.06 0.02 0.03dCO2 0.03 0.03 0.00 -0.00 0.00 0.09 0.01dS -0.00 -0.00 0.00 0.000.00 -0.00 0.01dTotal -0.38 -0.40 0.00 0.10 0.10 0.34 0.36285Table 6-Sb. Metasonatjc norns corrected for closure and absolute losses and gains of components (in grams)at Switch Back vein. Silver Queen mine, Owen Lake. central BCSernpteid 0A63-5 DA63-6 0A63-5D 0A63-5 0A63-4 DA63-4DA63-3D DA63-3D DA63-3 DA63-1D DA63-lAItation s-alt s-alt s-alt s-alt rn-alt rn-alt rn-alt rn-alt rn-alt w-alt w-altgramPyroxene 0.00 0.00 0.00 0.0