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Weathering and microbial activity in sulfidic mine tailings with implications in reclamation Robbins, James Milton 1979

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WEATHERING AND MICROBIAL ACTIVITY IN SULFIDIC MINE TAILINGS WITH IMPLICATIONS IN RECLAMATION by JAMES MILTON ROBBINS B.Sc. Southern Oregon College, 1970 B.Sc. Oregon State University, 1975 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN THE FACULTY OF GRADUATE STUDIES (Department of Soil Science) We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA September, 1978. (c) James Milton Robbins^ \ c\^°\. In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the Head of my Department or by his representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department nf SOIL SCIENCE The University of British Columbia 2075 Wesbrook Place Vancouver, Canada V6T 1W5 Date MARCH 3, 19 79 . iE-6 BP 75-S 1 I E i ABSTRACT The oxidation of sulfidic mine tailings and subsequent acid and salt accumulation results in acid drainage and poses a severe reclama-tion problem. The objectives of this study were to quantify the processes leading to these problems and propose feasible solutions. Characterization of 120 sulfidic surface samples, collected from the Sullivan mine tailings ponds, was carried out for dominant physiological groups of microorganisms, sulfur forms, water and acid extractable cations qualitative physical characteristics, pH, conductivity, organic matter and moisture content. Acid tolerant fungi and iron, sulfur and acid tolerant heterotrophic bacteria were enumerated by the most-probable-numbe technique. Iron bacteria (Thiobaci11 us ferrooxidans) occurred often and +2 can be implicated as the cause of Fe oxidation in samples not buffered at near neutral pH values by bases. Sulfur bacteria (thiobacillus species were commonly found and classified as T- thioparus, T. neapolitanus, or T. thiooxidans. A pH-dependent succession of these thiobacilli occurs in the tailings. Acid tolerant heterotrophic bacteria populations were highly correlated with those of the thiobacilli suggesting a symbiotic relationship, particularly in samples with pH >2.5. The numbers of acid tolerant fungi tended to increase proportionally with oxidation, sugges-ting increased colonization with time. Chemical analysis for major sulfur forms indicates that iron mono-sulfide oxidation is rapid resulting in the formation and persistence of +3 Fe (as amorphous Fe oxyhydroxides in mineralogical analysis) and i i elemental sulfur. Some accumulation of other oxidizable sulfur forms is indicated by the high levels of total oxidizable sulfur. A portion of this sulfur not accounted for by CS2 extractable elemental sulfur may be present as amorphous elemental sulfur. The oxidation of elemen-tal sulfur and other sulfur intermediates to sulfate is pronounced in the surface 0-2 cm based on the laboratory oxidation of a bulk tailings sample. Mineralogical analysis shows that gypsum is the predominant sulfate containing mineral at basic to slightly acid pH values. Under moderately to strongly acid conditions, jarosite type minerals occurred in high amounts. Mineralogical analysis also showed that the decomposi-tion of basic minerals and chlorite occurred ini t ia l ly , with the dis-solution of micas and K-feldspars being less rapid. The absence of detectable kaolinite or other Al silicate residues indicates that alumino-silicate dissolution may be congruent. Mineralogical results showing dissolution of minerals is supported by general increases in water extrac-table cations (including Fe, A l , Ca, Mg, K and Na) and decreases in these same acid extractable cations as weathering proceeds. These processes ultimately result in a highly oxidized surface in which acid production is slow. It is suggested that erosional processes be inhibited where an oxidized surface exists to prevent the exposure of reduced tailings beneath the surface. Furthermore, steps should be taken to minimize the addition of fresh tailings over oxidized surfaces. The use of correlations between the qualitative physical character-istics texture, structure and color, obtained in this study, can serve as guides to estimating the degree of tailings oxidation in the field. If more precision is required, the colorimetric determination of CS9 i i i extractable elemental sulfur is suggested, particularly on the more oxidized samples. Proper management of the tailings to maintain present oxidized surfaces should reduce the acid drainage considerably until reclamation is undertaken. The quantification of the changes in tailings properties with increases in weathering can be useful in evaluating reclamation strategies. iv TABLE OF CONTENTS Page ABSTRACT i TABLE OF CONTENTS iv LIST OF FIGURES ix LIST OF TABLES x ACKNOWLEDGEMENT xi 1.0 INTRODUCTION 1 1.1 Nature of the Problem 1 1.2 Purpose of Study 1 1.3 Choice of Study Sites 2 1.4 Scope of Study 2 2.0 LITERATURE REVIEW 4 2.1 Overview 4 2.2 Classification and Genesis of Sulfidic Soils 4 2.3 Weathering Products in Sulfidic Soils 5 2.3.1 Aluminosi1icate weathering products 5 2.3.2 Iron sulfide weathering products 8 2.4 Iron Oxidation in Sulfidic Soils 11 2.4.1 Physical-.and'.cfiemical^faetbrs • j" . . . 11 2.4fld:l Effects of surface area and crystal!inity on iron sulfide reactivity 11 2.4.1.2 Mechanisms and kinetics of iron oxidation from iron sulfides 12 2.4.2 Microbial Iron Oxidation 17 2.4.2.1 Iron oxidizing bacteria and their succession 17 2.4.2.2 Factors controlling the rate of iron oxidation by Thiobacillus ferrooxidans 19 2.5 Sulfur Oxidation in Sulfidic Soils 22 2.5.1. Chemical Oxidation of Inorganic Sulfur Compounds 22 2.5.1.1 The role of ferric iron in the oxidation of sulfides 22 V 2.5.1.2 Mechanisms and products of sulfide oxidation by oxygen 24 2.5.2 Microbial Oxidation of Inorganic Sulfur Compounds 31 2.5.2.1 Classification and succession of sulfur oxidizing bacteria 31 2.5.2.2 Oxidation pathways of sulfur compounds by the obligate autotrophic thiobacilli 32 2.5.2.3 Factors controlling the oxidation rates of sulfur compounds by the obligate autotrophic thiobacilli 37 2.6 Coupling of Iron and Sulfur Oxidation by the Thiobacilli 44 3.0 MATERIALS AND METHODS 47 3.1 Field 47 3.1.1 Sites Sampled 47 3.1.2 Sampling Technique 47 3.2 Laboratory 49 3.2.1 Microbiological 49 3.2.1.1 Most-probable-number determinations 49 3.2.1.2 Identification of sulfur bacteria 50 3.2.1.3 Iron bacteria colony type identification 51 3.2.1.4 Sulfolobus enrichment 51 3.2.2 Chemical 51 3.2.2.1 Percent moisture 51 3.2.2.2 pH 52 3.2.2.3 Conductivity 52 3.2.2.4 Elemental sulfur 52 3.2.2.5 Monosulfide sulfur 53 3.2.2.6 Total oxidizable sulfur 53 3.2.2.7 Organic matter 53 3.2.2.8 Water extractable sulfate 54 3.2.2.9 Acid extractable sulfate 54 . 3.2.2.10 Extractable cation determinations 55 3.2.3 Mineralogical 55 3.2.4 Qualitative Tailing Characteristics 55 3.2.5 Computer Methods 56 4.0 RESULTS 57 4.1 Chemical Transformations in Oxidizing Sulfidic Soils 57 4.1.1 Products of Iron Monosulfide Oxidation 57 4.1.1.1 Acid generating potential versus stage of iron monosulfide oxidation 57 4.1.1.2 Iron monosulfide oxidation in the siliceous tailings 58 4.1.1.3 Iron monosulfide oxidation in iron tailings with pH >2.5 61 4.1.1.4 Iron monosulfide oxidation in iron tailings with pH <2.5 -62 vi 4.1.2 Dissolution of Minerals with Iron Monosulfide 63 Oxidation 4.1.2.1 Introduction 63 4.1.2.2 Mineral dissolution in the siliceous tailings 64 4.1.2.3 Mineral dissolution in the iron tailings with pH >2.5 65 4.1.2.4 Mineral dissolution in the iron tailings with pH <2.5 ' 67 4.1.3 Accumulation of Salts with Iron Monosulfide Oxidation 68 4.1.3.1 Introduction 68 4.1.3.2 Accumulation of salts in the siliceous tailings 68 4.1.3.3 Accumulation of salts in the iron tailings with pH >2.5 71 4.1.3.4 Accumulation of salts in the iron tailings with pH <2.5 72 4.2 Occurrence and Role of Microorganisms in the Oxidation Process 72 4.2.1 Occurrences and Associations of the Main Physiological Groups of Microorganisms in the Tailings Material 72 4.2.1.1 Siliceous tailings 72 4.2.1.2 Iron tailings with pH >2.5 74 4.2.1.3 Iron tailings with pH <2.5 76 4.2.2 Role of the Main Physiological Groups of Microorganisms in the Tailings Materials 77 4.2.2.1 Siliceous tailings 77 4.2.2.2 Iron tailings with pH >2.5 77 4.2.2.3 Iron tailings with pH <2.5 78 4.2.3 Sulfur Bacteria Succession 78 4.3 Mineralogical Changes Due to Iron Monosulfide Oxidation 82 4.4 Correlations Between Qualitative Physical Tailings Character-istics and the Amount of Oxidation and Weathering 89 4.4.1 Texture 89 4.4.2 Structure 92 4.4.3 Munsell Color 93 4.4.3.1 Hue 93 4.4.3.2 Value 94 4.4.3.3 Chroma 95 4.5 Iron Monosulfide Oxidation and Weathering Versus Depth 95 5.0 DISCUSSION 101 5.1 Physical Factors Which Increase the Rate of Iron Monosulfide Oxidation in the Sulfidic Tailings 101 5.1.1 Concentrator Extraction Processes 101 5.1.2 Physiography of the Sullivan Sulfidic Tailings Ponds 102 vii 5.2 Water Pollution Control Strategies 105 5.2.1 Extent of the Acid Drainage Problem to Bodies of Fresh Water 105 5.2.2 Reduction of Acid Drainage Pollution from the Iron and Siliceous Tailings 108 5.3 Potential Reclamation Strategies 111 6.0 SUMMARY AND CONCLUSIONS 114 7.0 REFERENCES 119 APPENDIX A 139 APPENDIX A.l Aerial Photo of Sullivan Mine Iron and Siliceous Tailings Ponds 139 APPENDIX A.2 General View of Tailings Disposal Process 140 APPENDIX A.3 Profile of Iron Tailings Showing Discontinuous Horizons with Variation in Structure and Degree of Weathering with Depth 140 APPENDIX A.4 Fluvial Action in the Iron Tailings Illustrating the Discontinuous Deposition of Horizons 141 APPENDIX A.5 Initial Stages of Oxidation in the Iron Tailings Showing Cracking of Surface and Salt Crusts 141 APPENDIX A.6 Moderately Oxidized Surface Showing Pronounced Crusting 142 APPENDIX A.7 Highly Oxidized Surface in the Iron Tailings Pond with Ferruginous Caps 142 APPENDIX A.8 Pool of Wash Water from Concentrator Containing a High Population of Microscopic Green Worms in the Iron Tailings Pond 143 APPENDIX A.9 Salt Crusts and Ponded Water Discolored by Iron Compounds in the Lower Iron Tailings Pond 143 APPENDIX A.10 -Marsh Vegetation Growing in Ponded Portion of the Lower Iron Tailings Pond 144 APPENDIX A.11 Thiobacillus thioparus Colony X92, Transmitted Light, Showing Sulfur Deposition Throughout 145 APPENDIX A.12 Thiobacillus thioparus Colony X92, Reflected Light, Showing Sulfur Deposition Throughout 145 vi i i APPENDIX A.13 Thiobacillus neapolitanus X92, Transmitted Light, Showing Sulfur Deposition in Center 146 APPENDIX A.14 Thiobacillus thiooxidans X92, Transmitted Light, Showing Convex Surface 146 APPENDIX B APPENDIX B. 1 Key to Computer Symbols Used to Label Parameters 147 APPENDIX B. 2 Microbiological, Chemical and Qualitative Physical Analysis of the Surface Samples Collected from the Sullivan Iron and Siliceous Tailings 149 APPENDIX C APPENDIX C. 1 Correlation Matrix, Means and Standard Deviations for the Parameters Analyzed for in the Iron and Siliceous Tailings Samples as a Whole 160 APPENDIX C. 2 Correlation Matrix, Means and Standard Deviations for the Parameters Analyzed for in the Siliceous Tailings Samples 163 APPENDIX C. 3 Correlation Matrix, Means and Standard Deviations for the Parameters Analyzed for in the Iron Tailings Sample with pH >2.5 166 APPENDIX C. 4 Correlation Matrix, Means and Standard Deviations for the Parameters Analyzed for in the Iron Tailings Samples with pH <2.5 169 APPENDIX C. 5 Numerical Weightings of Texture, Structure and Color 172 APPENDIX D APPENDIX D. X-Ray Diffraction Patterns for the Samples Chosen for Mineralogical Study 174 APPENDIX E APPENDIX E. 1 Average Numbers of Microorganisms on a Per Site Basis 175 APPENDIX E. 2 Average Amounts of Sulfur Forms on a Per Site Basis 176 APPENDIX E. 3 Average pH, Conductivity, Moisture Content and Water Extractable Organic Matter on a Per Site Basis 177 APPENDIX E. 4 Average Amounts of Water Extractable Cations on a Per Site Basis 178 APPENDIX E. 5 Average Amounts of Acid Extractable Cations on a Per Site Basis 179 APPENDIX F. 1 Map of the Sullivan Mine - Cominco Ltd. Operations 180 ix LIST OF FIGURES Page Figure 1. Sample Sites of Sullivan Iron Sulfide Tailings 48 X LIST OF TABLES Page Table 1. Frequency of Occurrence (%) of Microorganisms for each Tailings Material 73 Table 2. Frequency of Association (%) of Microorganisms for each Tailings Material 75 Table 3. Thiobacilli Species Isolated in Samples and the pH they Lower a Thiosulfate Medium (S 5.5) To 80 Table 4. Chemical Analysis of Samples Selected for Mineralogical Study 83 Table 5. X-Ray Data for Samples Selected for Mineralogical Study 84 Table 6. Chemical Changes with Sample Depth 96 x i ACKNOWLEDGEMENTS I wish to extend my appreciation to Dr. Art Bomke ( Assistant Prof-essor, Dept. of S o i l Science ), who supervised ray M. Sc. program. His advice and emphasis on the p r a c t i c a l a p p l i c a t i o n s of research findings i s appreciated. My thanks a l s o go to the other members of my committee: Dr. C. A. Rowles ( Professor and Chairman of the S o i l Science Dept. ), Dr. L. E. Lowe ( Professor, Dept. of S o i l Science ) and Dr. G. M. Towns-ley ( Professor, Food Science-microbiology ) for t h e i r valuable c o n t r i -butions to my program. I extend my gratitude to Dr. L. M. Lavkulich ( Professor, Dept. of S o i l Science ) for providing f i n a n c i a l support f o r my research through his contracts. Thanks are also due Dr. D. Duncan ( Professor, Dept. of Metallurgy and B. C. Research ) f o r his advice on methods of microbiology applicable to the T h i o b a c i l l i species. I also appreciate the many c o n t r i -butions of my fellow students and the f a c u l t y and t e c h n i c a l s t a f f of the Dept. of S o i l Science, and to Ms. Diane Green for her patience i n the typing of t h i s thesis. I also wish to recognise the t r a i n i n g provided me by the professors at the Southern Oregon State College, University of Oregon, and Oregon State University,which prepared me for my succ e s s f u l research p r o j e c t . F i n a l l y , I am thankful that my wife Anne gave me encouragement and was patient while I was conducting my research. 1 1.0 INTRODUCTION 1.1 Nature of the Problem The mining of economic minerals produces as a waste, tailings which are generally stored in tailings ponds. If these tailings are high in sulfides, their exposure in an oxidizing environment leads to acid and salt formation. If the acids and salts remain in the tailings, vegetation establishment is prevented. However, the discharge of these materials as acid drainage into bodies of fresh water is deleterious to aquatic l i fe . Furthermore, potability of fresh water is seriously affected by even small amounts of this drainage. 1.2 Purpose of Study This work was initiated in order to study the oxidation and weathering processes leading to these reclamation and water quality problems. The specific objectives of this thesis are: (i) to review the literature concerning weathering and oxidation pro-cesses in sulfidic soils and factors affecting their rate; (ii) to study the oxidation of reduced forms of sulfur in sulfidic mine tailings soils; ( i i i ) to study the weathering trends in these soils; (iv) to determine the occurrence and role of microorganisms in their oxidation; 2 (v) to assess the implications of weathering and oxidation processes on acid drainage - inhibition and reclamation strategies. 1.3 Choice of Study Sites The iron and siliceous tailings ponds, near the Sullivan Mine concen-trator (Cominco Ltd. , Kimberley, B.C.), were chosen as sampling sites. These materials originate as waste products of the milling and extraction of economic minerals, mainly lead,.zinc, silver and tin and the by-products bismuth, cadmium, antimony, indium, copper and molybdenum. The iron and siliceous tailings encompass 235 and 67 hectares respectively (Appendix A.I). Iron sulfide contents, primarily pyrrhotite with some pyrite, in the iron and siliceous tailings, are as high as 90% and 22% respectively. The lower iron sulfide content in the siliceous tailings is due to higher amounts of siliceous materials. These tailings provide a relatively simple system, in which to study sulfide oxidation and concomitant weathering processes over a range of high sulfide soils in a field situation. It was hoped that an understanding of the oxidation and weathering processes occurring in these tailings ponds might lead to a better reclamation strategy. 1.4 Scope of Study The work involved the characterization of 120 representative samples from several sites in the field and four depth intervals of a bulk sample 3 allowed to oxidize in the laboratory. The samples from the field were analyzed for selected chemical parameters, microbial populations, miner-alogy and qualitative physical characteristics. The sample weathered in the laboratory was only analyzed for some chemical parameters. For the field samples, the chemical parameters measured included sulfur forms, organic matter, pH, conductivity, moisture content, and major water and acid extractable cations. The sulfur forms analyzed for were iron monosulfides, total oxidizable sulfur (excluding iron monosulfides), elemental sulfur, water extractable sulfate and acid extractable sulfate. The water and acid extractable cations included Fe, A l , Ca, Mg, K and Na. The microbial groups chosen for enumeration in the field samples included iron bacteria (Thiobacillus ferroxidans), sulfur bacteria (Thiobacillus species), acid tolerant fungi and acid tolerant heterotrophic bacteria. It was anticipated that there might be a succession of sulfur oxidizing bacteria in.the tailings, ,so the thiobacilli were classified to. species where possible. Mineralogically the field samples were analyzed for their qualitative content of crystalline sulfur and iron minerals, as well as clay minerals. Qualitative tailings characteristics including Munsell soil color, texture and structure, were determined on every field sample. The bulk tailings weathered in the laboratory were subjected to chemical analysis for sulfur forms, as well as water and acid extractable cations for each depth interval sampled. The sulfur forms and cations were the same as those analyzed for in the field samples. Results of these formentioned analyses are tabulated in Appendix B.2. 4 2.0 LITERATURE REVIEW 2.1 Overview This review deals with the mechanisms of sulfur oxidation in soils high in inorganic sulfur compounds. While most of the literature pertains to naturally occurring sulfidic soils, the processes are relevant to the discussion of the oxidation and weathering of iron sulfide mine tailings. The following review should be interpreted in this light due to the paucity of specific information on iron sulfide mine tailings oxidation and weathering processes. 2.2 Classification and Genesis of Sulfidic Soils According to the Canadian soil classification system (Canada Soil Survey Committee, 1978), no categories exist for soils high in sulfur. Furthermore, mine spoils such as the Sullivan mine tailings, do not qualify as soil under the Canadian soil classification system. However, materials high in sulfur such as mine spoils are considered sulfidic soils in the U.S. system of soil classification. Sulfidic soils are defined as water-logged mineral or organic soil materials with 0.75% (on a dry weight basis) or more total sulfur. The sulfur is mostly in the form of sulfides and there is less than three times as much carbonate (CaCO^ equivalent) as sulfur (Soil Survey Staff, 1975). In this classification there is a dis-tinction between potential and actual acid sulfidic soils. The latter are 5 characterized by the presence of sulfuric horizon(s). These horizons are defined as being either mineral or organic with a pH less than 3.5 (1:1 in water); with yellow jarosite mottles having hues 2.5 or yellower and chromas 6 or more in the Munsell notation. In the classification proposed (Soil Survey Staff, 1975), sulfidic soils fall in the Aquept suborder. In the temperate regions, the Typic Sulfaquepts and Sulfic Haplaquepts predominate. However, Sulfic Tropo-aquepts, derived from drained coastal marshes, considered as intergrades of Sulfaquepts, also occur. Sulfidic soils develop in sedimentary environments due to the action of sulfate reducing bacteria (Postgate, 1959; Peck, 1962; Postgate, 1965). Once formed the metal sulfides undergo transformations to form more stable sulfides (Rickard, 1973). Sedimentary metal sulfide ore bodies are the result of these past processes. 2.3 Weathering Products in Sulfidic Soils 2.3.1 Aluminosilicate Weathering Products The weathering of aluminosilicates present in sulfidic soils init ial ly involves alterations. As the pH is lowered, incongruent and ultimately congruent dissolution also occurs. Lynn and Whittig (1966) reported that mica, montmorillonite, vermicu-l i te , chlorite and interstratified chlorite-vermiculite are present in reduced sediments and recently oxidized ones in California. However, in sediments oxidized 60 years, they found all crystalline minerals showed 6 deterioration and diffuse x-ray diffraction patterns. The authors reported that as weathering proceeded, chlorite disappeared and suggested that it was altered to montmorillonite. These transformations appear typical and are in agreement with the alteration sequence of Jackson (1968). During incipient oxidation and acid formation, sulfidic soils are buffered by bases on the exchange sites and basic carbonates such as calcite (Bloomfield and Coulter, 1973). These bases have a high buffering intensity and tend to maintain the soil pH at near neutrality. Van Breemen (1973a) has singled out bases, particularly calcite, as having a high buffer capacity. Soils high in these bases can maintain high pH values even under rapid rates of acid formation until the bases are depleted. According to Coleman and Craig (1961), once the buffering capacity by basic cations is exhausted, the exchange sites on the clay minerals becomes hydrogen saturated. The authors indicated that H-clays are not stable but spontaneously decompose to a condition of largely Al-saturation. They found the rate of change to Al-saturated clays was doubled for a 10°C rise in temperature. This clay decomposition has been termed incon-gruent dissolution when the products are H^ S^ O^  or amorphous SiC^ and Al-silicate residues. Congruent weathering occurs upon complete dissolution to H4SiO^ or amorphous Si0 2 and Al . The incongruent dissolution of clay minerals tends to buffer the soil pH provided the rate of acid production does not exceed the rate of neutralization. In cases where there is rapid oxidation and high rates of s i l ica release, a much lower pH than 3.5-4.5 is reached i f the solution becomes 7 saturated with soluble si l ica (H^SiO^). Van Breemen (1973a) reported that the buffering intensity of Mg-ehlorite and montmorillonite plus amorphous SiC^ is moderately high but is very low for Mg-montmorillonite in the absence of amorphous SiC^. Congruent dissociation occurs primarily in the pH range of 4.0 to 3.5 (van Breemen, 1973a). Monomeric si l ica is released as amorphous Si0g or H^SiO^ which will precipitate as amorphous Si0g at H^SiO^ activities of -2 7 10 * . Theoretically, van Breemen (1973a) c.f. Bloomfield and Coulter (1973) has;; reported that green iron silicate minerals such as glauconite can be formed but are broken down under very acid conditions. Amorphous Si0g is the dominant form of si l ica in acid sulfidic soils. The Al is init ial ly present as amorphous Al hydroxide (Singh and Brydon, 1969). Van Beers (1962) has reported large amounts of white Al hydroxide in sulfidic soils. Normally these amorphous Al hydroxides would slowly crystallize to form gibbsite i f the solution were saturated with +3 respect to Al (Frink, 1973). However, Segalen (1971) has reported that gibbsite is low in Si rich soils such as acid sulfidic ones. The presence of anions also slows down the rate of Al hydroxide crystallization, and forms such as pseudo-boehmite can appear (Segalen, 1971). He also indicated that Al-hydroxides can only persist in soils i f the pH is higher than 4.2. In the presence of an excess of sulfate, Al hydroxides are converted to Al hydroxyl sulfates. At a high pH, in Ca-saturated solutions, hydroxides react with sulfate to form amorphous basic Al hydroxyl sulfates with the chemical composition of basaluminite (AI^(OH )^QSO^) according to Adams and Rawajfih (1977). Singh and Brydon (1969) found that Al-hydroxide forms 8 crystalline basaluminite at 50°C, in the absence of clays. Theoretically, _p basaluminite and gibbsite, i f present, cannot persist at (log(S0^ ) - 2 _p pH) values above -11. Generally (SO^ ) in acid sulfidic soils is fairly _3 constant at 5 x 10 , which corresponds approximately to a pH of 4.5 (van Breemen, 1973a). At pH values less than 4.5 the major Al hydroxyl sulfates have been postulated to be alunite and amorphous A10HS04. Alunite (KA13(S04)2(0H)g) +3 +3 forms as a result of the substitution of Al for Fe in jarosite (Brophy et aj_., 1962). Alunite formation is favored in high K or Na environments at 50°C (Adams and Rawajfih, (1977). Herbillion et _J_. (1966) c.f. Bloomfield and Coulter (1973), reported alunite on the surface of acid sulfate soils in Vietnam. Van Breemen (1973b) considered amorphous AlOHSO^ to be the most soluble form of Al at low pH values, based on analytical data on water samples from sulfidic soils. More recently, Adams and Rawajfih (1977) recalculated the solubility of alunite and basaluminite and concluded that they control the solubility of Al in acid soils. Van Breemen (1973a) found Na-alum (NaAl(S04)2.12H20) and tamurgite (NaAl(S04)2.6H20) in surface crusts from Thailand, but did not report on their stability in very acid soils. Pickeringite (MgAl2(S04)4.22H20) has been found surrounding fumarolic activity on lake shores in Guatemala (Ljunggren, 1960). Undoubtedly other soluble minerals will be found in more intensive studies on salt crusts , however, their presence would be transitory and localized. 2.3.2 Iron Sulfide Weathering Products In reduced sediments, iron is the principal form of sulfides although 9 other metal sulfides may occur in abundance locally (Hawley, 1972). The major iron sulfide minerals are pyrite, pyrrhotite, marcasite, mackinawite and greigite. Berner (1967) found that mackinawite and greigite are unstable at standard temperature and pressure, relative to pyrite and pyrrhotite. Marcasite, which forms in reducing conditions at pH values lower than 3.5, may be present in some sulfidic soils (Rickard, 1969). Potentially acid sulfidic soils normally contain from 1-4% pyrite sulfur (Bloomfield, 1972). Pyrrhotite commonly amounts to less than 0.01% sulfur (Bloomfield, 1973). However, in exposed ore bodies or in mine spoils, iron sulfides can be the principal mineral prior to weathering. Upon exposure to oxidizing conditions, the iron sulfides are init ial ly oxidized to fe oxide and elemental sulfur (Sato, 1960; Hart, 1962; Silverman, 1967; and Sorokin, 1970). The most common Fe oxide compounds in soils are amorphous Ee oxyhy-droxide (Fe(0H)3.nH20), lepidocrocite (YFe00H), gpethite (aFeOOH), and hematite ( F e ^ ) (Oades, 1963; Ponnamperuma et_ aj_., 1967). Under acid conditions the forms (Fe(H20)50H)+ 2 and (Fe(H 20) 4(0H) 2)+ have been reported (c.f. Ponnamperuma et al_., 1967). At pH values above 3, amorphous pe oxyhydroxide is the initial product of iron sulfide oxidation (Lees et a l . , 1969). It can be converted to lepidocrocite in the pH range of 5-9.5 and limonitic (poorly crystalline) goethite, goethite and hematite at a pH less than 5 (c.f. van Breemen, 1973a). +3 Below a pH of 3-4,the Fe and sulfate that is produced from elemen-tal sulfur can be incorporated into jarosite (KFe-^SO^^OH^). In very acid soils (pH < 3.7) jarosite is more stable than limonitic goethite (van Breemen, 1973a). However, he emphasized that limonitic goethite is 10 unstable in relation to goethite o r hematite. If either of these two F'e oxides are present, the jarosite stability field is shifted to pH values less than 0.6, provided the log(S04 ) activity does not exceed -2.3. It must be recognized that this is a theoretical thermodynamic relationship. The crystallization of goethite and hematite has been found to be inhibited by organic matter and adsorbed anions (Schwertmann, 1966). Thus the presence of sulfate should significantly retard the rate of Fe oxyhydroxide crystallization. This mechanism would favor the formation of jarosite under conditions where the oxidation of reduced sulfur com-pounds to sulfate is rapid. Under conditions of low levels of Ca or high levels of K at pH values less than 4 jarosite even forms at the expense of limonitic goethite. This occurs through a reaction between limonitic goethite and gypsum (van Breemen, 1973a). Often x-ray diffraction patterns ascribed to jarosite have been detected in sulfidic soils (Clark et a l . , 1961; Bloomfield, 1972; Duncan and Walden, 1972; Buurman and van Breemen, 1973a; Ivarson, 1973). It appears to be a major constituent in all sulfidic soils with pH values less than 4. According to Bloomfield and Coulter (1973), jarosite has been detected in soils with a pH above 4. They attributed this to the slow hydrolysis of jarosite. Several workers have shown that jarosite is not the only insoluble sulfate mineral in acid sulfidic soils. Brophy and Sheridan (1965) found that the major iron sulfate minerals under acid conditions were jarosite (KFe 3(S0 4) 2(0H) 6), natrojarosite (NaFe3(S04)2(0H)g) and hydronium jarosite (H 30Fe 3(S0 4) 2(0H) 6). They found that jarosite is strongly preferred over the other two species at equilibrium, assuming potassium is present. They found that natrojarosite is favored over the hydronium form of jarosite. 11 Even though jarosite is favored over other iron sulfates at standard temperature and pressure, there are conditions under which the other forms can dominate. In the absence of available K, natrojarosite and some hydronium jarosite are formed. At elevated temperatures and/or low pH values, the stability of hydronium jarosite increases (Brown, 1964). +3 Under special conditions Al has been shown to substitute for Fe in jarosite to a small degree to form alunite (KAl^SO^fOHjg). The degree of substitution increases with increasing temperatures and reduced acidity (Brophy et al_., 1962). Thus alunite formation is favored in alkali rich sulfidic materials at elevated temperatures. 2.4 Iron Oxidation in Sulfidic Soils 2.4.1 Physical and Chemical Factors 2.4.1.1 Effects of surface area and crystallinity on iron sulfide reactivity The potential for iron sulfides to be oxidized, by chemical and/or biochemical pathways, is primarily dependent on their particle size and crystallinity. Quispel et al_. (1952); Temple and Dechamps (1953); Hart (1963) have demonstrated that decreasing the particle size increases the rate of iron sulfide oxidation. Caruccio (1973, 1975) has used this grain size criteria to estimate the acid potential of pyritic coal mine refuse. Pyrite reac-tivity has been split into four particle size classes with framboidal pyrite - in the form of ordered microcrystals - being the most reactive 12 (Ruckard, 1973). The decrease in stability and lattice defects associated with high surface area may also contribute to the high rate of acid formation (van Breemen, 1973). Decreasing crystallinity from pyrite to pyrrhotite is associated with an increased reactivity (Sato, 1960 and Hawley, 1972). The high oxidation potential of pyrite and the correspondingly low one of pyrrhotite correlate well with their differences in crystallinity (Sato, 1960). Leathen et al_. (1953) and Silverman et al_. (1961) have indicated that highly crystalline "museum grade" pyrite specimens are less susceptible to oxidation than other pyrite specimens. Silverman and Ehrlich (1964) attributed these differences in pyrite oxidation to the degree of ordering of the crystal lattices and/or the amount of impurities incorporated1 in the crystal. 2.4.1.2 Mechanisms and kinetics of iron oxidation from iron sulfides Quispel e_t al_. (1952) were among the first to propose mechanisms of +2 iron sulfide oxidation. They assumed that Fe ions on the crystal are oxidized to Fe 20 3 leaving sulfur on the surface. Sato (1960) postulated that the metal atoms move into the surrounding solution to become aqueous cations, accompanied by a stepwise decrease in the metal to sulfur ratio of the solid crystal. Singer and Stumm (1970) considered that the release +2 of Fe was the initiator reaction of iron sulfide oxidation. In their +2 model, the free Fe is oxidized by dissolved 0^  in accordance to the equation: 4 Fe + 2 + 0 2 + 4 H+ > 4Fe + 3 + 2 H20 (1) 13 +2 They concluded that the rate of oxidation of Fe is the overall rate determining reaction since i t is significantly slower than the +2 release of Fe into solution. +2 The oxidation of Fe can be broken down into mainly chemically or biochemically catalyzed reactions. At pH values above 3.5, chemical mechanisms are significant and below that pH biochemical mechanisms predominate. +2 Stumm and Lee (1961) studied the rate of Fe oxidation at pH values above 6. They found the reaction fits the instantaneous rate expression: +2 ~d {H ) = k (Fe+ 2)(0H")2 P 0 2 (2) where k = 1.4 x 10 1 4 l i t e r 2 mole"2 atm - 1 min - 1 at 25°C. Singer and Stumm (1970) extended this relationship to pH values between 4.5 and 6 but used 13 2 2 1 1 o an equilibrium constant (k) of 8 x 10 l i ter mole" atm" min" at 25 C. +2 This relationship indicates that the rate of Fe oxidation is highly pH dependent, proceeding 100 times faster at pH 7 than at pH 6. +3 +3 The Fe produced in the reaction tends to form amorphous Fe hydrox-+3 ide. The amount of Fe in solution can be described, using the stability data of Si 11 en and Martell (1964) as: logFe + 3 = 4.2 - 3pH (3) +3 at an ionic strength of 0.1. The stability of amorphous Fe hydroxide +3 over Fe , in slightly acid to basic solutions, indicates that the presence +3 of Fe ultimately leads to acid production in accordance to the equation: 14 4Fe + 3 + 12H20 » 4 F e ( 0 H ) 3 ( s ) + 1 2 H + +3 +3 i f a source of Fe is available. However, in the absence of Fe , the chemical oxidation of pyrite is very slow (Temple and Delchamps, 1953; +2 Singer and Stumm, 1970). Overall the oxidation of Fe can be represented by the equation: 4Fe + 2 + Q 2 + 14H20 > 4Fe(0H)3 + 8H+ (5) (Singer and Stumm, 1970). This stoichiometry indicates that two equivalents +2 of acidity are produced from the oxidation of Fe under these slightly acid to basic conditions. As acidity is produced, the rate of chemical +2 Fe oxidation is decreased markedly, following the rate expressions of Stumm and Lee (1961) and Singer and Stumm (1970). +2 In the kinetics of Fe oxidation from iron sulfides, a transition +2 occurs between pH 4.5 and 3.5. . Below pH 3.5 the rate of Fe oxidation is independent of the pH and fits the relationship: = ^ ^ 1 = k" (Fe + 2)(0 2) (6) where k" = 1 x 10"7 atm"1 min"1 at 25°C (Singer and Stumm, 1970). At these +2 low pH values the rate of Fe oxidation by chemical mechanisms is very -4 +2 slow. They found that only 5% of a 9 x 10 M Fe solution was oxidized in 150 days. +3 At pH values below 3.5 the Fe produced is precipitated primarily +3 as jarosite. Thus the Fe concentration in solution is controlled by the 15 hydrolysis of jarosite: KFe 3(S0 4) 2(0H) 6 + 6H+ > K+ + 3Fe + 3 + 2S0~2 + 6H20 (7) At sulfate and potassium activities of -2.3 and -3.3, respectively, +3 the activity of Fe is a function of the pH: log(Fe+ 3) = -1.53 - 2pH (8) +3 (van Breemen, 1973a). According to this relationship, the amount of Fe in solution increases as the pH decreases. Garrels and Thompson (1960) +3 stated that the pyrite surface is saturated when the Fe concentration -4 +3 reaches 10 M. It can be postulated that at low pH values the Fe +2 adsorbed on the iron sulfides contributes to the reduced rate of Fe release in acid solutions. +2 The catalysis of Fe oxidation has been extensively studied by Singer and Stumm (1968, 1970). They were able to show that alumina, colloidal si l ica and montmori11onite significantly increased the reaction rate. In the case of alumina the rate was increased 10-30 times. The +2 Fe oxidation catalysis was slightly less for montmori 11 omte and +2 colloidal s i l ica. Light slightly increased the rate of Fe oxidation (2-3 times). Charcoal also showed a slight catalytic effect but kaolinite had no effect at al 1. +2 The inhibition of Fe oxidation by the formation of coating on the iron sulfide surface has been postulated by several workers. Van Breemen (1973a) mentioned the possibility .that Fe oxide (amorphous) coatings may help slow down the oxidation of pyrite. Quispel et_ al_. (1952) and Harmsen 16 +3 et_ a_T_. (1954) felt that Fe , in the presence of high levels of phos-phate, is precipitated as Fe phosphate. They attributed the reduction in pyrite oxidation to this precipitation reaction. Adsorption of +3 these Fe compounds to the iron sulfide surface may be due to a high sulfide surface charge. The alumina, colloidal sil ica and montmorillonite found to catalyze +2 the oxidation of Fe , also have surface charge. Perhaps the presence of these and other minerals with surface charges compete with the iron +3 sulfides as surfaces for precipitating Fe compounds. Such an action would keep the iron sulfide surface "clean" and result in an enhanced +2 rate of Fe oxidation. +2 This catalysis of Fe oxidation from pyrite, through the presence of an alternative surface, may also occur with organic matter, root surfaces and bacteria due to their surface charge. The precipitation of Fe is particularly apparent with bacteria. Macrae and Edwards (1972) found +3 that all bacteria tested could precipitate Fe from a Fe sol. Aristovskaya and Zavarzin (1975) even attributed the concentration of Fe in concretions to the microbial precipitation of Fe by specific groups of microorganisms. +2 The enhancement of Fe oxidation has also been attributed to micro-+2 bial oxidation. Singer and Stumm (1968, 1970) have shown that Fe oxidation in acid solutions is increased by a factor of 10 due to the action of X- ferrooxidans. Other workers have demonstrated this microbial +2 Fe oxidation by other groups of bacteria in soils at near neutral pH values. 17 2.4.2 Microbial Iron Oxidation 2.4.2.1 Iron oxidizing bacteria and their succession +2 Thus far, four types of Fe oxidizing bacteria have been isolated from sulfidic soils. These types include the species Thiobacillus  ferrooxidans and Gallionella ferruginea and members of the genera Metalloqeniurn and Sphaerotilus. T. ferrooxidans was first isolated by Colmer et_ al_. (1950) and des-cribed by Temple and Colmer (1951). A similar autotroph was later isolated by Leathen ejt al_. (1951) and named Ferrobacillus ferrooxidans by Leathen and Braley (1954). Kinsel (1960) proposed the name F_. sulfooxidans for +2 the Fe oxidizing isolate she obtained. Unz and Lundgren (1961) showed that X- ferrooxidans and F\ ferrooxidans are nutritionally similar and might be lumped together as one species. Hutchinson et a_U (1969) and Kelly and Tuovinen (1972) have concluded that all three isolates should be considered as the species T. ferrooxidans. Iron bacteria of the genus Gal 1ionella have been isolated and charac-terized by several authors (Vatter and Wolfe, 1956; Kucera and Wolfe, 1957; Nunley and Krieg, 1967). Of the species in this genus, only G, ferruginea has been isolated from sulfidic soils (Walsh and Mitchell, 1969). Its pH optimum for growth is considered to be between pH 6.3 and 6.6. However, its microaerophilic growth habit (Nunley and Krieg, 1967) and its growth optimum at near neutral pH limit', its contribution to +2 microbial Fe oxidation in sulfidic soils. A member of the genus Metallogeniurn has been isolated from several mine drainages in the eastern U.S. (Walsh and Mitchell, 1972a). They found it to have a pH tolerance of 3.5-6.8 and a growth optimum at pH 4.1. It 18 was proposed that this species was responsible for lowering the pH values in sulfidic materials to those where T. ferrooxidans could initiate its +2 Fe oxidation. However, the presence of this species in sulfidic +2 soils and its role in the oxidation of Fe has not been confirmed by other authors. Filaments comprised of colloidal FeCOH)^  aggregates which resemble Metallogenium have been observed in field drains by Ivarson +2 and Sojak (1978). Thus reports of its presence and Fe oxidizing ability must be accepted cautiously. Members of the genus Sphaerotilus have been isolated in environments +2 where Fe oxidation occurs, such as ti le drains (Spencer e_t al_., 1963; Ivarson and Sojak, 1978). The former authors identified them as members of the Leptothrix, Crenothrix and Cladothrix genera. These genera have been considered to be identical to Sphaerotilus by Romano (1973). However, more recently Sphaerotilus and Leptothrix have been considered to be separate genera (D. Duncan, personal communication). Sphaerotilus is composed of two species: Sphaerotilus natans and Sphaerotilus discophorus enclosed together in a sheath. Sphaerotilus natans (and undoubtedly Sphaerotilus discophorus) grows well in media low in organic matter and oxygen at neutral pH values (Stokes, 1954). Rogers and Anderson (1976a, 1976b) have shown that an organic component on the Sphaerotilus sheath is responsible for Fe deposition. This finding indicates that reports of +2 +3 Fe oxidation by this species may only be Fe deposition. +3 +2 The confusion of Fe deposition with Fe oxidation in Sphaerotilus may apply to the genera Metallogenium (Zavarzin and Hirsch, 1974). This theory is appealing, since the pH at which these bacteria are reported to +2 +2 oxidize Fe is also the pH where chemical Fe oxidation is rapid. The 19 Fe solubility of only a few mg/1 in most environments (Morgan and +2 Stumm, 1965) and the large amounts of Fe (^ 670 g) required to fix Ig of microbial cell carbon by autotrophic iron bacteria (Peterson, 1966) appear to limit biological Fe oxidation at near neutral to neutral pH values. Further studies must be conducted in order to determine the +2 role of the above three genera in Fe oxidation. 2.4.2.2 Factors controlling the rate of iron oxidation by Thiobacillus  ferrooxidans +2 The rate of Fe oxidation by T. ferrooxidans has been shown to be affected by pH, temperature, water potential, cations, anions, and organic compounds. +2 Landesman et_ al_. (1966a) studied the rate of Fe oxidation manometri-cally over the pH and the temperature ranges of 1-4 and 25-50°C respec-+2 tively. They found the maximum rate of respiration, equivalent to Fe oxidation, at a pH of 1.75 and a temperature of 40°C. For all temperatures between 25 and 40°C they found that respiration was unchanged between pH 4 and 3 and rose to a maximum at pH 1.75. Below pH 3 the respiration rate decreased until a pH of 1.25 was reached, then dropped rapidly and became negligible below 1. Schnaitman et aj_. (1969) measured the rate +2 of Fe oxidation colorimetrically over the pH range of 1.5 to 4.8, at a temperature of 35°C. They found the pH optimum was broad, ranging from 2.5 to 3.8. Using the above colorimetric procedure, Tuttle and +2 Dugan (1976) found that Fe oxidation was most rapid between pH 2,7 and 3.0 at a temperature between 35 and 40°C. +2 T. ferrooxidans would not grow or oxidize Fe beyond a water potential 20 somewhere between -18 and -32 bars (Brock, 1975). It is conceivable that the oxidation products could accumulate, increasing the osmotic potential, and further inhibit oxidation, particularly i f the matric potential is high. Alternatively, in water-logged soils, redox potentials may be too low to permit growth by aerobic bacteria such as T. ferrooxidans (Aristovskaya and Zavarzin, 1975). Cations have been shown to inhibit T. ferrooxidans only i f they are in high concentrations (c.f. Tuovinen and Kelly, 1974). In further studies Tuovinen and Kelly (1974a) found that uranium, Ni, Cu, Co and Zn sulfates were inhibitory in the concentration range of 0.1-1M. They found that Ni and particularly uranium were more inhibitory to T. ferrooxidans than the other three metals. However, T. ferrooxidans has been effective in the leaching of all these metals (Harrison e_t a__., 1966; Moshnyakova e_t al_., 1971; Torma et al_., 1972). Rittenburg (1969) summarized in a review, the evidence that not all organic compounds inhibit chemolithotrophs. Of the organic compounds found to be inhibitory to T. ferrooxidans, Lundgren et al_. (1964) reported that formate, lactate, oxaloacetate, succinate and pyruvate inhibited iron oxidation the most. Tuttle and Dugan (1976) screened 24 organic +2 compounds for their ability to inhibit Fe oxidation and found that a-keto acids were more inhibitory than their amino acid or hydroxyl acid analogs. Furthermore, the inhibition was strongest at pH values below the ionization constant of the organic acid. It was concluded that the relative electronegativity of the organic molecule was a major factor in the inhibition of iron oxidation. Tuttle and Dugan (1976) suggested +2 that this inhibition may be due to: (1) inhibition of the Fe oxidation 21 enzyme system, (2) chelation with Fe outside the ce l l , (3) disruption of the cell envelope, (4) interference with the roles of phosphate and +2 sulfate in Fe oxidation. Schnaitman and Lundgren (1965) showed that pyruvic acid is excreted by T. ferrooxidans. Their finding substantiates the view that cultures of T. ferrooxidans are inhibited by their waste organic materials. Kelly (1971) proposed that the sensitivity to organic inhibitors is most pronounced in the exponential phase of growth. +2 The inhibition of Fe oxidation by T. ferrooxidans has been inves-tigated for several inorganic anions. Lazaroff (1975) found that when the anions chloride, bromide, nitrate, tetraborate, chlorite, arsenite, phosphate, molybdate, chromate, tungstate, vanadate and tellurate were +2 added separately, no Fe oxidation took place. However, the anions +2 arsenite, phosphate, tungstate and tellurate stimulated Fe oxidation in the presence of selenate and sulfate. This work confirmed and expanded +2 the findings that Fe oxidation required the presence of sulfate (Lazaroff, 1963; Lees et al_., 1968; and Schnaitman et al_., 1969). Separately, chloride, nitrate, phosphate and molybdate have been +2 found to inhibit Fe oxidation in the presence of sulfate. In the presence of ferrous sulfate, chloride and nitrate were toxic at concen-trations of 0.14M (Razzell and Trussell, 1963). Phosphate has been shown +2 to inhibit Fe oxidation in work by Silverman and Lundgren (1959b). Tuttle and Dugan (1976) showed that phosphate concentrations of 0.1M +2 but not 0.01M strongly inhibited Fe oxidation. Molybdate has been found +2 to strongly inhibit Fe oxidation by T. ferrooxidans, even at a concen-tration of 2.5 x 10"3M (Schnaitman et al_., 1969). Certain organic compounds, notably those with surface active 22 capacities, have been shown to stimulate Fe oxidation by T. ferrooxidans. Duncan et al_. (1964) found that in the presence of organic surfactants, the lag in leaching by chalcopyrite by T. ferrooxidans was reduced. However, the presence of excreted surfactants such as phospholipids +2 was not detected in the growth medium of T. ferrooxidans during Fe oxidation (Schnaitman and Lundgren, 1964). These phospholipids were found associated with the semipermeable membrane and found to transport +2 Fe through it (Agate and Vishniac, 1970). The requirement for phosphate, +2 in the phospholipids responsible for Fe transport through cell membranes, +2 may explain the increase in Fe oxidation in phosphate depleted or aged cells supplemented with phosphate (Beck and Shafia, 1964). 2.5 Sulfur Oxidation in Sulfidic Soils 2.5.1 Chemical Oxidation of Inorganic Sulfur Compounds 2.5.1.1 The role of ferric iron in the oxidation of sulfides Numerous workers have shown that sulfide oxidation can take place +3 +3 using Fe as the oxidizing agent. The role of Fe in sulfide oxidation increases as the pH decreases according to equation (8) until the concen-+3 -4 tration of Fe in solution reaches TO : The oxidation product of Cu, Zn, Pb and Ag-sulfides is elemental sulfur (Sato, 1960). Sorokin (1970) found that iron monusulfide oxidation also yielded elemental sulfur. This product has been reported from the oxidation of iron disulfides by +3 +3 Fe . However, some workers have concluded that Fe can oxidize elemental sulfur to sulfate. Initially Stokes (1901) described the steps of pyrite and marcasite 23 +3 oxidation by Fe as fitting the equations: FeS2 + Fe 2(S0 4) 3 >3FeS04 + 2S (9) 2S + 6Fe 2(S0 4) 3 + 8H20 >12FeS04 + 8H2S04 (10) FeS2 + 7Fe 2(S0 4) 3 + 8H20 M5FeS0 4 + 8H2S04 (11) +3 Stokes' (1901) theory that Fe could oxidize elemental sulfur from disulfides was substantiated by Sato (1960). He concluded that the sulfur released, due to sulfide oxidation, was in the unstable diatomic form which would instantly oxidize in the presence of oxidizing agents. Garrels and Thompson (1960) concluded that sulfate is the end product of pyrite +3 oxidation by Fe in accordance to the equation: 8H20 + FeS2 + 14Fe+3 > 15Fe+2 + 2S0~2 + 16H+ (12) However, at near equilibrium, they concluded that the oxidation of pyrite +3 by Fe would yield colloidal (diatomic) sulfur according to the equation: FeS2 >Fe + 2 + 2S° + 2e" (13) +3 They postulated that any excess Fe would oxidize this sulfur through intermediate species to sulfate. Garrels and Thompson (1960) qualified this theory by admitting that intermediate sulfur products could be stable over a limited Eh range. Silverman (1967) added confusion to the literature by deducing that +3 soluble iron recovery in pyrite oxidation by Fe was in agreement with 24 equation (9) of Stokes (1901). However, his attempts to extract the elemental sulfur with CCl^ yielded much lower quantities than expected. Silverman (1967) concluded that either the elemental sulfur was inex-tractable or in a form other than the stable eight-membered ring and oxidized rapidly to sulfate in accordance with equations 10 and 12. According to Donohue and Meyer (1965) there are 16 known allotropes of elemental sulfur, two of which are insoluble in organic solvents. The presence of insoluble forms could account for the low yield of elemental sulfur found by Silverman (1967). Recently, Zinder and Brock (c.f. Brock and Gustafson, 1976) tested +3 the ability of Fe to oxidize colloidal sulfur. Presumably they used the same form of colloidal sulfur as found by Garrels and Thompson (1960). Zinder and Brock (c.f. Brock and Gustafson, 1976) found that both crystalline and colloidal sulfur are relatively stable to oxidation by +3 Fe at low pH. However, they detected a very slow oxidation of sulfur to sulfate by Fe + 3 at 70°C. It is reasonable to conclude that, unless researchers find that +3 sulfate is produced, the product of Fe oxidation of sulfides from iron disulfides is a form of elemental sulfur. The evidence of Silverman (1967) indicates that amorphous sulfur is the initial form produced. 2.5.1.2 Mechanisms and products of sulfide oxidation by oxygen In the absence of sulfur oxidizing bacteria or appreciable quantities +3 of Fe , the oxidation of sulfides is carried out by molecular oxygen. +3 3 In an iron.sulfide.system, the Fe activity decreases by a factor of 10 per pH unit increase above pH 3.7 (equation 3). Accordingly, sulfide 25 oxidation by oxygen is important above pH 6, but insignificant below this pH (Chen and Morris, 1972), The intermediates of the sulfide-oxygen reaction depend on the concentration of reactants, the pH and presence of other substances (Chen and Morris, 1972). At a low sulfide-to-oxygen ratio, the direct oxidation to thiosulfate and the polythionates is favored: 2H2S + 202 — >H20 + S20~3Z + 2H+ (14) At pH values above 8.5, the initial formation of thiosulfate is favored regardless of the sulfide-to-oxygen ratio (Chen and Morris, 1972; Cline and Richards, 1969). At high sulfide-to-oxygen ratios below pH 8.5, the formation of elemental sulfur occurs according to the equation: 2HS" + 0 2 + 2H+ > 2H20 + 2S° (15) (Roy and Trudinger, 1970; Chen and Morris, 1972). However, increasing the pH decreases the amount of elemental sulfur produced until it becomes insignificant at about pH 8. The reaction of sulfide with sulfur begins at around pH 6 and in-creases through pH 7, reaching a maximum at pH 8 (Chen and Morris, 1972). The products of the sulfide-sulfur reaction are polysulfides of S 2 to Sg chain length. Their formation has an autocatalytic effect on the rate of sulfur dissolution: H2S + S > H 2S 2 (16) H 2S 2 + S >H 2S 3 (17) H 2S 3 + S > H 2S 4 (18) H 2S 4 + S (19) Polysulfides of and Sg chain length are the dominant species formed. The polysulfides of a chain length greater than and the and species are either unstable or in such low concentrations that they are undetectable (Chen and Morris, 1972). The rate of sulfur dissolution is dependent on the mass transfer of the reactants and the product, the active surface of the sulfur and the rate of the chemical reaction. Hartler et al_. (1967) suggested that the mass transfer steps are limiting once polysulfides are formed. The maximum observed formation of polysulfides at around pH 7 _2 coincides with the maximum for the oxidation of a 10 M sulfide solution. Bowers e_t al_. (1966) proposed that this maximum for oxygen uptake, by relatively concentrated sulfide solutions at pH 7, is due to a more rapid reaction of oxygen with polysulfides than monosulfides. According to this mechanism, the oxidation of sulfide to thiosulfate appears to be catalyzed by the formation of polysulfides. In addition to the oxygen diffusion rate, the products of thiosulfate oxidation are dependent on the concentration of thiosulfate, pH and the presence of other substances. It is generally agreed that thiosulfate is stable at pH 7 but unstable at acid pH values. Some dissolution of thiosulfate occurs at a pH value as high as 6 (Chen and Morris, 1972). Davis (1958) found the decomposition of thiosulfate in dilute acid yields mainly elemental sulfur and bisulfite according to the equation: H + + Sz0~32 >SQ (colloidal) + HS0~ (20) 27 The rate of elemental sulfur formation follows the rate expression: = k (Na 2 S 2 0 3 ) 3 / 2 (HCI)15 (21) -3 -2 in solutions that are 10 M in S 20 3 and HC1. However, unless further reactions occur with either product, the complete decomposition of thiosulfate does not occur until the pH reaches approximately 3.6 (Sinha and Walden, 1966; Tuovinen and Kelly, 1974). Johnston and McAmish (1973) also found that the acidification of a relatively concentrated thiosul-fate solution rapidly yields mostly elemental sulfur and bisulfite. They found the thiosulfate reaction kinetics could f i t the equation: H S 2 ° 3 + S 2 ° 3 2 ~~~ > H S 0 3 + S 0 3 2 + S2 ^ 2 2 ^ for thiosulfate concentrations as high as 10 M. The rate expression for the formation was found to be: = k (H +)(S 20 3 2)^ (23) The rate expressions of Johnston and McAmish (1973) and Davis (1958) are essentially the same. However, the mechanisms of elemental sulfur for-mation differ. Davis (1958) proposed that the initial product of the bimolecular-thiosulfate reaction was HS303 according to the equation: HS203 + S 2 0 3 2 —> HS303 + S0 3" 2 (24) This product reacts with thiosulfate to yield H S ^ , A succession of 28 these condensation reactions occurs until HSgO^  is formed and decomposes to yield elemental sulfur: H S 9 ° 3 ~ > S 8 + H S 0 3 ^ 2 5 ^ Johnston and McAmish (1973) failed to propose a plausible mechanism for the formation of Sg. Davis (1958) also studied in detail the init ial reaction products and detected some hexatomic sulfur Sg and polythionates. He found that the hexatomic sulfur was unstable relative to the Sg colloidal suifur and decomposed readily. The colloidal sulfur slowly converts to the stable orthorhombic form at normal temperatures and pressures unless other reactions take place (Davis, 1958; Meyer, 1964). Davis (1964) outlined in a review, the major elemental sulfur decom--2 -position reactions. The anions SO^  , HS and CN all open the Sg ring according to the equations: Sg + SH" > "SgH (26) Sg + 2S0~ >S7°~3 + S 2 ° 3 ~ 2 ( 2 7) Sg + 2CN" >SyCN" + SCN" (28) These thiophilic reagents continue to degrade the remaining sulfur chain one atom at a time. Foss (1950) considered that these reactions occur even with the lower polythionates. The reaction of sulfite with elemental sulfur can conceivably account for part of the small quantities of poly-thionates produced in acidified thiosulfate solutions (Johnston and McAmish, 1973; Davis, 1958). 29 Another pathway of polythionate formation has been postulated by Pollard et al. (1964). They found that thiosulfate in 1M HC1 yielded -2 -2 -2 trithionate init ial ly with the later formation of S^ Og , SgOg and SgOg . The hexathionate was the ultimate predominant condensation product of the overall reaction sequence over the course of the experiment. The condensation reactions can be summarized as: H + + S 2 ° 3 _ 2 + S x ° 6 " 2 * x + l ° 6 _ 2 + H S 0 3 ( 2 9 ) However, as long as thiosulfate is present, only trithionate and tetra-thionate are stable (Pollard et aj_., 1964). The main difference between the study of Pollard et al. (1964) and the studies of Davis (1958) and Johnston and McAmish (1973) was the use of extremely acid (1-8M) HC1 solutions by the former workers. Highly con-centrated acids in contact with thiosulfate form the somewhat stable thio-sulfuric acid, delaying further condensation reactions (c.f. Davis, 1958). This product accounts for the very slow thiosulfate reaction rates encountered by Pollard et al. (1964). The slow reaction rate of thiosulfate in such highly acid solutions allows the oxygen diffusion rate to approach that of the thiosulfate condensation reaction. This results in the preferential production of polythionates over elemental sulfur. However, the formation of these polythionates substantiates the thiosulfate condensation sequence of Davis (1958) over the reaction of Johnston and McAmish (1973). It is accepted that the higher polythionates are stable in acid solution in the absence of sulfite (Pollard et_ al. , 1964). Postgate (1963) pointed out that sulfite readily auto-oxidizes to sulfate in air. Roy and 30 Trudinger (.1970) found that sulfite oxidation is catalyzed by the 2 "f°°2 2 "^*2 *^*2 j o presence of Cu , Zn , Co , Ni , Mn , Fe and Fe . Thus, higher polythionate formation is favored in aerobic conditions in the presence of soluble cations. This persistence of higher polythionates is limited to acid solutions since the presence of hydroxyl ions causes their decom-position: c Q QU—^  s 0 + S (30) V 6 * x-lU6 0^ (c.f. Roy and Trudinger, 1970), This mechanism may also account for the disappearance of trithionate and tetrathionate as the pH approaches 7 (Sinha and Walden, 1966). 2.5.2 Microbial Oxidation of Inorganic Sulfur Compounds 2.5.2.1 Classification and succession of sulfur oxidizing bacteria In environments where reduced sulfur compounds are significant, members of the phototrophic bacteria and/or the colorless sulfur bacteria predominate. The phototrophic sulfur bacteria are found in anaerobic aquatic environments (Pfennig, 1975),and are normally absent in soil systems. Of the colorless sulfur bacteria, most species are specific to limited oxygen and sulfide gradients (Kuenen, 1975). The members of the colorless sulfur bacteria have been shown to be the most widespread of the sulfur oxidizing bacteria in sulfidic materials such as sulfur deposits, sulfide ores, and sulfidic muds (Harmsen e_t aj_., 1954; Hart, 1959; Bloomfield, 1972). According to Vishniac (1974) there are eight species of thiobacilli: 31 T. perometabolis, T. thioparus, T. neapolitanus, T. novel 1 us, T. intermedius, T. denitrificans, T. thiooxidans and T. ferrooxidans. Recently two new species - X - rubellus and X - delicatus - have been described by Mizoguchi et_ aX- (1976). In addition, an unnamed salt water thiobacill i , which appears to be a unique species according to the diagnostic scheme of Hutchinson et_ aj_. (1969), has been discovered by Murphy et aj_. (1972). It remains to be seen i f these latter three species will be accepted. In the past, many of the species described, i .e . X - coproliticus and X - trautweinii, have been lumped into existing species or excluded from the group (Vishniac, 1974). These species exhibit a range of heterotrophic to autotrophic characteristics and they could just represent a gradation of types exhibiting various degrees of autotrophy (c.f. Vishniac, 1974). Hutchinson et aX - (1969) applied numerical taxonomy to the thiobacilli and found that all the species now listed in Vishniac (1974) were valid but that X - thiooxidans and X - neapolitanus were very similar. They differentiated the thiobacilli primarily on the characteristics of hetero-trophy/autotrophy and the final pH attained in a thiosulfate medium. X -novel!us and X - denitrifans, which do not lower the thiosulfate medium's pH below 5 are differentiated by the facultative autotrophic ability of X - novel 1 us which is missing in X - denitrificans. X - denitrificans, however, has the ability to grow as a facultative anaerobe utilizing nitrate in the presence of sulfur compounds. Three species of thiobacilli: X - perometabolis, X - thioparus and X -neapolitanus reduce the pH of the medium to between 2.8 and 4.0. X -perometabolis can be identified by its heterotrophic growth habit. X -32 thioparus lowers the pH of a thiosulfate medium down to 3.5, whereas the pH can be lowered to 2.8-3.5 in the presence of TV. neapolitanus. T. neapolitanus can be further differentiated from T. thioparus by its morphological differences and its resistance to inhibitors. Of the three thiobacilli which lower the pH of a thiosulfate solution below 2.8, T. intermedius can be characterized by its ability to grow heterotrophi-cally. T. thiooxidans and T. ferrooxidans are separated by the ability of the latter to oxidize Fe in addition to reduced sulfur compounds. The work of Hutchinson et a_l_. (1969) suggests that there is a succession of sulfur bacteria in acid sulfidic soils. Hagedorn(1975) described such a succession of thiobacilli in acidic soils in Oregon. He found that T. novellus and T. thioparus had the highest populations in slightly acid soils. The populations of T. thiooxidans and J_. ferrooxidans were largest in the highly acid soils. 2.5.2.2 Oxidation pathways of sulfur compound by the obligate auto-trophic thiobacilli +3 In contrast to the chemical oxidation of sulfides by Fe or oxygen, the oxidation by thiobacilli is enzymatic. The enzymology of sulfur oxidation is beyond the scope of this review, but is covered adequately by Roy and Trudinger (1970) and Kelly (1971). The enzymatic mechanism depends on direct contact between the sulfur and the surface of the bac-terial cell (Roy and Trudinger, 1970). This contact has been observed between sulfur crystals and X- thiooxidans (Schaeffer e_t a l - , 1963). There is s t i l l some controversy about the nature of the iron sulfide surface attacked by the thiobacilli . Amorphous elemental sulfur has been 33 shown to be the init ial product of sulfide oxidation in the presence +3 of Fe and has the potential of forming a surface coating. However, elemental sulfur has been shown to react spontaneously with sulfides to form polysulfides (Chen and Morris, 1972). These polysulfides are considered to be the initial substrate of the thiobacil1i.(Tano et a l . , 1977). The initial sulfur compound taken up is s t i l l unknown but is believed to be a derivative of glutathione or a membrane-bound thiol (Roy and Trudinger, 1970). These authors have suggested that microbial sulfide oxidation follows the scheme of: S~2 > X > SO"2 > S0"4Z (31) S° sso3 where X is the initial bacterially bound form of sulfur. The formation of SO^  as the init ial product of glutathione catalyzed oxidation of sulfur has been reported by Suzuki and Silver (1966) for T. thiooxidans and T. thioparus. S° + 0o + Ho0 — > SOI2 + 2H+ (32) 2 2 enzyme 3 x This product can be oxidized by an enzyme system from T. thiooxidans to sulfate (Adair, 1966). However, many workers consider that thiosulfate and polythionates are the main intermediates in sulfur oxidation by thiobacilli (Vishniac and Santer, 1957). Suzuki and Silver (1966) found that the formation of thiosulfate is a non-enzymatic condensation of sulfur with sulfite. S0~3Z + SQ ^SSO^ (33) 34 The oxidation products of thiosulfate and the intermediate poly-thionates by the thiobacilli depend primarily on the availability of electron acceptors in the environment. Under aerobic conditions, the oxidation rate curve for thiosulfate by T, ferrooxidans exhibits three breaks corresponding to thiosulfate tetrathionate and trithionate oxi-dation (Landesman et_ al_., 1966b). The general scheme for thiosulfate oxidation under aerobic conditions can be represented by: The formation of tetrathionate under aerobic conditions by T. ferrooxidans has been described by Landesman ejt al_. (1966b) and Tuovinen and Kelly (1974c). This finding has been reported for T. thioparus. J_. neapolitanus and X- novel!us when oxygen availability exceeded uptake (Vishniac and Trudinger, 1962). All three groups of workers found that tetrathionate accumulated. This reaction to form tetrathionate can be represented by the equation: and is alkali producing (Sinha and Walden, 1966). Tetrathionate has also been found to accumulate in the oxidation of thiosulfate by X- ferrooxidans (Landesman et aX-, 1966b; Tuovinen and Kelly, 1974c). This accumulation of tetrathionate is considered to be due to the slower rate of its oxi-dation to trithionate and sulfate compared to the oxidation of thiosulfate to tetrathionate or trithionate to thiosulfate and sulfate (Sinha and (34) 2Na2S203 + H20 + %QZ > Na 2S 40 g + 2NaOH (35) 35 Walden, 1966). The oxidation of tetrathionate has been found to yield sulfate but shows a stepwise oxidation kinetics (Kelly and Tuovinen, 1975). It has been suggested that trithionate is an intermediate in tetrathionate oxidation (Vishniac, 1952; Vishniac and Santer, 1957; London and Rittenburg, 1964). Trithionate accumulates during thiosulfate oxidation by T. ferrooxidans when the pH was allowed to drop to 2.5. Landesman et a l . (1966b) and Tuovinen and Kelly (1974c) detected a small quantity of t r i -thionate during the oxidation of thiosulfate by T. ferrooxidans during the log phase at a pH of 3.6-4.7. Landesman et al_. (1966b) postulated that the slower rates of tetra- and t r i - thionate oxidation by T. ferrooxidans compared to thiosulfate may be due to lower cell permeabil-ities to these former two compounds. Ultimately, the trithionate is oxidized to thiosulfate and sulfate by thiobacilli (Landesman e_t al_., 1966b; Sinha and Walden, 1966). S 3 ° 6 2 + H 2 ° > S 2 ° 3 2 + S 0 4 2 + 2 H + ( 3 6 ) The thiosulfate produced is available for polythionate formation and thus appears to be an intermediate in polythionate oxidation (c.f. Kelly and Tuovinen, 1975). Under anaerobic conditions, the formation of elemental sulfur from thiosulfate and the polythionates is favored, This anaerobic condition may be due to low oxygen diffusion rate or high substrate concentration (Vishniac, 1952). The elemental sulfur formed from sulfide oxidation by sulfur bacteria has been reported to be in the amorphous u form, which changes to orthorhombic sulfur on exposure to air (Lundgren, 1960). 36 Vishniac and Trudinger (1962) and Trudinger (1964) have shown that elemental sulfur accumulates in the medium at high concentrations of thiosulfate in the presence of T. thioparus, T. neapolitanus and T. novel 1 us. Pivovarova and Karavaiko (1973a, b) have found that the species T. neapolitanus and T. denitrificans excrete this colloidal sulfur through their cell wall. Elemental sulfur can also be formed from the anaerobic oxidation of tetrathionate by T. ferrooxidans and T_. neapolitanus (Kelly and Tuovinen, 1975). - 03S - S - S - SO" + OH" SSO3 + S° + HS0~ (37) Trudinger (1964a, b) has found that elemental sulfur is also produced from the anaerobic oxidation of t r i - and penta- thionate by T. neapolitanus. In the case of trithionate, the presence of traces of thiosulfate acceler-ates the reaction (Trudinger, 1964a). Once formed, elemental sulfur is available for oxidation by thio-baci l l i . Elemental sulfur and soluble sulfides are oxidized by a similar metabolic pathway (Suzuki, 1965a; London and Rittenburg, 1964). Elemental +3 sulfur can be oxidized either anaerobically using Fe as an electron +3 acceptor or aerobically with oxygen or Fe . The anaerobic oxidation of elemental sulfur by T. thiooxidans in the presence of carbon dioxide was first reported by Adair and Umbreit (1965). Brock and Gustafson (1976) were able to demonstrate that T. +3 ferrooxidans was able to oxidize elemental sulfur in the presence of Fe They postulated that other thiobacilli are also capable of carrying out 37 this oxidation of elemental sulfur using Fe as an electron acceptor. Ferric iron has also been shown to be involved in the oxidation of elemental sulfur under aerobic conditions. Brock and Gustafson (1976) showed that this process is carried out by T. thiooxidans and postulated that it could also be carried out by T. ferrooxidans aerobically but any +2 +3 Fe produced would be reoxidized to Fe immediately. The reaction between elemental sulfur and glutathione in thiobacilli mediated oxidation yields hydropolysulfides (Suzuki, 1965a). He suggested that glutathione hydropolysulfides are the true substrates of the sulfur-oxidizing system in thiobacilli . The initial product of elemental sulfur is thiosulfate. Landesman e_t al_. (1966b) and Suzuki (1965a) felt that the conversion from elemental sulfur to thiosulfate, in oxidation by T. ferrooxidans, is the rate determining step. Elemental sulfur oxidation by X- ferrooxidans results in a stepwise decrease in the medium's pH in work by Unz and Lundgren (1960). This pattern corresponds to the for-mation and oxidation of a series of polythionates starting with thiosul-fate. Iwatsuga and Mori (1960) and Unz and Lundgren (1960) found that elemental sulfur oxidation by X- thiooxidans yields thiosulfate and tetrathionate but that they do not accumulate due to their rapid con-version to sulfate. 2.5.2.3 Factors controlling the oxidation rates of reduced sulfur compounds by the obligate autotrophic thiobacilli Among the thiobacilli species, only X- denitrificans, X- thioparus, X- neapolitus, X- thiooxidans and X- ferrooxidans are strictly autotrophic (Vishniac, 1974). The oxidation of reduced sulfur compounds by these 38 species appears to be affected by many of the factors which influence iron oxidation by T. ferrooxidans. The factors thus far found to affect the rate of oxidation of sulfur compounds by one or more of these species include: pH, temperature, cations, anions, organic matter and surfactants. The pH for optimum oxidation of sulfur compounds has only been studied for T. thiooxidans and T. ferrooxidans. For the other three forementioned thiobacill i , the pH optima is somewhere above 3.5 for T. denitrificans and T. thioparus and above 2.8 for T. neapolitus (Vishniac, 1974). The pH optimum for growth and sulfur oxidation by T. thiooxidans was originally set at between 2 and 5.5 with no growth at pH 7 (Waksman and Starkey, 1922). Rao and Berger (1971) showed that elemental sulfur was oxidized by T. thiooxidans between the pH range of 0.9 and 7. However, they found the maximum growth range was between pH 2 and 3 with no growth occurring above pH 4.3. Iwatsuga and Mori (1950) found a range for optimum elemental sulfur oxidation of between pH 3 and 6. In addition, they found that oxygen uptake fell off rapidly below or above these pH values. They reported Qq 2 (N) values of up to 2500 at a pH optimum of 3-6 for elemental sulfur oxidation. In the case of tetrathionate, the Q Q 2 (N) values were much lower, being about 200 (Iwatsuga and Mori, 1960). For J_. ferrooxidans, the maximum oxidation rate of elemental sulfur was at pH 5 with a Qq 2 (N) of 726 ( .Landesman at 'al., 1966b) Overall elemental sulfur was oxidized between pH 1.25 and 7, but the rate fell off rapidly below pH 3 and above pH 5. The maximum rate of growth of T. ferrooxidans on thiosulfate was at pH 3.6 with a range of 3.6-4.7 (Tuovinen and Kelly, 1974c). Landesman e_t al_. (1966b) found the maximum oxidation rate for thiosulfate to be at pH 4.0 with a Q 9 (N) of 514. 39 When tetrathionate was the substrate, this species had a growth maximum over the pH range of 2.3-2.5 (Tuovinen and Kelly, 1974c). However, Landesman et_ al_. (1966b)'found that the maximum oxidation rate for tetra-thionate by J _ . ferrooxidans was at pH 6 with a Q Q 2 ( N ) of 103. Kelly and Tuovinen (1975) commented that Landesman et al_. (1966b) used a highly unfavorable pH for tetrathionate oxidation on the mistaken assumption that i t was unstable at low pH. The. low Q Q 2 ( N ) of tetrathio-nate oxidation at pH 6 may be partly due to chemical oxidation by T. ferrooxidans^ Landesman et_ aj_. (1966b) found a pH optimum at 6 with a Q Q 2 ( N ) of 113. However, as in the case of tetrathionate oxidation, the oxidation of trithionate at pH 6 may be due in part to strictly chemical pathways. The temperature optimum for growth of the obligate autotrophic thiobacilli has only been reported for T_. thiooxidans and T. ferrooxidans. The optimum temperature for growth on sulfur by T. thiooxidans was origi-nally determined to be between 28 and 30°C (Waksman and Joffe, 1922). Recently, Rao and Berger (1971) confirmed this in finding a temperature optimum of 30°C. For T. ferrooxidans the temperature optimum for oxidation of elemental sulfur as well as thiosulfate, tetrathionate and trithionate oxidation has been found to be 40°C (Landesman et aJL. 1966b). The influence of cations on the oxidation of reduced sulfur compounds by obligate autotrophic thiobacilli has only been studied for T. ferrooxidans  a n c ' X* thioparus when grown on thiosulfate and tetrathionate respectively. In the case of J_. ferrooxidans growing on thiosulfate, i t was found that the addition of trace metals depressed the linear rate of thiosulfate utilization and resulted in some precipitation of elemental sulfur at pH 4 40 (Kelly, 1969). The rate of tetrathionate oxidation by J_. thioparus was slow when the cells were grown in a low K environment (Jones and Happold, 1971). They attributed this inhibition to a restriction of phosphate entry into the cells when K is low. This low K inhibition of tetrathionate oxidation is essentially a suppression of growth in the absence of phosphate. The effects of anions on the oxidation of sulfur compounds by thio-bacilli has only been extensively studied in the case of phosphate. Santer (1959) found a 30 percent decrease in oxygen consumption by J_. thioparus in the absence of inorganic phosphate. He found that tetrathion-. ate accumulated although some sulfate was produced. It was suggested that phosphate is necessary for tetrathionate oxidation. Santer et_ al_. (1960) reported that inorganic phosphate is also required to maintain the maximum rate of conversion of thiosulfate to sulfate. These findings are in agreement with earlier work showing that inorganic phosphate is converted to high energy phosphate-containing compounds during substrate oxidation (c.f. Vishniac and Santer, 1957). Apparently these high energy phosphate-containing compounds are neces-sary for the production of enzymes and cofactors involved in sulfur compound oxidation by the thiobacilli . These organic compounds, in particular the cofactor glutathione, have been found necessary for the oxidation of elemental sulfur to thiosulfate (Suzuki and Lees,.1964. Suzuki, 1965b). Glutathione is also involved in the oxidation of sulfide and sulfite to elemental sulfur and sulfate respectively (Peck, 1962). In the absence of glutathione, Trudinger (1961) found that thiosulfate was oxidized to tetra-thionate by thiobacilli cell free extracts. This mechanism of tetrathionate 41 accumulation may explain the lack of tetrathionate oxidation in the absence of phosphate found by Santer (1959), assuming that phosphate was required in glutathione synthesis. The inhibition of growth and oxidation of reduced sulfur compounds by thiobacill i , in the presence of organic matter, has been studied by many authors.-, Until the reviews of Rittenburg (1969) and Kelly (1971), i t was widely held that autotrophs were inhibited by all organic compounds. It is now known that not all organic compounds are inhibitory, in fact some are stimulatory. Among those organic compounds found to inhibit sulfur oxidation by obligate thiobacill i , the alcohols, amino acids and carboxylic acids appear to be the most effective. Inhibition of thiobacilli species by alcohols has been reported for ! • ferrooxidans (Iwatsuga and Mori, 1960). Landesman et aJL (1966b) and Tuttle and Dugan (1976) reported that the inhibition by primary alco-hols of sulfur oxidation by J_. ferrooxidans • increased with the length of the carbon chain. The inhibition is apparently tied to increases in membrane permeability with increases in the carbon chain length (Iwatsuga and Mori, 1960). Rittenburg (1969) theorized that amino acid imbalances are the cause of the inhibition of thiobacilli by amino acids. Lu et al_. (1971) were able to reproduce some of these amino acid imbalances in J_. thioparus, T_. neapolitanus and _T. thiooxidans. However, the addition of casein hydro-lysate was found to reverse the inhibition by single amino acids. Several authors have studied the inhibition of growth and sulfur oxidation in the thiobacilli by carboxylic acids. Tuttle and Dugan (1976) even proposed that the degree of inhibition is a function of the 42 electronegativity of the carboxylic acid. Iwatsuga and Mori (1960), Landesman e_t aJL (1966b) and Tuttle and Dugan (1976) all found that carboxylic acids were inhibitory below the pK of the respective acid. The latter two groups of workers found that the a-keto analogs of the carboxylic acids exhibited the strongest inhibition on obligate autotro-phic thiobacilli . This inhibition prompted workers to investigate the autoinhibition by waste products in the thiobacilli . Butler and Umbreit (1966) proposed that growth of X- thiooxidans in the presence of aspartic acid was due.to the accumulation of some toxic biproduct in the growth medium. Borichewski and Umbreit (1966) proposed that the inhibition of X' thiooxidans was due to excreted pyruvate. Borichewski (1967) concluded that the accumulation of keto acids in solution resulted in the cessation of growth by X-thiooxidans growth. Pyruvate and oxaloacetate were found to inhibit growth at a concentration of 2 x 10"^ M. Pan (1970) and Karavaiko and Pivovarova (1973) detected these two acids as well as a-keto-glutaric acid as excretion products from T. thioparus, X- neapol itanus and J^. thiooxidans respectively. Kelly (1967) and Smith et |_X. (1967) suggested that the utilization of organic matter by obligate autotrophs is prevented by a blocking of the TCA cycle at the level of a-keto-glutarate oxidation. Pan (1970) found the excretion of these three organic acids was most pro-nounced during the exponential growth phase for J_. thioparus and J_. neapol - itanus. Karaviko and Pivovarova (1973) reached the same conclusion in metabolic studies using T. thiooxidans. The metabolic pathways of the formation of organic inhibitors have been studied using the finding of Lundgren et a l . (1964) that T. ferrooxidans 43 would grow on glucose. Borichewski and Umbreit (1966) found that in-hibition did not occur when T. thiooxidans was grown on glucose by means of a continuous flow dialysis system to remove the inhibitors. This finding was duplicated by Pan (1970) for X- thioparus and T\ neapolitanus, indicating that the thiobacilli are capable of growth on glucose, i f there is sufficient solution available to dilute the inhibitors. The relationship between the pyruvate concentration and the degree of inhibition of sulfur compounds by X' thiooxidans has been studied by two groups of workers. Oka e_t a l . (1976) found that ImM pyruvate inhibited colloidal sulfur oxidation by approximately 85 percent. A lOmM concen-tration of pyruvate was required to inhibit pentathionate and tetrathionate oxidation to the same degree. At this pyruvate concentration, thiosulfate and sulfide oxidation were inhibited 30 and 70 percent respectively. Tano et_ aj_. (1977) found pyruvate inhibition decreased according to the length of the sulfur chain. However, sulfide oxidation was strongly inhibited. These two groups of workers have theorized that pyruvate inhibits the cleavage of the Sg ring in elemental sulfur and the splitting of the di-sulfide bonds in polysulfides. Organic compounds in the form of wetting agents have been suggested to aid sulfur oxidation by thiobacilli . Jones and Starkey (1961) found that growth of X* thiooxidans resulted in the wetting of elemental sulfur and attributed this action to the production of surface active agents. Adair (1966) found that the wetting agents lecithin, cephalin, phosphatidyl inositol and particularly Tween-80 enhanced elemental sulfur oxidation by X* thiooxidans. Cook (1964) postulated that wetting agents promote a firm attachment 44 between sulfur particles and sulfur bacteria. A wetting agent released by J_. thiooxidans has been extracted and found to have a chromatographic mobility similar to phosphatidyl inositol and diphosphatidyl inositol (Herson, 1967). Jones and Benson (1965) and Shively and Benson (1967) detected excreted phospholipids in J_. thiooxidans cultures but were unable to detect phosphatidyl inositol. They did detect phosphatidyl N-methylethanolamine, phosphatidyl glycerol, diphosphatidyl glycerol and traces of lysophosphatidyl N-methylethanolamine and lysophosphatidyl glycerol. Rao and Berger (1970) confirmed that surface active agents, probably phospholipids, are released by J_. thiooxidans wetting the normally hydrophobic elemental sulfur. The excretion of lipids and phospholipids by J_. thiooxidans has been found to have a maximum/unit biomass at the end of the log phase (Karavaiko and Pivovarova, 1973). They were able to show that most of the lipids and phospholipids were bound to sulfur. It is possible that inorganic phosphorus may be required as a compon-ent of the wetting agents released by thiobacilli in order to maintain an optimum sulfur oxidation rate. 2.6 Microbial Coupling of Iron and Sulfur Oxidation from-Iron Sulfides The dramatic increases in the oxidation of iron sulfides by iron and/or sulfur oxidizing bacteria have been attributed to either a direct contact action of the bacteria on the ore or to an indirect effect. In the indirect +3 effect, Fe oxidizes the sulfide and is reoxidized by J_. ferrooxidans to +3 complete the cycle. However, all experimental evidence indicates that Fe oxidizes sulfide to elemental sulfur (Silverman, 1967) but cannot oxidize 45 this product any further (Brock and Gustafson, 1976). In order for an oxidizing agent to be effective, a substrate must be available for oxidation. In the case of iron disulfides there is growing evidence that surface coatings of elemental sulfur, particularly +3 colloidal, can inhibit sulfide oxidation by Fe . Silverman (1967) found that acid pretreatment of pyrite, to remove acid soluble iron, resulted in a dramatic decrease in the oxidation rate by T_. ferrooxidans. He +3 found that the addition of Fe salts to the acid pretreated pyrite res-tored about two-thirds of the bacterial oxygen uptake, after an initial +3 lag in oxygen consumption. These treatments indicated that Fe is necessary for T. ferrooxidans oxidation of iron sulfides but cannot account for all the oxygen uptake. In the absence of other evidence, the lag in oxygen uptake and reduced overall oxidation rate by ferrooxidans on a pyrite substrate depleted in Fe, can be interpreted as an interference +3 with sulfide oxidation by Fe with surface coatings of elemental sulfur. Beck and Brown (1968) found that aged suspensions of J_. ferrooxidans, +2 which had a high activity on Fe but had lost the ability to oxidize sulfur, were unable to oxidize pyrite. They theorized that the sulfur and +2 Fe oxidation systems were different and that the former was required for +2 the oxidation of metal sulfides. Landesman et_ al_. (1966b) found that Fe and sulfur were indeed oxidized by T_. ferrooxidans at the same time, +2 resulting in an oxidation rate equal to the sum of maximum rates of Fe and sulfur oxidation separately. However, based on the respective +2 (N) for Fe and sulfur, they concluded that the molar oxidation ratio +2 for Fe and S Q was 180:1. This agrees with the conclusion of Unz and +2 Lundgren (1961) that T. ferrooxidans oxidized Fe preferentially to 46 elemental sulfur. Beck and Shafia (1964) and Beck and Brown (1968) showed that the efficiency of CC^ fixation by T. ferrooxidans was much higher during +2 the oxidation of elemental sulfur than Fe . However, the carbon dioxide +2 uptake of T_. ferrooxidans on Fe was twice that of carbon dioxide on elemental sulfur (Silver.et.ah , 1967).' They-found9that the C02 fixation +2 efficiency on pyrite was nearer to the Fe values indicating that rela-+2 tively more Fe than sulfur was being oxidized. J_. ferrooxidans is normally found with T. thiooxidans in sulfidic soils. This latter thio-bacilli has about three times the sulfur oxidizing capacity as J_. ferro- oxidans. It is conceivable that the presence of J_. thiooxidans can enhance the sulfur oxidizing rate. The association of T. ferrooxidans and T_. thiooxidans together undoubtedly tends to reduce the accumulation of +2 sulfur on the pyrite surface. This coupling of Fe and sulfur oxidation supports the direct oxidation mechanism of iron sulfides. 47 3.0 MATERIALS AND METHODS 3.1 Field 3.1.1 Sites Sampled Samples of Sullivan iron sulfide mine tailings (Cominco Ltd. , Kimberley, B.C.) were collected from eighteen sites during the period of August 15th to 20th, 1977 (Figure 1). Sites were selected to reflect the range of minerological composition and weathering states in the tailings. Waterlogged areas, slopes and areas covered by ferruginous crusts were avoided for the sake of practicability. Between four and eleven samples were collected from each site for a total of 120 samples. Thirty samples were from the siliceous tailings and ninety from the iron tailings. Samples from the iron tailings included eleven from the 1948 tailings spill arid nine miscellaneous samples. These latter samples were efflorescences (four) and iron oxide residues from tailing fires (five). 3.1.2 Sampling Technique The samples were collected from the surface 2.5 cm of the tailings and were chosen for their relatively high degree of homogeneity. A metal coring ring was used to collect the samples. Each sample was divided into two subsamples and transferred in the field to moisture tins and sterile plastic screwtop containers respectively. The subsample in the moisture tin was later used for moisture and structure determinations. All other ure 1. Sanple Sites of Sullivan Iron Sulfide Tail inns LOWER 14 O SILICEOUS TAILINGS 1948 TAILING SPILL 49 laboratory analyses were conducted on the subsample in the sterile plastic screwtop containers which were stored under refrigeration at 0°C until the study was completed. 3.2 Laboratory 3.2.1 Microbiological 3.2.1.1 Most-probable-number determinations To estimate the activity of microorganisms in the tailings, the number of iron-oxidizing bacteria, sulfur-oxidizing bacteria, acid tolerant fungi and acid tolerant heterotrophic bacteria were determined by the most-probable-number technique. Numbers of iron-oxidizing bacteria were esti-mated using the 9-K iron-salts medium of Silverman and Lundgren (1959). Sulfur-oxidizing bacteria were estimated by using the standard mineral base plus thiosulfate medium of Vishniac and Santer (1957). Acid tolerant fungi were estimated by using the basal salts medium of Allen (1959) as modified by Belly and Brock (1974). Acid tolerant heterotrophic bacteria were estimated by using the medium for fungi, except that cycloheximide, 0.1 mg/ml, was added to inhibit fungi. One gram of each moist tailings sample, after mixing to ensure homo-geneity, was added to an erlenmeyer flask containing 100 mis of sterile distilled water. Thorough mixing of each sample was also carried out prior to each of the analyses later conducted. Serial 10-fold dilutions were prepared in triplicate for each sample using the appropriate medium in 13 x 150 mm test tubes. All incubations were carried out at room temperature 50 (18-26°C) for 30 to 45 days. Growth of the iron-oxidizing bacteria was init ial ly determined by the formation of potassium jarosite in the tube. Sulfur-oxidizing bacteria were indicated by the development of tur-bidity and in many cases a pellicle. Acid tolerant heterotrophic bacteria were indicated by turbidity. Acid tolerant fungal growth was determined by the presence of mycelia. All initial determinations of bacterial growth were confirmed by microscopic examination. The most-probable-number of microorganisms per gram of tailings were determined using the tables of Collins (1964). 3.2.T.2 Identification of sulfur bacteria Sulfur-oxidizing bacteria were identified by colony morphology, potential for heterotrophic growth, and the final pH of the thiosulfate medium. For each tube found positive for sulfur bacteria, one drop of medium was spread on a petr.i. p.late containing the thiosulfate medium of Vishniac and Santer (1957) solidified with 1.5% purified agar (Difco). The plates were incubated at room temperature and enriched with carbon dioxide using a sulfuric acid-calcium carbonate generator. After colonies developed they were described using characteristics outlined in Vishniac (1974). The colony morphology was used in conjunction with the thiosulfate medium's final pH to classify the sulfur bacteria as described by Hutchinson et a l . (1969). Heterotrophic growth was tested for by replica plating colonies growing on YES (yeast extract-thiosulfate) media (Mizoguchi e_t jilL, 1976). 51 3.2.1.3 Iron bacteria colony type identification An attempt to characterize iron bacteria by colony type was carried out. Serial dilutions using the 9-K iron-salts medium of Silverman and Lundgren (1959) were conducted on bulk tailing samples collected in prelim-inary work. Tubes found positive for iron bacteria were streaked onto an iron-salts media solidified with 0.7% purified agar L28 (oxoid) (Manning, 1975). The agar.plates were incubated in the same manner as were the sulfur-oxidizing bacteria and subsequently examined for iron bacteria colony types. 3.2.1.4 Sulfolobus enrichment Enrichment for the genus Sulfolobus was conducted on the same tailing samples used for iron bacteria colony type identification. One gram of tailings was added to 100 mis of the basal salts medium of Allen (1959) containing 0.1% yeast extract (Brock et al_., 1972). Enrichments were carried out at 85°C for 7 days and examined for turbidity and surface pellicle. 3.2.2 Chemical 3.2.2.1 Percent moisture The moisture content of the samples was determined gravimetrically after oven drying at 105°C for hours. The moisture content was used to convert all the values obtained from chemical and microbiological analysis to a dry weight basis. 52 3.2.2.2 pH The sample pH determinations were carried out on a (1:1) soil extract using the method of Peech (1965). The pH was measured with a combination electrode and a Fisher Accumet model 420 pH/ion meter. 3.2.2.3 Conductivity Conductivity of the samples was determined using the SD-B15 Solu Bridge Soil Tester, using the method of the U.S. Salinity Laboratory Staff (1954). The (2:1) dilution was obtained by diluting the extract used in the pH measurement. Where the conductivity exceeded 10 mnrh'os/cni further dilutions were made and the conductivity was extrapolated back to the original dilution assuming the activity of the sulfate anion remains constant with concen-tration. 3.2.2.4 Elemental sulfur The percent elemental sulfur content of the tailings samples was determined using a modification of the method of Fliermans and Brock (1972). One gram of tailings was added to a 100 ml volumetric flask followed by 10 ml of carbon disulfide and 20 ml of distilled water. The volumetric flasks were tightly sealed and shaken for three hours. The contents were poured into a 50 ml centrifuge tube and the water-carbon disulfide emulsion was separated by low speed centrifugation. The water layer was aspirated off the denser carbon disulfide layer using a pasteur pipet and suction flask assembly. A portion of the carbon disulfide was analyzed for elemen-tal sulfur content using a Turner model 330 spectrophotometer at 382 nM. 53 The absorbance was converted to-elemental sulfur concentration in mg/g using a standard curve obtained from elemental sulfur standards in the range of 0-50 mg/10 ml of carbon disulfide. This absorbance versus concentration relationship for elemental sulfur was found to be linear in the range of 0-50 mg/10 ml, extending the range used by Fliermans and Brock (1972). 3.2.2.5 Monosulfide sulfur Monosulfide sulfur, principally pyrrhotite, was determined using an adaptation of the method of Smittenburg et_ al_. (1951). The digestions were carried out in a modified Johnson-Nishita apparatus on a Kjeldahl heater unit. Standard iodine and thiosulfate solutions used in the titrations were prepared as described in Skoog and West (1963). 3.2.2.6 Total oxidizable sulfur The total oxidizable sulfur excluding monosulfides, was determined by the method of Smittenburg e_t al_. (1951). The digestions and titrations were the same as those used in the monosulfide analysis. 3.2.2.7 Organic matter The percent water soluble organic matter in the tailings samples was determined by the Walkley-Black method for soil extracts. Fifty ml of a distilled water extract of the tailings samples were dispensed into 50 ml erlenmeyer flasks and evaporated to dryness over a seven day period in an oven set at 45°C. The residue was redissolved in 10 mis of a pH 7 buffer solution and taken to dryness over a two day period. The subsequent analysis 54 by dichromic plus sulfuric acid digestion was carried out as described by Allison (1965). 3.2.2.8 Water extractable sulfate Sulfate was determined by the turbidometric method outlined in Beaton et al_. (1968). Five grams of each tailings sample were shaken with 50 ml of distilled water in 100 ml plastic bottles on a mechanical shaker for one hour. The solutions were filtered through Whatman #42 f i l ter paper and diluted to 100 mis in volumetric flasks. Further dilutions were made, as necessary, to obtain sulfate concentrations of between 4 and 20 ppm in the sample solution to be analyzed. The absorbances of the solutions were measured at 440 nM using a Turner 330 spectrophotometer. 3.2.2.9 Acid extractable sulfate Acid extractable sulfate was determined by the same turbidometric method as used in the water extractable sulfate determination. However, concentra-ted hydrochloric acid was used to solubilize the insoluble sulfate. One gram of each tailings sample was extracted with 10 mis of hydrochloric acid in a 50 ml erlenmeyer flask under the fume hood. The samples were stirred using a glass rod and allowed to react with the concentrated hydro-chloric acid for 48 hours. The solution was diluted to approximately 50 mis, filtered into a 100 ml volumetric flask and brought up to volume. Fur-ther dilutions were made, as necessary, and the total sulfate concentration of the sample was determined as for water extractable sulfates. The water extractable sulfate concentration in the tailings was subtracted from the total sulfate concentration to obtain the concentration of acid extractable 55 sulfate in the tailings. 3.2.2.10 Extractable cation determinations The acid and water extractable concentrations of Fe, A l , Ca, Mg, K and Na were measured using standard atomic absorption spectrophotometry methods. The acid extractable concentrations were determined on the concentrated HCI extract and the water extractable concentrations on the distilled water extract. 3.2.3 Mineralogical Seven samples selected to represent a range of weathering states and mineralogical compositions were prepared and analyzed qualitatively for mineralogical composition. About five grams of the tailings material was mixed with 10 mis of distilled water and allowed to settle for half a minute to permit the coarse feldspar, pyrite and quartz particles to settle. The slurry was pipetted on an x-ray slide and allowed to dry overnight in a dessicator under nitrogen current. The powder x-ray diffraction patterns were made with a Phillips x-ray diffraction unit using Co radiation (CoKa = 1.7889), at settings of 36 KV and 20 MV. The slides were scanned between 3 and 45° 29 at a rate of l° /minute . 3.2.4 Qua!itative Tai1ings Characteristics Each sample was color coded (Munsel1-mixed color), hand textured and characterized structurally using the guidelines set out by the U.S. Depart-ment of Agriculture (1975). The color, texture and structure were weighted 56 numerically for computer analysis as shown in Appendix C5. 3.2.5 Computer Methods Means, standard deviations, correlations, simple and multiple linear regression were conducted using programs in the UBC TRP manual. Analysis of subsets were carried out interactively using the MTS MIDAS manual and in some instances using the HP97 programmable calculator. 57 4.0 RESULTS 4.1 Chemical Transformations in Oxidizing Sulfidic Soils 4.1.1 Products of Iron Sulfide Oxidation 4.1.1.1 Acid generating potential versus stage of iron monosulfide oxidation The oxidation of iron monosulfides is actually the semi-independent +2 +2 oxidation of Fe and sulfide. The initial oxidation of Fe in iron monosulfides produces acid according to the equation: 2Fe + 2 + h02 + 5H20 2Fe(0H)3 + 4H+ (Singer and Stumm, 1970). Much of the acid produced is consumed in the oxidation of sulfide to elemental sulfur: 2S"2 +02 + 4H+ • — 2S04 + 2H20 (Chen and Morris, 1972). However, the acid is regenerated in the subsequent oxidation of elemental sulfur, through a series of intermediates, to sulfate as shown in the overall reaction: 2S° + 2H20 + 302 • 2S0~2 + 4H+ (Torma, 1978). The amount of acid produced or consumed at any given time depends on +2 +3 the rates of the Fe -Fe , sulfide-elemental sulfur and elemental sulfur-58 sulfate reaction sequences. +2 If all the Fe and sulfide are oxidized, the reactions yield two moles of acid per mole of iron monosulfide according to the overall reaction: 6FeS + 27H20 + 27_ 0 2 >6Fe(0H)3 + 6S0~2 + 12H30+ However, below pH 4.0, three moles of acid are consumed for each mole of iron sulfate minerals of the jarosite series formed: 6Fe(0H)3'+ 4S0~2 + 8H30+ > 2H 30+(Fe 3(S0 4) 2(0H) g)" + 8H20 Assuming that all Fe is incorporated in jarosite type minerals, the overall iron monosulfide oxidation yields one mole of acid per mole of iron monosulfide, according to the equation: 6FeS + 27H20 + 27 0 2 » 2 ( H 3 0 ) + (Fe3(S04)2(0H)g)" + 12H20 + 2H2S04 Comparably, the oxidation of one mole of iron monosul'fides to Fe hydroxides produces two moles of hydronium ions, whereas the production of jarosite results in the formation of only one mole of hydronium ions. 4.1.1.2 Iron monosulfide oxidation in the siliceous tailings The amount of iron monosulfide in the siliceous tailings was highly cor-related with pH (r = 0.79**), despite variation in init ial iron monosulfide content in these samples (Appendix C.2). This very significant correlation indicates that there is a high buffering capacity and intensity in these tailings. Otherwise, the initial oxidation of monosulffdes would cause a 59 precipitous drop in pH, resulting in a lack of correlation between pH and iron monosulfide content. This slow decrease in pH is also implicated in the significant cor-relations between iron monosulfide content and its products. Iron mono-sulfide content is correlated with total oxidizable sulfur (r = T0.31*), elemental sulfur (r = -0.56**), water extractable sulfate (r = -0.57**) and acid extractable sulfate (r = -0.52**). These sulfur forms are also very significantly correlated with pH,^  total oxidizable sulfur (r = -0.46**), elemental sulfur (r = -0.59**), water extractable sulfate.(r = -0.68**) and acid extractable sulfate (r = -0.71**). The method used for determining total oxidizable sulfur potentially measures the contribution of pyrite too. However, the flotation process, for the waste siliceous tailings, excludes traces of pyrite found in the ore (Anon., 1973) for the most part. Thus, total oxidizable sulfur rep-resents the sulfide oxidation products excluding sulfate for the siliceous tai1ings. Total oxidizable sulfur amounts to 59% of the total sulfur or 3.55% of the sample dry weight. This high level of total oxidizable sulfur indicates that there is a significant accumulation of sulfur intermediates in the tailings. A portion of these intermediates may be accounted for by the high association between total oxidizable sulfur and elemental sulfur (r = 0.53**). The remaining 1.35% total oxidizable sulfur not accounted for by elemental sulfur (Appendix C.2) must be in the form of other sulfur intermediates or amorphous elemental sulfur not soluble in carbon d i s u l f i d e . The most likely sulfur intermediates that could exist in significant 60 quantities in these tailings include thiosulfate and polythionates. These sulfur intermediates have been detected as products of elemental sulfur in soils where it was added (Nor and Tabatabai, 1977). Their work indicated that i t is possible to accumulate thiosulfate and tetrathionate in quantities much greater than sulfate, in the initial oxidation of elemental sulfur in some soils. Thiosulfate and polythionate production has been shown to be highly favored when oxygen is limiting and the sul-fide or elemental sulfur substrate is high (Vishniac, 1952). The relatively fine clay loam to silty clay loam textures (Appendix C.2) combined with the large quantities of oxidizable sulfur, would tend to favor thiosulfate and polythionate production in the siliceous tailings. Such products could account for most of the difference between average levels of total oxidiz-able sulfur and elemental sulfur. Other intermediates such as polysulfides (Chen and Morris, 1972) and thiocyanides (Davis, 1958) may also be short term intermediates in sulfide oxidation. The formation 0 f SCN can be expected from the reaction of elemental sulfur with the NaCN added in the flotation process (Anon., 1973). The product of this reaction, thiocyanate in the Fe form is probably responsible for the red discoloration of the tailings seepage ponds shown in Appendix A.9. The relatively slow rates of elemental sulfur and total oxidizable sulfur production are reflected by their lack of correlation with water or acid extractable sulfate (Appendix C.2). This slow oxidation of sulfur intermediates is also apparent from the relatively low levels of water and acid extractable sulfate, 0.43% and 0.14% respectively. A high correlation exists between water and acid extractable sulfate levels (r = 0.69**). The forementioned high correlations between the 61 tailings pH and water and acid extractable sulfate (Appendix C.2) can account for the correlation between the two types of extractable sulfate. 4.1.1.3 Iron monosulfide oxidation in iron tailings with pH >2.5 For the iron tailings with pH >2.5, iron monosulfides were found in all but one sample and averaged 5.17%. The levels of iron monosulfides were not significantly correlated with any of the other sulfur forms or with pH (Appendix C.2). The absence of these correlations may be par-t ial ly due to a flow buffering intensity, allowing the pH to drop rapidly compared -to siliceous tailings samples. Total oxidizable sulfur and elemental sulfur were found in high quantities, averaging 7.17% and were correlated with pH (r = -0.46**) and elemental sulfur (r = 0.66**). Elemental sulfur averaged 5.2% and was also associated with pH (r = -0.66**). Thus total oxidizable sulfur appeared to be primarily elemental sulfur. In addition, small quantities of pyrite, seen as sand size crystals in visual and microscopic examin-ation, occurred in the samples. The pyrite grains appeared to be highly resistant to oxidation since they occur as visible inclusions in ferruginous caps like those shown in Appendix A.7. Their resistance to oxidation, and the theoretical reduction in the accumulation of thiosulfate and poly-thionates as the pH is reduced (Sinha and Walden, 1966), combine to make pyrite a significant contribution to the total oxidizable sulfur. The complete oxidation of reduced sulfur compounds appears to be slow as both water and acid extractable sulfate were low, 0.39 and 0.16% res-pectively. A significant correlation was found between pH and water ex-tractable sulfate (r = -0.42*) and acid extractable sulfate (r = -0.47**). 62 On the average, water and acid extractable sulfate compounds were cor-related (r = 0.39*), indicating that the levels of precipitated sulfate may partially control the sulfate solubility in some way. 4.1.1.4 Iron monosulfide oxidation in iron tailings with pH <2.5 Iron monosulfides were only detected in 2 of the 57 iron tailings samples with pH <2.5 (Appendix B). However, total oxidizable sulfur s t i l l amounted to an average of 2.53% (Appendix C.4) and was very highly cor-related with elemental sulfur (r = 0.91**). This correlation indicates that elemental sulfur is the predominant form of oxidizable sulfur in these highly oxidized iron tailings. The average elemental sulfur content of approximately 2.6%, equivalent to that of total oxidizable sulfur supports this finding. The apparent almost total absences of oxidizable sulfur other than elemental sulfur can be explained by the low pH (discussed previously) and fluvial action. It is conceivable that repeated erosion and deposition of oxidizing iron tailings could result in the burial of horizons which contain pyrite. Oxidation processes could also account for some depletion of pyrite in the surface horizons. The relatively low -levels of elemental sulfur in these samples were accompanied by relatively high levels of water and acid extractable sulfate, 0.75 and.0.80% respectively. Sulfate in the water and acid extractable forms were correlated (r = -0.35**). However, only the former was associ-ated significantly with pH (r = -0.37**). The apparent increase in soluble sulfate in the tailings, as the pH is reduced, can be implicated as a cause of sulfur depletion as the tailings are oxidized. Admittedly, appar-ent sulfur depletion may also occur due to dry weight additions of oxygen 63 with iron and sul f ide oxidation processes. 4.1.2 Dissolut ion of Minerals with Iron Monosulfide Oxidation 4.1.2.1 Introduction The d isso lu t ion of minerals in the iron and s i l i ceous t a i l i n g s was estimated by decreases in acid extractable A l , Ca, Mg, K and Na as iron su l f ide oxidation proceeded. The levels of these acid extractable cations were compared to iron su l f ide oxidation parameters. The parameters chosen for comparison were i ron monosulfides, to ta l oxidizable su l fur , elemental su l fu r , water extractable su l fa te , acid extractable su l fa te , and pH. The amounts of each sulfur form in a sample can be used to calcula te the amount of acid produced assuming: ( i ) sulfur forms are not los t from the system through erosional processes; ( i i ) the dry weight is corrected for additions of oxygen in iron s u l -fide oxidat ion; ( i i i ) to ta l oxidizable sulfur does not include th iosulfa te which rep-resents the formation of two moles of acid per mole of th iosul fa te (Chen and Morr is , 1972); ( iv ) pyr i te does not occur in the t a i l i n g s , thus e l iminat ing the con-t r ibut ions of pyr i te to the to ta l oxidizable su l fur . In pract ice these assumptions may not be v a l i d and only an estimate of acid produced can be obtained. The a c i d i t y produced can ei ther be neutral ized by basic carbonates, exchangeable bases or basic cations wi th in clay minerals. The a c i d i t y produced in iron su l f ide oxidation minus that 64 consumed by bases is represented by the' pH. Thus, at any given time the pH is dependent on the buffering intensity. 4.1.2.2 Mineral dissolution in the siliceous tailings In the siliceous tailings samples the amount of iron monosulfides was only correlated with acid extractable Ca (r = 0.66**). This obser-vation infers that Ca in these tailings is mainly in a readily neutralized form such as calcium carbonate. These Ca containing minerals doubtlessly consume a portion of the acidity generated in the oxidation of iron from iron monosulfides. Most of the remaining acid is consumed in the oxi-dation of sulfides to elemental sulfur, as elemental sulfur accumulates markedly. The initial products of sulfide oxidation represented by total oxidizable sulfur were negatively correlated with acid extractable alu-minum (r = -0.43**). While the majority of the total oxidizable sulfur can be accounted for as elemental sulfur, a portion of it is theoretically in the form of thiosulfate and polythionates. The acid produced due to their formation may be partly responsible for the dissolution of Al from clay minerals. The non-significant correlation between total oxidizable sulfur and Ca (r = -0.24) indicates that most of the readily available Ca was consumed in the oxidation of iron. No explanation can be given for the lack of correlation between total oxidizable sulfur and acid extractable Mg (r = -0.28). The levels of elemental sulfur were negatively correlated with acid extractable Ca (r = -0.35*). Elemental sulfur unlike total oxidizable sulfur was not associated with acid extractable Al (r = -0.28). However, 65 as the formation of elemental sulfur consumes acidity, any. correlation would be due to associations between elemental sulfur and its oxidation products. Water extractable sulfate was negatively correlated with acid extract-able Ca (r = -0.41**) but not with the other cations. This correlation further demonstrates that the dissolution of Ca was mainly from minerals other than those from which Al and Mg were obtained. No correlations were found between acid extractable sulfate and acid extractable cations. This may be due to the high pH in most siliceous tailings samples (Appendix B and C.2) suppressing the precipitation of sulfate containing minerals such as jarosite (van Breemen, 1973a). It is also possible that the acid extractable cations included significant quantities of cations adsorbed on exchange sites. The best correlations were found between pH and acid extractable Al (r = 0.57**), Ca (r = 0.66**) and Mg (r = 0.42**). This supports the previous hypothesis that the siliceous tailings samples had a high buffering intensity. The high correlation between pH and acid extractable Al also indicates that the weathering of clay minerals was significant. The absence of correlations between any of the oxidation indices and acid extractable K and Na is most likely due to their low levels and rapid precipitation as components of jarosite type minerals once they are liberated from clay minerals. 4.1.2.3 Mineral dissolution in the iron tailings with pH >2.5 The iron tailings samples with pH >2.5 did not have correlations between iron monosulfides and any of the acid extractable cations 66 (Appendix C.3). The absences of these correlations may be the conse-quence of a low buffering intensity in these tailings allowing a rapid drop in pH. This hypothesis is supported by the lower average percent water extractable Ca in these iron tailings samples of 0.295% compared to 0.435% for the siliceous samples. The generally high iron monosulfide content in these iron tailings samples means that the buffering of the pH by clay minerals and their exchangeable bases is not significant. The lack of these bases associated with clay minerals further supports the theory that buffering intensity is low in these iron tailings. Total oxidizable sulfur was negatively correlated with acid extract-able Ca (r = -0.41*). This correlation was approximately the same as. that for the siliceous tailings (Appendix C.2). A negative correlation also exists between total oxidizable sulfur and acid extractable K (r = -0.35*). Apparently, increases in total oxidizable sulfur result in decreases in acid extractable K. Elemental sulfur was negatively correlated with acid extractable Ca (r = -0.55**), Mg (r = -0.62**) and K (r = -0.55**). On theoretical grounds, elemental sulfur production consumes acid and would not be respon-sible for decreases in acid extractable Ca, Mg and K. The high correlation between elemental sulfur and total oxidizable sulfur (r = 0.66) may be indirectly responsible for the significant correlations between elemental sulfur and Ca, Mg and K. The correlations between water extractable sulfate and acid extract-able K was negative (r = -0.36*). Apparently the acid produced from water extractable sulfate was associated with a decrease in acid extractable K. No association was found between water extractable sulfate and the other 67 acid extractable cation levels. Acid extractable sulfate was associated with acid extractable Mg (r = -0.33**) but not with the other cations. No explanation can be forwarded for the lack of other correlations. The tailings pH was associated with acid extractable Ca (r = 0.62**), Mg (r = 0.82**), and K (r = 0.61**). The correlation between pH and acid extractable Al was not significant (r = 0.23). Thus, pH appeared to be a good predictor of decreases in acid extractable cations in the iron tailings with pH >2.5. The correlations of pH with acid extractable Mg and K may be due to a selective stripping of Mg and K from the interlayer positions of clay minerals. 4.1.2.4 Mineral dissolution in iron tailings with pH <2.5 The iron tailings samples with pH values <2.5 did not have any cor-relations of iron monosulfides, total oxidizable sulfur, or elemental sul-fur with acid extractable cations. This absence of significant correlations may be due to the high degree of mineral dissolution in these tailings. Soluble sulfate was correlated with acid extractable Al (r = 0.34*). No reason can be given for this positive correlation. Insoluble sulfate was correlated with acid extractable K (r = -0.25*). No other acid extractable cations were associated with insoluble sulfate. pH appeared to be the best index of mineral dissolution as measured by correlations with acid extractable cation. The tailings pH was correl-ated with acid extractable Al (r = 0.24*), Ca (r = 0.39**), Mg (r = 0.39**) and K (r = 0.26*). 68 4.1.3 Accumulation of Salts with Iron Monosulfide Oxidation 4.1.3.1 Introduction The oxidation of iron monosulfides and the dissolution of minerals in the iron and the siliceous tailings results in the formation of soluble salts. They accumulate on the surface, particularly along cracks (Appendix A.4). Their eventual loss from the profile results in the formation of salt crusts, such as that shown in Appendix A.5, and acid drainage. The amount of salt formed with the degree of weathering can be esti-mated by the determination of water extractable cations levels. The cations Fe, Al , Ca, Mg, K and Na were chosen because they are the major cations released in iron sulfide oxidation and clay dissolution. The water extractable level of these cations is a good estimate of salt release assuming: (i) amounts of cations on the clay CEC are minimal in comparison to those in solution; (i i) the loss of cations through leaching and surface erosion is minimal. 4.1.3.2 Accumulation of salts in the siliceous tailings In the siliceous tailings the amounts of iron monosulfides in the samples are negatively correlated (Appendix C.2) with the levels of water extractable Al (r = -0.37*), Ca (r = -0.61**) and Mg (r = -0.35*). The best correlation between iron monosulfides and Ca appears to be due to a greater reactivity of Ca than Al and Mg. Iron monosulfides are correlated positively with the levels of water extractable K (r = 0.47**) and Na (r = 0.32*). It is possible that these positive correlations are due to 69 the precipitation of K and Na as constituents of iron sulfate minerals of the jarosite series (van Breemen, 1973a). Overall, for the siliceous tailings samples, the amount of iron monosulfate was negatively correlated with conductivity (r = -0.38**). Thus iron sulfide oxidation appears to result in an increase in water extractable A l , Ca, Mg, and a decrease in water extractable K and Na. Total oxidizable sulfur and elemental sulfur unlike iron monosulfides, were negatively correlated with water extractable K, r = -0.31* and r = -0.43** respectively. Even higher negative correlations were found between water extractable K and water extractable sulfate (r = -0.47**) and acid extractable sulfate (r = -0.58**). These negative correlations most probably reflect a depletion of K in the tailings. The depletion of K is likely on theoretical grounds due to the high solubility of K-sulfate salts above pH 4. It is also possible that some K may be adsorbed onto cation exchange sites of aluminosilicates or Fe and Al hydroxides. However, the high levels of water extractable Fe (0.16%), Ca (0.43%) and Mg (0.12%) combined with their high selectivity for cation exchange sites, tends to suppress the adsorption of K on such sites. The correlation between water extractable sulfate and Na was not significant (r = -0.14). However, water extractable Na and,-K were highly correlated (r = 0.66**). This correlation suggests that Na may also be depleted as oxidation and mineral dissolution proceeds. Sulfate is the predominant water extractable anion in the tailings based on its very high correlation with conductivity (r = 0.91**). The cations associated in the water extract with sulfate include Fe (r = 0.53**), Al (r = 0.78**), Ca (r = 0.49**), and Mg (r = 0.82**). The relatively 70 stronger associations of Al and Mg with the level of sulfate implies their solubilization is more dependent on the oxidation of sulfur intermediates to sulfate. The high association between water extractable Al and Mg (r = 0.50**) indicates that Mg solubilization is dependent on aluminosili-cate dissolution. Such clay dissolution is theoretically enhanced due to acid release upon oxidation of sulfur intermediates to sulfate (Coleman and Craig, 1961). Acid extractable sulfate was only associated positively with levels of water extractable Al (r = 0.67**) and Mg (r = 0.57**). These correla-tions are likely due to the decomposition of clays by the prior production of the now insoluble sulfate and concomitant acid. There was a linear p relationship (R = 0.60) between soluble Mg and the total extractable sulfate concentration in the tailings samples: soluble Mg = - 0.08 +0.34 (total extractable sulfate). 2 A similar but more significant relationship (R = 0.68) was found between soluble Al and total extractable sulfate in the samples: soluble Al = •- 0.06 + 0.17 (total extractable sulfate). Admittedly, these two relationships oversimplify the dependence of the level of water extractable Mg and Al on acid formation. These relation-ships did not take into account acid production in thiosulfate formation above pH 4 and its consumption in jarosite formation below pH 4. If these sources of acid production and consumption were considered, a more approp-riate relationship between water extractable Mg and Al and acid produced could be found. The acid remaining in solution after neutralization by minerals is .represented by the pH. The pH levels were negatively correlated with water 71 extractable Al (r = -0.60**), Ca (r = -0.44**) and Mg (r = -0.51**). On the other hand, pH was positively correlated with water extractable K (r = 0.81**) and Na (r = 0.48**). These correlations indicate that the siliceous tailings samples had a high buffering intensity which allowed a slow decrease in the pH with the increase in weathering of minerals. 4.1.3.3 Accumulation of salts in the iron tailings with pH >2.5 For the iron tailings samples with pH >2.5, the levels of water extractable Fe were highly correlated (Appendix C.3) with total oxidizable sulfur (r = 0.69**) and elemental sulfur (r = 0.93**). Water extractable Fe is also highly correlated, but in a negative way, with pH (r = -0.73**). Total oxidizable sulfur and elemental sulfur were correlated highly with pH, (r = -0.46**) and (r = -0.66**) respectively. Thus, the correlations between the water extractable Fe and total oxidizable sulfur and elemental sulfur are probably coincidental. Water extractable Ca was correlated negatively with total oxidizable sulfur (r = -0.33*) and elemental sulfur (r = -0.46**). However, water extractable Ca was not associated with pH (r = 0.15). No explanation can be given for the correlation of water extractable Ca with total oxidizable sulfur or elemental sulfur. Water extractable K and Nawere correlated negatively with total oxidizable sulfur (r = -0.40*) and elemental sulfur (r = -0.47*). It is possible that K is solubilized when the total oxidizable sulfur and elemen-tal sulfur are oxidized. The same correlations hold between water extract^ able Na and total oxidizable sulfur (r = -0.39*) and elemental sulfur 72 (r = -0.33*). 4.1.3.4 Accumulation of salts in the iron tailings with pH <2.5 For the iron tailings with pH <2.5, water extractable Ca was nega-tively associated with total oxidizable sulfur (r = -0.28*) and elemental sulfur (r = -0.25*). These correlations were similar to those found in the iron tailings with pH >2.5. The absence of correlations between reduced sulfur forms and the other water extractable cations were con-founding. The levels of water extractable sulfate were associated with the levels of water extractable Fe (r = 0.52**), Al (r = 0.48**), Ca (r = 0.29**) and Mg (r = 0.51**). Overall water extractable sulfate is highly associated with conductivity (r = 0.89**), indicating that sulfate is the predominant anion in the iron tailings with pH <2.5. The water extractable cations were not correlated with acid extract-able sulfate. 4.2 Occurrence and Role of Microorganisms in the Oxidation Process 4.2.T Occurrences and Associations of the Main Physiological Groups of  Microorganisms in the Tailings Materials 4.2.1.1 Siliceous tailings In the siliceous tailings, the most prevalent groups of microorganisms are acid tolerant fungi and sulfur oxidizing bacteria with frequencies of occurrences of 93% and 70% respectively (Table 1). Comparably, the acid Table 1. Frequency of Occurrence {%) of Microorganisms for Each Tailings Material MICROBIAL GROUP TAILINGS MATERIAL SILICEOUS TAILINGS IRON TAILINGS pH > 2.5 IRON TAILINGS pH < 2.5 iron bacteria 13 42 28 sulfur bacteria total 70 88 19 identif ied as : - Thiobacillus thioparus 3 27 0 - Thiobacillus neapolitanus 43 4 0 - Thiobacillus thiooxidans 10 20 4 acid tolerant fungi 93 . 77 81 acid tolerant heterotrophic bacteria 30 . 58 67 74 tolerant heterotrophic bacteria and iron oxidizing bacteria were found in/only 30 and 13% of the samples respectively. Among the microorganism groups, the sulfur bacteria and the acid tolerant fungi have the highest frequency of association (Table 2). How-ever, on the basis of population, only the sulfur bacteria and the acid tolerant heterotrophic bacteria are associated together (r = 0.74***). It is unlikely that this high correlation is due to sulfur bacteria taking on a heterotrophic growth habit for three reasons: (i) The species of sulfur bacteria isolated, when replica plated on YES medium were not stimulated by the presence of yeast extract, (ii) The enumeration of acid tolerant heterotrophic bacteria was carried out at a pH where the sulfur bacteria isolated are inhibited. ( i i i ) Small heterotrophic colonies were often found in the thiosulfate media used to isolate sulfur bacteria. A plausible explanation for their association, is a symbiotic relation-ship. The regression equation was significant at the 0.001% level: acid tolerant heterotrophic bacteria = - 191 + 0.5 (sulfur bacteria) R2 = 55% The low occurrence of iron bacteria in the samples studied makes it hard to evaluate their similar relationship with acid tolerant bacteria in this tailings material. 4.2.1.2 Iron tailings with pH >2.5 The iron tailings with pH values greater than 2.5 tended to have a higher frequency of occurrence for sulfur bacteria (88%), acid tolerant Table 2. Frequency of Association {%) of Microorganisms for each Tailings Material* SILICEOUS TAILINGS. MICROBIAL GROUP IRON BACTERIA SULFUR BACTERIA ACID TOLERANT FUNGI ACID TOLERANT HETEROTROPHIC BACTERIA iron bacteria sulfur bacteria acid tolerant fungi acid tolerant heterotrophic bacteria 7 10 7 63 17 30 • IRON TAILINGS pH > 2.5. iron bacteria sulfur bacteria acid tolerant fungi acid tolerant heterotrophic bacteria 38 38 23 59 46 42 IRON TAILINGS pH < 2.5. iron bacteria sulfur bacteria acid tolerant fungi acid tolerant heterotrophic bacteria 13 20 15 17 15 . 61 * frequency of association based on number of samples positive for both microbial group out of the total number of samples of that tailings material. 76 heterotrophic bacteria (58%) and iron bacteria (58%) than in the compar-able siliceous tailings. The acid tolerant fungi were not present as often, occurring in 77% of the iron tailings samples. All four groups of microorganisms were more frequently associated with each other than in the siliceous tailings. However, the only correl-ation was between the iron bacteria and the acid tolerant heterotrophic bacteria (r = 0.98***). The numbers of acid tolerant heterotrophic bacteria can be predicted by the equation: acid tolerant heterotrophs= -157.3 +0.1 ( iron bacteria ) This high correlation indicates that there may be a symbiotic relation-ship between these two groups whereby the acid tolerant heterotrophic bacteria are dependent on the organic matter excreted by the iron bacteria as an energy source. Such a relationship has already been postulated by Manning (1976). 4.2.1.3 Iron tailings with pH <2.5 Acid tolerant heterotrophic bacteria and fungi occurred in 67% and 81% of the samples analyzed in this pH range (Table 1). Iron bacteria and particularly sulfur bacteria were less frequent, present in 28% and 19% of the samples respectively. Obviously, the acid tolerant bacteria and fungi were found frequently in the same sample (61%), but their numbers were not significantly correl-ated. The only correlation in the iron tailings, at these low pH values, was between the iron and sulfur bacteria (r = 0.84**). The regression 77 equation for sulfur bacteria, in terms of iron bacteria, is: 2 sulfur bacteria = 313 + 0.01 (iron bacteria) R = .71 This relationship appears to be reasonable, as iron bacteria are also capable of oxidizing sulfur. 4.2.2 Role of the Main Physiological Groups of Microorganisms in the  Tailings Materials 4.2.2.1 Siliceous tailings No acceptable correlations between the type of microorganism and its source of energy were found for the samples analyzed.' Associations between microorganism group and other tailings parameters were only found in the case of fungi. The populations of fungi were correlated with pH (r = -0.40*), conductivity (r = 0.65**), iron monosulfides (r = -0.33*), soluble sulfate sulfur (r = 0.60**) and insoluble sulfate sulfur (r = 0.52**). These associations do not appear to reflect any chemical relation-ship. It is likely that this correlation reflects the slow rate of colonization ' of fungi paralleling oxidation in these tailings samples. 4.2.2.2 Iron tailings with pH >2.5 The physiological groups of microorganisms studied were not correlated with their source of energy for the samples analyzed. As in the case of the analogous siliceous samples, fungi were associated with iron monosulfide (r = -0.38*), soluble sulfate sulfur (r = 0.59**) and insoluble sulfate sulfur (r = 0.67**). Again, a slow colonization of fungi is implicated as the cause of the associations. 78 Compared to the siliceous tailings, the iron tailings with pH >2.5 had a higher percentage of samples positive for iron bacteria, 10 and 38% respectively. This allowed a comparison between tailings samples positive and negative for these bacteria. It was found that samples positive for iron bacteria had lower pH, lower iron monosulfide, and higher elemental sulfur content than samples negative for them. Further-more, those iron tailings with iron bacteria were mostly in the pH range of 3.6-4.2. Only two samples with pH values above this range were positive for iron bacteria. These two samples positive for iron bacteria had pH values of 4.7 and 6.3. If the latter sample is ignored, iron bacteria populations are related to pH: log (iron bacteria) = -10.7 + 3.5 (pH) R2 = 0.56 4.2.2.3 Iron failings with pH <2.5 The physiological groups of microorganisms were not correlated with their;source of energy or other parameters. Furthermore, no relationship was found between pH and the numbers of iron bacteria. 4.2.3 Sulfur Bacteria Succession In addition to J_. ferrooxidans, three other sulfur bacteria were iso-lated and identified from the tailings samples. The identification was based on colony morphology and the pH to which they lowered a thiosulfate medium. The three species that were recognized are T. thioparus, T_. neapolitanus and T. thiooxidans. J_. thioparus colony morphology is shown 79 in Appendices A. 11 and A. 12. The typical morphology for J_. neapol itanus and J_. thiooxidans colonies are illustrated in Appendix A.13 and A.14 respectively. The three species vary in their tolerance to acid conditions. ! • thioparus has the least tolerance for acidity, reducing a thiosulfate medium of pH:5.'5 to 4.0, on the average. J_. neapol itanus reduces the pH of the thiosulfate medium to about pH 3.3. T. thiooxidans is shown to be capable of lowering the pH of this medium to 1.9. These findings imply that a succession of thiobacilli from J_. thioparus to T. neapol itanus and eventually to T. thiooxidans occurs. This hypothesis is borne out by the average pH where these species occurred: 4.95 for T. thioparus, 3.55 for J_. neapol itanus and 3.3 for T. thiooxidans. The tailings pH range over which these species occurred were 6.86-2.45 for T. thioparus, 6.4-2.8 for J_. neapol itanus and 4.16-1.95 for J_. thiooxidans. The species of thiobacilli predominating was also dependent on the type of tailings material. A majority of the siliceous tailings samples positive for thiobacilli contained J_. neapol itanus 43%, with J . thioparus and J_. thiooxidans occurring in 3% and 10% of the samples respectively (Table 3). For the iron tailings samples with pH >2.5, T. thioparus and ! • thiooxidans occurred most often, 27% and 20% respectively. T_. thiooxidans only occurred in 4% of these iron tailings samples. However, those iron tailings samples with pH <2.5 did not contain either T. thioparus or T. neapolitanus. Even the acid tolerant species T. thiooxidans was rarely observed in samples with these low pH values. The relatively uncommon occurrence of thiobacill i , even J_. thiooxidans, in iron tailings samples with a pH <2.5 is probably due to very low levels of oxidizable sulfur in the upper portion of the samples. Table 3. Thiobacilli Species Isolated in Samples and the pH They Lower a Thiosulfate Medium (S 5.5) To. THIOBACILLUS THIOPARUS THIOBACILLUS NEAPOLITANUS THIOBACILLUS THIOOXIDANS SAMPLE S5.5 pH SAMPLE S5.5 pH SAMPLE S5.5 pH NUMBER NUMBER NUMBER 13 4.3 44 3.45 39 1.9-1.95 15 4.0-4.1 49 3.75 77 1.6-1.7 16 4.05-4.55 50 3.25 78 1.65-1.8 55 3.45 51 3.3 79 1.80 56 3.7-4.05 52 3.2-3.3 80 1.85-2.1 63 , 4.1 53 2.3-3.25 81 1.7 97 4.05-4.1 55 3.3-3.35 86 1.8-2.25 98 3.95-4.05 57 3.4-3.55 94 2.45 99 4.15 58 3.3 101 3.90 59 3.35 62 3.35-3.4 64 3.2 65 3.3 66 3.15 101 3.9 81 The predominance of J_. thioparus in the iron tailings with pH >2.5 and T_. neapol itanus in the siliceous tailings with the same pH range suggested that some nutritional factor was selecting for a particular thiobacilli species. Since Jones and Happold (1971) reported that T_. thioparus was inhibited by a lack of K, this relationship was investigated. For the iron tailings with pH >2.5, the log J_. thioparus population was found to be related to the water extractable K and Na concentrations: log (T_. thioparus)+3 = 0.72 + 0.11 (water extractable Ca) +116 (water extractable K) R 2 = 0.77 The fact that only three of the siliceous tailings samples were positive for J . thioparus made any relationship questionable. This relationship between T. thioparus and water extractable Ca and K in the iron tailings should be investigated further to check its validity. The possible stimulation of growth in the presence of Ca and K was investigated for T. neapolitanus in the siliceous tailings samples. It was found that relationship was weak With R - 0.15"and fitted the equation: log (J_. neapol itanus) +3 = 1 .89 + 3.27 (water extractable Ca) -49.4 (water extractable K) It seems that T_. neapol itanus populations are not markedly related to the water extractable Ca and K concentrations in the siliceous tailings. 82 4.3 Mineralogical Changes Due to Iron Monosulfide Oxidation Mineralogical analyses were conducted on seven samples selected to represent the range of weathering from relatively unoxidized to highly oxidized tailings. The seven samples selected were numbers 3, 17, 28, 36, 54, 65 and 87. The l a s t three samples were from sites 1, 5 and 8 respectively, from the siliceous tailings pond (Figure 1). Samples 17, 28 and 36 were from sites 17, 11 and 15 respectively, on the upper iron tailings pond. Sample 3 was collected from site 16 - .a 30 year old sur-face developed from the 1948 iron tailings sp i l l . All samples except 17 represent degrees of weathering by a gradual oxidation process mediated by iron and sulfur oxidizing thiobacilli . Strictly speaking,.the mineral-ogical changes in sample 17 are'primarily the result of a sulfur fire on the tailings rather than biological oxidation. The powder x-ray diffraction patterns are shown in Appendix D. The patterns are arranged by descending pH from sample 65-17. This descending pH ordering of the samples is- a rough guide to the degree of weathering (Table 4) as represented by the percent oxid.izable sulfur. The approximate d-spacings in Angstroms, of the x-ray peaks shown in each pattern in Appendix D are given in Table 5, along with the mineral(s) responsible for each peak. Minerals indicated represent major constituents in the samples as the resolving power is low compared to camera patterns obtained with a Guinier Holgg camera (Ivarson et_ a_l_., 1976). The weathering of minerals and their alteration or dissolution products +2 in the Sullivan tailings are mainly due to Fe and sulfur oxidation. It +2 appears that Fe oxidation is extremely rapid as evidenced by the absence of detectable amounts of pyrrhotite in all samples except 65. In this Table 4. Chemical Analyses of Samples Selected for Mineralogical Study PARAMETER SAMPLE NUMBERS 3 17 28 36 54 65 87 PH 2.04 1.84 2.16 2.16 2.73 6.95 3.69 conductivity (mmho's/cm ) 8.6 10.4 12.4 11.5 8.0 2.1 3.1 monosulfide sulfur {%) 0.0 0.0 0.13 0.0 0.01 2.69 0.79 elemental sulfur {%) >0.2 1.7 5.2 4.2 2.9 0.3 3.6 soluble sulfate {%) 0.68 0.78 0.91 0.86 0.66 0.23 0.56 insoluble sulfate {%) 0.64 0.67 0.88 0.86 0.66 0.0 0.38 % sulfur oxidized to sulfate • > 99 46 25 29 31 7 18 soluble Al {%) 0.093 0.065 0.338 0.11 0.209 0.0 0.009 soluble Ca [%) 0.115 0.25 0.175 0.071 0.452 0.369 0.534 soluble Mg {%) 0.073 0.043 0.241 0.098 0.308 0.049 0.056 soluble K (%) 0.002 0.0 0.0 0.0 0.0 0.019 0.002 soluble Na (%) 0.002 . 0.002 0.0 0.002 0.002 0.013 0.009 insoluble Al {%) 0.0 0.30 0.67 0.40 0.60 1.00 0.60 insoluble Ca (%) 0.057 0.263 0.086 0.061 0.129 0.379 0.467 insoluble Mg (%) 0.063 0.063 0.368 0.136 0.500 0.980 0.593 insoluble K (%) 0.190 0.188 . 0.123 0.272 0.143 0.131 0.150 insoluble Na (%) 0.0 0.0 0.0 0.070 0.0 0.0 0.0 s i te location (Figure I) 16 17 11 15 5 1 8 Table 5. X-Ray Data for Samples Selected for Mineralogical Study J r n „ „ „ ^ SAMPLE NUMBERS d-SPACINGS A 65 87 54 28 36 3 17 14 .3 chlori te chlorite chlorite chlorite chlorite 12. .2 montmorillonite (?) 10, .1 mica mica mica mica mica mi ca 7 .6 gypsum gypsum gypsum gypsum 7 .1 chlori te chlorite chlorite chlorite chlorite chlorite chlorite 5. .95 ja ros i te jarosite jarosite jarosite jarosite jarosi te 5. .71 jarosite 5 .10 jarosite jarosite jarosite jarosite jarosite 5. .00 mica mica mica mica mi ca mi ca mica 4. ,72 chlorite chlorite chlorite chlorite 4, .28 gypsum gypsum gypsum gypsum 4. ,27 quartz quartz quartz quartz quartz quartz quartz' 4. .17 goethi te goethi te 3. .87 • sulfur sul fur sulfur sulfur 3. .80 gypsum gypsum gypsum 3. .67 jarosite jarosi te jarosi te jarosite jarosite 3. .55 chlorite chlorite chl ori te chlorite chlorite chlorite 3. ,36 quartz quartz quartz quartz quartz quartz quartz 3. ,34 mica mica mica 3. .22 sul fur sulfur sulfur 3. ,20 K-feldspar K-feldspar K-feldspar K-feldspar K-feldspar K-feldspar K-feldspar 3. ,13 sulfur sul fur sulfur & jarosite sulfur & jarosite jarosite jarosite Continued . . . Table 5. Continued . . . 3.09 3.07 gypsum gypsum gypsum 2.99 pyrrhotite 2.83 chlorite chlorite chlorite 2.70 2.65 pyrrho ti te 2.52 2.46 quartz quartz quartz jarosite jarosite jarosite jarosite gypsum chlorite hematite hematite quartz quartz quartz quartz 86 latter sample, the presence of pyrrhotite (7.4%) is indicated by peaks at 2.99 and 2.65 %. Pyrite was not detected in the samples selected but has been observed in the microscopic examination of bulk samples of fresh iron tailings. Normally these pyrite crystals are among the largest particles in the fresh tailings and appear to be resistant to oxidation. Pyrite crystals are frequently observed visually as inclusions in ferruginous crusts on the tailing pond surface. The accumulation of elemental sulfur in the iron and siliceous tailings is indicated by peaks at 3.87 and 3.22 8 , attributable to the crystalline rhombohedral form of sulfur. This form of sulfur appears to be present in samples 17, 28, 36 and 54 but absent in fresh and highly weathered tailings samples. The amount of elemental sulfur detected colorimetrically corresponds roughly to the peak heights except in the case of sample 87, where no sulfur peaks could be detected in the x-ray pattern. The detection of crystalline elemental sulfur by these two methods indicates that sulfur accumulates and is oxidized slowly compared to Fe + 2 . The aluminosilicate minerals chlorite, mica and feldspar were detected in several samples. These minerals could be expected, based on the min-eralogy of the sediments and rocks associated with the Sullivan ore body. Little (1970) stated that the hanging-wall sediments were heavily aT.bitized and locally chloritized and tourmalized. The foot-wall sediments contained a few conglomerate lenses and were heavily tourmalized. The presence of chlorite is indicated by peaks at 14.3, 7.1, 4.72, 3.55 and 2.83 8 . Chlorite appears to be especially abundant in samples o 54, 65 and 87. Based on the strongest peak at 7.1 A, chlorite is much 87 lower in samples 28 and 36, being lowest in the latter more weathered sample (29% sulfate). In samples 3 and 17 only traces of chlorite were detected. The levels of acid extractable Mg in the samples (Table 4) were roughly equivalent to the peak heights, although some of the Mg extracted may be derived from mica. Mica is indicated by the occurrence of major peaks at 10.1, 5.00 o and 3.34 A. The latter peak is indicative of the 3T type of muscovite o mica. The first two peaks are present in all samples; the 3.34 A peak shows up in samples 17, 36 and 87 where the 3.36 ft quartz peak does not obscure i t . The relatively high level' of mica in sample 3 is undoubtedly due to dust or soil eroded from the nearby dirt road (Appendix A.l) sep-arating site 16 from the iron tailings pond. The addition of minerals to soils via dust has.>been emphasized by earlier workers (Coen and Arnold, 1972). However, in the case of sample 3, the dust additions are much more appreciable since the surface is 30 years old and highly oxidized. This hypothesis is backed up by the high levels of quartz found in this sample. Mica additions may also account for the abnormally high levels found in samples 17,and 36 which are also near roads. o All samples had a 3.20 A peak attributable to K-feldspars. However, the peak was partially obscured in samples 17, 28 and 36 due to low levels of K-feldspars and the presence of other peaks in the region. As in the case of mica, levels of K-feldspars were highest in sample 3, indicating a recent addition primarily through dust. It is notable that evidence for the presence of albite (the sodium form of feldspar) and tourmaline was-.not detected. Both these minerals predominate in the sediments surrounding the Sullivan ore body and would 88 be expected to occur in fresh tailings. The absence of them is confirmed by the very low levels of water extractable and acid extractable Na in these samples (Table 4). Of the clay minerals deemed to be present in the selected samples, evidence for alteration products is lacking except in the case of chlorite in sample 87. This product is represented by a weak diffuse peak at o 12.4 A and is probably due to the presence of a chlorite-vermiculite intergrade (Berkeland, 1974) or montmorillonite (Lynn and Whittig, 1966). The absence of evidence for kaolinite as an incongruent weathering product is remarkable. According to van Breemen (1973a), kaolinite is the normal end product of clay mineral weathering in sulfidic soils. The absence of detectable kaolinite indicates that clay mineral weathering in the Sullivan iron and siliceous tailings ponds may be congruent. Undoubtedly, the Al released is in an amorphous hydroxide or sulfate form as peaks for gibbsite or the Al sulfate minerals were not detected. The high levels of water extractable Al in samples 28, 36 and 54 (Table 4) indicate that water extractable forms of Al are the major species present. Most likely, the soluble aluminum species AlOHSO ,^ postulated by van Breemen (1973b), is the predominant form. The major crystalline weathering products in these selected samples appear, to be the sulfates gypsum and jarosite. The presence of gypsum is represented by a strong peak at 7.6 ft and lesser ones at 3.80, 4.28 and 3.07 ft. Gypsum appears to be present in samples 28, 54, 65 and 87. It is most apparent in sample 87 as evidenced by the strong 7.6 ft peak. The levels of gypsum appear to decline in samples 28 and 54 corresponding to a reduction in pH. The decrease in gypsum content 89 in these low pH samples is probably due to its dissolution by a reaction to form jarosite at pH values less than 3.7 (van Breemen, 1973a). The presence of jarosite is shown by peaks at 5.96, 5.72, 5.10, 3.67, 3.13 and 3.09 ft. The jarosite concentration appears to increase as weathering proceeds, reaching a maximum in sample 28. The peak heights for jarosite generally follow the levels of acid extractable sulfate in the samples (Table 4). The lower levels of jarosite in the highly weathered samples may be_the result of a gradual depletion of sulfate-sulfur from the surface. The Na and H^O*; substituted forms of jarosite were not detected. The presence of ample amounts of insoluble K in even the highly oxidized samples substantiates its presence over the other members of the jarosite series. Jarosite cannot account for all the Fe present in the tailings samples. Probably most of the Fe is in the x-ray amorphous oxyhydroxide form. Langmuir (1969) stated that one of the characteristics of Fe oxyhydroxides is their transformation to hematite during heating. The presence of hematite, exhibiting strong x-ray peaks at 2.70 and 2.52 ft, substantiates this hypothesis. Some goethite may also be present as evidenced by the o weak diffuse peak at 4.17 A in samples 17.and 36. The crystallization of goethite is expected to be slow in the presence of anions such as sulfate (Schwertmann, 1966). 4.4 Correlations Between Qualitative Physical Tailings Characteristics  and the Amount of Oxidation and Weathering 4.4.1 Texture 90 Considering all samples collected, the texture of the tailings, as measured by the hand texturing technique, varies from loams to clays. The weighted average texture for the Sullivan iron and siliceous tailings is a si lty clay (24). Comparably, Morton (1976) found these tailings varied in texture from sandy loams to clay.loams, using the particle size analysis method. He found the average texture, for both.the iron and siliceous tailings, to be a s i l t loam. It is highly probable that the average texture is somewhere between the values obtained by these two methods of obtaining texture, due to the inherent errors in using them on this type of sample. Overall, the progression of textures to finer classes (rated numeri-cally in Appendix C.5) followed the increase in oxidation and concomitant weathering of the tailings material. Negative correlations were found between the texture class and iron monosulfide and total oxidizable sulfur content, r = -0.27** and -0.23** respectively. This correlation is reflected in the positive association between texture and water extractable sulfate (r = 0.18*) and acid extractable sulfate (r = 0.48**). Parameters, associ-ated with increases in weathering, also tended to be associated with texture. The relative increase in fineness of the tailings texture class was negatively associated with pH (r = -0.59**) and positively associated with conductivity (r = 0.53**). The main cations contributing to conduc-tivity also appeared to be correlated in varying extents with texture (Appendix C. l ) . Furthermore, texture was negatively associated with de-. creases in acid extractable Ca (r = -0.59**) and Mg (r = -0.51**) and positively associated with acid extractable Al (r = -0.364**). Comparing the siliceous tailings textures with those of analogous iron 91 tailings of a pH greater than 2.5, both have average textures in the silty clay loam class. Of the siliceous tailings samples analyzed, 20% were clays, 40% silty clays and 40% were loams (Appendix B.2). Compar-ably, the analogous iron tailings samples were 65% silty clays and 25% loams (Appendix B.2). This bimodal distribution of textures, for both tailings materials, indicates that the sampling was probably biased. Such biases would likely be more pronounced in the siliceous tailings, due to the higher content of relatively inert quartz. Even though there are doubts that the changes in siliceous tailings textures are due to oxidation processes, correlations with such processes were found. The texture, in this tailings material, was found to be associated with a decrease in total oxidizable sulfur (r = -0.38*) and an increase in water extractable sulfate (r = 0.49). No correlation was found between texture and pH, probably because of the high but variable amount of bases in this material. The texture in the siliceous tailings was found to be associated with increases in conductivity (r = 0.31*). The high correlation between texture and water extractable Ca (r = 0.48) and, to a lesser extent, water extractable Mg (r = 0.36*), tend to explain the lack of association between texture and pH, in this material. For the iron tailings with pH values greater than 2.5, texture was associated with the degree of oxidation. Texture was correlated with increases in elemental sulfur (r = 0.43*) and insoluble sulfate (r = 0.40*). Unlike the siliceous tailings, the textures in the iron tailings, with pH values greater than 2.5, were highly associated with pH (r = -0.74**). This texture-pH correlation is related to the lack of association between texture and water extractable Ca and Mg. On the other hand, texture was .92 highly associated with decreases in acid extractable forms of Ca (r = -0.76**) and Mg (r = -0.68**). Texture was also associated with conduc-tivity (r = 0.37*) and with water extractable iron (r = 0.48**). In the highly weathered iron tailings with pH values less than 2.5, the correlation between texture and degree of weathering was not as pro-nounced. Texture was associated with a decrease in total oxidizable sulfur (r = -0.32*) and elemental sulfur (r = -0.40**). As with these same tailings of pH greater than 2.5, texture was correlated with pH (r = -0.36**) and conductivity (r = 0.34**). 4.4.2 Structure The tailings structures varied from coarse granular to massive-structureless. About 20% of the samples were granular, 35% blocky, 20% platy and 25% massive-structureless (Appendix B.2). Although the numerical weighting for structure (Appendix C.5) may be somewhat arbitrary, general trends of its change with tailings oxidation processes can be perceived. For the tailings as a whole, increases in the structure weighting are associated with water extractable sulfate (r = 0.25**), water extract-able sulfate (r = 0.42**), pH (r = -0.55**) and conductivity (r = 0.54**). Lesser associations were generally found between structure and the water extractable cations. There were relatively high correlations between structure and the levels of acid extractable Al (r = -0.42**), Ca (r = -0.58**) and Mg (r = -0.55**). This may reflect the increase in structure with increasing weathering of aluminosilicate minerals. 93 For the siliceous tailings samples, the increase in structure was associated with increases in water extractable sulfate (r = 0.50**), acid extractable sulfate (r = 0.34**) and conductivity (r = 0.45**). In the case of the iron tailings with pH values greater than 2.5, structure was correlated with iron monosulfides (r = 0.42*), total oxidizable sulfur (r = 0.38*) and elemental sulfur (r = 0.36*). However, no correlation was found between structure and water or acid extractable sulfate. Associations were found between structure and pH (r = -0.63**) and conductivity (r = 0.32*). Structure was only correlated with pH (r = -0.49) in the iron tailings with pH values less than 2.5. However, since most of the samples have massive or platy structure, the lack of variability may make cor-relations insignificant. 4.4.3 Munsell Color 4.4.3.1 Hue The hue, or dominant spectral color (given a numerical rating in Appendix C.5) in the tailings samples as a whole, is associated with acid extractable sulfate (r = 0.30**) and pH (r = -0.40). Basically, the color appears to be related to the amount of acid extractable sulfate as jarosite, which becomes the dominant sulfur containing mineral at low pH, in sulfidic soils. However, i f samples of iron and siliceous tailings with a pH greater than 2.5 and iron ones with a pH of less than 2.5 are considered separately, the association is weak or insignificant. For the slightly to moderately oxidized siliceous tailings,.hue is 94 associated with iron monosulfides (r = -0.51**), total oxidizable sulfur (r = 0.55**), elemental sulfur (r = 0.50**) and pH (r = -0.48**). These high associations indicate that color is dependent on the iron sulfide and elemental sulfur content of the tailings, as total oxidizable sulfur is primarily elemental sulfur. In the case of the iron tailings with pH values greater than 2.5, hue is strongly correlated with total oxidizable sulfur (r = 0.50**), elemental sulfur (r = 0.59**) and pH (r = -0.58**). The slight correlations with water and acid extractable sulfate (r = 0.34* and r = 0.35* respec-tively) may indicate that these tailings samples are more weathered than the analogous siliceous tailings. This seems to be borne out by the lack of a significant association between hue and iron monosulfide content. For the iron tailings with pH values less than 2.5, the hue was only associated with total oxidizable sulfur and elemental sulfur (r = 0.26* and r = 0.27* respectively). These low correlations and the lack of any others is most likely due to the uniformly oxidized nature of these tailings. 4.4.3.2 Value The value, or relative lightness of color (given a numerical rating in Appendix C.5), when considering all tailings samples, was associated with iron monosulfides (r = -0.60**), total oxidizable sulfur (r = -0.33**), water extractable sulfate (r = 0.38**), acid extractable sulfate (r = 0.45**) and pH (r = -0.67**). However, these associations are not signifi-cant for the iron tailings samples, regardless of their pH, except in the case of a weak correlation between value and iron monosulfides (r = -0.35*). 95 For the siliceous tailings, the value is highly associated with iron monosulfides (r = -0.71**), elemental sulfur (r = 0.49**) and pH (r = -0.59**). Lesser correlations of value with water and acid extractable sulfate (r = 0.33* and r = 0.31* respectively), are apparent in this tai1ings material. 4.4.3.3 Chroma Chroma, otherwise known as the color's strength (given a numerical rating in Appendix C.5), is correlated with iron monosulfides (r = -0.65**), total oxidizable sulfur (r = -0.32**), acid extractable sulfate (r = 0.61**) and'pH (r = -0.80**). As with the value, chroma is poorly cor-related with sulfur forms in the iron tailings. The only exception is water extractable sulfate in the iron tailings with pH values greater than 2.5 (r = 0.50**). The siliceous tailings had chromas which were highly associated with iron monosulfides (r = -0.73**), elemental sulfur (r = 0.60**), water extractable sulfate (r = 0.50**) and acid extractable sulfate (r = 0.52**). In addition, the chroma was highly correlated with pH (r = -0.76**) in this tailings material. 4.5 Iron Monosulfide Oxidation and Weathering Versus Depth The analysis for the percentages of sulfur in each of the sulfur forms and the water and acid extractable cations, for each of the horizons sam-pled, is shown in Table 6. Table 6. Chemical Changes with Sample Depth WEATHERING PARAMETER 0-0.4 cm 1 0.4-2 cm 2-5 cm 5-10 cm iron monosulfides [% S) 0.22 elemental sulfur (% S) 5.8 total sulfate {% S) '2.51 total sulfur (% S) 8.53 water extractable cations Fe (%) 0.202 Al (%) 0.005 Ca {%) 0.118 Mg (%) 0.403 K (%) 0.002 Na {%) 0.0 acid extractable cations Fe (%) 6.48 Al (%) 0.20 Ca (%) 0.145 Mg {%) 0.123 K {%) 0.447 Na {%) 0.056 1.98 11.65 15.56 14,9 7.1 3.7 0.66 0.28 0.21 17.54 19.03 19.47 0.248 0.253 0.162 0.003 0.003 0.003 0.227 0.240 0.271 0.119 0.035 0.025 0.006 0.007 0.009 0.003 0.003 0.001 24.9 33.0 39.7 0.55 0.80 0.65 0.251 0.215 0.231 0.754 0.850 0.603 0.251 0.200 0.201 0 0 0 The data indicate that the total amount of sulfur increases with depth from 8.53% at the 0-0.4 cm depth to 19.47% at the 5-10 cm depth range. This increase in total sulfur with depth is associated with an increase in the level of monosulfide sulfur. These results show that monosulfides are being oxidized at a much higher rate on the surface 0-0.4 cm than at a depth of 5-10 cm, since the monosulfide levels were 0.22% and 15.56% respectively. The lower levels of total sulfur, in the two surface horizons, compared to the two deeper depth intervals, cannot be explained by sulfur translocation. Sulfate, the most soluble form of sulfur, is highest in the surface 0-0.4 cm (2.51%) and lowest in the 5-10 cm horizon (0.21%). In the absence of mineral additions, the only source of additional dry weight is the oxygen atoms incorporated to form Fe oxyhydroxides and iron sulfates in the oxidation process. Such additions tend to accentuate real decreases in the amount of oxidizable sulfur compounds and underestimate the increase in the amount of oxidized sulfur produced. The complete oxidation of iron sulfides can be represented by the equation: 6FeS + 27H20 + 27. 0 2 > 6Fe(0H)3 + 6S0~2 + 12H30+ (38) on a molecular weight basis there is a 109% weight increase in the oxidation of FeS to products. For this bulk sample, with a sulfide sulfur content of approximately 20%, the oxidation of one gram would yield about 1.7 gram of dry weight. The additions of oxygen to the dry weight can also be implicated in minimizing the increase in the amounts of mineral weathered and the soluble 98 salts produced due to the ''dilution effect". This phenomenon must be considered seriously, in the interpretation of any changes in the amount of any inorganic parameter with weathering. With the above viewpoint in mind, i t is evident that most of the oxidized monosulfide can be accounted for by increases in elemental sulfur and to a lesser degree by increases in sulfate. The proportion of elemen-tal sulfur to sulfate produced is highest for the 0-0.4 cm depth 2.1:1 and between 17:1 and 25:1 for the other three depths. This large differ-ence in the ratio of sulfate to elemental sulfur produced, between the upper 0.4 cm and the other depths, indicates that oxygen is being consumed before it has a chance to diffuse to greater depth. This would appear to be more pronounced i f i t is considered that approximately 0.069% HgSO^  is added to the tailings in the concentrator process (Anon., 1973). If this init ial ly added sulfate is corrected for, the levels of sulfur as sulfate are lower than the results indicate. Correcting for added sulfate, the ratio of sulfate sulfur to elemental sulfur between the 0-0.4 cm depth interval and the others, is enhanced somewhat. It is also very likely that a considerable amount of the elemental sulfur and sulfate found in the lower depth ranges, is due to oxidation in the field prior to sampling and mixing. If steps to correct this source of apparent sulfur oxidation were taken at the onset of weathering, the ratio of sulfur oxidized on the surface 0-0.4 cm to that at the 5-10 cm depth would be even more marked. As pointed out earlier, a major source of oxygen additions is as hydroxyl ions combined with oxidized Fe to form Fe oxyhydroxides. At the 0.4-2 cm depth range, the decrease in iron monosulfide content and the high level of elemental sulfur detected can be interpreted as a preferential 99 incorporation of oxygen into Fe oxyhydroxides over sulfate formation. The high levels of acid extractable Fe compared to sulfate in the surface 0-2 cm, substantiate the conclusion that iron is preferentially oxidized over sulfur when oxygen is limiting. The oxidation of iron monosulfides appears to contribute to the release of Al and Mg from minerals. Both these elements are elevated in the water extraction of the surface 0-0.4 cm despite the increases in dry weight with oxidation. This increased solubility of Al and Mg with weathering can contribute to their gradual depletion from the tailings via leaching. The relatively marked solubilization of Mg at the surface is coupled by a decline in acid extractable Mg. The Mg appears to be associated with Al in minerals, since the ratio of acid extractable Mg to Al is fairly constant at 0.94 and 1.0, in the 2-5 and 5-10 cm depth ranges respectively. The levels of water and acid extractable K and Na appear to be associated with the respective levels of Mg and Al in the three lower depths. However, the acid extractable K and Na are much higher than the respective levels of Mg and Al on a relative scale. Furthermore, the levels of water soluble K and Na do not increase in the 0-0.4 cm depth interval as the Al and Mg levels do. This evidence points to the depletion of K and Na from minerals, in the weathering process, and their incorpor-ation in the K and Na forms of jarosite. The potassium form of jarosite has been detected in the x-ray mineralogical analysis of selected samples. , This precipitation of K and Na in jarosite minerals, undoubtedly leads to their conservation in the tailings. The source and fate of a large portion of calcium appears different 100 from the other cations. In the 2-5 and 5-10 cm depth ranges, the relative levels of water extractable Ca are very high compared to A l , Mg, K and Na. At these depths, the level of calcium is associated with the level of total sulfate indicating the presence of Ca as gypsum. As gypsum has a high solubility in water (0.241 g/100 ml), this can also account for the high levels of soluble Ca in the relatively unweathered 2-10 cm depth range. The presence of gypsum has been confirmed for other relatively fresh tailings samples, in the mineralogical analysis. As lime and sul-furic acid are added to the tailings at the concentrator (Anon., 1973), i t is likely that this is the source of gypsum in the 2-10 cm depth range. 101 5.0 DISCUSSION 5.1 Physical Factors Which Increase the Rate of Iron Monosulfide Oxidation  in the Sulfidic Tailings 5.1.1 Cone e n t r a tor E xtract i o n.- P r o c e s s e s The milling and flotation processes at the concentrator are primarily responsible for the high initial oxidation rates in the iron and siliceous tailings. The milling or crushing of the Sullivan Mine ore reduces the particle sizes of the iron sulfide minerals. Under a microscope the crystals of pyrite appear to be in the fine sand particle size range and pyrrhotite in the s i l t and clay ranges. The predominance of pyrrhotite and its ease of milling (Anon., 1973) leads to a high iron sulfide surface area in the sulfidic tailings. The subsequent exposure to oxygen results in a rapid oxidation rate as pyrrhotite has a low electrode potential (Sato, 1960). It is said to react up to 81 times as fast as "good quality" pyrite (Hawley, 1972). The flotation process used to extract economic minerals uses surfactants:, to increase the adhesion of metal sulfides to air bubbles (Anon., 1973). They are primarily in the form of K or Na ethyl xanthates, which are init ial ly found in the tailings at a concentration of approximately 0.013%. These surfactants serve to enhance the contact between elemental sulfur crystal and sulfur oxidizing bacteria in the tailings (Cook,,1964; Duncan et a l . , 1964; Adair, 1966). Thus the mineral extraction at the concentrator sets the stage for 102 rapid oxidation of the tailings by promoting the contact of oxidizing agents with the iron sulfide minerals. 5.1.2 Physiography of the Sullivan Sulfidic Tailings Ponds The Sullivan Mine sulfidic iron and siliceous tailings ponds have been formed by the additions of tailings materials over a period of decades. These tailings are sent, from the concentrator to their respective tailings ponds, via a system of main and side launderers. The concentrator, launderers and iron siliceous tailings ponds are shown in an aerial photo (Appendix A . l ) . Three separate iron tailings pond surfaces (upper, middle and lower) and one siliceous pond surface now exist. In addition, there is a small tailings spill from a 1948 dam failure at the lower edge of the iron tailings- pond. Tailings are gravity fed through the launderers . as an aqueous slurry at a 1 2/3 percent grade for the iron tailings and 1% percent grade for the siliceous tailings (The Sullivan concentrator staff, personal communi-cation). These iron and siliceous tailings slurries are 35-40 and 20% solids, respectively (A. Winkers, Sullivan Mine, personal communication). The tailings are distributed along the length of the tailings dams, allowing fluvial action to distribute the tailings toward the center of the ponds (Appendix A.2). This distribution system results in the formation of wide crest dams with gently sloping faces. Since fine particles tend to move further than coarse ones, there is a general trend toward the accumulation of coarser materials along the tailings dam and finer materials (slimes) toward the center of the ponds. 103 In the case of the siliceous tailings pond, material is often added to the center of the pond once the init ial dam has been built. As the fineness of the material varies with the assay of the ore at the concentrator, the relative particle size distribution deposited varies with time. Characteristically, the materials are deposited in horizons of varying thickness, particle size distribution and chemical composition. Fluvial action, in the form of meandering water channels, tends to result in discontinuous horizons (Appendix A.3), particularly at a distance from the tailings dam. Additional water enters the tailings ponds through rainfall , springs and wash water from the concentrator. The former sources are a major cause of gullying, particularly at the base of sloping surfaces such as dams. This action is pronounced during a heavy rain, especially on the iron tailings due to their relatively low mean hydraulic conductivities, 14 cm per day compared to an average of 60 cm per day in the siliceous tailings (Morton, 1976). Springs from the center of the iron tailings pond result in only minimal water erosion since the area they arise from is re l -atively flat. Comparably, more water enters the tailings as wash water from the concentrator than from the other two sources. However, its extent of fluvial action is limited to mainly the lower portion of the upper iron tailings pond (Appendix A . l ) . These sources, combined with water in the launderer slurry, result in movement, segregation and redeposition of materials repeatedly over a period of time (Appendices A.3 and A.4). Once a surface, often comprised of several horizons, is deposited, the oxidation of iron sulfides occurs rapidly provided it is given a chance to dry out. This dessication of the surface characteristically results in 104 cracking of the surface and formation of coarse prisms, or polyhedrons (Appendix A.5). The surface cracks, at this stage, sometimes are >5 cm wide and 50 cm deep, qualifying them as vertisols in the USDA soil clas-sification system (Soil Survey Staff, 1975). At this point, salt crusts begin to appear on the surface due to evaporative water loss. As oxidation proceeds, the cracks tend to f i l l in due to the falling or washing of:materia1 from the upper horizons into them. Oxidation pro-cesses themselves tend to cause an irreversible expansion of the prisms closing in the cracks, especially in the iron tailings. Salts, organic matter and some elemental sulfur further f i l l in the crack and most often result in microknoll formation (Appendix A.6). The salt crusts apparently accumulate in the cracks, due to the lateral movement of salt bearing water (interflow) upon meeting a horizon of different particle size dis-tribution and hydraulic conductivity. The much higher mean hydraulic conductivity of the siliceous tailings precludes the extensive crusting of salts. Ultimately, the salts are leached or washed away leaving an oxidized surface. In iron tailings, i f the iron content is high, the swelling of the prism can be so marked that ferruginous caps form,' in the later stages of oxidation and weathering (Appendix A.7). Salts, lost from the upper surfaces, accumulate in low areas and form crusts around pools of water in the iron tailings ponds (Appendices A.8 and A.9). In ponded areas,,where the tailings are under reducing conditions, the surface is often stabilized by the establishment of a salt marsh plant community, as in the lower iron tailings pond (Appendix A.9). There are 1.05 presently five species of plants growing in these wet areas. Typha (cat-tail) predominates with localized inclusions of Juncus (rush) and three much shorter plant species. Of the latter, two are higher plants and the other is a bryophyte. The persistence of these species appears, due to the less acid conditions in these wet areas and the maintenance of a relatively constant water level by a system of spillways. Separate drainage systems exist for the iron and siliceous tailings. These drainage lines go under a gypsum pond and ultimately are joined at a water sampling station where they enter James Creek (Figure 1). Thus, this creek is the point of discharge of the salts, organic matter and suspended solids from tailings oxidation and weathering processes. 5.2 Water Pollution Control Strategies 5.2.1 Extent of the Acid Drainage Problem to Bodies of Fresh Water The final reclamation of the Sullivan surfidic iron and siliceous tailings ponds must await the cessation of mining activities. Since the mine has a projected economic l i fe of at least another 20 years, the re-clamation problems are not pressing. However, the acid drainage water pol-lution problems deserve immediate attention. The drainage from the iron and siliceous ponds has been shown to contain appreciable amounts of contaminants. Since sampling began in 1970 and up to and including 1976, the combined iron and sili'ceous effluents have, exceeded the pollution guidelines for Pb, Zn, dissolved solids and pH (Cominco Ltd. , 1970-1974; Cominco Ltd. , 1975; Ministry of the Environment, 1976). 106 Beginning in 1975, the iron and siliceous tailings effluents have been sampled separately for contaminants. This monitoring has shown that the siliceous tailings effluents are less hazardous than the iron tailings ones. This latter drainage greatly exceeds the pollution guide-lines for Pb, Zn, pH and dissolved solids. This effluent contains, on the average, 1.4 mg/1 Pb, 16 mg/1 Zn, 7,500 mg/1 dissolved solids, with a pH of 4.0 (Cominco Ltd. , 1975; Ministry of the Environment, 1976). Comparably, the pollution guide!ines permit the disposal of 0.2 mg/1 Pb, 0.5 mg/1 Zn, 25 mg/1 dissolved solids, and an effluent pH of 6.0 (Fisheries and Environment Canada, 1977). The siliceous tailings only exceed the pollution guidelines for Zn (1.4 mg/1) and total dissolved solids (2,700 mg/1). It must be recognized that the effluent may s t i l l be deleterious to water quality, even i f i t meets the pollution guidelines. The guidelines only consider As, Cu, Pb, Ni, Zn, pH, Radium 226 and suspended solids as prescribed deleterious substances, and ignore potentially deleterious heavy metals such as Cd and Cr and anions such as phosphate, sulfate and fluorine. The guidelines are also deficient in the fact that they make no reference to the dilution capacity of the receiving waterway(s). Further-more, they only apply to the concentration of contaminants in solution at the point of discharge. This approach, in estimating the pollution potential of an effluent, ignores the concentration of toxic substances of bottom sediments in the receiving waters. Such an approach is viable from a drinking water quality standard, but is inappropriate when considering potential detrimental effects of effluent contaminants on aquatic organisms. The effluent from the iron and siliceous tailings flows into James 107 Creek and ultimately the St. Mary River. James Creek is basically the drainage channel for tailings effluent since very l i t t l e contaminant dilution occurs. Once the effluent reaches the St. Mary River, signifi-cant dilution occurs as the minimum flow of this river is approximately 8,490 l i t e r s /second (Department of the Environment, 1976). Comparably, the effluent flow has been averaging 3.4-4.2 l i t ers -'-./second (Cominco Ltd. , 1975; Ministry of the Environment, 1976). Even with the high dilution of the St. Mary River, the levels of contaminants s t i l l exceed the standards of potability for Mn, Pb, As and pH at Wycliffe, several miles downstream from the point of discharge (Department of the Environment, 1976). Admittedly, contaminants enter the St. Mary River from the Sullivan Mine and ferti l izer plant. However, these sources do not significantly influence the levels of Mn, Pb and As. In situ, fish-caging experiments have demonstrated the presence of contaminants. Rainbow trout in cages located at Wycliffe showed a 47.5 percent survival rate compared to 100 percent above the Sullivan Mine (Department of the Environment, 1976). These effluents were also deleteri-ous to the benthic invertebrates and periphyton which are a major part of the fish diet. Downstream from the Cominco Ltd. operations, at Kimberley, the benthic invertebrates were reduced in number by up to 95 percent (Department of the Environment, 1976). These workers also found that the periphyton diversity decreased, in agreement with thetfindings of Bull et_ al_. (1969). Even i f the amounts of contaminants entering the St. Mary River were greatly reduced, their presence in the sediments would probably continue to have deleterious effects on aquatic organisms. The heavy metal uptake 108 by aquatic organisms has been found to be determined by the sediment levels of these contaminants (Delisle et al_., 1975). The analysis of sediments, downstream from Cominco's operations at Kimberley, indicates that sediments generally contain much higher levels of Pb and Zn than above the operations (Department of the Environment, 1976). It is likely that other contaminants found in the siliceous and iron tailings effluent are also concentrated in St. Mary River sediments. The determination of the extent of this problem in the St. Mary River will have to await further work. 5.2.2 Reduction of Acid Drainage Pollution from the Iron and Siliceous Tailings There are two solutions to reducing the acid drainage pollution from the Sullivan sulfidic tailings: chemical treatment of the effluent and inhibition of microbial sulfur oxidation. Presently, chemical treatment of the tailings effluent by a limestone/ lime treatment plant is proposed (Kuit and Jackson, 1975). This plant will be built to treat the combined effluent of the concentrator wash water, mine domestic wastes, 1189 meter mine portal drainage and the drain-age from the tailings ponds. The proposed treatment plant is expected to remove 75-99 percent of the contaminants and produce an effluent which meets the pollution guidelines, with the possible exception of lead. It is planned that sludge be disposed of on the surface of the siliceous tailings pond. A reduction in the contaminant load in effluents can result in sig-nificant savings in limestone, lime and chlorine consumed in treating the 109 effluent. In addition, expenses involved in transporting and perhaps dewatering the voluminous sludge, produced mainly from the precipitation +3 of Fe and sulfur, can be saved. Such a reduction in the amounts of contaminants can be obtained by inhibiting Fe and sulfur oxidation. This goal can be realized by judicious tailings pond design and tailings disposal. In the future, attempts should be made to minimize the association of iron and sulfur oxidizing bacteria with oxidizable Fe and sulfur forms, in the presence of air or other oxidizing agents. There are three techniques of obtaining this objective: (i) limit additions of fresh unoxidized tailings to low areas, already under reducing conditions; (ii) maintain a surface of water over the reduced tailings, during the economic l ife of the mine; ( i i i ) eliminate extraneous sources of surface erosion on the already oxidized tailings. The first technique will reduce the surface area of contact between highly oxidizable tailings and air. This method of tailings disposal will prevent the occurrence of highly oxidized sulfidic horizons (Appendix A.2) which cumulatively magnify the acid drainage problem. It is understood that ponding is only practical on the iron tailings due to the low hydraulic conductivity required to maintain such a water surface. However, the siliceous tailings are a much lesser contributor to acid drainage. If necessary, a high flow rate into the siliceous tailings can maintain a ponded surface in the center of the pond. The maintenance of a ponded surface results in a much lower oxygen diffusion rate to the highly oxidizable tailings. The inhibition of oxidation no and concomitant acid production from such a strategy is manifested by the growth of marsh vegetation in ponded areas upon the iron tailings (Appendix A.10). The prevention of extraneous water from flowing across the tailings should significantly reduce gullying and channeling on the iron tailings which is the main source of acid drainage. This reduction in water erosion should decrease the washing away of oxidized surfaces arid the exposure and transport of reduced tailings (Appendices A.3 and A.4). If these forementioned measures are undertaken, the major source of acid drainage will be the oxidation of the tailings dams in the respective ponds. A choice of materials low in oxidizable iron sulfides, may reduce the production of acid and other contaminants from this source. Additional acidity and other contaminants can be removed from the effluent, prior to limestone/lime treatment, by biological oxidation and reduction processes. +2 Biological oxidation of Fe by J_. ferrooxidans is practical and can be carried out rapidly in the presence of oxygen at low pH values (Glover, 1967). Olem and Unz (1977) found biological oxidation of iron by a rotating biological contractor, potentially useful as an init ial step in the treatment of acid mine drainage. Biological oxidation can result in reductions of approximately 50 percent in the operation of a conventional lime treatment plant (Glover, 1973). In the field, this oxidation process requires one or two oxidation and settling ponds. +2 Following the oxidation of Fe and other reduced ions, a biological reduction process may eliminate some of the remaining acidity and dissolved salts. Moulton et a l . (1957) reported that sulfate reducing bacteria I l l increased thepH of a lactic acid-mineral salts medium from 5 to 8.9 in eight days. Work by Tuttle et al_. (1969) demonstrated that this process can be used in reducing acid mine water pollution. Further work is necessary to evaluate the potential uti l i ty of microbial reduction in abating acid pollution in the field. Thus, an understanding of biological oxidation and reduction processes is - essential to devising means of reducing acid drainage from the Sullivan iron and siliceous tailings. 5.3 Potential Reclamation Strategies Since maintaining a ponded surface for perpetuity is not practical, reclamation plans must be devised before the cessation of mining activities. There are basically two solutions to the Sullivan sulfidic tailings reclam-ation problem which should be investigated in the future: (i) utilization of the tailings as raw materials in industry; (ii) covering the tailings with a surface of non-toxic materials followed by vegetation establishment. Potential uses now exist for the iron and siliceous tailings. The iron tailings can be used for sulfuric acid, iron, and steel production and the siliceous tailings as a component in railroad ties. Presently, a portion of the iron tailings is used in the production of sulfuric acid. The sulfuric acid is used to make super-phosphate and results in the production of gypsum, which is now stored in the gypsum ponds. Ultimately this tailings material must also be reclaimed or utilized. .112. Furthermore, i t is not known whether the production of super-phosphate will be' sufficient to consume the iron tailings. Perhaps additional markets for sulfuric acid can be found before reclamation is necessary. If markets for sulfuric acid are found, its production could be coupled with iron or steel production. Cominco operated plants producing pig iron, between 1961 and 1972, and steel, between 1966 and 1971. They were closed down soon after an explosion at the plant resulted in the loss of l ife (Jim Packenham, personal communication, 1977). This closure appears to have been a result of the accident and damage to the plant. The resumption of iron and steel production could be considered in the future, i f economical. The siliceous tailings are now being considered as a constituent in railroad ties (J. Packenham, Sullivan Mine,,personal communication, 1977). It remains to be seen i f this venture will be carried out. It is expected that i f this is practicable, not all of the material in the siliceous tailings pond will be utilized due to contamination with iron tailings between 1973 and 1976 (Anon., 1976b). Efforts should be made to maximize the amount of iron and siliceous tailings utilized to minimize the reclamation effort. However, pollution from tailings ponds should not be replaced by pollution of waterway by effluent from the ferti l izer, iron and steel plants. Undoubtedly, more imaginative utilization schemes will be developed in the future. If the tailings materials are not utilized, i t will be necessary to cover the ponds with a non-toxic material and establish a vegetative cover. This alternative is highly problematic due to the evaporation rate (560 mm/year) exceeding the precipitation rate (380 mm/year). There is a 113 potential for salts buried below the non-toxic surface to move upward as evaporation proceeds, eventually forming salt crusts on the surface. The additions of a surface layer of non-toxic material with various physical barriers to the upward movement of salts are now being studied. In Australia, an impermeable clay layer next to the tailings is being used to prevent upward salt movement (Craze, 1977). The application of a coarse material next to the tailings surface, followed by a layer of top-soi l , is being evaluated by S. Ames in the Soil Science Department at The University of British Columbia. Other approaches are being considered by the reclamation staff of Cominco Ltd. The evaluation of the successfulness of this approach should await the completion of these studies. 114 6.0 SUMMARY AND CONCLUSIONS The major findings of this study are: +2 1) The initial oxidation of Fe from iron monosulfides (particularly pyrrhotite) to yield amorphous Fe oxyhydroxides was rapid. These Fe compounds remain in an x-ray amorphous form, except in areas where sulfur fires have, occurred. In these places the crystalline iron oxide hematite was formed. +2 2) Concomitant with the oxidation of Fe , sulfide was oxidized to elemen-tal sulfur and.;to some extent to other partially oxidized sulfur forms determined as total oxidizable sulfur. However, some of the total oxidiz-able sulftir not accounted for by CS2 extractable elemental sulfur, may be in an amorphous non-extractable form of elemental sulfur. Polysulfides thiocyanates, thiosulfate and polythionates should to varying degrees account for the remainder of the total oxidizable sulfur. 3) Sulfate, produced from the oxidation of elemental sulfur through a series of intermediates, occurs mainly as gypsum in basic to slightly acid samples. At more acid pH values, gypsum was less evident and K-jarosite became the predominant sulfate containing mineral. 4) The primary water extractable cation in relatively unoxidized tailings are Ca and Mg. The water extractable Fe and Al increased as the pH decreased. Concomitantly, levels of acid extractable cations generally 115 declined with decreases in pH. 5) Among the aluminosi1icates, chlorite appeared to undergo rapid dissolu-tion while micas and K-feldspars seemed to be more resistant to decom-position by acid. No crystalline Al silicate residues from the clay dissolution were detected, indicating that dissolution may be congruent. 6) Iron bacteria (Thiobacillus ferrooxidans) were most prevalent in the iron tailings with pH >2.5, occurring in 42% of the samples. In the iron tailings with pH <2.5 and in siliceous tailings, they-occurred in only 28 and 13% of the samples respectively. No correlation was found between the numbers of iron bacteria and the amount of iron monosulfides or soluble Fe. The lower occurrence of iron bacteria and higher levels of neutralized bases indicate that chemical iron oxidation is more important in the siliceous tailings than in the iron tailings^ 7) Sulfur bacteria of the Thiobacillus genus occurred in 70% of the siliceous tailings samples and 88% of the iron tailings with pH >2.5. In the iron, tailings with pH <2.5 they occurred in only 19% of the samples. 8) The thiobacilli enumerated were found to consist of four species: J_. thioparus, J. neapolitanus, J . thiooxidans and T. ferrooxidans. A succession of thiobacilli from J_. thioparus to J_. neapol itanus and ultimately to J_. thiooxidans and T_. ferrooxidans occurred as the pH decreased in the iron and siliceous tailings. 116 9) In the iron tailings with pH >2.5, X* thioparus predominated at the high pH values and X- thiooxidans at low pH, with occurrence frequencies of 27 and 20% respectively. Thiobacillus thioparus populations were found to be dependent on the Ca and K levels in these tailings samples. This may be somehow related to inhibition of phosphate uptake by ]_. thioparus in low K environments as described by Jones and Happold (1971). Thiobacillus neapolitanus was the most prevalent sulfur bacteria in the siliceous tailings, occurring in 43% of the samples. By comparison, ! • thioparus and T? thiooxidans were only present in 3 and 10% of the samples. 10) Acid tolerant heterotrophic bacteria were frequently present in the iron and siliceous tailings. Their populations were highly correlated with sulfur bacteria in the siliceous tailings (r = 0.74**). In the iron tailings with pH >2.5, .acid tolerant heterotrophic bacteria were highly associated with iron bacteria (r = 0.98**). These relationships indicate that acid tolerant heterotrophic bacteria may have a symbiotic relationship with thiobacilli species. 11) Of the four physiological groups of microorganisms, fungi occurred most often but were not correlated with the other groups in either the iron or siliceous tailings. Fungal populations appeared to increase with increases in weathering. Perhaps this observation reflects an increased colonialization of the tailings with time. 12) With oxidation and weathering processes came changes in textures,, structure and color. Overall texture changed from an average of s i l t loam 117 to finer textures as jarosite was produced. This trend was more pronounced in the iron tailings samples due to their much lower content of s i l ica. Structure changed from granular to blocky in the siliceous tailings with increases in oxidation. In the iron tailings, platy and often massive structures occurred in the highly weathered samples. Color, as represented by hue.value and chroma, increased as pH decreased and sulfate increased, which would be expected as jarosite content increased. These qualitative physical characteristics can be used in the field to estimate the potential for acid production on a tailings surface. 13) The ultimate reclamation of the iron and siliceous tailings will have to wait until cessation of mining. However, the acid mine drainage problem should be alleviated immediately. The inhibition of acid drainage must involve the inhibition of oxidation and the limiting of erosional pro-cesses. While iron monosulfide oxidation is the primary cause of acid drainage, its rate would decline progressively as the surface was oxidized. It is the erosional processes in the tailings ponds which dictate the amount of acid drainage produced. Erosional processes contribute to acid production in two ways: (i) erosion of oxidized tailings, exposing reduced ones to an oxidizing environment; (ii) covering oxidized tailings with reduced ones in the tailings disposal process resulting in a fresh oxidizable surface. If steps are taken to eliminate these two means by which reduced iron ta i l -ings surfaces are exposed to an oxidizing environment, the overwhelming majority of the acid drainage would be prevented. 118 Three means of preventing the exposure of reduced tailings to an oxidizing environment can be undertaken: (i) reduce the movement of water over oxidized tailings; (ii) avoid covering oxidized tailings with reduced ones; ( i i i ) add reduced tailings to limited areas as much as possible, and maintain a ponded surface to inhibit oxidation. 119 REFERENCES Adair, F.W. and W.W. Umbreit. 1965. Anaerobic oxidation of elemental sulfur by Thiobacillus thiooxidans. Bacteriol. Proceedings. Abstr. The 65th Annual Meeting. 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Appendix A.l Aerial Photo of Sullivan Mine Iron and Siliceous Tailings Ponds 140 Appendix A.2 General View of Tailings Distribution Process in the Impoundment Appendix A.3 Profile of Iron Tailings Shov/ing Discontinuous Horizons with Variation in Structure and Degree of Weathering with Depth 141 Appendix A.4 F l u v i a l A c t i on i n the Iron T a i l i n g s I l l u s t r a t i n g the Discontinuous Depos i t ion o f Horizons Appendix A.5 I n i t i a l Stages o f Ox idat ion i n the Iron T a i l i n g s Showing Crack ing o f Surface and S a l t Crusts 142 • • • • • • • • • • • • • • • I Appendix A.6 Moderately Oxidized Surface in the Iron Tailings Showing Pronounced Crusting of Salts and Organic Matter I Appendix A.8 Pool o f Wash Water High Popu la t ion of Iron T a i l i n g s Pond from Concentrator Conta in ing a M ic roscop ic Green Worms i n the Appendix A.9 S a l t Crusts and Ponded Water D i sco lo red by Iron Compounds i n the Lower Iron T a i l i n g s Pond 144 145 I Appendix A.11 Thiobacillus thioparus Colony X 92, Transmitted Light, Showing Sulfur Deposition Throughout Colony I Appendix A.12 Thiobacillus thioparus Colony X 92, Reflected Light, Showing Deposition of Sulfur Throughout Colony I Appendix A.13 Thiobacillus neapolitanus X 92, Transmitted Light, Showing Sulfur Deposition in Center 147 APPENDIX B.l Key To Computer Symbols Used to Label Parameters SYMBOL PARAMETER FEBACT Iron oxidizing bacteria M-P-N x 103 SBACT Sulfur oxidizing bacteria M-P-N x 103 3 OMBACT Acid tolerant heterotrophic bacteria M-P-N x 10 FUNGI Acid tolerant fungi M-P-N x 103 FES Iron monosulfides (%) TOS Total oxidizable sulfur-excluding iron monosulfides (%) ELEMS Elemental sulfur (%) SSO^ Water extractable sulfate (%) INSS04 Acid extractable sulfate (.%) OM Organic matter (%) pH pH CONDT Conductivity (mmhos/cm) MOIST Moisture (%) TEXT Texture STRUCT Structure HUE Hue (MunseTl color notation) VALUE Value (Munsell color notation) CHROMA Chroma (Munsell color notation) SOL Fe Water extractable iron (%) SOL Al Water extractable aluminum {%) SOL Ca Water extractable calcium (%) SOL Mg Water extractable magnesium {%) 148 SOL K Water extractable potassium (%) SOL Na Water extractable sodium {%) HCI Fe Acid extractable iron (%) HCI Al Acid extractable aluminum (%) HCI Ca Acid extractable calcium (%) HCI Mg Acid extractable magnesium (%) HCI K Acid extractable potassium (%) HCI Na Acid extractable sodium (%) SITES Sites samples (categorical variable) K JARO Potassium jarosite (%) Na JARO Sodium jarosite (%) H JARO Hydronium jarosite {%) Jarosite forms are derived variables based on theory that K and Na in acid extract due to dissolution of jarosite. Appendix B.2 Microbiological, Chemical and Qualitative Physical Analysis of the Surface Samples Collected from the Sullivan Iron and Siliceous Tailings INPUT DATA FEfrACT SBACT FUNGI FHHACT F £ i TPS £LE±LS iSQ4 INSS34 OS PH CONDT MOIST TEXT STRUCT HUE VALUE CHROMA SOLF5 SOL AL SOLCA SOL MO SOLK SOLNA HCLFE HCLAL HCLCA rtCLMG HCLK. HCL.NA SITES KJARO NAJARO __ HJARQ _ l ' o . o '"6 .0 c .o o .o o.o O . S O O O E - O I O . I O O O o . » i o o 0.5100 0.3210^-01 2 . O C O 10.60 27.85 30.00 46.00 6.000 4.000 4.000 2.530 0 .59GJE-01 .- 0.5900E-01 0.46Q0E-01 0.2030E-02 0 .4C00E-02 6.320 pLtS 0.3300E-01 O . 0 6 O O E - O I 0.132C O.70:0s-31 16.00 0.30006-01 0.2000E-01 0.8000E-01 2 0 .0 0.0 4.000 15.00 0..0 ... 0.1200 0.10.00 O.iCCC _C.870C._._ 0.2C0CE-31 2.030 10.60 24.93 30.00 46.00 6.000 4.000 4.000 1.950 0 . 9 9 ' j O E - J l 0.3110 0.7300E-01 0 .4000E - 0 2 0 .2000E -02 8.290 0 .0 0.1580 0.O300E -01 0.1270 0.0 16.CO 0.3000E-01 C . 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J 2.370 0.6600E -01 0.3600E-01 0.0 84 0.0 1.920 O.C 1 0.60 41.00 74.62 C O 30.00 0.0 26.00 3.560 6.000 5.200 5.000 O . 0 8 O O 6.000 0.8600 2.130 0. 3600E-01 0.4500E-01 0.1300E-12.00 01 0.2600E-01 0.300CE-C1 0.2000E C O -02 0.0 0.1100 5.030 0.0 0.6000E-•02 O.J 0.1260 0.0 85 12.00 2.300 0.6000 500.0 2.650 0.1200E-01 2600. 31.46 C 6 0 0 0 E -0? 0.2600E+05 1 5.00 0.2OOOE-O2 0.0 26.00 13.50 1.010 2.000 0.0 0.2000 7.000 0.2430 0.5100 6.000 O.J 0.1300 0.3800E 1.320 -01 0.4000E-02 0.2200E-01 0.2100 12.00 0.2000E-01 C O 0.0 86 0.0 470.0 42.00. 170.0 0.0 0.8000 0.7000 O.aOOO 1.130 _0.8030E-02 1.960 0.3790 12.CO 7.500 0.7300E-C1 0.4000E-01 30.91 C.2000E C O -02 30.00 0.2COOE-02 0.1400 46.00 8.620 6.000 0.0 5.000 0.1310 6. COO 0.-.900E-01 0.456C C 1 3 8 0 0.14COE-01 0.7000E-01 87 32.00 3.690 310.0 3. 100 C O 35.95 0.0 30.00 0.7900 23.00 2.890 6,000 3.600 3.000 0.5600 3.000 0.3800 0.6400c -_Q1_ 0.0 0.900CE-02 0 - 5 340 8.000 0.5600L-C1 0.4000E-01 0.2C00E 0.0 -02 0.9000E-02 0.2000E-01 7.190 6.6000 0.4670 6.5930 0.1500 0.0 88 0.0 2.730 0.588C 0.0 5.500 0.52O0E-O1 25.00 20.2 2 C 2 0 0 0 E -02 0.0 5.000 C 2 0 0 0 E - 0 2 0.2900 1.000 14.50 7.710 8.000 0.6000 6.900 4.000 0,2620..... 0.4100 4.000 0.5950 0.1600 0.2890 0.1190 0. 1600E-01 0.5000E-01 O.C 8 .066" O.3C00E-C1 0.0 0.0 89 6. OCO 0.0 2600. 3.000 0.0 1.290 1.800 1. 130 0.450C C.4C00E-C2 2.310 0.4230 8.000 2C.00 0.3200 0.5000E-01 29.03 C.2000E 0.0 -02 30.00 0.0 . 0,20.00-E.TP.1_ 46.00 6.780 6.000 0.7400 5.000 0.2080 6.000 0 . j040 0.7140 0.2010 0.3760 0.0 90 0 .0 3.000 0.0 10.10 480.0 72.83 3.000 25.00 0.2000 2.000 2.710 6.000 2.700 4.000 0.7800 4.000 0.260C 0.2900 0.4COOE-02 0.12C0 0.5470 8-000 0.3190 0.4000E-01 0.0 0.0 0.2000E-02 0.1000E-01 8.470 0.8600 0.4970 1.040 0.1840 0.6000E-01 91 3.000 3.280 0.3540 0.0 11.60 0.3650 470 .0 13.28 C 7 C 0 0 E --0? 0.0 5.000 C O 0.9300 2.000 12.00 4.290 6.000 0.8200 3.600 4.000 0.3000 0.6100 3.000 1. 150 0.1600 0.1010 0.1640 "0V0 0.5800E-01 0.0 8.000 0.3000E-01 0.0 C O _ - 9 2 0 .0 0.0 250.0 ...CO . ... 0.1600 5.45C 6.500 0.2700 0.1400 0.4000E-02 4.060 0.3630 8.000 1.500 0.1000E-01 C 2 0 0 0 F - 0 1 15.26 C.3000E-02 C O 5.000 C O 0.0 4.000 18.20 6. 000 0.7900 4.000 0.3540 3.000 0.6 740 C 5 0 0 0 E 0.1690 -01 0.5000E-02 C O • 93 0.0 4. 890 0.2900 8.000 44.00 1.500 6.1300E-01 0.2000E-01 470.0 13.72 C 5 0 0 0 E - 0 2 0.0 C O 5.000 0.0 C O 1.610 2.000 12.10 3. 660 6.000 0.8200 0.7000 4.000 0.1760 0.1800 3.000 0.o590 0.1100 C 2 9 0 0 E 0.1650 -01 0.32COE-01 0-0 0.0 ! c n en c 94 0.1100E+05 2.500 0.4510 9.000 5.500 0.89COE-01 24.00 21.33 ..0..2.000E- 02 24.00 5 .0C0 .0.0... 0 .0 4.000 13.50 9. 590 8.COO 0.2 COO 0.4000 4.000 0.1990. 0.-.200 4.000 ...0..J610 . 0.3500 0.7700E .0.1200 -01 0.0 0. 7000E . 0.0 -01 8.000 0.3000E -C1 0.0 0.3000E -01 V 95 C.O 0.0 160.0 24.on 0.7100 2.770 0.8000 (1.0600 n.annriF -ni 0.74nr.F -01 ? 3.110 0.6940 9. OCO . 7.800 0.1430 .0. lCC0fc-01 27.06 0.2000E-C.O 02 25.00 0.2000E 0.0 -02 22.00 4.710 2.000 0.4000 3.COO 0.2880 2. 000 0.4580 0.4230 0.1300 0.92CCE 0-0 -01 96 0.0 3.210 1200. 14.30 2600. 29.56 0.0 30.00 0.5000E-01 46.00 3.600 6. 000 1.800 4.000 0.9500 4.000 0.2500 0.1500 0.4000E C.6600F -02 -0 1 0.4710 8.000 0.6870 0.3000E-01 0 .2000E-0.0 02 0.2000E 0.1000E -02 -01 4.860 0.5000 0.1960 O.dlOO 0.1350 0.0 97 "676 6. 790 0.3220 24.00 3.100 O.710OE-01 ~ "37oo6 18.78 0.5000E- 02 3.000 5.000 0.2000E -0? 4.400 1.000 10.50 ' 5.000 2.000 0.5000 0.7000 3.000 0.9060 0.2600 2.000 O.B770 0.0 . 0.2000E 0.1170 -02 " 0 .0 0.0 0.0 2.000 O.C 0.0 0.0 98 0.0 . 7 8 - 0 0 . 44.00 0 .0 3 ..7.70 6. 710 0.7000 0, A 8.0.0 „0..1.0.00E - 0 1 . _0.2CCCc -02 __. 6. 340 0.3090 2.000 1.650 0.2600E-01 0.0 19.86 0 .9000E-0.0 02 5.000 0.0 0 .0 1.000 8.760 2.000 0.8300 3.000 1.240 2.000 1.070 0.120CE 0.1780 -01 0. 3000c 0.0 -02 99 0.0 6. 860 23.00 3.550 0 . 0 6.780 0.0 5.000 3.050 3.000 5.000 2,000 0.4000 3.000 0.2000 2.000 0.1000E 0.1300E -01 -01_ 0.2J00E 0.30CCE -02 -02 ~ 6.2040" 2.000 0.7200E-01 0.0 C.6C03E-0.0 62" 0.2000E 0.0 -02 20.40 6.7100 1.380 1.120 0.1530 0.0 100 0 .0 6. 720 0.3020 2.000 0.0 2.950 0.4000E -C1 0.1000E-01 98.00 24.81 G.7000E-0.0 .02.. 24.00 5.000 0.2000E 0.0 -02 9.100 1.000 8.350 7.990 2. 000 ,0.8 800 1.200 3-000 1. 160 0.3300 3.000 1. 140,. C.8000E 0.2000E 0..190C -01 -02 0-4000E 0.0 0.0 -02 101 0.0 24.00 3.000 24.00 2.660 4.220 0.6000 O . 1 8 O C 0.400CE -01 C.200CE -02 C.4C0 0.2300 2. OCO... 5.700 0.7400F.-01 ..0.10.00 Er.0.1. 21.97 0 .7000E-...0.0 02 5.000 0 .4000E-02 0.0 2.000 9.210 2.000 0.9100 3.000 1. 550 2.000 1.460 0.2000E 0.3050 -02 0.0 0.0 102 2600. • 2. 12C 2600. 8.COO C.O 30.46 0 . 0 30.00 0 .0 38.00 2.280 6.000 1.400 6.000 0.5800 6. OCO .1.210 0.7090 0.4000E 0-1400 -02 0 .1800E-14.00 01 0.8900E-01 0.7000E-01 0 .2000E -0.0 02 0.0 0 .1200 10.30 0.2000 0.7000E -02 0 .3420 0.2740 0.7000E -01 103 31.00 2.020 0.90GC E- 0? 0.0 5.000 0.280CF-C1 2600. 35.54 0 .2000F - 0? 100.0 30.00 0.0 0.0 36.00 9.780 3.000 6. 000 0.0 1.900 6. COO 0.7000E -0? 0.9000E 6. 000 0.7400E -01 -01 1.560 0.1980 0.1470 0.1000E 0.34COE 0.0 -01 -01 14.00 0.4000E-01 0.0 0.2000 104 3.CCO O.C 2600. 16.00 0.0 2.100 1.800 0.3200 1.250 0.8000E -02 2.040 C.200CE-14.00 02 5.700 C.4500E-01 0 .5000E-01 33.12 0 .2000E -0.0 02 30.00 0.0 0.1500 36.00 13.70 6.000 0.2000 6.000 0.7000E -02 6.000 0.1400 0.2950 0.2130 0.5900E 0.0 -01 105 0.0 2.050 0.2000E-14.CC 0? 0.0 6.400 0.3900E-C1 0.6000E-01 26C0. 36.74 0 .2000E -0.0 02 10.00 30.00 0.0 0.1400 0.0 21.00. 9.170 6.240 6.000 0.0 1.900 5.000 0.8000E -02 0 .3600 6.000 0.1500 1.300 0.4980 0.2260 0.10C0E 0.5400E 0.0 -01 -01 106 0.0 2.060 0.7500E-r01 14.00 0.0 7.200 .0.82006-01 0.4000E-01 2700. 39.82 C O C O 48.00 30.00 0.0 0.1900 0.0 41.00 10.20. 4.230 3.200 0 . J 5 0 0 1.480 0.8C0CE-02 6.000 5.000 8.000 0.6380 0.1300 .0.6000 0 . 8 0 0 0 E - 0 2 . 0,2360 . 0.1580 0.0 3.000 0.0 2500.. 0 .0 Q . Q -.4.800 0.<.700 0-5700 n.4finoF-op 2.120 0.1400E-01 ...10.00 8.000 0.4700E-01 0.3COOErCl 21.11 C O C O 3C.00 0.0 . C 6 0 0 0 E - 0 1 21.00 6.930 6.000 0.0 5.000 0.6000E-02 6.000 0.1200 C.4770 0.1200 0.8200E-31 0.0 1 0 8 0.0 7.230 0.0 4. 700 500.0 15.5? 3.000 30.00 0.0 ?? .no 1. 120 -h.ono C.8000 5.000 0.1200 6.000 0.6000 C O 0.4900F-OI 0.3100f=-0l 0.1570 10.00 0 .0 2. 370 0.40nOE-07 0.1600E-01 0.4000E-01 C C 1.500 0.5nOOE-O7 0.0 0.0 C O 0.6000E-01 6.800 2500. 21.91 C 2 0 0 0 E - 0 2 45.00 30.00 0.0 0.0 21.00 6.710 0 .0 0.8 000 6.000 jua 0.4500E-01 0.J600E-01 0.1700 0.3000 0.3000E-01 0.6900 5.000 8.000 0.200CE-OZ 0.6000E-Q2 Q__J C I 200 0.0 0.0 0.4000E-02 C O 110 10.00 0.0 2.200 0.2100E-01 10.00 0.4000E-01 _0._Q 7.000 C.3C0OE-C2 0.3000E-01 0.0 2500. 0.7000E-01 0,0 15.21 0.0 C O 30.00 0.0 0.8000E-01 0 . 0 _ 43.66 4.470 0.8200 6.000 0.0 .0.3000 5.000 C 6 0 0 0 E - 0 2 J3.J000 0-6800.. 6.000 0.27C0 0.56C0E-01 0.1120 0.2000E-02 0.1200 C O 111 0.0 __2.0.6.0_ 0.2600E-01 10.CO 0.0 . 11.60 0.6000E-01 0.3000E-C1 2500. _..26..90 C O C O 6.000 30.00 0.0 0.8O00E-01 0.0 1.120 1.000 1.120 C.67C0 0.6000E-02 ... 2.6.00 6. 000..._ _,5.000 8. 0.0.0 2. 3.6.0 .0,L3_9.Q 7.530 6.0 0.2000E-01 0.65C0E-01 0.1300 0.0 7.000 1.590 0 .3000E-02 18. CO 0.0 20.00 0.1500 0.2000E-01 C O 44.22 O.3C00E-0 .6 02 7.000 30.OC 0.0 0.3700 0.0 1.050 0.1000 4.600 2.510 0.4360 46.00 4.000 7.000 6.000 26.70 0.4130 2.310 0.3000 0.9000E-02 0.8600E-01 _0-86C0E-01 0-0 JL13 Q.Q 0.0 210.0 0.0 C O 7. 040 5.800 ..2>.56 C O 0.6660 1.980 0 . 4 8 4 C 18.00 12.00 C 3 1 7 C 0.0 62.70 0.0 C C 30.00 0.0 0.0 47.00 8.570 4.000 0.0 6.000 3. 000 59.00 0.2000 C7400E -01 0.5500E-01 0.8300E-01 0.3000E-01 114 O.C 1.350 O.C 2 C Q 0 C O 39,32 0.0 30.00 0 .0 47.00 0.7300 4.000 0.6000 7.000 7.900 8.000 0.0 22.10 0.4200 0.3390 O.2CU0E-02 18.00 0.9000E-01 0.0 C.2000E-02 C O 0.2000E-02 0.0 24.50 0.0 C 8 0 0 0 E - 0 2 C i 5 6 0 0.78CCE-01 0.8GOOS-01 115 120.C 310.0 4.000 30.00 0.0 0.3800 1.40C 13.39 C O C. 1680 2.480 20.00 71.27 30.00 47.00 4.000 8.000 6.000 37.00 0.1400E-31 0.290CE-01 0.5700E-01 0.5000E-02 0.0 5.630 0.0 0.33J0E-01 0 . . 660 0.1660 . C O 18.00 C O C O 0.0 .116. .0 .0 . 5.610 0.4020 4.000 0.0 4.000 0.2100E-01 0.3000E-C1 0.0__ 2 6.98 C 8 0 0 0 E - 0 2 C O  1 0 . 0 0 _ 25.CO C 4 0 0 0 E - 0 2 0.1000E-01 10.99 38.00 22.70 3.570 2.000 0.6500 0.5000 2.000 C.4610 0.3800 . O.J 0.9090 0.2500 0.2000E-02 0.1300 0.5200E-C1 0.0 0.0 117 0.0 5.630 C.3930 4.000 0.0 6.000 o . i n o 0.0 3.000 16.37 C.8000E-02 C O 3.000 .. .25.00 6.7000E-02 0.0 9.290 38.00 26.70 3.730 2.000 0.0 0.5000 2.000 0.2050 O. f lOO . O.J 0.1700 C O 0.200CE-02 0.57COE-01 C 4 0 0 0 E - 0 1 C O C O 159 u-> O O * • • o o o o o o O O *M o o o o o *r N O O O O U o iTt O 'Si o o o ^ o o c o o o o o H O O «J c M r-\ O o o o o d o o m o CD f**i o c ( o c* -o o • o o o o o o o o o m o o •O O N •O IM -t — t o o m o o \ o -o • a* • t o o r— a o • o o o o o o o rt o • o 0 * fM • • o o O a I O «o o *A O _H o 0 o 1 I UJ UJ 0000 O if\ o o 1 o o o 0 o 1 I UJ ai d o o o O IA O O » rv r- o 00 O tJ O Oi o c o o o o *r o n —« 000 N O O 000 o o oi o o r-t o o •t) -T O o » ~ » i Appendix C.l Correlation Matrix for the Parameters Measured in the Iron and Siliceous Tailings as a Whole _-U " F l A T T O . M A T ? T X , . i • FEuACT S8AC T FUNGI OHBACT FES TQS E L E M S SS04 INSS04 OM P H F E a l C T ' 1.0000 s & A C T ' 0.2108 1.0000 : — • •— F W i i l - C . C 4 7 7 - 0 . 0 7 4 7 1 .0000 i.MSACT 0.1183 0 .3526 0 .1234 1 .0000 FES -0 .0128 0.0068 -0 .231 ? 0 .0880 1.0000 , — U S - C . 0 3 1 1 0.0621 - 0 . 0 9 3 8 0.0C51 0.3934 1.0000 ElEMS - 0 . 0 1 9 3 0.1002 - 0 . 0 5 2 1 - 0 . 0 2 1 8 0 .0389 0 .7422 i . 0000 5S04 _ _ - 0 . 0 2 9 0 _ - 0 . 0 5 5 5 - 0 . 0 7 1 4 - 0 . 0 3 9 8 rO... 140.7 -0.0.450 . . . 0 . 0 0 1 6 1 ,_C0J.0 . ;  i r . S - ? 4 0 . 1 3 8 5 - 0 . 0 9 7 3 0.2372 - 0 . 1195 -0 .3917 -0 .2249 - J .0816 - 0 . 0 7 i O 1.0000 JM - C . 0 0 7 2 - 0 . 0 6 8 7 - 0 . 1 6 4 0 0 .0246 0 .1750 0.2401 J.2102 0 . 7 2 J 6 -0 .0822 1.3000 PH - C . 0 5 1 4 0. 1672 - 0 . 2 1 6 7 0. 1042 0.5780 0.1629 -0 .1098 - 0 . 2 1 j 9 -0 .6765 __0. 1081 1. 00-33. CONOT -0 .0778 - 0 . 1 8 9 7 0 . 0672 - C . Id09 - 0 . 4 0 7 8 -0.2732 -u .0825 0.42J2 0.4303 0.3005 - G . e i O S •falST 0.C474 0.1650 0.0660 0.1212 -0 .2069 -0 .0329 J .0683 0.62o0 0. 1238 0.3752 -C.2261 TEXT C .C629 0.0674 0 . 1 2 4 7 - C . 0 4 1 7 -0 .2740 , . , -0.2246 -0 .0019 • 0.17i_6 0.4807... 0 .1535. -0.5661 STRUCT - 0 . 0 1 0 7 " ' - 0 . 0 5 2 2 0 . 0 1 1 2 - O . W O O " - 0 . 1054 -0.0475 j . 0677 0 .24*7 0.4177 0-3099 - C .5:533 HUE - 0 . 1 3 8 7 - 0 . 0 2 4 0 0.1012 - 0 . 1 1 6 3 - C . 2 9 6 0 0.0075 - J . 1368 - 0 . 0 4 j 3 0.2992 - C . 1 4 6 3 -0 .4020 _vit. 0.0914 - 0 . 0 7 4 7 0. 2239 -C .0002 -0 .5950 -0.3308 - J . 1 1 1 0 0.38-.B Q.4544 0.1871 6714 Ch 'U 'x i C .05G9 -0 .C998 0.3274 -0 .0853 -0 .6480 -0 .3205 - J . 0 3 5 0 0 . 1 2 i 5 0.6056 -0 .03 57 -C .7999 j-JLrE - C . 0 2 8 3 - 0 . C 5 7 4 - 0 . 0 8 9 6 - C . 0 3 8 4 - C . 1 2 5 5 -0.0452 -C.00C5 0 . 9 7 j 3 0 .0029 0.7753 - 0 . 2081 5CLAL -0 .0774 -0 .1 175 0 . 1573 - 0 . 1114 -0.3831 .. -0 .2510 .. - j . 1056 0.257 1 0.3584 ..- 0.2301 .-0.535'j JOLCi C .0952" " 0.C958 - 0 . 1 4 2 7 0 .1843 0 .1732 -0 .0154 - ^ .1330 -0 .05oO - C . 3 6 2 3 - 0 . 1 1 3 5 0.3460 jOL.".ii - 0 . C 6 7 9 - C . C 3 5 5 0 .1940 - 0 . 0 S 4 1 - 0 .2461 - 0 . 1 0 2 4 - u . 0 4 2 9 0 . 2 U 0 0 .0629 0 . 1 2 3 2 - 0 . 2 i j o _5,ji^ - 0 .0816 0.3093 - 0 . 1953 C . 1619 0.3570 0.PO5? - j . 1857 -Q . 12 -3C -Q.4997. -Q. - ; t43 0 . 7 9 1 3 SCI'; A - C . C 1 - 4 0.3207 - 0 . 1 798 C .1759 0.2441 -0.034.0 - u . 1299 - C . 1 2 . . 2 - C . 3 5 5 8 . - 0 .0262 C. 573 3 HCL C = - 0 . 0 7 7 4 - 0 . 0 1 0 6 - 0 . 1 5 5 6 0.0440 0.3968 0-5500 J . 5 0 8 7 - 0 . 0 4 , 0 -0 .2234 0.2653 .0.1206 h C L A L _ -0 .0328 0.2560 -0 .1331 _. C .1173 . 0.3165 . 0 . 1 2 2 9 - J . 0 6 0 3 . . . . - 0 . 2 0 / 1 _..rC.4707 - 0 . 0 9 5 0 0.6703 riCICA " - C . C 3 4 C ' 0.C216 - C . 1 4 4 2 C .C025 0.2905 C .0159 - v .2142 - 0 .15 .1 -0 .3645 - 0 . 1340 0.6545 -iCL-.i - C . 1 C C 5 - 0.0536 - 0 . 1 0 4 7 0-C5&9 0.3745 0.1125 - j - 1 6 3 3 - 0 . 1tp2 -0 .5559 -0 -0942 • 0.7SS6 __CLX 0.0355 0.0036 0.2553 0.5136 - 0 . 1394 - C - 1 8 9 4 z^l.,2XJJt -Q.Q7d,6 P.CC47 _il,J_L7__ - J . C 5 : 4 H C L ' . A C . 1 9 1 0 -0 .C1C3 0.0650 C .3581 - 0 . 1816 - G . 1583 - 0 . 1122 0 .10/2 0.0636 0.0549 - 0 . 2 4 3 7 SITES 0.0506 - 0 . 2 0 0 2 0.0819 -0 .C938 -0 .5268 -0 .3004 - j . 0 5 0 9 0.3Eo9 0.6579 C . 1 9 6 7 -0.O769 «JAV3 0.2213 0.0330 0.1953 0.0040 -0.3851 - 0 . 2 2 6 9 ' - j . 1377 - C . 1 9 j 7 . C . 5842 - 0 . 2 7 52 - 0 . 5618 NAJA^.O 0.3431 0.0199 - 0 . 1 1 0 9 - 0 . 0 3 4 9 -0.1472 -0 .0913 -u .0453 -0 .0213 0.1999 - 0 . 0 5 8 5 - 0 . 2012 Hj i i . n 0.0572 - 0 . 1 3 4 5 0. 1843 - C . 1 3 2 3 -0 .3253 -0 .2103 - 0 . 0 7 5 2 -0.02..1 0.9470 - 0 . 0 1 3 0 . - C . 5 9 3 6 CCHAEIATICN MATF I X i •CONUT MOIST TEXT STRUCT HUE VALUE CHROMA SOLFE SOLAL SCLCA SCLKG.. ! CLNDT 1.0000 HOI ST C.2366 1.0000 TEXT 0.5271 0.3&59 1.0000 • . • STRUCT 0.5360 0.3160 C.6602 1.00CC | HUE 0-2121 -0 .0061 0.1772 0.1293 1.0000 ; .VALUE 0.5963 0.3396 0.3604 ...0.3068 0.0836... 1.0000 . . _ CHROMA 0.5594 0.1827 0.4090 0.3487 0.3865 0.7499 1.0000 j SOLFE 0.4446 0.6214 0.1713 C.2605 -0 .0329 0.3977 0.1270 l.OOjO sm al 0.739ft r-1 1 3fi 0 . 3643 c .yxn? n . ih36 0.5567 . 0.5319 0.7.M9 1 .0000 J SOLCA - 0 . 3 1 6 0 0-0042 - 0 . 2 3 3 6 - 0 . 2 9 0 0 -0 .0113 -0 .3165 - J . 3 5 0 3 -0 .1198 -0.2373 1.0000 1 SGL'MG 0.5566 0.0930 0.2225 0.1590 0.0461 0.2355 j .1752 0.1531 0.5755 0.1155 I.CC30 j _ 50LK : - 0 . 5 0 5 9 _ 0.0123..... .-0.286.0 -.0.367.6.... ..-0.3C07 -0 .4374 . -U .5940 r0...1 li.Z .-0. 3996 . 0.2802 . - 0 .1876 . j SOLNA - 0 . 3 0 9 7 - 0 . 0 5 4 8 - 0 . 0 3 2 0 -C .1699 -0 .1514 -0 .3782 - J . 4 6 7 5 -0 - l 2 - ,8 -0.3C78 0.3027 0.C891 ! HCLFE -0 .1338 -0 .1203 -0 .0835 0.0682 0.1927 -0.4330 - j . 3 1 3 0 -0 .02o8 -0 .1926 - 0 . 0 9 4 9 -0 .1903 i HXLAL -0 .3485 -0 .0855 -0 .3635 -0 .4216 -0 .1866 -0 .4093 - - i -5398 - 0 . 7 W 4 -0.0993 0.3752 Q, 145S j riCLCA -C.4311 - 0 . 3 5 7 5 - 0 . 5885 -0 .5761 -0 .2238 -0.4993 -0.4460 -0 .1815 - 0 . 3427 0.4075 -0 .0966 | HCLMG -0 .3858 -0 .2013 -0 .5131 - 0 . 5 4 5 7 -0 .2686 -0 .4702 -0.5984 -0 .17u5 -0.2605 0.3348 0.1393 i hCLK - 0 . 0 7 5 3 .0,0.885 - 0 . 0 6 5 9 - 0 . 0 * 2 8 -0.168.8 0.2319. o . 1243 - 0 . 10i6 -0.037.7... 0.0859... -0 .0368 __j ~HCLNA~ " 0 . 1 1 7 0 " 0.1430 0.0942 0. 1090 - 0 . 1509 0.3569 0.2039 0.0834 0.0638 0.0036 - 0 . 0 2 2 0 j SITES 0.6793 0.2790 0-5304 C.5610 0.4166 0.6419 a.7298 0.37-»0 C.4193 - 0 . 3 5 8 0 0.0630 < KJASO 0.2850 0.0272 0.4060 0.2861 0. 1302 0.3374 0.4774 -0 .7777 0.7774 - 0 . 2 8 3 7 0^16.13. ! NAJARO 0.1602 0.0169 0.1629 0.1322 -0 .1313 0.1993 0.1409 -0 .04d2 0.0740 -0 .1526 0.0023 j HJARO 0.3835 0.1248 0.4072 0-3676 0.3240 0.3942 J.5505 0-O7o2 0.3051 -0 .3154 0.O0G5 I C O R R E L A T I O N M A T R I X SOLK S O L N A H C L F E H C L A L H C L C A HCLMG H C L K H C L N A S I T E S K.IARO NAJARO SOLK 1 . 0 0 0 0 SOL.N'A 0 . 7 3 8 5 1 . 0 0 0 0 _ H C L F E - 0 . 0 1 9 1 - 0 - 0 0 0 5 1.-.0.00.0 ., HCLAL 0 . 6 3 S 6 0 . 5 2 1 5 0 . 0 1 2 0 1 . 0 0 0 0 riCLCA 0 . 4 3 6 0 0 . 3 4 0 1 - 0 . 0 0 0 9 0 . 4 5 5 2 1 . 0 0 0 0 hCLMG 0 . 6 3 4 9 0 . 5 5 3 5 - 0 . 0 1 1 6 0 . 8 0 9 6 0 . 6 2 4 1 1 . 0 0 0 0  rlCLK C . C 5 6 7 0 . 0 0 7 2 - 0 . 1 C 8 6 0 . 0 0 3 3 - 0 . 0 0 4 8 0 . 0 2 6 2 1 . 0 0 0 0 HCLNA - 0 . 1 2 8 2 - 0 . 1 0 4 3 - 0 . 0 3 9 9 - 0 . 2 0 2 7 - 0 . 1 5 5 2 - 0 . 2 0 2 7 U . 7 1 0 1 1-OOjO S I T E S _ _ - 0 . 6 9 2 3 - 0 . 5 3 7 8 - 0 . 0 8 0 9 -0.70.81. . . -0.543.2 - 0 . 7 5 6 5 _ j...03.6.8.,.. ...Q...241? _1...00.00_ K J A R O ' - C . 4 3 1 3 - 0 . 2 3 1 5 - 0 . 2 1 3 3 - 0 . 2 4 7 7 - 0 . 3 9 4 7 - 0 . 3 7 3 8 0 . 2 3 9 5 0. 2 6» 5 0 . 4 2 2 5 1 . 0 0 0 0 NAJARO - 0 . 1 4 9 2 - 0 . 0 9 1 2 - 0 - 1 0 8 7 - 0 - 1 0 0 5 - 0 . 1 5 0 2 - 0 . 1 8 6 0 u - 1 1 8 6 0 . 5 2 3 6 0 . 1 9 3 4 0 . 3 7 9 4 1 . 0 0 0 0 HJARO - 0 . 4 3 0 5 - 0 . 3 2 6 0 - 0 . 2 C 1 2 - C . 4 7 8 8 - 0 . 2 7 8 4 - 0 . 5 7 0 8 - u - 0 8 5 4 -0-07..4 0 . 6 2 2 2 0 . 3 5 8 3 Q.<~ZQ9 .. CCRRELAT I CIS...MATRIX ; _ HJARO H J A P O i.eooo NAME MEAN STANDARD DEVIATION FE8ACT 12770.6 111736. ' j SBACT _ 1216.35 _ . . ^_ .4672.04 ., _ - I FUNGI 418.383 794.383 ! OMBACT 679.625 4C76.08 j FES LfdS9JL5J> 3.06177 ; TGS 3.73017 3.82165 ' j ELEMS 2.84333 3.78142 j _ _ SS04 1,02567 . . ...2.55738 __ _ . ! INSS04 0.489S17 0.438936 '< DM 0.480333E-01 C.9E0482E-01 i FH 3.43I5B 1 .78352 . , ; 1 CONDT 7.46500 4.56459 j MOIST 24.5792 1C.9856 TEXT . 24.0417 8.67954 ... _ .. j STRUCT 28.4083 16.0013 I HUE 5.C8333 2.37488 s VALUE- 4. 33333 1.29857 J CHROMA 4 . 1 5 0 0 0 2. 1 8 3 4 0 S O L F E 1 . 9 5 1 8 9 7 . 1 0 7 8 4 S O L A L C . 9 1 8 2 5 0 E - 0 1 0 . 1 2 6 0 8 5 V S O L C A 0 . 2 7 7 0 3 3 0 . 1 8 0 7 3 7 SOLMG 0 . 1 0 4 6 6 7 0 . 1 1 4 4 9 6 SfU K P.417SPPF-07 0. 5 78 1 43F-07 J ? S O L N A 0 . 2 8 3 3 3 3 E - 0 2 0 . 4 2 1 5 4 8 E - 0 2 H C L F E 1 1 . 4 6 8 6 7 . 6 2 9 3 3 H C L A L C . 4 4 7 0 0 0 0 . 3 6 2 C 7 8 \ H C L C A 0 . 3 3 0 7 9 2 0 . 3 7 8 9 9 0 H C LMG 0 . 3 9 6 9 9 2 0 . 3 8 8 1 0 4 Hf.l K P. 1 4 9 7 5 0 0 .171010 H C L N A 0 . 9 0 8 3 3 3 E - 0 2 0 . 2 7 6 8 3 6 E - 0 1 S I T E S 9 . 2 7 5 0 0 5 . 1 3 1 8 1 KJi.RO 0. 2 6 4 1 6 7 E - 0 1 0 . 1 8 0 9 3 9 F - 0 1 .NAJARO 0. 1 9 1 6 6 7 E - 0 2 0 - 7 2 5 2 4 5 E - 0 2 H J ARC O . 4 9 2 5 0 0 E - O 1 0 . 5 9 5 9 4 7 E - 0 1 1 2 0 O B S E R V A T I O N S T O T A L 1 2 0 O B S E R V A T I O N S A R E C O M P L E T E 1 1 9 D E G R E E S OF FREEDOM A C I D S U L F I D E M I N E T A I L I N G R E S E A R C H CONTROL CARD NO. 3 * * END * * * * END * * * * END * * * * ENO ***!» END » * « * END * * * * END * * C ONTROL CARD NO. 3 E X E C U T I O N T E R M I N A T E D 0 8 : 0 7 : 0 7 T = 1 . 3 4 8 R C = 0 $ 1 . 0 8 S S I G N O F F • j CT> IN3 Appendix C.2 Correlation Matrix for the Parameters Studied in the Siliceous Tailings Samples l . o o o n STANDARD DEVIATION-. 2008. 07 7323.-55 7 70.2 1 2 : - ~ 4 = 22.69 1 .91952 1.97356 0...23 77J9.. C.149677 CI 0.24C3 725-01 751 10. 7288 10.7866 " 14.8926 ' 1.86437 0.961321 .77 c -:n'. ! .77596 0. 1 7 « S 4 ! _J?.37C33?E-01 0. 79 39 235-0 . 4 3 4 O ) p 0. 11276-01 0 . I 1 ? 2 3 ? 44 165313 0.701591E-C2 "VCLCA 0. 7-'=700n_ "5 .4 7623 3 63 64F-G2 5 ,O'J065 .0..352148. C. 2714S7 0.346467 n " J A = . 1 " 0 . , . r _ 1 7 6 - ^ 77-01 C. i r 9 5 4 : F - C l 2.916 46 _0. 1590565-01 - M l o . o .60"*C-:p~-02 0.122051E-01 I V ! 7 ' 1 > : $ T O "A I i f . - * C C \ - 0 N O . rTPRFG * ^ « » S T P C E G «««•* S T J R E G » * « * 5 T Q R E G " « ' STP'.EG ».»««' S T P 3 E 5 •«««« STo^FC » * CQN'RCL CARD NO. 2 CI" 5 - CO; >j ; - n = R~EG P E S STO N~E 60 AT"; OKI FOR" SBACf ~ " 55^0159 F-PROBABIL ITY LEVEL = 0.0500 S 3 A C T 5154. I S " 00 CONOT MO! " T E X T ~ T f 5 Lie T HU" 0. 03 6 4 -0.06 34 0.2 340 0. 03°0 - 0 . 1 5 9 2 0 . 3 5 P 5 0.?.42t_ " o . i 2 c * 0.1 26 ? ' 0 . 0 5 3 2 0.6523 -0 .0742 0.1454 ___ 3 , c ^ • -0.0252 0.2V80 -0 .0914 0. 2538 0.1200 0.0641 0.0807 -0.1578 -0.3349 -0.2395 -0.1478 6.0073 - 0 . 5094 -0.7036 0.0139 -0.2520 -0.3790 - " . 1 0 42 0. 5527 0.2553 0.1340 0.0382 -C.0231 6.05 97 0.4990 P.4882 C.9148 0.2443 J).4880_ ' 0.5011 0.2935 0.3286 0.6351 0.0434 0.2489 6.3 355 0.379 ' 0.3072 0.0672 -0 .2217 0.2040_ 0.1235 -0 .0172 -0.0 8 89 -0.6211 -0 .0407 -0 .0723 - 0 . 1671 -C .4785 -0.5902 SO'.FF SOl&L 'SOLCA SOL^'G SOL K P. 1 208 -0.0910 0.0 737 0.0754 0.0 569 -0.1179 0.41 31 0.2547 0.6063 -0.1991 0.1723 -0.0379 0.0 274 •0.0333 •C. 1748 0.2 526 -0.1097 0 . ! 6 4 4 -0 . 02 25 0. 5703 -0.4016 0. 156 7 -0.0448 0.3109 - 0 . 7 2 7 3 - 0 . 1 0 8 1 - 0 . 3 75 2 - 6 7 6 0 8 3 - 0 . 3 5 1 9 0 . 4 6 8 3 0.3919 -0.1503 -_0.J_412_ "0.1399 0.0514 -0 .3115 0.6002 -0.0532 0.0646 "0.3571 0.1724 -0.4268 0.4984 0.5339 0 . 7 75 1 0.4903 0.8216 -0.4671 0.5221 0.2732 _P_. 6719 0.248 8 0.5719 -0.5763 - 0 . 0 6 76 0.0838 -0 .1485^ -6.0191 0.1710 C.25C9 - 0 . 7623 -0 .1948 -0_.59 50_ -0.43 66 -0 .5147 0.8141 HCLFE HC L AL ~vcTfX~ HCl v 0 HCLK 0 . !527 -0.32^6 -0 ,T9 ?P _ -0.2172 -C . 0 ° 1 2 0.2 376 -0.1196 0.2273 -0.06.42 0.049C -0 .1306 -0 . 34 90 -0.2770 -0.1421 - 0 . 1 8 9 ' -0.053 5 0. 1998 0 .34!8 0.0710 0.4311 6.1147 0.3116 0.0665 0. 3185 0. 5299 0.2082 0. 6592" 0. 1 766 - 0 . 1347 -0 . 1126 0. 2M5 -0.4327 -0.7430 -C.2H04 -0.1912 -0.1216 -0.0378 -0.2776 -0.3498 -0.2634 -0.1420 -0.1423 -0.3503 -0.1274 -3 .4058'' 0.050 2 0.2824 -0.1644 - 0 . 1127 -0.2386 -0.2700 -0.1160 0.1836 0.6309 0.1702 0. 1956 0.3339 0.2991 0. 1459 0. 4804. 0.2579 0. 5 7 04 " 0.656.7 C.4228 0.0309 HCLMA SI T ~ S xj s - a "NA J'AV-HJ A 5 0 ; A 6 0. 1475 '"O.O 0.3722 -0 .0567 -0.1744 0.0330 " o . o " " -0 .1456 0.0219 0.3592 0. 58 64 ' o"."6 0.2743 -0 .0345 -0.2376 0. 146 3 "6.6 -0.0926 -0.1445 -0.7587 -0.5464 "6.6 -C.369C -0.0828 0.40 31 0.1683 6.0 0. 1946 0.0501 " .5042 0.3212 0.6 0.1721 0 .2 79 6 0. 5505 0 .6672 0.0 0.5236 0.1463 0.5479 0.9075 0.0 0 . 8709 -0 .0946 -0.2161 -0 .0176 O.C 0.1514 -0 .2069 -0 .3387 -0 .6369 0.0 - 0 . 54 75 C r *RELATION * A T » I X C OMOT " C I S T T S X T S T R U C T HUE V ALU- C H R O M A _.SQLFJE SOL AL SOLC A SCLMG C O N T l.^OOC ! Mj- s * -0 .0252 1.0000 TC yT C 3137 0.6 S 5 8 1.00 00 S*- UC" 0 . 4 4 B 6 C.3100 0. 53 3 7 1.000 0 H','F 0.2179 -0 .0545 - 0 . 1440 0.0353 1.0000 V-U'J-" 0 . 2 4 ? 3 -0 .0283 -0 .0865 0.0303 0.6003 1.0000 : . 4 - i i o . o 2'7 6 - 0 . 0! 3 2 ' 6 . 2 800" " 6.5 915 ' " 0 .79!7 1.0000 SOLE? 0 . ? 5 3 5 0.1120 0. 39 30 0.3943 0.2212 0.0591 0.1717 1 .0000 SOLAL 0.3149 0.1139 0. 29 56 0.4086 0.1772 0.3349 0.4376 0.6145 1•0C00 I S -"-(" A 0 . 1 >' ? 5 0 . 5 f i 6 0. 43 I P. 0.1395 0.2578 0.1760 0.3441 0.3 550 0.183 7 1.0000 s n v o 0.3493 0.0250 0.3614 0.4962 0.1936 0.1857 0. 2963 0.2671 0.5019 0.1749 l.OOOC SOAK - ? .4341 C.7475 0. 2031 -0.0809 -0 .2657 -C.4152 -C.5622 0.0479 -0.4635 - 0 . 0 7 0 0 -.0.42 2 9 '. -0 .16 59 "b"."i"e"8"5 0.4860 0. 1933 -0.1232 - C . 3149 -0.3663 0.1938 -0.3393 0.0583 - 0 - 0 2 9 2 " " | H C L " -0 .1204 -0.3713 - 0 . 3 3 5 7 -0.2661 -0 .0142 -0.4541 -0.4056 0.0200 -0.2012 -0.4721 -0.1491 i HC L A L - 0 . ISA', 0.1564 0. 206R -0 .1953 . -0.0626 -0.2433 -0 .4357 0.3001 - 0 . 2101 0.0159 -0 .1095 i HCLCA -0 .3102 -0 .312 1 - 0 . 1596 -0 .2341 -0 .3554 -0 .4341. -0.5176 -0.0721 -0.4055 -0 .3343 -0.2441 | HCL M0- 0.1011 -0 .0715 0. 157! -0 .189 2 -0.0195 -0.269 2 -0 .4430 0.2966 - 0 . 1600 - 0 . 0 3 9 9 0 .1970- i Hf.L". " . 3 1 3 ! - 0 . 0 83 5 0. 1499 - 0 .0319 0. 2 02 1 -0.0030 -0.0537 0.5 72 7 0. 24! 1 0.0461 .0. 1945 i HCL'15 0 . 7 Of: 6 -0 .0375 0.1196 -0 .1894 0.0810 C.0393 0. 1205 0.1330 0. 1974 0.1578 0.2287 j SI ~-? 0. « 3 i -0 .1174 - 0 . 1 7 9 0 -0 .0347 0.4565 0.5239 0.6436 0.0211 0.4331 0.3 232 0.3916 j K.i 3:T> 0. 6140 - 0 . 0 570 0.1249 0.1376 0.4000 0. 2342 0.5257 0.3084 O.6000 0.2 752 0.5286 ! \'1J A•» 0 0.0 0.0 0.0 0.0 0.0 C.O 0.0 0.0 0.0 0.0 0.0 i " . 4663 C.1237 0.2329 0.4177 C.3091 0.2527 0. 3563 0.1359 0.5720 0.1533 0.4977 ; C3=RFLA T!0W MA-?IX SCL< S O L N A H C L F E H C L A L . H C L C A HCLMG HCLK H C L N A SI T E S KJAR G N A J A R O SOLK SCLNi " U C L . A L ' U C L C A 0.4663 o. A o 7 7 1 .0000 0.1262 0.5338 0.4553 0.5701 l.COCO ""b.26'B7" 0.5176 0. 23 81 1.0000 0.4390 p.8365 1.0000 C .5024 1.000 0 . 0 7 . 0 5 0 O . 4 3 C 0 TVbob' o.o 2 6 0 . 0 1 . 3 S 0 0 . 1 2 0 0 9 - 0 1 2 5 0 . 0  3 . 3 0 0 2 9 . 7 8 0 . 1 4 0 0 ? b.b 9 . 0 0 0 - 0 1 1 C . 0 0 2 5 . 0 0 O . 4 0 O 0 E - O 2 'o.o 0 . 0  5 . 1 9 0 1 7 . 0 0 6 . 0 1 0 9 . 4 9 0 1 . 7 1 3 2 . 0 0 0 3 . 6 0 0 0 2 . 7 2 0 0 . 4 0 0 0 2 . 0 0 0 0 . 3 3 8 0 . 0 . 1 0 0 0 0 . 2 9 0 0 0 . 0 0 . 4 0 0 0 E - C 2 0 . 0 0 . 2 0 0 0 F - 0 2 0 . 3 0 . 4 7 3 0 0 . 6 8 0 0 E - 0 1 0 . 3 0 . 5 3 0 0 E - 0 1 0 . 3 0 0 3 E - 0 1 0 . 0 • 0 . 2 9 3 3 1 . 3 3 ? 0 . 4 3 0 0 = 3 . 0 - 0 1 0 . 1 6 C 0 E 0 . 0 - 0 1 C . 1 6 0 0 E - 0 1 0 . 0 1 1 . 0 0 1 . 0 0 3 0 . 8 1 9 0 0 . 9 6 4 0 0 . 1 2 0 ? 0 . 3 ; 2 5 0 . 3 6 . 9 3 0 0 . 3 5 5 3 2 4 . 0 0 3 . 8 3 0 0 . 7 3 0 0 " - 0 1 0 . 0 2 0 . 9 7 0 . 1 6 0 0 E - 3 1 0 . 0 2 5 . 0 0 0 . 1 2 0 0 E - 0 1 3 . 6 1 0 1 6 . 0 0 9 . 3 4 0 1 . 7 1 0 6 . 0 0 3 1 . 1 0 3 0 . 1 0 0 C 3 . 0 0 0 0 . 6 2 7 0 0 . 3 1 0 3 1 . 3 0 0 1 . 0 8 3 C . 4 0 0 C 6 - 0 1 0 . 2 6 9 0 0 . 1 3 1 3 C . 3 0 0 0 E - D 1 i . 0 . 3 i 3 . 0 7 . 0 0 0 0 . 1 1 9 ? 1 . 0 0 0 1 . 5 0 0 0 . 1 0 0 0 " - 0 1 3 . 0 1 5 . 6 5 0 . 5 0 0 0 " - 0 2 0 . 0 2 4 3 . 0 7 . 1 0 0 O . O 2 . 6 5 0 4 5 . 0 0 2 1 . 0 3 5 . 0 0 0 0 . 2 3 0 0 - - 0 2 0 . 0 0 . 0 2 5 . 0 0 1 7 . 0 0 2 5 . 8 0 4 . 6 1 0 2 . 0 0 0 2 . 0 0 0 0 . 4 3 0 0 2 . O O C 1 . 1 2 0 0 . 0 0 . 3 9 3 0 0 . 2 0 0 C E - C 2 0 . 5 6 0 0 E - 0 1 0 . 0 0.0 2 . 3 5 0 2 . 0 0 0 0 . 5 0 0 0 3 . O O P 0 . 2 1 0 0 0 . 0 . 0 0 . 6 2 0 C E - 0 1 0 . 2 0 0 0 E - O 2 0 . 0 1 . 0 0 3 2 6 0 . 0 C . 1 0 0 3 . - 0 1 0 . 3 1 0 0 E + 0 5 2 9 . 0 0 7 . 2 2 3 3 . 5 2 8 0 ' . 3 0 3 2 . 4 2 0 0 . 7 9 0 0 E - 0 1 3 . 3 0 Q 3 F - 0 I 3 9 . 3 4 0 . 2 3 0 0 E -0 . 0 0 1 0 . 0 0 . 2 7 0 0 E + 0 5 2 5 . C ? 0 . 1 5 0 0 E - 0 1 3 . 0  3 . 7 4 0 " 2 2 . 3 3 1 1 . 3 0 2 . 3 0 0 6 . 0 0 3 1 . 6 0 0 0 . 3 0 0 0 3 . 0 3 0 0 . 6 4 1 0 0 . 4 2 0 0 1 . bob 1 . 3 3 0 3 . 1 5 0 C 6. 3 2 7 ? 0 . 1 5 6 0 ' . 0 . 4 3 0 0 E - 0 2 . . 0.0 2 7 3 . 0 7 . 4 2 0 _ _ _ _ „ 3 _ 1 . 0 3 0 1 9 0 . 0 2 . 1 5 0 5 5 . 0 0 3 3 . 4 0 0 . < W 0 3 _ - 0 1 o. m o o - - o i 0 . 2 3 0 0 = - 0 1 0 . 0 3 0 . 0 0 2 5 . 0 0 3 . 1 2 : 0 0 = - 0 1 0 . 0 2 . 5 5 9 2 . 0 0 0 1 5 . 0 0 1 . 6 4 0 0 . 3 0 0 0 0 . 4 0 0 0 0 . 8 0 0 3 E - 0 1 0 . 2 2 0 3 E - 0 1 6 . . 0 0 0 _ 3 . 0 0 0 1 . 3 0 3 _ 0 . 4 3 2 0 _ _ 3 . 3 1 . 9 0 3 1 . 3 ? ? 1 . 6 4 ? C . ? ! 4 ? 0 . 0 . 2 ? 0 . 0 5 . 8 7 0 0 . 4 0 1 0 1 5 0 3 . 5 . ? 0 0 0 . 7 6 0 3 " - 0 1 ° 5 . o o 1 4 . 9 8 0 . 1 9 0 0 " - 0 1 O . O 2 5 . 0 0 _ J 3 J - . I 8 . og ; - C I 3 . 6 9 0 2 2 . 0 0 1 5 . 1 3 4 . 7 8 3 6 . 0 0 0 1 . 1 0 0 2 . 0 0 0 4 . 0 0 0 0 . 7 5 4 0 0 . 3 3 0 0 3 . 0 0 0 1 . 2 3 3 0 . 8 0 0 0 " 0 . 4 3 5 0 0 . 2 2 3 3 - 0 1 0 . 6 6 0 0 - - 3 1 3 . 3 3 , 0 . 1 . 3 0 - O . 1 3 C 0 " - 5 7 " " ? R O o. ? ? O 0 . 0 ''fc.OO 3 . 0 0 0 0 . 0 2 . 6 9 0 2 . 3 5 3 0 . 3 0 0 0 0 . 2 3 0 3 0 . 3 C . 3 0 3 3 3 - 3 2 fc. « c 1 0 . 2 6 9 0 1 . 3 0 0 2 . I F " 0 . 4 9 0 0 3 0 . 0 - 0 1 2 7 . 5 3 0 . ! 9 0 0 E 0 . 0 - 3 1 2 5 . 0 0 0 . 1 3 0 0 E 0 . 0 - 0 1 2 2 . 3 ? 6 . 6 7 0 2 . 0 3 3 1 . 0 0 0 3 . 3 0 ? 3 . 3 7 9 0 1. C O O 0 . 9 8 0 0 0 . 1 9 3 0 0 . 1 3 1 3 c,o 0 . 0 3 3 O . O 7 . 0 6 0 3 6 0 . 0 ?.. 1 5 C 2 3 . 0 0 8 . 1 7 0 0 .0 5 . 0 0 0 6 . 1 8 0 4 6 . 0 0 4 . 4 9 0 6 . 0 0 3 1 . 3 0 0 3 . 0 0 0 0 . 2 4 0 0 3 . 0 0 0 0.0 0 . 3 0 4 0 0 . 1 2 0 0 E - 0 1 0 . 3 p . . 3 1 . 0 0 3 ~ . ^ F N 0 ; 0 . 0 - 0 1 0 . I O O C ? 3 . 0 - 3 1 3 . 6 0 0 0 E 0 . 0 - 3 2 1 3 . 6 ? 9 . 6 7 3 0 3 . 6 1 1 0 0 . 6 2 2 0 0 . 1 5 5 0 C O F E 3 A C T S " U C T " F U ' H r N'.' r> -F H S F F B A C T 1 . ^ O ^ O - 0 . 3 5 6 7 - 9 " . ' 0 8 "9 9 i - i ^ Q - M 6 ! ? « B A C T L . - O O O C - 0 . 1 2 2 5 3 . 7 A 2 F 3 . 3 2 8 3 F U N G I 1 . 0 0 0 0 - 0 . C 8 8 9 - C . 3 2 5 5 O M B A C T 1 . 0 0 3 0 0 . 1 5 2 3 F F 5 1 . 0 0 0 3 T Q S E L E M S S S 0 4 I N S S 0 4 P H ! 7~c 3 . 3 9 3 - 0 . O S 3 8 - 0 . 2 2 1 8 - 0 . 1 2 3 3 - C . 3 1 0 1 1 . 0 3 0 0 1 1 6 C 6 0 . 0 1 5 4 - 0 . 0 3 3 9 - 0 . 1 8 3 3 - 3 . 5 5 9 4 0 . 5 2 9 4 1 . 0 0 0 3 S S " - 3 . 0 0 = 7 - 0 . 0 2 3 5 0 . 6 0 4 2 - 0 . 0 0 6 2 - 0 . 5 7 0 8 - 0 . 0 3 0 4 0 . 2 3 7 4 1 . 0 3 3 3 J 9 . 2 6 1 5 ~~-B".":>43~6' ' 0 . " 5 2 4 0 0 . 0 0 3 1 ' - 0 . 5 1 , 8 ? 0 . 1 9 1 1 0 . 3 3 1 6 3 . 6 8 7 4 " " " L . O C O O " " - " . ! . 3 6 7 - ' - . 1 3 7 4 - 3 . 1•> 44 - 0 . 0 9 5 0 0 . 0 3 9 8 0 . 2 0 8 3 C . 1 2 5 5 - 3 . 0 1 5 7 0 . 0 6 6 1 1 . 3 0 0 0 1 . 3 3 0 0 j - 0 . 2 6 1 5 • 3 . 1 3 1 2 - 0 . 4 0 2 6 0 . 2 4 9 4 0 . 7 9 4 8 - 0 . 4 6 1 2 - 3 . 5 9 3 3 - 3 . 6 7 7 ? - 0 . 7 0 7 6 0 . 3 3 S 1 Appendix C.3 Correlation Matrix for the Parameters Studied in the Iron Tailings Samples with pH >2.5 M** S8ACT FUN'CI OVHACT FES TOS ELEXS SS04 INSS04 0". P H • c f r* £ C " i , S-i-C. ~ ? 1 03 1.0000 - J \ - T A 0.162? 1. 30 00 0 7 q 7 -O.O? 7 -? 0. 2126 1.0003 "" c - <: '."»7 3 " - 0 . 2 6 30 - 0 .3763 0.363 7 1.0333 0.0671 -C.01 88 0.3451 0.2434 1.0333 -1 r •_ " "}77* 0.2 112 3.138= 0.3 70 2 -0 .1534 0.6606 1.03 00 ? <* 1 16'? 0.0=63 0. 5946 -O.C .90 - 0 . 0 72 3 0.C7C3 0.1672 1.9030 ? -. 0 0.1318 0.67 IC- C.0476 -0 .1200 0. 0252 0.00 73 0 .3933 1.3000 2 - 3 -0 .1113 - 0 . 0 7 4 O 0.2327 . 3.4322 0.5134 0.4929 0.1341 - 9 . 1 5 6 4 1.3330 — " o-. ' " : 7 ? t - C .1660 - ? . 2.55 ' 1641 " " - 0 . 0332 " -0.45 75 -'"-(..66 39 - 0 . 4 23 1 - 0 . 4 744 - 0 . 5 0 7 " 1> :?3C c 3., e,-. 0.0-+79 0.1731 -0.2701 -0 .0397 - 0 . 3156 0.1374 0.2040 3.4122 -0 .36 32 — 7 . 4 : 3 7 -»-!<!- 0 . -123 - 3 . 3 4 0 3 C.2346 " .2394 0.3824 0.3339 0.0134 0.2351 0 . 1 ? 9 3 -r,. 4'. ?6 i - y , - 7 3 0 , 2 2 0 '. 3 . 13 94 0.1372 0.1253 0.2534 0.4277 0.1974 3.4043 0.4092 - 0 • 7 3 5<-t _ a 0.0933 -0 .04C6 0.064 1 0.4196 9.3841 0.35oi 0.0946 0.2324 3.5653 _ r _ i 342 "^ r I T 1726 * . 1 0 R 4 0. 2646 - 0 . 1 3 9 5 -C.199 9 n # ^oan " .5353 0.3398 0.3523 0. 1 197 — 0. 5 7 62 ! •3 5 0 3"" 6".-9 7 2 4" " 3 . 4 7 6 6 "0.042 3 - 0 . 3 43 8 0. 05 51 0 .131 . 0.018 2 ' 3.3232 0.3839 _ *. s 3 3 14 i . 3 2 6 3 0.0514 3 . 4 i 12 0.3768 -0 .2709 3.2113 0. 2460 0.4997 0. COS-9 0-1 75" j > 7 •_ P - 7 - i P ~.1338 . 3. 02 89 0 . 1 5 0 9 -C.0921 .0.6302 . 0.9314 0 .0828 0.9651 3. 5796 - n . 73 33 1073 - 0 . 1 5 1 0 -0 .22 34 -0 .0906 0.3041 0.2227 -0.1338 -0 .167 7 -0.3103 0.2 6 23 7 . 2 4 23 i ? :LC 7 . ** i i . 1 : - 0 . 5 7 6 1 0.1164 0.9273 0. 3 29 9 -C.3383 -0.4642 0.0 84 1 0.2663 -C .2555 7 • 1423 5 ~ _. v ','."5 0. 62 33 - 0 . 1299 - 0 . 242 4 -0.2239 -0.16 24 0.1736 0.4558 -9.1 856 c. 1305 ;4 1A~ " 0 7 5 5 4 5 ' -0 .02 71 - 0 .2333 -0 .112 5 - C . 4335 " " " - 0 . 4 7 11" " ~ -3 .0377 -0.3383 -9 . 2 8 1 3 7 • 4 0 13 -n. 0 ?•»{• 0. 3 81 1 0. 3^83 - O . C179 - 0 . 179 6 -3.3917 -0.3321 - 0 . C 3 9 ? C.3214 - " . 1 3 5 5 C. 2302 _. 1 *> i "> 0.1300 - 3 . 18 26 - 0 .0339 0. 1 147 3.6681 0.7661 0 .0568 -0.1223 0 . 4 0 . 7 1 - 0 . 5396 K L I - ">. l ) . ? H 8 -0 .1176 -0 .0570 0. 1240 -0 .0640 -0.3C65 -0 .0311 -0.0135 - 0 .10 29 23 15 ; L C i _ ^ ?!69 - 0 . 1 3 3 9 0.2362 -0.1853 -0 .2392 -0.4103 - 0 . 5524 0.2578 - 0 . 9840 - 0 . 5 2 4 4 c. 52 15 i _ -. ? ! 4 4 T O . 3 4 6 0 -0.21 12 - 0 . 1848 0. 379 5 -0.2956 -0.6263 -0 .3956 -3.3303 - 1 . 7 9 5 6 .134 ] 5". 1.63 A . 11 c 0 -0.26 34 " " ' 0 .0130 -0.1110 - 0 . 3477 -0 .5514 - 0 .3610 -0.2734 -0 .34S2 S. 76 7 l_ • J. C. "> 3.0 3.0 O . i 0.0 0.0 3 .0 0. 0 3.3 7 . ? 0.3516 0.35 17 ,0 .1544 -0 .1132 0. 42 4 ? 0 . 6 O 5 5 0.556O 3.4290 0.3 7 1 4 _ r ^ = 963 a-i a. NAJ 4= 0 HJARO 0 . 2 5 6 4 0 . 0 - 0 . 1 7 7 3 0 . 2 9 3 2 0.0 - 0 . 1 * 1 5 C. 1 5 7 1 0.0 0 . 7 0 4 6 C . 2 1 2 1 0 . 0 = P . .109 3 0 . 0 1 8 7 0 .0 - 0 . 161.1 - 0 . C 7 6 2 0. 0 - 0 . 1534 - 0 . 1 7 4 9 0.0 - 0 . 0 6 6 0 .... - 0 . 0 1 8 0 0 .0 0 . 6 0 3 9 0 . 6 2 6 1 0 . 0 0. 3036. - 0 . 0 1 4 1 0.0 _ - 0 .Z l_38. - 0 . 3 0 2 1 i 0.0 ! - C . 3 5 1 8 . | >. CORR ' L A T j J C O N D T * o : s ~ COND" 1 . P O 0 0 1 . 2 1 7 3 MO I S T 1 .0000 " E X T S T R U C T HUE V A L U E CHROMA S O L F E S O L A L S O L C A S C L « G \ i j T=>:T s uc ' 0.3725 0. 3 24 0 0 . 0 7 6 6 0 . 3 3 1 2 0.4 73 3 0 . 1 5 4 0 1.0000 C . 7 6 5 7 0. 2 8 7 6 1 . 0 0 0 0 0 . 1 0 1 2 1 .0000 i V A L U E S O L c E 0.2071 1 152 o . l 0 5 6 -0 .0 520 - 0 . 0 70 5 0.402 3 - 0 . 1 2 9 6 - 0 . 3 0 6 8 0.47 86 - 0 . 1 9 5 1 - 0 . 4 2 3 9 0 . 4 0 7 5 C. 1 5 7 7 R . 206 2 0 . 6 5 2 1 1 .0000 0 . 5 S 5 9 0 . 1 2 8 4 1.0000 0. 1 7 3 6 1 .0000 1 | I SOLAL SC-LC A SOL^'G - 0 . 2 506 0 . - 4 5 5 0 .5431 -07221T''" - 0 . 1 7 6 5 -0 . " 777 - 0 . 3 0 0 9 ~ C . C 0 2 0 0 . 1 136 - C O C O 5 0 . 0 5 5 9 0. 0 3 5 7 - 0 . 3362 - 0 . 0 9 0 2 - 0 . 1 7 1 5 0.0853 - 0 . 1 7 9 5 0.46 86 0. 1 3 7 9 - 0 . 3 4 4 8 0.0465 - 0 . 1 9 8 0 - 0 . 3 6 7 9 - 0 . 2 4 7 6 l.COOO - 0 . 1 903 - 0 . 1 4 3 5 1.0000 0 . 1 4 2 0 1 1.0003 i SOLK SOL MA H C L F F HC L AL HCL C A HC L VC< — 0.0062 - .3 3a? 0.1577 - P . 0937" -0 .2958 - 0 .3 714 -0 .0191 - 0 .1048 0.2931 9.2 77 7 " - 0 . 4 3 3 2 -0 .4036 -0 .13 15 0. 17 51 0 . 4 5 1 3 - o 7 3 0 9 3 ' ' . ~ ~ " - 0 . 7 6 1 8 -0 .6665 - 0 . 1 6 5 2 0 . 0 0 2 9 0 . 4 5 8 6 "> .0218 - 0 . 7901 - 0 . 4 9 6 1 - 0 .4 75 7 - 0 . 2 7 2 4 0.4301 " " - 0 . 3 342 - 0 . 1927 - 0 . 5733 - 0 . 0 2 5 ! 0.3310 - 0 . 3 2 7 7 0.16,!'. 3 0.1133 0 . 0 9 2 0 - - . 0 6 6 9 - 0 . 1 2 7 8 - 0 . 0 7 4 3 P .O2T2" 0.4384 0. 0 5 3 1 - 0 . 5 4 7 8 - 0 . 3 8 2 9 0 . 7 6 9 9 - " . 3 6 9 3 " - 0 . 6 3 5 7 - 0 .6 305 0 . 0 9 9 8 - 0 . 1 8 3 4 - 0 . 0 6 4 6 0. 3 855" 0.1934 • 0. 3390 - 0 . 1 3 4 4 0 . 0 0 0 1 - 0 . 3 3 9 7 - 0 . I 3 74 0 . 1 ! 3 5 0 .1943 0. 3 2 0 6 i 0 . 7 7 6 6 j - 0 . 2 5 3 3 0. 02 05 j 0 . 0 3 0 2 1 0 . ? 5 6 2 HC'.X HC L NA ^ ' 7 - ^ K J A = 0 S'\j:.~0 u j A - r* — - r - . 2 0 7 1 0.0 0 . 1 0 7 7 . p. 0 0 . ^ 1 4 4 0.0054 0.0 0 . 2 6 3 7 - . 3 2"88~ 0.0 - 0 .0230 - C . 4 6 6 0 0.0 0 . 5 8 5 2 ~0. 4276 0 .0 0 .1b5n - 0 . 4 1 3 7 n . o 0 . 4 2 0 2 " 0 . 3 1 6 6 ' 0. 0 0 . 0 0 2 9 - 0 . 5 1 5 3 0. 0 0.738 2 0 . 1 1 0 8 0.0 0.3013 0. 1022 0.0 0 . 0 3 7 6 0 . 1 0 8 3 C. 0 0. 3 4 8 5 0.0263 0.0 0. 1922 - 0 . 2 9 3 7 0.0 0 . 2 6 6 5 - 0 . 5 4 3 7 0.0 0 . 7 3 2 7 " - 0 . 0 4 1 2 0.0 - 0 . 0 5 3 0 0 . 1 3 0 2 0 .0 -•>. 3325 - 0 . 3 1 9 3 0.0 - 0 . 22C9 - 0 . I 443 0.0 - 0 .0 4 62 0.0721 0.0 0 . 4 1 2 1 - 0 . 0 3 5 9 \ . . -C.I 959 0 . 2 0 9 3 ; 0.0 1 0.49 18 r - R ^ E i A T «!.* = !X 1 SOLK SOL'IA ! .0000 0.6647 SOL ' iJA -1.0000 H C L F F HC L Al. H C L C A HCLMG MCLK H; LNA S I T ? S K JAR 0 N A J 4 3 0 ~ I j I HC L f = HCL AL H C L C ^ - 0 . 4 ~ ? 3 0.3212 0 . 7 7 = * - 0 . 4 0 3 7 0 .093 2 - 0 . 0 0 7 8 l.CO 0 0 - 0 . 4 6 5 0 - 0 . 59 92 1.0000 0 . 2 4 4 7 1 .0000 1 HCLMG HCL". "CL \A 0.27S1 0 . 4 5 2 0 0 . P 0 . 1 1 6 1 0 . 2 3 0 9 0.0 - 0 . 6 6 5 3 - 0 . 5 7 1 6 0 .0 " 0 . 4 2 7 1 ' 0 . 5 4 3 4 0 . 0 0. 634"4 ~ 0. 4 6 7 6 0.0 1.COCO 0 . 7232 0.0 1.0000 ".0 1.0000 1 I i si T~S KJA^.O N A. J A - 1 - - . 5 6 '4 A 0.3113 0. 0 -C .3931 0 . 4 5 4 7 0.0 0. 5 4 8 3 - 0 . 1 3 2 3 0.0 - 0 . 4 0 3 8 0 . 2 4 5 0 O.P - 0 . 3 93 2 - 0 . 300 0 0 .0 - 0 . 7 9 9 6 - 0 . 2 0 3 7 0.0 - 0 . 7 0 4 7 0. 1 1 0 5 P.O 3 . 0 0 .0 0 . 0 1.0000 0.0976 0. 0 1 .0000 0.0 1 ! 1 .5000 I 4 i ^ c r. -O.IC-PO 0 . 1 5 0 8 - 0 . 1 8 9 5 - 0 . 1 5 7 3 0. 1933 - 0 . 2 1 3 0 - 0 . 3 4 5 6 0.0 0.4110 0 . 2 0 7 C j CP^-.ELAT H J A ^ O I O N MAT"!. 7 X H.Ji 1 .0000 1 1 f 1221 3. 3 ST ANOAR 49 5 1 D P E V ! A T I ON 0 . 7 1 i i S ? A T-C = 1 : .'.r -1 7 2 . ? 4 6 K J S . 3 1 " " " 5. 1 6803 T . ! 7 2 3 ! 4. 6 3 4/- 7 5546.85 3 0 7.716 4 395. 50 3 .98905 5 .502 17 5. «7396 1 1 i 1 1 1 J — •NSSO'-0.385769 0.177046 0. 160385 0. 1371 .5 0 . 7 S 6 ° 2 3 = - 0 ! 0.964823E-01 C0M0 T STRUCT HUE 4.26 53 8 19 23. 26^2 3 .30769 2 . " ?3~8 1.69 231 0.287769 1.19194 1.56657 3 56 mm—tm CHROMA "OLFE S Q L U SOI OA ? OL VG " s o u r " S 01 N A _____ 3.A61 538 — 03 0.2055-->0 0.637ft^2F-01 0 . 6 - ? 3 0 R c - 0 ? 0 . 4 ? 6 ° 2 3 ' = - 0 2 1 7 . 7 Q T 7 21 17.4696 1.6916! 0 : 3 9 2 2 32"" C. 9703 29 0.3706S6 HC L AL HCLOA H C L V G •.:>. K " C L M A S T " 1 ; 0.56692 3 0 . 5 9 A C 7 3 . 6 0 9 0 Q M "o""."T220"77_ 0.0 4.57c=2 0. 110384E-02 0. 1056 30 0.728007E-01 "0.46 91 89F-C2" 0. 478797E-02 10.2176 0. 262903 0.5491 16 0.410788 K J A R O N A J A P O HJA'O __ 26 25 "0.59C3 62F.-C! 0.0 2 .06249 p . : 65335 C -C1 0.123101E-01 0.0 0.0 3.846 1 . 4^-02 0. 166595E-01 " op - ; - rovaT i ' ' f f i T " " tOTAL " " " " " " ' " ' 035 e RVA TT":NS AR E COMPLETE •"COM*«C~C"A'5"P" fro; S T » " : (V •*'-»« STI'R'G STPftCG" S'TPPfg" **"*» "STPRF G" »"***"" S T P R E G ' * * * » S"t"p5"EG" *"* CONTROL C !•?.': NO." » » » S T = P N»M.t<=e 3 R"0R"SSI0N EQU A T . ON FOR SB ACT R - 3 ? ' J £ - " C = •"'345965 F-PP.03 AB! L I T Y L r V ^ l = 0.0500 ?TAV:.AP.O' E 7 R n o " ' S B A C T = 5 6 1 0 . '" F - r c - ' B M ! l L i T V = .85165947 • V . ' . - ! tBL c C " C F E ! C ! C M T ST D. ERR. F-RATTQ F-°R0B ,r"-. c c i Q T c .3?.'.84180E-01 3.1?7"208 -0.45039307 3.871 187 0.7412 0.4242 ?072 NOP M COEFF FF3AC T F'J'40! 7Zo3T3?r9"'" 1.18_____ 0.1079 0.6777 J ._i . . I f -571 0 . 3 4 3 5 0 . 1 7 6 5 -0 .3979 076 0.2530 > » > > > S r " ? ••;U"3E? R EGRESS ION FOI.'ATIOM FOR SBACT 0.0293630 F-PP08ABILITY LEVEL _ - . _ _ _ _ _ . _ - 5 g < ? ™ - - _ - -"S'TAf.3'A''0~=o:5oo = TBAFIL , T Y = .70988934 V-2* * AH _ = C r .F^ !C IENT STD. ERR . 0.0530 " T T T C T 3. 16 251 7c 3.795 C'-i'.AC" - n . 6^246966F-01 3.2381 C ; N ? 7 » ' ! r 148(3. 1402 1291. F-RAT to -07694T" 0.S455E-01 1.- 325 ,. 3RQB 0.4180 0. 7657 0.2609 NORM COEFF 0.1752 -0.6112E-0 I 0.2679 P C " E M T T n ! . V « F W r ANO 'OTHER VARIABLES IN THE REGRESSION ANALYSIS FOR S R A C 'Al_ CPRR. * PL E c AN C E -RAT TQ _F-PP0B_ 0 0 Appendix C.4 Correlation Matrix for the Parameters Studied in the Iron Tailings Samples with pH <2.5 -LAI !GM MATKI X fi.ii.VC T S oACT T Fb.S I- E jACT l.COOO 0•3402 - o . •:.;<.-3 O.OlP? -i_'.0J09 StSACT 1 .0000 -0.1105 0.0293 - 0.04V1 FUiNG I. 1 .0000 0.2801 -0.0553 QMBACT 1.0000 -0. 032 7 FES 1.0000 TOS ELEMS SS04 INSS04 CM PH TLS - ( ; . o /7 ? - 0 . 0 46V 0.0280 -0.0778 0.0287 1.0000 -Li .Go29 -0.0 300 -0. 0756 - C . 1031 -0.0038 0.9073 i.0000 . . . . . . . . i —0 .15 9 3 -0.1213 -O.H-442 -0.1175 0.1395, -0. 1079 -v.0435 l.OOJO O . i l 0. 1 79o 0.1670 -0.327* -0.112 2 0.1523 U.0045 -0.35^1 i.oooo r .• - P . 10 3 3 -0.14 70 -0 . 3 731 -0. 143 I 0.0645 .0.1121 u. 1B42 0.55 J6 -0.0323 I .0000 0.1:> 7a 0.10 4 4 0.3321 0.267 5 0.0017 -0 .025 7 -v i . 0295 -0. 37., 3 -0. 1 538 -0 .23 11 1 .003 0 j 0 s t) O O \f n*l N «0 >TJ -< O 0 —* LA > rv ro ~* m 4 o o o o o o o o 35 i n o o o O N ^ N O - 0 —« f- -J-LA o o ro o —* o o o o o o O co r\j IA C fNJ O ro -« AJ r- ro m rg co o —• rg (M -* <MO O o o o o o o (\ | iT\ ifi S (M O -« rt *V t> "O .0 ^ ~* oM > co ro CO rt -*| -« o o o o o o o o I I I —< r-o: A- in 4" o ^ rO .A O -« CM o 00 o o - * O fM -* O 3 O O 3 3 t)> O] N -t N rg —* eo -o 4- r-eg co LA -0 -f rg (T1 o . CO w*\ -« -J" ^ O Al r- xt f\J O O O -o o o ; o o o rn r - r» —• rsj rO O O' -O JO 33 r n ^ ^ O O ' J 1 .-ft -* •*] rg r o O O o: O O O r - o o j ro <v O ; r— >o 'A N ,-1 » •J- 4r t -r-J rt —> 0 0 0 : 0 0 0 i 1 t o o o f I 0 o o 1 t -O -JO 'Ml •* 4 O ^A'CO O i/) t-1 o -J 3C <-]wI > f— i A m 4" i A -Q » n o r- o « ^ (M O CO . A - t rj iA rj r\i fM o o o o o o o —* o f- cr o (N* -t O ro r*-n ^ s j - .T) co IA -* -o o o o o o m "-A ;r 4 - ro r— c  o 4 - o o rv •O D H O O rt Al o -« o OOOiOOO I til t I cr o 4-|c* r- -H 0 -< -I1 \J 3 4 m rg x>\ o o rt iA 4- j r g 'A o o o o l o o o ^ O 4 r - i ' S j> o rn 4 1 O'^O LA rO r- O o ! 4" <NJ •> ^ « 0 | N O H  3 O 3 O 3 f I I 4 - -H rg! » a* CO (Ni ro >ni LA o -* O O fM O O O ro 4 - : AJ CO r» 4 - o o cr - *• O O N O ^ M o o o o o o •0 rO —': IA >\i 4 -r\l O LAIAJ ;A r\| O —« fO — o o o l o o o i i i i 4 - O 4>d" 4 - o -< m - « ; A -t 4 ^ O CO OJ rO (V O —* —* w O c ) o o o -J- O IA o O f\l o fN,- r-ir- r» * tA 35 ' O ' f ^ t r rjr> o ~« O J ~ ( o o o o o ' o o o I I c ~* rO'CO *o o . J JN O i l T i CO iA 4" o l o O m •.~ IA. < , o -*: : t _ j - J , ~ J _ X O O ' C D O L) LO VI ^1 »-4 ro rO l A IA O i A J> ro LA ,-0 t> !> -O — —* r y .•o r o r\f O O O O O O O rO ,"0 f \J fO IA c r o IA o o —1 r- O X> ro -3-- 4 - ^ - ^ 0 0 ^ O O O O O O I r— <\J rj —. zf ~< ^ —' -J^ -r c> en r— o -o >f LA O O O O O IN OOOOOO l i t ac -o ."<V f- O O" -5 M A 0 0 co co -j- -1 o m O —* m -* ~* o 0 0 o 0 o O , 1 -OO >J (D rO -n r— .-0 20 ro r\j •—' r o O -« 43 0 0- O 3: D D 3 LA ij» N-O -\| !M  rsj cr! 'A j- -4--< O -TO N ^  o o o o o o o o ' A m o f i CO —< —• A r\J CO i A N N 35 O O O —t o ^ o o o 0 0 o o co =0 -co cr r- -o m r— 4 - o f i o o 4 -o o o ; o o o IA f\i O i O O -3* X O —1 f\l O -O O iA W O rt -O rg r^.Ai c fg CT r o ! -C ro cj 1 rt ^ rto o o o o 0 0 o o r\j o -« r-j f j LO rt CO CO •,- o r o ; j A r -rvj o . O ~ i o O O O i O O O 00 O -4 J - vO rO LA CJ* ro -« r- i A o rt IA o o r g 0 0 0 0 0 l i l t —1 rO rg O O CO co ro 4 -O N ro N CO O rg o o O o o o o A J l A CO CO —4 r o t A rg m to g- r- rg rt rt O 30 o o o o o cr i A co; cr •-» 3 'A g n CO r- IA o rg 0 rt rt m o o o o o 1 I I o m A l rt pg ro rg cr cr cr o o IA <f r -•~< rg rg o O rt m »0: rt. co , f ~4 rt O 30 AJ o rt ca rt rO rt o *^  O - 0 rO 3? —' •M <*g 4- -g r^ o A^ 0 o o — O rt O rt o o o o o II II 4- CO 4 - . r 0 CM rg <r o ro m r\i ro LA: 4" <J NOrtON o o 0 . 0 o I I I I O r n 4 -•_n =0 JV ro 4" ~4 UN J- ; f\J LA O rj rtff\j rt O O o^O O I I I I •Or- rg; m co co rg m; a> so f- rn oi1^ ^  rt m i ' M o O O 0 ; 0 O ro o -01 -C 4 -O rj r o ' r O r-rj 4 —* o ^ ro o O O 0;0 O O AJ O LA o - * o o o o c x : o x ; rt i - : 0 r-^ CO rt O LA r g 4 " rg •O ro r» CO 4* 0 CO rg O 4 A l O r - g j r- r~ cr 4 O JO O O O r> O O > O r\i ;n -NJ i n •X. O O 0 O ^  —< r-n4 rt 4- O O rg < rt 0 O O O O O O O O O O O 1 f 1 1 1 I 1 1 O lA rt no •O O O O rT 4 - rg ro ro •a ON © ~o O rt rt 0 CO rg rt 0 a- cr •O (A Cr O O OJ (N| cr O 4- O 0 0 rt O A l rg O r - 0 rsi rg O ro O O ct <jrt 0 0 0 0 0 O O O O O O O O -> t 1 1 1 1 O r*- r- O 4 - co 00 m UN CO -0 IA r» O O 4- 4 f *A vO rt -o co m rg cr ,n 4A O ~ i O CO  0 ^ LA i A ."NJ O 4 -0> r - O O rt cr O  0 N 0 rt (NI 4" O O rg UJ rt. OOOO 0 0 0 0 O O O O O O t 1 1 1 t 1 1 t 1 0 O '• ro 4* co m r g r - ro ro r» m O CO O LA 0 1 -3 O -1 •v. ,f NJ A -•4 A 0 ro rt r - rg ro 0 O ro tr 0 ro 4 - ro m < 0 O D O C I M O rg rg 4 - i-n 0 _j rt O OOO O O O 0 0 O O O 0 O 0 0 1 1 1 1 1 t 1 1 1 1 1 X 0 •O 0 m A l -A ,-0 r> O ro •0 O O 0 r-O - 0 r- -4" cr ro 30 LA CO CO r-4 - ro LA 0 ro O 4- m uv <M ro m ro O O LA co 4" O ro 0 O O OOO O O 0 rt 0 O 0 O A J -t O O D -J> O ~> O 0 O ~i O 0 O t> j 1 1 I 1 1 1 l 1 1 1 X •c rg 2) m =0 4/ - rn O 4 - > r» m ro 4 / •O A m ^ rg O 4 - O cr ^ rg Cr O -> T7> •O rt O rn 0* m rt 33 33 4 - O rt O CO O ro O - 1 0 0 <M O O -* O 4" O ro O rt - J O O 1  t OOO O 1 O O 1 O O 1 1 O O O 1 O O O 1 30 O 4 CO =0 CO r~ LA •JD CO T) O O •NJ rg LA LA O O rn r~ •cr rg rt IA O O O 7* rn r-•n T> O CO 4" 0 O -O INI CO O CO m O < f \ J <r rg -« rt O rt r o 0 rt rg ro ro O rO r\ rg O O O OOO O 0 0 O 0 O O O O O O u 1 1 t 1 1 1 1 1 I X ro 4 - rg rg m O cr m rn •O 4" a* r-•> co A •O •0 r- ro rt •N» gr» i n - 0 4 •O JO r- 4" fN| rt *A r— rt -< O 4" ••gi ro Ln fM i A r- r- -0 •O A _l NJ rg '•Ni rt rsj 0 r 4 O rt rg - 1 O O 4 O O rt _J O O O 0 0 o i o 0 0 O O O O 0 O O O u 1 1 1 1 1 1 1 1 1 1 X O rt IA A r» IA O O LA CO O A J 0 rg X O rg ro l A s 0 CO rt r-=0 rg N-O 4" 0 CN) O O rg 4 zo r~ m r LA O ro 4- ro O •NI UJ rt rt O — 0 0 4" O •J" O ro -NI OJ m rt O IX - J O O O OOO 0 O O c O O O O O O O O 1 t l 1 1 t 1 1 1 X 3 - a* •7* O 4" CO rt CD 0* cr 4 -Cr r~ rg c cr ro r- 0 rt 4 -O 0 a> r- i i A LA ro O CO 4- 4" rt M ^ XI UN n> ro ro CQ - 0 rt 'O AJ tr- < —4 O rt rt O -4 rt rO O fO O rglrt rg rg O rg 1 : _ J O O O OOO O O O O O O 0 0 O O O 0 1 1 1 t 1 1 1>1 "g 4" -JO A 7> EM O O "\ 4 r> *A 0 rt. u> ro LA O O •-.o A m 03 ro c 0 rg LA •r rt •JO rt •r g^ 4 . 3 0 —4 " J 4" C r g —1 —* r g 4" •0 O O rt O rt 4* O ro A rg O C". ro O O O OOO O O O 0 0 O O O 0 rzj O <. 0 1 1 1 1 1 1 1 1 7? 1 *X ~J _J «T O < LU _ J < f t~r> a ; "J •JJ u . •.r _j *f X < ' _ J -*! u - -1 a : :Y —J -i —J -j -J -j w _J —) — l _i —> :i tn .71 C j ^ 3 o ; a • J O (.) rt * t 0 • \f, </> t o r x x r r •-0 U HCLK KCLM4 _S ITJf S N JARu I.4JAK0 HJARU 0 .4DV2 0 . 4 1 5 5 0 . 0 V 5 8 -0.1315 -0 .0016 -0 .0376 0.1265 0.2559 0.2879_ -6.1300 0.1979 -0 .0839 0.2101 0.1681 -0._14 70 0.0168 0.0C34 - 0 . 0425 -0 .0559 -0 .4825 0. 1225 0.1233 -0.0363 -0.0024 -0.1514 -0.3218 -0.0569 -0.0946 -0.1446 -0.4927 -0.0264 -0.0620 -0.1165 i .0000 0.7927 -0 .0367 . U.1443 0.0686 -0.3370 l.OOuO 0.02d2_ 0.2 5.1 0.5 1/3 - 0 . 1.0000 0.0469 0. 0660 0. 1.0000 0.3942 1.0000 CORK t LA TI C N MATRIX hJARU HJARD 1 . 0 0 0 0 NAME FEBACT SBACT MEAN 22291.6 530.185 STANDARD DEVIATION 163290. 1893.66 FUNG 1 UrtBACT ECS 610.611 512.833 0 . 92592t. E-02 578.077 3536.43 0.4165&8E-01 T3S EL ENS SS04 2.52852 2.585 19 0.747037 2.78012 3.27681 0.301353 INSS04 UM PH 0.8040 74 0.198389E-01 2.099 81 0. 275897 0.159736E-01 0.1C5714 CG.NDT MOIST TE XT 9.3 3519 24 .8837 28.3333 2.86580 6.29588 4.12082 SIR,LT nut VALUE 34.611 1 5.33333 5.14815 11.5357 1 .78040 0.656101 CiihUMA SOLFE SOLAL 5.B1481 0.922222 0.148204 1.04744 0.784222 0.121193 SULCA SULKG SOLN 0.19 16 11 0.112333 0.122222E-02 0.178549 0.938704E-01 0. 125392E-02 si: LNA HCLF E HCLAL O.87037OE-O3 8.33056 0.239630 0.10996BE-02 3.31539 0.239803 HCLC A hCL 1G HCLK 0.146889 0.-144870 0.175500 0.217438 0. 126329 0 . 167920 HLL JA SITES K.J AKU 0.170370E-01 12.6111 0 .3777 76 E-01 0.374987E-01 2.46C38 0.152547E-01 -NAJARO HJARU 0 .425926E-02 0.850JOOE-01 0.103890E-01 0. 439876E-01 5*. CESFRVAT I CKS TOTAL 54 53 OoSEKVA I IUI-.S AR E CCKRLETE DEGREES OF FREEDOM CONTROL CARD Ni » * STPREG **** STPREG » * * » STPREG » « » * STPREG «»»» STPKEG «»«« STPREG »»»» STPREG »» CONTROL CARD NO. > » > > > S T E P UUNbtR 3 REGRESSION EQUATION F UK SBACT K-SOUAKEU = 0.70.0667 F-PKGBAB1LITY LEVEL STANDARD ERROR SBACT - 1 053. 0.0500 172 Appendix C.5 Numerical Weightings of Texture, Structure and Color HUE WEIGHT VALUE WEIGHT 10R 12 2 1 2.5YR 10 3 2 7.5YR 8 4 3 10YR 6 5 4 5Y 4 6 5 2.5Y 2 7 6 8 7 CHROMA WEIGHT TEXTURE WEIGHT 0 1 clay 30 1 2 silty clay 25 2 3 silty clay loam 20 3 4 clay loam 15 4 5 s i l t loam 10 5 6 loam 5 6 7 8 8 WEIGHT STRUCTURE PLATY BLOQCY GRANULAR STRONG C 45 30 15 M-C 44 29 14 F-C 43 28 13 VF-M 42 27 12 VF-F 41 26 11 MODERATE C 40 25 1.0 M-C 39 24 9 F-C 38 23 8 VF-M 37 22 7 VF-F 36 21 6 WEAK C 3D 20 5 173 M-C 34 19 4 F-C 33 18 3 VF-M 32 17 2 VFTF 31 16 1 STRUCTURE WEIGHT Sal t crusts 47 Structureless : - massive 46 - single grained 0 *• Patterns for the Samples Chosen for Mineralogical Appendix D. X-Ray Diffraction Patterns K Study 1 A N G S T R O M S (A) Appendix E . l Average Numbers of Microorganisms on a Per Site Basis NUMBER OF SAMPLES MOST - PROBABLE - NUMBER OF MICROORGANISMS/g DRY TAILINGS* SITE NUMBER IRON OXIDIZING BACTERIA SULFUR OXIDIZING ACID TOLERANT BACTERIA HETEROTROPHIC BACTERIA ACID TOLERANT FUNGI 1 10 - 3.5 X 106 (9) 3.5 X 106 (4) 2.5 x 10 4 (8) 2 5 - 3 X 104 (4) 1 X 10 4 (3) 3 x 10 4 (4) 3 5 1.5 X 10 3 (1) 5 X 106 (5) 3 x 105 (5) 4 5 - 1 X 104 (3) 9 X 10 3 (4) 1 x 10 3 (1) 5 10 - 3 X 106 (8) 1 X 103 (1) 4.5 x 105 (1) 6 5 6 X 10 7 (4) 5 X 105 (5) 5 X 106 (5) 1 X 105 (4) 7 5 3.5 X 106 (5) 4.5 X 106 (5) 2.5 X 105 (4) 2 x 105 (5) 8 10 1.0 X 106 (4) 1.5 X 105 (8) 5.5 X 103 (4) 4.5 x 105 (10) 9 10 5 X 104 (3) 1 X 106 (3) 2 X 104 (8) 5 x 105' (9) 10 5 1 X 103 (1) 1 X 104 (3) 2.0 x 106 (5) 11 5 4 X 10 4 (3) 7 X 105 (4) 6 X 10 3 (3) 4 x 105 (4) 12 5 2.5 X 106 (1) 2 X 105 (2) 5 X 106 (3) 6 x 105 (5) 13 10 1 X 10 8 (3) 1 X 106 (1) 1 X 106 (7) 3 x 104 (8) 14 5 5 X 10 5 (3) 5 X 105 (1) 3.5 X 104 (4) 2 x 106 (4) 15 5 8.5 X 10 4 (1) 3 X 103 (5) 2.5 x 105 (5) 16 10 - 9 X 10 3 (4) 2 x 10 3 (5) 17 5 1 X 10 3 (1) 9.5 X 103 (5) 4.5 X 10 3 (2) 1.5 x 105 (5) 18 4 3 X 10 4 (2) 8 X 104 (1) 9 X 103 (2) 5.5 x 104 (4) * Numbers in parenthesis refer to the number of positive samples/site. Appendix E.2 Average Amounts of Sulfur Forms on a Per Site Basis SITE MONOSULFIDE TOTAL OXIDIZABLE ELEMENTAL WATER SOLUBLE ACID SOLUBLE TOTAL NUMBER SULFUR (%) SULFUR (%) SULFUR {%) SULFATE (SULFUR %) SULFATE (SULFUR %) SULFUR {%) 1 4.50 2.55 0.6 0.04 0.02 7.7 2 4.60 5.78 0.7 0.27 0.03 11.4 3 2.46 1.67 0.8 0.34 0.21 5.5 4 10.22 8.44 2.2 0.42 0.12 21.4 5 0.80 3.71 3.1 0.41 0.16 8.2 6 6.33 6.93 4.2 0.32 0.25 18.0 7 3.26 13.71 16.1 ' 0.44 0.14 33.7 8 0.47 4.40 2.9 0.60 0.23 8.6 9 0.01 4.21 3.7 0.81 0.75 9.5 10 0.0 • 1.12 1.4 0.40 0.64 3.6 11 0.05 2.77 2.8 0.84 0.75 7.2 12 ' 0.0 5.97 7.8 0.60 0.72 15.1 13 0.03 1.61 1.5 0.89 0.79 4.8 14 0.0. 3.58 2.0 0.38 1.36 ; 7.3 15 0.0 2.37 3.1 1.00 0.58 7.1 15 0.0 0.31 0.34 0.83 0.82 2.3 17 0.0 1.73 1.3 0.90 0.88 4.8 18 0.0 2.30 2.0 12.37 0.63 17.3 Appendix E.3 Average pH, Conductivity, Moisture Content and Water Extractable Organic Matter on a Per Site Basis SITE CONDUCTIVITY WATER EXTRACTABLE pH (1:1) - MOISTURE {%) NUMBER mMHO/CM (2:1) ORGANIC MATTER {%) 1 6.98 2.5 26.0 0.022 2 6.72 3.4 18.4 0.002 3 5.85 4.4 12.2 0.026 4 5.13 4.3 18.5 0.138 5 4.50 3.3 26.0 0.018 6 3.94 4.6 26.0 0.098 7 3.82 4.8 22.9 0.146 8 3.28 8.1 22.8 0.009 9 2.39 9.8 20.0 0.019 10 2.20 6.5 20.1 0.002 11 2.10 10.8 24.6 0.016 12 2.07 7.0 30.7 0.020 13 2.07 10.1 24.7 0.020 14 2.06 6.5 35.1 0.080 15 2.06 11.5 22.1 0.043 16 2.05 9.8 24.2 0.024 17 2.01 10.0 21.6 0.024 18 1.85 "7 20.0 59.4 0.423 Appendix E.4 Average Amounts of Water Extractable Cations on a Per Site Basis SITE Fe (%) Al {%) Ca {%) Mg (%) K (%) Na {%) NUMBER 1 0.197 0.0 0.385 0.046 0.016 0.010 2 0.006 0.001 0.273 0.057 0.007 0.002 3 0.004 0.0 0.300 0.139 0.012 0.012 4 0.113 0.001 0.336 0.057 0.008 0.004 5 0.075 0.265 0.448 0.103 0.007 0.005 6 0.448 0.0 0.357 0.037 0.003 " 0.002 7 0.920 0.0 0.192 0.532 0.003 0.002 8 0.219 0.085 0.472 0.205 0.002 0.002 9 0.557 0.272 0.246 0.223 0.002 0.001 10 0.632 0.085 0.044 0.026 0.0004 0.0 11 0.992 0.275 0.214 0.200 0.0004 0.0004 12 1.057 0.023 0.204 0.027 0.002 0.001 13 0.200 0.119 0.210 0.113 0.001 0.0004 14 0.468 0.083 0.021 0.056 0.002 0.0 15 1.994 0.178 0.244 0.107 0.0 0.0004 15 1.656 0.087 0.254 0.071 0.002 0.002 17 1.908 0.064 0.329 0.047 0.0004 0.002 18 36.2 0.242 0.130 0.154 0.003 0.001 Appendix E.5 Average Amounts of Acid Extractable Cations on a Per Site Basis SITE Fe (%) Al [t) Ca (%) Mg [%) K {%) Na (%) NUMBER 1 12.15 1.057 0.687 0.974 0.149 0.0 2 11.44 0.766 1.247 1.133 0.189 0.0 3 7.22 0.558 0.773 0.794 0.153 0.0 4 21.94 0.586 0.366 0.683 0.105 0.0 5 5.82 0.701 0.447 0.608 0.120 0.0 6 16.58 0.578 0.160 0.311 0.115 0.0 7 33.32 0.380 0.115 0.172 0.062 0.0 8 10.23 0.633 0.294 0.694 0.154 0.006 9 9.04 0.522 0.495 0.326 0.134 0.006 10 6.49 0.0 0.017 0.059 0.130 0.0 11 8.37 0.524 0.164 0.241 • 0.187 0.012 12 12.21 0.0 0.079 0.060 0.346 0.056 13 6.91 0.280 0.152 0.100 0.191 0.031 14 10.63 0.200 0.007 0.188 0.204 0.014 15 9.72 0.340 0.158 0.099 0.127 0.014 16 6.11 0.0 0.149 0.069 0.131 0.007 17 25.20 0.240 0.376 0.075 0.124 0.0 18 10.25 0.075 0.031 0.116 0.103 0.028 180 Appendix F . l Map of the Sullivan Mine - Cominco Ltd. Operations Source: Department of the Environment (1974). 1*3 CONTROL CARD NO. 1 ** INMSDC **** INMSDC **** INMSDC INMSDC INMSDC **** INMSDC •***• INMSDC ** CONTROL CARD NO. 1 / ' WARNINGS LOGICAL UNIT 4 IS NOT TRP WILL READ DATA FROM LOGICAL FORMAT CARDS ASSIGNED. UNIT 5. \ (2X,1GF7.G/2X,IGF7.G/2X FEBACT SBACT tl0F7.0/2X,4F7.0) FUNGI EMBACT INPUT DATA FFS Tns Fl FMS KS04 TNSS04 OM. PH SOLCA SITES CONDT SGLMG KJARQ MOI ST SOLK NAJARO TEXT SOLNA HJARO STRUCT HCLFE HUE HCLAL VALUE HCLCA CHROMA riCLMG SOLFE HCLK SOLAL HCLNA 1 0.0 2.000 0.5900E-01 0.0 10.60 0.4600E-01 0.0 27. 85 G.2O00E-02 0.0 30.00 0.4000E-G2 0.0 46.00 6.320 0.80G0E-6.000 0.0 01 0.1000 4.000 0.33G0E-01 0,9100 4.000 0.6600E-Q1 0,5100 2.530 0.1320 0.3200E 0.5900E 0.7000E -01 -01 -01 16.00 0.3000E-G1 G.20G0E-01 0.8000E-01 2 0.0 0.0 4.000 15.00 0.0 0.1200 0.1000 0.9000 0.8700 0..200.QE. -01 2.030 0.3110 16.00 10.60 0.7300E-01 0.3000E-01 24.93 0.40Q0E-02 0.0 30.00 0.2000E-02 0. 1100 46.00 8.290 6.000 0.0 4.000 0.1580 4.000 0.630QE-01 1.950 0.1270 0.9900E 0.0 -01 3 0.0 2.040 0.0 8.600 45.00, 24.97 0.0 30.00 0.0 46.00 0.200GE-6. 000 01 0.10G0 5.000 0.6800 6.000 0.6400 1*.1.40 ; 0.800GE 0 S93GG£. -02 d B l _ 0.1150 16.00 0.7300E-01 0.5000E-01 0.2OO0E-02 0.0 0.2C0QE-02 G.5000E-01 5.380 0.0 0.5700E- 01 0.63GGE-01 0.1900 0.0 4 0.0 2.070 G.61G0E-01 0.0 8.600 0.6800E-01 4.000 18.98 0.2000E-02 3.000 30.00 0.3000E-02 .0.0 46.00 5.960 0.210G 6.000 0.0 0*1000 5.000 G.290QE- 01 0.7 300 8,000 0.59G0E-G1 0.7900 1.600 0.1750 0.1800E 0.9800E 0.0 -01 -01 16.00 0.4000E-01 0.0 0.8000E-01 5 0.0 0.0 0,0 3.000 0.0 0.1200 0.1000 0.6500 0.9100 0.8000E -02 2.090 0.260G 16. 00 8.000 0.6200E-G1 0.30G0E-01 21.94 0.2G00E-02 0.0 30.00 0.2000E-02 0.1100 46. 00 5.240 6.000 0.0 5.000 0.9800E- 01 6.000 O.olOCE-01 1.070 0.1220 0.7200E O.G -01 6 0.0 2.110 0.0 9.500 0.0 28.90 0.0 30.00 0.0 46.00 0.7700 6.000 0.7000 5.000 1.04G 6. 000 1.240 1.820 0.5G00E 0.9100E -01 -01 0.7240 16.00 0.75GQE-01 G.3000E-G1 0.0 0.0 0.2000E-02 0.1600 5.8 70 0.0 0.5000 0.o70Q£-01 0.1330 0.0 7 0.0 2.01G 0.1310 0.0 12.40 0.1010 45.00 22.35 G.2000E-02 0.0 30.00 0.2000E-02 C O 46.00 7.800 0.2400 6.000 0.0 0.1000 5.000 0.9200E- 01 0.9900 6. 000 0.6100E-01 G.5500 . 2.130 0.1220 0.280GE 0.8500E 0.0 -01 -01 16.00 0.30G0E-O1 0.0 0.600GE-01 8 0.0 0.0 0.0 0.0 0.0 G.3000E- 01 0.1000 0.67GG 0.9600 0.1800E -01 2. 060 0.2100 16.00 8.800 0.7700E-01 0.3000E-01 24.81 0.2000E-02 0.0 30.00 0.2000E-02 0.1200 46 . 00 4.110 6.000 0.0 5.000 Q.82GQE-01 6.000 0.1270 1.210 G.1270 0. 1100 0.0 9 0.0 2.050 0.0 11.60 0.0 24.72 3.000 . 30.00 0,0 46.00 1.380 6.000 1.900 5.000 1.070 6. 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GOO 0 . 2 8 8 0 2. 000 0 . 4 5 8 0 0 . 4 2 3 C 0 . 1 3 0 0 0 .92G0E 0 . 0 -01 \ 96 0 . 0 3 . 210 1 2 0 0 . 1 4 , 3 0 2 6 0 0 . 2 9 . 56 0 . 0 30.00 0 .500QE -01 4 6 . 0 0 3 .600 6 . 0 0 0 1 .800 4 . 0 0 0 0 ,9 500 4.000 0 .2 500 0.1500 0 .4000E 0.66OOF - 0 2 -01 0 . 4 7 1 0 8 . 0 0 0 0 . 6 8 7 0 0 . 3 0 0 0 E - 01 0 . 2000 ' E -0 . 0 02 0 . 2 0 0 0 E 0 .1000E-- 02 -01 ' 4 . 8 6 0 G.5000 0 . 1 9 6 0 0 . 8 1 0 0 G . 1 3 5 0 0.0 97 0 . 0 6 . 7 9 0 0 . 3 2 2 0 24.. 00 3 . 1 0 0 0 . 7 1 0 0 E - 01 3 . 000 18 . 78 0 . 5 0 0 0 E - 02 3 . 0 0 0 5 . 000 0 . 2 0 0 0 E - 02 4 . 4 0 0 1 .000 10 . 50 .5.000 2 . 000 0.5000 0 . 7 0 0 0 3 . 000 0 . 9 0 6 0 0 . 2 6 0 0 2 . 0 0 0 0 . 8 7 7 0 0 . 0 0 . 2 0 0 0 E 0 . 1 1 7 0 - 0 2 0.0 0 . 0 0 . 0 2 .000 0.0 0 . 0 0 . 0 98 0.0 7 8 . 0 0 4 4 . 0 0 0 . 0 3 . 770 6 . 7 1 0 0 . 7 0 0 0 Q.i.8.Q.Q. 0.1..Q.Q.QE -.0.1 Q.M.Z.Q.Q.QR - 0 2 6 . 8 4 0 0 . 3 0 9 0 2 . 0 0 0 1 . 650 0 . 2 6 G 0 E -0 . 0 01 1 9 . 8 6 0 . 9 G 0 0 E -0 . 0 02 5 . 0 00 O.G 0 . 0 1.000 8 . 760 2.000 0 . 8 3 0 0 3 . 000 1 .240 2 . 0 0 0 1 .070 0 . 1200E 0 . 1 7 8 0 - 0 1 0. 3000E 0 . 0 - 0 2 99 0 . 0 . 6 . 8 6 0 2 3 . 0 0 3 . 5 5 0 0 . 0 6 . 7 8 0 0 . 0 5.000 3 .050 3 .000 5 . 000 2 .000 0 . 4 0 0 0 3 . 0 0 0 • 0 . 2 0 0 0 2. 000 0 . 1 0 0 0 E 0.1300E - 0 1 - 01 G .2000E 0 .3000E - 0 2 - 0 2 0 . 2 0 4 0 2 . 0 0 0 0 . 7 2 0 0 E -0 . 0 01 ' G . 6 0 0 0 E -0 . 0 02 G.200QE 0 . 0 - 02 2 0 . 4 0 0.7100 1 .380 1.120 0 . 1 5 3 0 0 . 0 100 0 . 0 6 . 7 2 0 0 . 3 0 2 0 0 . 0 2 . 9 5 0 0 . 4 0 0 0 E - 01 9 8 . 0 0 24 .81 0 . 7 0 0 0 E - 02 2 4 . 0 0 5 . 0 00 0 .2000E--02 9 . 1 0 0 1.000 8 . 350 7 . 9 9 0 2 . 0 00 0.8800 1.200 3 . 0 0 0 1.160 0 . 3 3 0 0 3 . 0 0 0 1. 140 0 . 8000E 0 . 2 0 0 0 E 0 . 1 9 0 C - 01 - 0 2 0 . 4000E 0 . 0 Q.M.Q - 0 2 2 . 0 0 0 0 . 1 0 0 0 E - 01 0 . 0 0 . 0 101 0 . 0 2 4 . 0 0 3 . 0 00 24.00 2 .660 4 . 2 2 0 0 . 6 0 0 0 0 . 3 8 0 0 0 .400GE - 01 0.200GE - 0 2 6 . 400 0 . 2 3 0 0 2 . 0 0 0 5 . 7 0 0 0 . 7 4 0 G E -0 . 1 0 0 0 E -01 01 2 1 . 9 7 G . 7 G 0 0 E -0.0 02 5 . 000 0.4000E-0 . 0 -02 2 . 0 00 9 . 2 1 0 2 . 000 0 . 9 1 0 0 3 . 0 0 0 1. 550 2 . 0 0 0 1 . 460 0 . 2 0 0 0 E 0 . 3 0 5 0 - 0 2 0 . 0 0 . 0 102 2 6 0 0 . 2. 120 2 6 0 0 . 8 . 000 0 .0 . 3 0 . 4 6 0 . 0 30.00 0 . 0 3 8 . 0 0 2 . 2 80 6 . 000 1 .400 6 . 0 0 0 0 . 5 800 6 . 000 1 .210 0 . 7 0 9 0 0.4000E 0 . 1 4 0 0 - 0 2 0 . 1 8 0 0 E -14 . 00 01 0 . 8 9 0 0 E -0 . 7 0 0 0 E -01 01 0 . 2 0 0 0 E -0 . 0 02 0,0 0 . 1 2 0 0 1 0 . 3 0 0 . 2 0 0 0 0 . 7 0 0 0 E - 02 0 . 3 4 2 0 0 . 2 7 4 0 0 . 7 0 0 0 E - 0 1 103 3 1 . 0 0 2 . 0 2 0 0 . 9 0 0 G E - 02 0 . 0 5 . 0 0 0 0 .2 8OOE- 01 2 6 0 0 . 3 5 . 5 4 G . 2 0 0 0 E - 02 1 0 0 . 0 3 0 . 0 0 0 . 0 0 . 0 3 6 . 0 0 9 . 7 80 3 . 000 6 . 0 0 0 C.O 1 .900 6 . 000 0 . 7 0 0 0 E - 02 0 . 9 0 0 0 E 6 , 0 0 0 0 . 7 4 0 0 E -01 -01 1 . 56 0 G . 1 9 8 0 0 . 1 4 7 0 0 . 1 0 0 0 E 0.340GE 0 . 0 - 01 -01 1 4 . 0 0 0 . 4 0 0 Q E - 01 0 . 0 0 . 2 0 0 0 104 3 . 0 0 0 0.0 2 6 0 0 . 1 6 . 0 0 0 . 0 2.100 1.800 0 . 3 2 0 0 1 .250 0 . 8000E - 0 2 2 . 0 40 0 . 2 G 0 G E -1 4 . 0 0 02 5 . 7 0 0 0 . 4 5 0 0 E -0 . 5 0 0 0 E -01 01 3 3 . 1 2 0 . 2 0 0 0 E -0 . 0 02 3 0 . 0 0 0.0 0.1500 3 6 . 0 0 13 .70 6 . 0 0 0 0.2000 6 . 0 0 0 0 . 7 0 0 0 E - 02 6. 00 G 0 . 1 4 0 0 0 . 2 9 5 G 0 . 2 1 3 0 0 . 5 9 0 0 E 0 . 0 - 01 105 0 . 0 2 . 0 50 0.0 6 . 4 0 0 2 6 0 0 . 3 6 . 7 4 10 . 00 3 0 . 0 0 0 . 0 21 .00 . 6 . 2 4 0 6 . 0 0 0 1.900 5 . 0 0 0 0 . 3 6 0 0 6 . 0 0 0 1 .300 0 . 4 9 8 0 0.10GGE 0 .5400E -01 -01 0 . 2 0 0 0 E -14 .00 02 0 . 3 9 0 0 E -0 . 6 0 0 0 E -01 01 0 . 2 0 0 0 E -0 . 0 02 0 . 0 0 . 1 4 0 0 9 . 1 7 0 0 . 0 0 . 8 G 0 0 E - 02 0 . 1 5 0 0 0 . 2 2 6 G 0 . 0 J r 106 0 , 0 2 . 0 60 0 . 7 5 0 0 E - 01 0 . 0 7 . 2 0 0 0 - 8 2 O 0 E - 0 1 , 2 7 0 0 . 3 9 . 8 2 0 . 0 4 8 . 0 0 3 0 . 0 0 0 . 0 0 . 0 4 1 . 0 0 10.20 4 . 2 8 0 6 . 0 0 0 0 . 6 0 0 0 3.2G0 5 . 000 0 .800GE - 0 2 0 . 5 5 0 G 8 . 0 0 0 0 . 2 3 6 0 1.480 0 . 6 3 8 0 0 . 1 5 8 0 0 . 8 0 G 0 E 0 . 1 3 0 0 0 , 0 - 0 2 1 4 . 0 0 0 . 4 0 0 0 E - 0 1 0 . 0 0 . 1 9 0 0 S 107 3 . 0 0 0 0 . 0 2 5 0 0 . 0 , 0 0 . 0 1.750 4 . 800 0 . 4 2 0 0 . 0 . 5 7 0 0 0 . 4 0 0 0 F - 0 ? ? 2 . 120 0 . 1 4 0 0 E -10 . 00 01 8 , 0 0 0 0 . 4 7 0 0 E - 0 1 0 , 3 0 0 0 E - G 1 21 .11 0 . 0 0 , 0 3 0 . 0 0 0 , 0 Q..,60QGE -01 21 .00 6 .930 6 . 0 0 0 G.O 5 .000 0 . 6 0 0 0 E - 0 2 6 . 0 0 0 0 . 1 2 0 0 0 . 4 7 7 0 0 . 1 2 0 0 0 . 8200E 0 . 0 - 0 1 108 0 . 0 2 . 2 3 0 0 . 0 4 . 2 0 0 5 0 0 . 0 1 5 . 5 ? 3 . 000 3 0 . 0 0 0 . 0 ? ? . n n 1. 120 6 . O 0 0 G.8000 5 . 0 0 0 0 . 1 2 0 0 fS . O O O 0 . 6 0 0 0 0 . 4 9 0 0 F - 0 1 0 . 0 0 . 3 1 OOF -01 0 . 1 5 7 0 1 0 . 0 0 0 . 1 6 0 0 E - 0 1 0 . 4 0 0 0 E - 0 1 0 , 0 0 . 0 0 . 0 0 . 6 0 0 0 E -01 6. 800 O.G 0 . 4 5 0 0 E -01 0 . 5 6 0 0 E - 0 1 G . 1 7 0 0 O.G 1 0 9 0 .0 2 . 3 70 0 . 4 0 0 0 £ - 02 0 , 0 1 . 5 0 0 0 . 5 0 0 0 E - 0 2 2500 . 21 .91 0 . 2 0 0 0 E - 02 4 5 . 0 0 3 0 . 0 0 0 . 0 0 - 0 2 1 . 00 6 .710 0 , 8000 6 . 0 0 0 0 . 0 0 . 3 0 0 0 5 . 000 0 - 6 0 0 0 E - 0 2 0 . 3 0 0 0 E 8. 0 00 0 . 0 - 0 1 0 . 6 9 0 0 0 . 2000E 0 . 1 ? 0 0 - 0 2 0 . 0 0 . 4000E 0 . 0 - 0 2 1 0 . 0 0 0 . 4 0 0 0 E - 0 1 0 . 0 0 . 7000E -01 110 0 . 0 0 . 0 2 5 0 0 . 0 . 0 0 . 0 0 .8 200 0 . 3 0 0 0 0 . 3 0 0 0 0 . 6 8 0 0 0 . 2000E - 0 2 2 . 2 00 0 . 2 1 0 0 E -1 0 . 0 0 01 7 . 0 0 0 G . 3 0 0 0 E - 0 2 0 . 3 0 0 0 E - 0 1 15 .21 0 . 0 0 . 0 3 0 . 0 0 0 . 0 0.8000E--01 4 3 . 0 0 4 . 4 7 0 6 . 0 0 0 0 . 0 5 . 000 0 . 6 0 0 0 E - 0 2 6 . 000 0 . 5 6 0 0 E - 0 1 0 . 2 7 0 0 0 . 1 1 2 0 0 . 1 2 0 0 0 . 0 111 0 . 0 2 , 0 60 0 . 0 1 1 . 6 0 2 5 0 0 . 2 6 . 9 0 6 .000 3 0 . 0 0 O.G 2 6 . 0 0 1 .120 6 , 0 0 0 1.000 5 .000 1. 120 8 . 0 0 0 0 . 6 7 0 0 2 , 3 6 0 0 . 6000E 0 . 1.89.Q...... - 0 2 0 . 2 6 0 0 E -10 .00 01 0 . 6 0 0 0 E - 0 1 0 . 3 0 0 0 E - 0 1 0 . 0 0 . 0 o.o O.'SOOOE -01 7 .530 0 . 0 0 . 2 0 0 0 E -01 0 . 6 5 0 0 E -01 0 . 1 3 0 0 0 , 0 112 7 . 0 0 0 1.590 0 . 3 0 0 0 E - 02 0 . 0 2 0 . 0 0 0 . 1 5 0 0 0 . 0 4 4 . 2 2 0 . 3 0 0 0 E - 02 7 . 000 3 0 . 0 0 0 . 0 0 . 0 4 6 . 0 0 2 .310 1 .050 4 . 0 G 0 0 . 3 0 0 0 0 . 1 0 0 0 7 . 0 0 0 0 . 9 0 0 0 E - 02 4 . 600 ' 6 . 0 0 0 0 . 8 6 0 0 E -01 2 . 5 1 0 2 6 . 7 0 0 . 8 6 0 0 E - 0 1 0 . 4 3 6 0 0 . 4 1 3 0 0 . 0 1 8 . 0 0 0 . 2 0 0 0 E - 0 1 0 . 0 0 . 3 7 0 0 113 0 . 0 0 . 0 2 1 0 . 0 0 . 0 0 . 0 7 . 0 4 0 5 . 800 2 3 . 5 8 0 . 0 0 . 6 6 8 0 1 .980 0 . 4 8 4 0 1 8 . 0 0 1 2 , 0 0 0 . 3 1 7 0 0 . 0 8 2 . 7 0 0 . 0 0 . 0 • 3 0 . 0 0 0 . 0 0 . 0 4 7 . 0 0 8 .570 4 . 0 0 0 0 . 0 6 . 0 0 0 0 . 7 4 0 0 E -01 3. 0 00 0 . 5 5 0 0 E - 0 1 5 9 . 0 0 0 . 8 3 0 0 E - 0 1 0 . 2 0 0 0 0 . 3000E - 0 1 114 0 . 0 1 .350 0 . 0 2 0 . 0 0 0 . 0 3 9 . 3 2 0 . 0 3 0 . 0 0 0 . 0 4 7 . 0 0 0 . 7 3 0 0 4 . 0 0 0 0 . 6 0 0 0 7 . 0 0 0 7 . 9 0 0 8 . 0 0 0 0 . 0 2 2 . 1 0 0 . 4 2 0 0 0 . 3 3 9 0 0 . 2 0 0 0 E -1 8 . 0 0 02 0 . 9 0 0 0 E - 0 1 0 . 0 G . 2 0 0 0 E -0 . 0 02 0 .2000E-0 . 0 - 0 2 2 4 . 5 0 0 . 0 0 . 8 0 0 0 E - 0 2 0 . 1 5 6 0 0 . 7 8 0 0 E - 0 1 0 .8G0 0E -01 115 1 2 0 . 0 2 . 4 8 0 0 . 2 9 0 0 E - 01 3 1 0 . 0 2 0 . 0 0 0 . 5 7 0 0 E - 0 1 4 . 000 7 1 . 2 7 0 . 5 0 0 G E - 02 3 0 . 0 0 3 0 . 0 0 0 . 0 0 . 0 4 7 . 0 0 5 .630 0 . 3 8 0 0 4 . 0 0 0 G.O 1.400 8 . 000 0 . 3 3 0 0 E -01 1 3 . 3 9 6 . 0 0 0 0 . 1 6 6 0 0 . 0 3 7 . 0 0 0 . 1 6 6 0 0 , 1 6 8 0 0 . 1400E O.G -01 18 .00 0 . 0 0 . 0 0 . 0 116 0 . 0 0 . 0 O.G 1 0 . 0 0 10 . 99 3 . 5 7 0 0 . 5 0 0 0 0 . 3 8 0 0 0 . 2 5 0 0 0.52.Q.GE. -01 5 . 610 0 . 4 0 2 0 4 . 0 0 0 4 . 0 0 0 0 . 2 1 0 0 E - 0 1 0 . 3 0 0 0 E - 0 1 2 6 . 9 8 G . 8 0 0 0 E -0 . 0 02 25 . 00 0 .4000E-0 .1000E-- 02 -01 3 8 . 0 0 2 2 . 7 0 2 . 000 0 . 6 5 0 0 2 . 0 0 0 0 . 4 6 1 0 O.G 0 . 9 0 9 0 0 . 2000E 0 . 1 3 0 0 - 0 2 0 . 0 0 . 0 117 0 . 0 5 .630 0 . 0 6 . 0 0 0 3 . 0 0 0 1 6 . 3 7 3 . 0 0 0 25 . 00 9 . 2 9 0 3 8 . 0 0 3 . 7 3 0 2 . 000 0 . 5 0 0 0 2 . 000 0 . 4 1 0 0 0 . 0 O.G 0 .20G0E - 0 2 0 . 4 0 0 0 E 0 . 0 - 01 0 . 3 9 3 0 4 . 0 0 0 0 . 1 1 1 0 0 . 0 0 . 8 0 0 0 E -0 . 0 02 0 . 7000E 0 . 0 - 02 2 6 . 7 0 O.G 0 . 2 0 5 0 0 . 1 7 0 0 0 . 5 7 0 0 E - 0 1 0 . 0 118 0 . 0 5 . 2 5 0 0 . 4 0 2 0 4 . 0 0 0 2 4 . 0 0 3 . 0 5 0 Q.7000.E-01 0 . 2 0 0 0 E - 0 1 2 4 . 0 0 0 . 0 15 .51 C,8.0.001-fi.2... 0 . 0 0 . 0  9 . 0 0 0 25 . 00 0.*.20.00E-0.2 0 . 0 2 4 . 0 0 5 .800 4G.00 2 4 . 7 0 6 . 650 2 . 000 0 . 6 2 0 0 2 . 2 00 2 . 0 00 0 . 4 0 4 0 0 . 4 0 0 0 0 . 0 0 . 6 2 0 0 0 . 1 2 0 0 0 . 5 2 0 0 E - 0 1 0 . 1 1 0 0 0 . 0 Q 0 . 1 1 2 0 0 . 0 LP" 8 .670 15 .51 3 . 7 0 0 0 . 4 9 0 0 0 . 1 5 0 0 0 . 1 9 6 0 -< 4 . 7 0 0 0 . 2 4 4 0 4.000. 4 . 2 5 0 0 . 4 7 0 0 E - 0 1 .Q..20.0Q.E-Q.1.. 2 1 . 36 O. IOOOE-O l 0 . 0 2 5 . 0 0 0 . 5 0 0 0 E - 0 2 0 . 0 4 4 . 0 0 1 7 . 5 0 2 . 0 00 0.9 600 3 . 0 0 0 0 . 4 0 0 0 2 . 0 00 0 . 9 0 4 0 0 . 1 0 1 0 0 . 1 2 0 0 0 . 3 0 0 0 E - 0 2 0 . 0 120 0 . 0 4 . 4 7 0 9 . 0 0 0 4 . 0 0 0 0 . 0 1 2 . 1 0 O.G 2 0 , 0 0 16 . 34 4 5 . 0 0 1 2 . 7 4 2 . 000 4 . 0 0 0 3 . 000 0 . 4 0 0 0 2 . 0 0 0 0 . 8 0 0 0 E - 0 1 0 . 3 5 0 0 0 . 3 4 8 0 Q .3000E -Q2 0 . 2 4 0 0 4 . 0 0 0 0 . 3 4 0 0 E - 0 1 0 . 1 0 0 0 E - 0 1 0 . 5 0 0 0 E - 0 2 0 . 0 0 . 2000E -0 . 0 02 18 .10 0 . 7 0 0 0 0 . 3 6 2 0 0 . 8 1 1 0 0 . 1 0 8 0 0 . 0 CtlRRFI ATION MATRIX \G0 FEBACT SBACT FUNGI QMBACT FES FEBACT 1 . 0 0 0 0 0 . 2 1 0 8 SBACT FUNGI QMBACT FES TOS EL EMS SS04 INSS04 OM PH 1 . 0000 - 6 . 6 7 4 7 0 . 3 5 2 6 0 . 0 0 6 8 - 0 . 0 4 7 7 0 . 1 1 8 3 •0 .0128 1 .0000 0 . 1 2 3 4 - 0 . 2312 1 .0000 0 . 0 8 8 0 1.0000 TOS ELEMS SS04 - 0 . 0311 - 0 . 0 1 9 3 - 0 . 0 2 9 0 0 . 0 6 2 1 0 . 1 0 0 2 - 0 .0555 -0 .093 8 -0 .0521 - 0 . 0714 0 .0051 - 0 .0218 - 0 . 0398 0 .3934 0 . 0 3 8 9 -0 . 1407 1.0000 0 .742 2 -0 . 0450 INSS04 QM PH 0 . 1 3 85 -0 .0G72 - 0 . 0 5 1 4 - 0 . 0973 - 0 . 0687 0 . 1 6 7 2 0 . 2 3 7 2 •0.1640 •0.2167 •0.1195 0 . 0 2 4 6 0 . 1042 •0.3917 0 . 1750 0 . 5 7 8 0 -0 .2249 0 .2401 0 . 1 6 2 9 1 . 0 0 0 0 G ,0016. - 0 . 0816 0 . 2 1 0 2 - 0 . 1 098 .1.00.00. -0 .0 710 0 . 7 2 3 6 -0 .213 9 1 . 0000 •0.0822 •0 .6765 1 . 0000 0 . 1 0 8 1 1 . 0000 CONDT HOIST TEXT - 0 . 0 778 0 . G 4 7 4 0 . 0 6 2 9 - 0 . 1897 0 . 1 8 5 0 0 . 0 6 7 4 0 . 0 6 7 2 0 . 0 6 6 0 0 . 1 2 4 7 •G.1809 0 . 1 2 1 2 •0.0417 •0.4078 •0.2069 •0.2740 -0 .2732 -0 .0329 -0 .2246 • 0 . 0 8 2 5 0 . 0 6 8 3 - 0 . 0 0 1 9 0 . 4 2 8 2 0 .6 260 0 . 1 7 6 6 0 . 4 3 0 3 0 . 1238 0 . 4 8 0 7 0 . 3 0 0 5 0 . 3 7 5 2 0 . 1 5 35 •0.690 5 •0.2261 •0.5861 STRUCT HUE VALUE - 0 . 0 1 0 7 - 0 . 13 87 0 . 0 9 1 4 - 0 . 0522 - 0 . 0 240 - 0 . 0 7 4 7 0 . 0 1 1 2 0 . 1 0 1 2 0 . 2 2 3 9 - 0 . 0300 - 0 .1163 -C .000 2 •0.1054 •0.2960 •0.595Q -0 .0475 0 . 0 0 7 5 -0 .3308 j . 0 6 7 7 0 . 1 3 6 8 •Q.1110 0 . 249 7 •0.0433 0 . 3 8 4 8 0 . 4 1 7 7 0 . 2 9 9 2 0 . 4 5 4 4 0 . 3 0 9 9 •0.1488 0 . 1 8 7 1 •0.5535 •0.4020 •0 .6714 CHROMA SOL FE SOLAL 0 . 0 5 0 9 - 0 . 0 2 8 3 - 0 . 0 7 7 4 - 0 . 0998 - 0 . 0 5 7 4 - 0 . 1 1 7 5 0 . 3 2 7 4 •0.0896 0 . 1573 - 0 . 0853 - 0 . 0384 •0.1114 •0.6480 •0.1255 •0.3831 - 0 .3205 -0.0 452 - 0 . 2510 • 0 . 0 8 5 0 - 0 .0005 • 0 . 1 0 5 6 . 0 . 1 2 5 5 0 . 9 7 3 8 0 .2 571 G.6G56 G.G029 0 . 3 5 8 4 -0 .03 57 0 . 7 7 5 3 ..0,2.301.. - 0 . 7999 •0.2081 •...Q..,...5.35.'.6... SOLCA SOLMG SOLK 0 . 0 9 5 2 -0 .06 79 - 0 . 0 8 1 6 0 . 0 9 5 8 - 0 . 0 355 0 . 3 0 9 3 - 0 . 1427 0 . 1 9 4 0 - 0 . 1953 0 . 1 8 4 3 •0.0941 0 . 1 6 1 9 0 . 1 7 3 2 •0.2461 0 . 3 5 7 0 - 0 . 0154 - 0 . 1024 0.Q052 •0.1336 •0.0429 •0. 18 57 - 0 .0 580 0 . 2 1 3 0 •0 .1280 •0.3623 0 . 0 6 2 9 •0.4997 - 0 . 1 1 8 5 0 . 1 2 32 - 0 . 0 6 4 3 ' 0 . 3 4 6 0 •0 .2336 0 . 7 9 1 3 SOLNA HCLFE HCLAL - 0 . 0 1 4 4 - 0 . 0 7 7 4 - 0 . 03 28 0 . 3 2 0 7 - 0 . 0 106 0 . 2 5 6 0 - 0 . 1798 - 0 . 1 5 5 6 -0.1.331 0 . 1759 0 . 0 440 0 . 1 1 7 3 0 .2441 0 . 3 9 6 8 0 . 3 1 6 5 -0 .0360 0 . 5 5 0 0 0 . 1 2 2 9 - 0 . 1 2 9 9 0 . 5 0 8 7 - 0 . 0603 •0. 1262 - 0 . 0440 •0. 2071 •0.3558 •0.2284 •0.4707 - 0 . 0262 0 . 2 6 5 8 :0.,.09.5..0... 0 . 578 3 0 . 1 2 0 6 0 , 6 7 0 3 HCLCA HCLMG HCLK - 0 . 0 3 4 0 - 0 . 1 005 0 . 0 8 5 5 0 . 0 2 1 6 0 . 0 5 3 6 0 . 0 0 3 6 -0 . 1442 - 0 . 1 0 4 7 0 . 2 5 5 3 0 . 0 0 2 5 0 . 0 5 6 9 0 . 5 1 3 6 0 . 2 9 0 5 0 . 3745 •0.1394 0 . 0 159 0 . 1126 -0 .189 4 -U.2142 - 0 . 1 6 8 3 •Q.2174 -0 .1591 - 0 . 1652 -0 .0 78 6 •0.3645 •0.5559 0 . 0 0 4 7 •0 .1840 - 0 . 0942 •0.17 73 0 . 6 5 4 5 0 . 7 8 9 8 •0.0504 HCLNA S ITES KJARO 0 . 1 9 1 0 0 . 0 5 0 6 0 . 2 2 1 3 - 0 . 0108 - 0 . 2002 0 . 0 3 3 0 0 . 0 6 50 0 . 0 8 1 9 0 . 1 9 5 3 0 .3581 •0.G938 0 . 0 0 4 0 •0.1816 •0.5268 •0.3.851 NAJARO HJARO 0 . 3 4 3 1 0 . 0 5 7 2 0 . 0 1 9 9 - 0 . 1 3 4 5 •0.1109 0 . 1 8 4 3 •0.0349 •0.13 23 •0.1472 •0.3253 -0 .1583 - 0 .3004 •0.2269 -0 .0913 •0.2103 • 0 . 1 1 2 2 •0.0509 - 0 . 1377 0 . 1 0 7 2 0 . 356 9 :0.1957. •0.0453 • 0 . 0 7 5 2 - 0 . 0213 -0 .0221 0 . 0 8 3 6 0 . 6 5 7 9 0 . 5 8 4 2 0 . 1999 0 . 9 4 7 0 0 . 0 5 4 9 0 . 1 9 6 7 :0. ...2.7.5.2. •0 .0585 - 0 . 0 130 •0 .2437 •0.8789 :.0.....56,l..a... - 0 . 2012 - 0 . 5936 CORRELATION MATRIX ; CONDI CONDT 1 . 0 0 0 0 MOIST 0 . 2 3 66 TEXT 0 . 5 2 7 1 ..MQ.I..SI I.EX.T : SIR.UC.I HUE VA L U.E.. 1 . 0000 0 . 3 6 5 9 1 .0000 .CHROMA... ...S..Q.L.EE SOLAL '. SOLCA '. SOLMG.. f STRUCT HUE VALUE 0.5360 0.2121 0.5963 0.3160 -0.0061 0.3396 0.6602 0.1772 Oo 36 04 1.0000 0.1293 Oo 3068 1.0000 0.0836 loOOOQ 1 CHROMA SOL FE SOL AL 0.5 5 94 0.4446 Oo 7396 0.1827 0.6214 0. 1 138 0.4090 0.1713 0. 3649 0.348 7 0.2605 0.2802 0.3865 -0.0329 0.1636 0.7499 0.3977 0.5567 1.0000 0.1270 0.5319 1.0000 0.2689. 1.0000 ) SOLCA SOLMG SOLK -0.3160 0.5566 -0.5059 0.0042 0.0930 0.0123. -0.2336 0 . 2225 -0.2860 -0.2900 0.1590 -0.3676 -0.0113 0.0461 -0. 3007 -0.3165 0o2355 -0.4374 -0.35 03 0.1752 -0.5940 -0.1198 0. 1561 -0.1122 -0.2373 0.5755 -0.3 996 1.0000 Oo 1 1 f5 0.2802 1. 0000 -0.1876 SOLNA HCLFE HCLAL -0.3097 -0.1338 -0.3485 -0.0548 -0.1203 -0.0855 -0.0320 - G« 08 35 -0.3635 -0.1699 0.0682 -0.4216 -0. 1514 0.1927 -0. 1866 -0.3782 -0.4330 -0.4093 -0.4675 -0.3130 -0.53 98 -0. 1248 -0 .0268 -0.2174 -0.3078 -0.1926 -0.0993 0.3027 -0.0949 0.3752 0.0891 -0.1903 0.1^ 68 HCLCA HCLMG HCLK -0.4311 -0.3898 -rO.0758 -0.3575 -0.2013. 0.0885 -0.5885 -Oo 5131 -0.0659 -0.5761 -0.5457 . -0.0428 -0.2238 -0.2686 -0.1688 -0.499 3 -0.470 2 0.2319 -0.4460 -0.5984 0.1243 -0.1815 -0 .176 5 -0.1018 -0.3427 -0.2605 -0.0377 0.4075 0.3848 0.0859 -0.0966 0. 1393 -0.03 68 HCLNA SITES KJARO 0.1170 0.6793 0.28 50 0.1430 0.2 790 0.0272 0.0942 Oo 5304 0.40 60 0.1090 0.5610 0.2861 -0. 1509 0.4166 0.1302 0.3569 0.6419 0.3374 0.2039 0.7298 0.4774 0.0834 0.3740 -0.2277 0.063 8 0.4193 0.2274 0.0036 -0.3580 -0.2837 -0. 0220 0.0630 0.1685 . NAJARO H JARO 0.1602 0.3835 0.016 9 0.1248 0.1629 0.4072 0.1322 0.3676 -0.1313 0.3240 0.1993 C. 39,42 0.1409 0.55 05 -0 .048 2 0.0762 ' 0.0740 0.3051 -0. 1 526 -0.3154 0.0023 0.0005 CORRELATION MATRIX SOLK SOLNA HCLFE HCLAL HCLCA HCLMG HCLK HCLNA SITES KJARO NAJARO SOLK SOLNA HCLFE 1.0000 0.7385 -0.0191 1.0000 -0.0005 1. 00 00 HCLAL HCLCA HCLMG 0.6396 0.4380 0.6349 0.5215 0.3401 0.5535 0.0120 -0.00 09 -OeOl 16 1.0000 0.4552 C.8096 1.0000 0.6241 1.0000 < HCLK HCLNA SITES 0.0567 -0.1282 -0.6923 0.0072 -0.1043 -0.5378 -0.1086 - 0 . 03 99 -0.0809 0.0033 -0.2027 -0.7081 -0.004 8 -0.1552 -0.5432 0.0262 -0.2027 -0.7565 1.0000 0.7101 0.03 68 1 .0000 0.2419 1.0000 KJARO NAJARO H JARO -0.4313 -0.1492 -0.4305 -0.2315 -0.0912 -0.3260 -0.2133 -Oo 1087 -0.2012 -0.2477 -0.1005 -0.4788 -0.3947 -0.1502 -0.2784 -0.3738 -0.1860 -0.5208 0. 23 95 0.1186 -0.0854 0.268 5 0.5236 -0 .0264 0.4225 0 . 1934 0.6222 1.0000 0.3 794 0.3 583 1.00 00 0.0209 CORRELATION MATRIX HJARO HJARO 1.0000 NAME MEAN STANDARD DEVIATION FEBACT 12770.6 1 11736. L SBACT 1216.35 4672.04 [ FUNGI 418. 383 794.383 OMBACT 679„625 4076o 08 FES 1.69158 3.06177 TOS 3.73017 3.82165 ELEMS 2.8433 3 3.78142 SS04 1.02567 2.55738 INSS04 0.489917 0.438936 OM 0.480333E-01 0.980482E-01 PH 3.43158 1.78352 C O N O T 7.46500 4.56459 MOIST 24.5792 10.9856 TEXT 24.0417 8.679 54 f STRUCT 28.4083 16.0013 HUE 5.0 8333 2.37488 I VALUE 4.33 33 3 1.29857 CHROMA 4.15000 2d8340 ] SOLFE 1.95189 7.107 84 i i i . SOLAL 0.918250E-01 0.126085 SOLCA 0.277033 0, 18.07 37 SOLMG 0.104867 0.114496 SOLK 0.417500F-02 0.528143E-02 : : . J HCLFF. HCLAL HCLCA HCLMG HCLK 11.4686 0.447000 6.'3 3 079 2 0.396992 0. 149250 7.629 33 0.362078 0.378990 0.388104 0.121010 HCLNA SITES KJARO HJARO 120 0.908333E-9.27500 0.264167E-0.19166 7E-0 . 4 9 2 5 0 0 E -OBSERVATIONS 02 0.276836E-01 5.13181 01 0. 18G939E -01 02Q™yY5245l-"02" 01 0.595947E-01 TOTAL 120 OBSERVATIONS 119 DEGREES OF FR ARE COMPLETE EEDOM CONTROL CARD NO. ** STPREG **** STPREG **** STPREG **** STPREG **** STPREG **** STPREG **** STPREG ** CONTROL CARD NO. »»»STEP NUMBER 3 REGRESSION EQUATION FOR SBACT R-SGUAR. ED = 0.1650888 F-PROB ABI LI T Y LEVEL STANDARD ERROR SBACT = 432 4. = 0.0500 F-PROBABILITY = .00013427 VARIABLE COEFFICIENT STD. ERRo F-RATIO F-PRGB NORM COEFF FEBACT 0.68819863E-02 0.35805-02 3.696 0.0540 0.1646 FUNGI -0.64447584 0 . 50 38 1 .636 0.2 004 -0.1096 OMBACT 0 . 3 9 7 3 0 3 9 6 0.9877E-01 16. 18 0.0 002 - 0.3466 CONSTANT 1128.0830 . 451 .2 6.251 0.0133 0.2415 » » » S T E P NUMBER 4 REGRESSION EQUATION FOR SBACT R-SQUARED = 0.1533112 F-PROBABILITY LEVEL = 0 . 0 5 0 0 STANDARD ERROR SBACT = 4336. F-PROBABILITY = .00008580 VARIABLE COEFFICIENT STD. ERR. F-RATIO F-PROB FEBACT 0.71716090E-02 0.3582E-02 4.008 0.0450 o T 9 T 2 l 3 i " ^ 1 5 . 6 4 d T d l K T i f 403. 1 4.615 0 ,0 319 OMBACT CONSTANT 0 . 3 8 0 8 6 7 9 9 865. 91 666 NORM COEFF 0.1715 073 323 0.1853 POTENTIAL INDEPENDENT AND OTHER VARIABLES IN THE REGRESSION ANALYSIS FOR SBACT PARTIAL CORR. TOLERANCE F-RATIO F-PROB FUNG! . - 0 . 1 179 0.9808 1. 636 0,2004 CONTROL CARD NO. 3 ** STPREG **** STPREG **** STPREG **** STPREG **** STPREG **** STPREG **** STPREG ** CONTROL CARD NO »>>»STFP NUMBER 5 REGRESSION EQUATION FOR FES R-SQUARED = 0.4890008 F-PROBABILITY LEVEL 0.050G r HCLK 0.1497 0 . 2 2 0 3 0.1776 0.638 8 0.1562 0 . 7192 1.0000 ) HCLNA - 0 . 2 2 7 9 - 0 . 1 1 6 9 -0.03 48 0 . 0 3 3 8 0.0144 0 . 1532' 0.1886 1 . 0 0 0 0 SITES - 0 . 8 3 1 4 - 0 . 6 3 4 6 - 0 . 1989 -0 . 5144 -0.6043 - 0 . 3 5 9 9 0.0153 0.2159 1.0000 KJARO -0.5585 -0.2183 -0.08 21 -0.1152 - 0 . 2 2 5 7 0.0121 0. 2895 0 .265 2 0 . 6 2 1 9 1.0000 NAJARO 0.0 0.0 0 . 0 0.0 0.0 0 . 0 0 . 0 0.0 0.0 0.0 l.DOOO . HJARO -0.4365 -0.0598 - 0 , 1404 -0 . 2925 - 0 . 2 701 - 0 . 1 8 4 1 0.0306 0.0619 0.3197 0.6075 0.0 J CORRELATION MATRIX HJARO HJARO 1.0000 NAME MEAN STANDARD DEVIATION FEBACT 368.033 2008.07 SBACT 2200.37 7323.55 FUNGI 390.700 770.212 OMBACT 904.367 4928.69 FES 1 .92333 2.25171 TOS 3.55167 1.9.1952 ELEMS 2.17667 1.973 56 SS04 0.428000 0.237739 INSS04 0.143667 0.149677 DM • 0 . 160667<=-01 0. 2403 72E-01 PH 4.91833 1.75103 CONDT 4.62700 4.56153 MOIST 24.963 0 10.72 88 TEXT 18.1667 10.7866 STRUCT 16.9333 14.8926 HUE 5.20000 1.86437 VALUE 3.80000 0.961321 CHROMA 2.86667 1.77596 SOL FE 0.163 500 0. 179641 SOLAL 0.370333E-01 0.793923E-01 SOLCA 0.434900 0. 112 7 60 SOLMG 0.118233 0.165813 SOLK 0.846667E-02 0.701591E-02 SOLNA 0.556667E-02 0. 576364E-02 HCLFE 9.40200 5 .06 065 ' HCLAL • 0.797000 0.352148 HCLCA 0.476233 0 . 2714 87 " HCLMG 0.75 8933 0.346467 HCLK 0.140900 0.431632E-G1 HCLNA 0.200000E-02 0 . 109545E-01 . SITES 4.66667 2.91646 KJARO 0.176667E-01 0. 159056E-01 NAJARO 0.0 0.0 HJARO 0.600000E-02 0. 122051E-01 30 OBSERVATIONS TOTAL 30 OBSERVATIONS ARE COMPLETE 29 DEGREES OF FREEDOM CONTROL CARD NO. ** STPREG **** SIP REG **** STPREG STPREG **** STPREG STPREG **** STPREG ** CONTROL CARD NO. » > > » S T E P NUMBER 3 REGRESSION EQUATION FOR SBACT R-SOUAREO = 0.5560159 F-PROBABIL ITY LEVEL = 0.0500 STANDARD ERROR SBACT = 5154. ( CONDT MOIST [ TEXT 0.0364 - 0 . 0 6 3 4 -0.2 299 .-0.1592 0.3505 0.2426 0 . 6523 -0. 0742 0 . 14 54 -0.0914 0. 253 8 0.1200 -0.3849 -0.2395 -0.1478 0.0139 -0.2520 - 0 . 3 7 9 0 0 . 13 40 0.0382 .-0.0231 0 . 9148 0.2448 : 0.4880 Oo 6351 0.0434 0 . 2 4 8 9 0.0 672 -0.2217 0.2040 -0.6211 ^ - 0 . 0407 r:0.07..2.3....\M j STRUCT HUE I VALUE -0.1637 0.2840 0.13390 • . 0 . 1204 0.1269 0.0532 0.33 06 • -0.0252 0. 29 80 •0.0641 . 0.0807 -0. 1578 0.0073 -0. 5094 -0.7086 -0.10 42 0.552 7 0.2553 0.0597 •0.4990 0.4882 • .0 .5011 0.2935 0 . 3 28 6 0.3355 0.3791 0 . 3 0 7 2 0.1335 -0.0172 -0.0889' - 0 . 1 6 7 1 -.0.4785 -0 .5902 •J f CHROMA SOLFE SOLAL • 0 , 1\20 8 -0.0910 0.0787 0.0754 0.0569 - 0 . 1 1 7 9 0.4131 0.25 47 0.60 63 -0.1991 0.1723 -0.0879 -0.7273 -0.1081 -0.3 75 2 0.3918 -G. 1503 -0.1412 0.6002 -0.0532 0.0646 0 . 4 9 8 4 0.5339 0.7751 0. 5221 0.2732 0 . 6 7 1 9 -0.0 676 0 . 0 8 3 8 -0.1485 -0 .7623 - 0 . 1 9 4 8 -G.59 50 : \ SOLCA SOLMG SOLK 0.0274 - 0 . 0 3 3 3 -0.1748 0.2526 -0.1097 0.1644 -0.02 25 0.5703 -0.4016 0. 1567 -0.0448 0 .3109 -0.6083 -0.3519 G.4683 0. 1399 0.0514 "• -0.3115 0.3571 0.1724 - 0 . 4 2 6 8 0.4903 0 . 8 2 1 6 -0.4671 0.2488 0 . 5 7 1 9 -0.5763 -0.0191 0.1710 0.2 509 - 0 . 4 3 6 6 - 0 .5147 0.8141 SOLNA HCLFE HCLAL -0.1823 0.1527 -0.3206 0.2 376 -0.1196 0.2 273 " -0. 3490 -0.2770 -0.1421 0.3418 .0.0710 0 .4311 0.3185 0.5299 0.208 2 ' -0.11.26 0 .2615 -0.4327 -0.1216 - 0 . 0 3 78 -0.2776 -0.1423 -0.3503 -0.1274 -0.1644 -0.1127 -0.2386 0.6309 0.1702 0 . 1 9 5 8 0 . 4 8 0 4 0 . 2 5 79 0 . 5 7 0 4 HCLCA HCLMG HCLK -0.1930 . -0.2172 -0.0912 . -0.0642 0.0490 -0.1306 . -0.18 97 -0.0585 0. 1998 0.1147 0.3116 0.0665 0.6592 ' 0.1766 -0.1347 -0. 2430 -G, 2804 - 0 . 1 9 1 2 -0.3498 -0.2634 -0.1420 -0.4058 0.050 2 •0 . 2 8 2 4 -0.2700 -0.1160 •0. 1836 0 . 3 3 3 9 0.2 991 0.1459 0.65.67 0 . 4 2 2 8 0.03 09 HCLNA SITES KJARO -0.0346 0.2167 0.1475 -0.0567 -0.1744 • 0.0380 0.02 19 0.36 92 • 0. 58 64 -0.0345 -0.237 6 0. 146 3 -0.1446 -0.7687 -0.5464 -0.082 8 0.4031 0 .1683 0.0501 0.50 42 0.3212 0 .2 79 6 0.5505 0 .6672 0.1468 0.5479 0.9075 -0.0948 -0.2161 -0.0176 -0 .2069 - 0 . 8 8 8 7 - 0 .6869 NAJARO HJARO 0.0 0 . 3722 0.0 -0.145 6. 0.0 0.274.3 0.0 -0.0926 0.0 -0.3690 0 . 0 0.1946 0.0 0. 1721 0.0 0.523 6 0.0 •0. 8709 0.0 0.1514 0.0 -0.54 75 ' CORRELATION MATRIX CONDT MOIST TEXT STRUCT HUE VALUE CHROMA SOLFE SOLAL SOLCA SOLMG CONDT - MOIST TEXT 1 . 0 0 0 0 -0.0252 0.3137 1.0000 0.6858 1.00 00 STRUCT HUE VALUE 0.4486 0.2179 0.2488 0.3100 -0.0545 -0.0283 0. 53 3 7 -0.1440 -0.0865 ' 1.0000 0.03 53 0 . 030.3 • 1.0000 0.6003 1.0000 CHROMA . SOLFE SOLAL 0.4011 0 . 5 5 8.5' 0.8149 0.0270 0.1120 0.1139 -0. 0132 0.39 80 0. 29 56 0. 2800 0.3943 0.4086 0.5915 0.2212 0.1772 0 . 7917 0.0591 ' 0.3349 1.0000-0.1717 0.43 76 1 . 0 0 0 0 . 0.6145 1.0000 SOLCA, SOLMG SOLK 0.1930 0.8493 -0.4841 - 0.5636 0.0250 0.2475 0. 4818 0.3614 . 0. 20 31 0. 1395 . 0.4962 •-0.0809 0.2578 0.1936 -0.2657 0 .1760 0.1857 - 0 . 4 1 5 2 0.3441 . 0.2963 -0.5622 0 .3550 .0 .2671 0 . 0 4 7 9 0.183 7 0.5019 -0.4685 1 . 0 0 0 0 0.1749 -0 .0 .700 1.00 00 -0.42 29 SOLNA HCLFE HCLAL -0.1659 -0.1204 -0.1546 0.1685 -0.3718 0.1564 0.4860 - 0 . 3 8 5 7 0.2068 0.1933 -0.2661 - 0 . 1 9 5 3 -0.1232 - 0 . 0 1 4 2 -0.0626 ' - G . 3 1 4 9 -0.4541 . -0.2483 -0.36 63 - 0 . 4 0 5 6 -0.4357 0.1938 0.0200 0 . 3001 -0.3393 -0.2012 -0.2101 0 . 0 583 -0.4 721 0. 01 59 - 0 . 0 2 9 2 - 0 . 1 4 9 1 -G .1095 • HCLCA HCLMG HCLK -0.3102 0.1011 0.3181 -0.3121 -0.0715 -0.0835 -0.1596 0.15 71 0.1499 -0.2341 -0.189 2 -0.0319 • -0. 3554 -0.0195 0.2 021 - 0 . 4 8 4 1 -0.269 2 -0.0030 -0.5176 '-0.44 30 - 0 . 0 5 3 7 - 0 . 0 7 2 1 0.2966 0*5727 -0.4055 -0. 1600 0 . 2411 - 0 . 3 843 .-0-.03 99 0 . 0 4 6 1 - 0 . 2 4 4 1 0.1970 0. 1 945 HCLNA SITES KJARO 0.2 266 0.4934 G.634G -0.0375 -0.1174 . -0.0570 0. 1196 -0.1790 0. 12 49 -0.1894 -0.0847 ' •0. 1376 0.0810 • 0.4566 .0.4000. 0 .0393 0.5289 0. 2842 0.1205 0 . 6 4 3 6 0.52 57 0.1.330 C.0211 •0.3084 0. 197.4 •0.4331 0 . 6 0 0 0 0.1878 0.3232 0.2 752 0.2287 0.3916 0.52 8 6 NAJARO .HJARO 0 . 0 0.4668 0.0 0.1237 0.0 0.28 29 O.,0 0.4177 0 . 0 . 0.3091 0.0 0.2527 0.0 0 . 3 5 6 3 0 .0 ' 0 . 1 3 5 9 . 0 . 0 -0.5720 0..0 0.1533 0.0 0.4977 CORRELATION MATRIX SOLK. SOLNA .HCLFE HCL AL . HCLCA HCLMG . HCLK HCLNA SITES KJARO . NAJARO SOLK SOLNA 1 . 0 0 0 0 0.6618 1.0000 - • HCLAL HCLCA I HCLMG 0 . 6732 0.4663 0.4927 0.5838 0.4568 0.5 701 0. 20 87 0. 5176 0. 2881 1.0000 0.489 0 0.8865 1.0000 0 . 5 0 2 4 . 1.0.000 J f 22 0.0 7*050 0.4390 260.0 1.380 0. 1200E-01 3. 000 29.78 0. 1400E-01 10.00 25. 00 0.4000E-02 5. 190 17.00 6.010 1 .710 2.000 0.6000 0.4000 2.000 0.3380 0.2 900 0.0 0.4730 0.0 0.2000E 0.6 800E -02 -01 0.4000E-02 0.0 0.0 1 1. 000 0.0 0.0 0.0 I 23 0.0 250.0 9.000 0.0 9. 490 2.720 0.1000 0.5000E -01 0.3000E -01 0.0 7.000 0o1190 1.000 1. 500 O.IOOOE-Ol 0.0 15.65 0. 5Q00E-02 0.0 5.000 Oo 2000E-02 0.0 1 7 . 00 25. 80 2.000 .0.4000 2.000 1.120 0.0 0.3930 0. 2 000E 0.5600E -02 -01 0.0 0.0 s 0.0 7. 100 OoO 2.650 45.00 21 .03 OoO 25.00 4o610 2.000 2.350 2.000 0.6000 3.000 0.2 100 0.0 0.0 0.200QE -02 0.6200E-01 0.0 0.2980 1*000 0.4300E-01 OoO 0.160GE-Q1 OoO 0.1600E-01 0.0 1 1 .00 1 .000 0.8190 0.9 640 0. 1 200 0.0 25 0.0 6. 930 0.3550 24.00 30 800 0.7300E-01 0.0 20o97 0.1600E-01 0.0 25.00 0.1200E-01 3 .610 16. 00 9.340 1.710 6.000 1.100 0.1000 3.000 0.6270 0.3100 1.000 1.080 0. 40G0E 0.2690 0.1810 -01 0.3000E-01 0.0 0.0 1.000 . 0. 10005-01 0.0 0.0 26 0.0 0.310GE+05 29.00 0.2700E+05 3.740 2.300 0.3000 0.4200 0.1500 0.4000E-02 7. 220 0.5280 1.000 2.420 0.7900E-01 0.3000F-01 39 .34 0.2000E-01 0.0 25.00 0.160QE-01 0.0 . 22 .00 11.30 6.000 1 .600 3.000 0.6410 1. 000 1. 330 0.3270 0.1560 0.0 0.0 27 OoO 7.420 190.0 2. 150 55o00 33 .40 30o00 25.00 2.560 2.000 1 .640 6.000 0.8000 3. 000 0.4000 1. 000 0.8 000E 0.4320 -01 0.2 200E-01 0.0 0.5660 1 o 000 0. 4700E-01 Oo 1000F-01 0.2300E-01 0.0 0.1200E-01 0.0 15.00 1 .900 1.020 1. 640 0. 2140 0.0 28 0.0 5.870 0.4010 1500. 5.000 0.7 600E-01 95.00 14.98 0.1900E-01 0.0 25o 00 0.1800E-01 3.690 22 . 00 15.10 4.780 6.000 1.100 . 2.000 4.000 0.7 540 0.3 300 3.000 1. 230 0. 8000E 0.4350 0.2230 -01 0.6600E-01 0.0 0.0 1.000 0. 1000E-01 0.0 0.0 • 29 0.0 46.00 3.000 0.0 2.6 90 2.050 0.3000 0.2300 0.0 0.8000E-02 6. 950 0„3 690 1 . 000 2. 100 0.4900E-01 0.0 2 7.53 0. 1900E-01 0.0 25.00 0.1300E-01 0.0 22.00. 6. 670 2.000 1.000 3.000 0.3790 1. 000 0.9800 0. 1930 0.1310 0.0 0.0 30 OoO 7.060 • 360.0 2.150 23.00 8. 170 0.0 5.000 6. 180 46.00 4.490 6.000 1.300 3.000 0.2400 3. 000 0.0 0.3 040 0.1200E-01 0.0 0.3280 I. 000 0. 3600E-01 0.0 0.10G0E-01 0.0 0.6000E-02 0.0 10.60 0.6700 0.6110 0.6220 0.1550 0.0 CORRELATION MATRIX FE8ACT SBACT FEBACT 1.0000 -0.0567 SBACT 1.0000 FUNGI OMBACT FES TOS ELEMS SS04 INSS04 OM PH FUNGI OMBACT FES -0.0899 -0. 0339 -Oo1617 -0.1225 0.7426 0.0283 1.00 00 -0.0889 -Co 3255 1.0000 Oo1523 1.0000 TQS ELEMS SS04 0.5939 -0.1696 -0o0057 -0.0838 0.0154 -0.0285 -0.2218 -0.03 39 0.60 42 -0. 123 3 -0.1803 -0.0062 -0.3101 -0.5594 -0.5708 1.0000 0.5294 -0.0304 1.0000 0.2374 1.0000 INSS04 OM I PH 0.2615 -0.1267 -0« 2615 -0.0439 -0.1374 0.1312 0.5240 -0.1944 -0.4026 0.0081 -0.0950 0.2484 -0.5180 0 .0898 0.7948 0.1911 0.2089 ' -0.4612 0.3016 0.12 55 -0.5933 0.6874 -0.0157 -0 .6770 1.0000 0.0661 -0.7076 1.0000 0.0881 1.0000 J ( 22 OeO 5. 610 0.4020 0.0 4. 000 n.2100F-01 0.0 26.98 0. 8000E-02 10. 00 25.00 0.400QE-02 10. 99 38.00 22.70 3.570 2.000 0.6500 0.5000 2.000 0.4610 0.3 800 0.0 0.9090 0.2500 0. 2 000E 0. 1300 -02 0.5200E 0.0 0.0 -01 ] 4.000 0.3000E-01 0.0 0.1000E-01 23 0.0' 0.0 3.000 3.000 9„ 290 3.730 0.5 000 0.4100 Oo 0 0.40005 -01 / f 5.630 0.3930 \ 4.000 6.000 0.1110 0.0 16 .37 0.8O0OE-02 0.0 25.00 0.7000E-02 0.0 38.00 26. 70 2.000 0.0 2.000 0.2050 0.0 0.1700 0.2 000E 0. 5700E -02 -01 0.0 0.0 \ 24 "o\o 5.N250 24.00 3.050 0 .0 15.51 9.000 25.00 5.800 40 0 0 0 6.650 2.000 2. 200 2.000 0.4000 0.0 0. 1200 0. 1 100 0.5200E 0.0 -01 0.4020 4.000 0.7000E-01 0.2000E-01 0.8000E-02 0.0 0.2OO0E-O2 O.G 24. 70 0. 6200 0.4040 0.6200 0.1120 0.0 25 0.0 4. 700 0.2440 24.00 4.250 Oo 4700E-01 0.0 21 .36 0. lOOOE-Gl 24.00 25 .00 Oo 5000E-02 8. 670 44.00 17.50 15.51 2.000 0.9600 3.700 3.000 0.4000 0.4900 2. 000 0.9040 0.1500 0.1010 0.1200 0.1960 0.300GE 0.0 -02 4.000 0.2000E-01 0.0 0.0 26 o .b • • 9.000 . 0.0 0.0 16.34 12.74 4.000 0.4000 0. 8000E -01 0,3 480 4.470 0.2400 4.000 4.000 0.3400E-01 Oo 1000E-01 12.10 0.5000E-02 0.0 20.00 0.2000E-02 0.0 45.00 18.10 2.000 0.7000 3. 000 0.3620 2.000 0.8 110 0.3500 0. 1080 0.3000E 0.0 -02 \(c<o CORRELATION MATRIX FEBAC T FEBACT 1.0000 SBACT FUNGI OMBACT FES TOS ELEMS SS04 INSS04 OM PH SBACT FUNGI OMBACT -0.0103 0.2046 0.9797 1.0000 0.1622 -0.0239 1.00 00 0.2126 1.0000 FES TOS ELEMS 0.0873 0.0829 0.0776 -0.2630 0.0671 0.2112 -0.37 63 -0.01 88 0.1085 0.0607 0.0451 0 .0702 1.0000 0.2434 -0.1534 1.0000 0.6606 1.0000 SS04 INSS04 OM -0.1160 0.0729 0.2478 0.0968 0.1818 -0.1.113 0. 5946 0.6718 -0.0749 -0.0890 0.0476 0.2327 -0.0723 -0. 1200 0.4 32 2 0.0703 0.0252 0.5104 0.1672 0.0073 0.49 29 1oOOOO 0 .3933 0.1341 1.0000 -0.1564 1. 0 000 PH CONDT MO I ST -0.1796 -0.3165 0.2380 -0.1660 0.0479 0.4123 -0. 21 55 0.1731 -0.0493 -Oo1641 -0.2701 0.2046 -0 .033 2 -0. 030 7 0.2094 -0.45 75 -0.0156 0.3824 -0.6639 0.1374 0.3339 -0.4231 0.2040 0.0184 -Oo 4744 0.4622 0.2351 -0.5079 -0.0632 0.1398 1.0000 0.4037 0.4486 TEXT STRUCT HUE 0.1630 0.1148 -0.0726 0.2265 0.0933 0.1094 0, 1094 -0.0406 0. 2646 0. 1372 0.064 1 -0.1395 0.1253 0.4196 -0.1999 0,2504 0. 3841 0.4990 0.4277 0.35 91 0.5853 0 .1974 0.0946 0.339 8 0.4043 0.2324 0.3528 0.4092 0.5653 0.1197 0.73 54 0.6342 0.5762 VALUE CHROMA SOLFE 0.0503 0.0263 0.2048 0.0724 0.0514 0.1338 0.47 86 0.44 12 0.02 89 0.042 3 0.0768. Oo 1599 -0. 348 8 -0.2709 -0.0021 0.0561 0.2110 0.6902 • 0.1313 0.2460 0o9314 0.0182 0.4997 0.0828 0.3202 0.0069 0.0651 0.0839 0.1750 0. 5796 0.0814 0.0811 0.7333 SOLAL SOLCA SQLMG--0.1073 0.0445 - 0 . 1405 -0.1510 -0.5 761 0.1441 -0.2284 0,1164 0.62 33 . -0.0906 0.0273 -Go 1209 0.3041 0.3299 -0o2424 0.2227 -G.3383 -0.2289 -0.1838 -0.4642 -0.1624 -0.1677 0.0 841 0.1736 -0.3103 0.2668 0.4558 0. -0. -0. 2628 2555 1 856 0.2420 0.1483 0. 1005 SOLK SOLNA HCLFE -0.2414 -0.0376 -0.0240 0.5545 0.3811 0.0300 -0.0271 0.3583 -Oo 1826 -0.2000 -0.0179 -0.0339 -0.1125 -0.1796 0,1147 -0.4036 -0.3917 0.6681 -0.47 11 -0.3321 0.7661 -0.0377 -0.0392 0 .0568 -0.0083 0.3214 -0.1223 -0.2818 -0.1855 0.4971 0.4010 0.2302 0.5396 HCLAL HCLCA HCLMG -0.0492 -0.2169 -0.2144 0.2148 -0. 13.3 9 -0.3460 -0.1176 0. 2362 -0. 21 12 -0.0570 - 0 . 1853 -0.1848 0.1240 -0.289 2 0.0795 -0.0640 -0.4103 -0.2956 -0.30 66 -0.5524 -0.6263 -0.0811 0.2578 -0.305 6 -0.0135 -0.0840 -0.3303. -0.10 29 -0.5244 -0.29 56 0.2315 0.62 16 0.8184 { HCLK HCLNA SITES 0.0163 0.0 0. 1838 0.1159 0.0 0.0516 -0.26 34 Oo 0 0.35.17 0.0180 OoO 0.1544 -0. 1110 0.0 -0.113 2 -0.3477 0.0 0.4242 -0.5514 0.0 0.6955 -0.3610 0 .0 0.556 9 -0.2734 0.0 0.4290 -0.3452 O.G 0.3714 0.6076 0.0 0.8963 K J A R O N A J A R O H J A R O 0 . 2 5 6 4 OcO - 0 . 1 2 7 8 0 . 2 9 3 2 0 . 0 - 0 . 1 4 1 5 G . 1 5 7 1 0 . 0 0 . 7 0 4 6 0 . 2 1 2 1 0 . 0 - 0 . 1 0 9 3 0 . 0 1 8 7 0 . 0 - 0 . 1 6 1 1 - 0 . 0 7 6 2 0 . 0 - 0 . 1 5 3 4 - 0 . 1 7 4 9 0 . 0 - 0 . 0 6 6 0 - 0 . 0 1 8 0 0 . 0 0 . 6 0 3 9 0 . 6 2 6 1 0 . 0 0 . 8 0 3 6 - 0 . 0 1 4 1 0 , 0 - 0 . 2 1 3 8 - 0 . 3 0 2 1 0 . 0 1 - 0 , . 3 5 ! 8.Ifcl. s C O R R E L A T I O N M ATRT X J ? C O N D T MOIS"*" C O N D T 1 . 0 0 0 0 0 . 2 1 7 3 M O I S T 1 . 0 0 0 0 T E X T S T R U C T H U E V A L U E C H R O M A S O L F E S O L A L S O L C A S O L M G T E X T S T R U C T H U E 0 . 3 7 2 5 0 . 3 2 4 0 0 . 0 7 6 6 0 . 3 3 1 2 0. 4 7 3 3 0 . 1 5 4 0 1 . 0 0 0 0 0 . 7 6 5 7 0 . 2 8 7 6 1 . 0 0 0 0 0 . 1 0 1 2 1 . 0 0 0 0 V A L U E C H R O M A S O L F E 0 . 2 0 7 1 - 0 . 1 1 5 2 0 . 1 0 5 6 - 0 . 0 5 2 0 - 0 . 0 7 0 5 0 . 4 0 2 8 - 0 . 1 2 9 6 - 0 . 3 0 6 8 0 . 4 7 8 6 - 0 . 1 9 5 1 - 0 . 4 2 3 9 0 . 4 0 7 5 0 . 1 5 7 7 0 . 2 0 6 2 0 . 6 5 2 1 1 . 0 0 0 0 0 . 5 6 5 9 0 . 1 2 8 4 1 . 0 0 0 0 0 . 1 7 3 6 1 . 0 0 0 0 S O L A L S O L C A S O L M G - 0 . 2 5 0 6 0 . 0 4 5 5 0 . 5 4 8 1 - 0 . 2 2 1 2 - 0 . 1 7 6 5 - 0 . 0 7 7 7 - 0 . 3 3 0 9 0 . 0 0 2 0 0 . 1 1 3 6 - 0 . 0 0 0 5 0 . 0 5 5 9 0 . 0 8 5 7 - 0 . 3 36 2 - 0 . 0 9 0 2 - 0 . 1 7 1 5 0 . 0 8 5 3 - 0 . 1 7 9 5 0 . 4 6 8 6 0 . 1 3 7 9 - 0 . 3 4 4 8 0 . 0 4 6 5 - 0 . 1 9 8 C - 0 . 3 6 7 9 - 0 . 2 4 7 6 1 . 0 0 0 0 - 0 . 1 9 0 3 - 0 . 1 4 3 5 1 . 0 0 0 0 0 . 1 4 2 0 1 . 0 0 0 0 S O L K S O L N A H C L F E 0 . 0 0 6 2 0 . 3 3 9 9 0 . 1 5 2 2 - 0 . 0 1 9 1 - 0 . 1 0 4 8 0 . 2 9 3 1 - 0 . 1 3 1 5 0 . 1 7 51 0 . 4 5 1 3 - 0 . 1 6 5 2 0 . 0 0 2 9 0 . 4 5 8 6 - 0 . 4 7 5 7 - 0 . 2 7 2 4 0 . 4 3 0 1 - 0 . 0 2 5 1 0 . 3 3 1 0 - 0 . 3 2 7 7 - 0 . 0 6 6 9 - 0 . 1 2 7 8 - 0 . 0 7 4 8 - 0 . 5 4 7 8 - 0 . 3 8 2 9 0 . 7 8 9 9 0 . 0 9 9 8 - 0 . 1 8 3 4 - 0 . 0 6 4 6 - 0 . 1 8 4 4 0 . 0 0 0 1 - 0 . 3 3 9 7 0 . 3 2 0 6 0 . 7 7 6 6 - 0 . 2 5 3 3 H C L A L H C L C A H C L M G - 0 . 0 9 8 7 - 0 . 2 9 5 8 - 0 . 2 7 1 4 0 . 2 7 7 7 - 0 . 4 8 8 2 - 0 . 4 0 3 6 - 0 . 3 0 9 3 - 0 . 7 6 1 8 - 0 . 6 6 6 5 0 . 0 2 1 8 - 0 . 7 9 0 1 - 0 . 4 9 6 1 - 0 . 3 3 4 2 - 0 . 1 9 2 7 - 0 . 5 7 3 3 0 . 1 6 8 3 0 . 1 1 8 3 0 . 0 9 2 0 0 . 0 2 1 2 0 . 4 3 8 4 0 . 0 5 8 1 - 0 . 3 6 9 8 - 0 . 6 3 5 7 - 0 . 6 8 0 5 0 . 3 8 5 5 0 . 1 9 8 4 0 . 3 8 9 0 - 0 . 1 3 7 4 0 . 1 1 3 5 0 . 1 9 4 8 0 . 0 2 0 5 0 . 0 5 0 2 0 . 0 5 6 2 H C L K H C L N A S I T E S - 0 . 2 0 7 1 0 . 0 0 . 1 9 7 7 0 . 0 0 5 4 0 . 0 0 . 2 6 8 7 - 0 . 4 6 6 0 0 . 0 0 . 5 8 5 2 - 0 . 4 1 3 7 0 . 0 0 . 4 2 0 2 - 0 . 5 1 5 3 0 . 0 0 . 7 38 2 0 . 1 0 2 2 0 . 0 0 . 0 0 7 6 0 . 0 2 6 3 0 . 0 0 . 1 9 2 2 - 0 . 5 4 3 7 0 . 0 0 . 7 3 2 7 0 . 1 3 0 2 0 . 0 - 0 . 3 3 2 5 - 0 . 1 4 4 3 0 . 0 - 0 . 0 4 6 2 - 0 . 0 0 5 9 0 . 0 - 0 . 1 9 5 9 K J A R O N A J A R O H J A R O 0 . 2 1 6 5 0 . 0 0 . 5 1 4 4 0 . 3 2 8 8 0 . 0 - 0 . 0 2 8 0 0 . 4 2 7 6 0 . 0 0 . 1 6 5 6 0 . 3 1 6 6 0 . 0 0 . 0 0 2 9 0 . 1 1 0 8 0 ; 0 0 . 3 0 1 3 0 . 1 0 8 3 0 . 0 0 . 3 4 8 5 - 0 . 2 9 3 7 0 . 0 0 . 2 6 6 5 - 0 . 0 4 1 2 o.o - 0 . 0 5 3 0 - 0 . 3 1 9 3 0 . 0 - 0 . 2 2 0 9 0 . 0 7 2 1 0 . 0 0 . 4 1 2 1 0 . 2 0 9 3 0 . 0 0 . 4 9 1 8 C O R R E L A T I O N M A T R I X S O L K S O L N A . S O L K 1 . 0 0 0 0 0 . 6 6 4 2 S O L N A 1 . 0 0 0 0 H C L F E H C L A L H C L C A H C L M G H C L K H : L N A S I T E S K J A R 0 N A J A R O H C L F E H C L A L H C L C A - 0 . 4 0 8 3 0 . 3 2 1 2 0 . 2 2 5 5 - 0 . 4 0 3 7 0 . 0 9 3 2 - 0 . 0 0 7 8 1 . 0 0 0 0 - 0 . 4 6 5 0 - 0 . 5 9 9 2 1 . 0 0 0 0 0 . 2 4 4 7 1 . 0 0 0 0 H C L M G H C L K H C L N A 0 . 2 7 8 1 0 . 4 6 2 0 0 . 0 0 . 1 1 6 1 0 . 2 3 0 9 0 . 0 - 0 . 5 6 5 3 - 0 . 5 7 1 6 0 . 0 0 . 4 2 7 1 0 . 5 4 3 4 " 0 . 0 0 . 6 3 4 4 0 . 4 6 7 6 ' 0 . 0 1 . 0 0 0 0 0 . 7 2 3 2 0 . 0 1 . 0 0 0 0 0 . 0 1 . 0 0 0 0 S I T E S K J A R O N A J A R O - 0 . 5 6 3 6 0 . 3 1 0 3 0 . 0 - 0 . 3 9 3 1 0 . 4 8 4 7 0 . 0 0 . 5 4 8 3 - 0 . 1 8 2 3 0 . 0 - 0 . 4 0 3 8 0 . 2 4 5 0 0 . 0 - 0 . 3 9 3 2 - 0 . 3 0 0 0 0 . 0 - 0 . 7 9 9 6 - 0 . 2 0 3 7 0 . 0 - 0 . 7 0 4 7 0 . 1 1 0 5 • 0 . 0 0 . 0 0 . 0 0 . 0 1 . 0 0 0 0 0 . 0 9 7 6 0 . 0 1 . 0 0 0 0 0 . 0 1 . 3 3 0 0 H J A R O - 0 . 1 5 0 0 0 . 1 5 0 8 - 0 . 1 8 9 5 - 0 . 1 5 7 3 0 . 1 9 3 8 - 0 . 2 1 8 0 - 0 . 3 4 5 6 0 . 0 0 . 4 1 1 0 0 . 2 0 7 0 0 . 0 C O R R E L A T I O N H J A R O M A T R I X H J A R O 1 . 0 0 0 0 N A M E F E B A C T M - AN 1 2 2 1 3 . 3 S T A N D A R D D E V I A T I O N 4 9 5 1 0 . 2 S B A C T F U N G I 1 9 6 0 . 1 5 1 7 2 . 3 4 6 1 C 2 5 . 8 1 5 5 4 6 . 8 5 3 0 7 . 2 1 6 4 8 9 5 . 5 0 Fi=S T O S E L * MS 5 . 1 6 8 0 8 7 . 1 7 2 3 1 4 . 6 8 4 6 2 3 . 9 8 9 0 5 5 . 5 0 2 1 7 5 . 8 7 8 9 6 ) SS04 TNSS04 OM 0.385769 0. 160385 0.786-92 3 c - 0 1 0. 177046 0.13 7185 0. 964820E-01 PH COMDT MOIST 5.05423 4.26538 19.1531 1.19194 1.56657 8.113 56 TEXT STRUCT HUE 19.6154 23.2692 3.30769 8.476 21 17.4896 1.69161 VALUE CHROMA SOLFE 2.92308 1.69 231 0.287769 0. 392.232 0. 9703 29 0.3706 86 SOL AL 0.461538F-03 SOLCA 0.295500 SOL MG 0.687692E-01 0.110384E-02 0.105680 0.728007E-01 SOLK SOLNA HCLFE 0.642308E-02 0.426923E-02 17.7077 0.469189E-02 0.478797E-02 10.2176 HCLAL HCLCA HCLMG 0.566923 0.59492 3 0.608808 0.262903 0.549116 0.410788 HCLK HCLNA SITFS 0. 122077 0.0 4.57692 0.590362E-01 0.0 2 .06249 KJARO NAJARO HJARO 26 26 25 Oo 165385E-01 0.0 0.846154E-02 0. 123101E--01 0.0 0. 166595E-01 j(yjj^ OBSERVATIONS ARE COMPLETE DEGREES OF FREEDOM CONTROLCARDNO. :"*'STPREG'*'***S'T'PP E G S T P R E G S T P P . r G * * * * * s ^  ^ ^  ^ CONTROLCARDNO. » » > > S T E P NUMBER 3 REGRESSION EQUATION FOR SBACT R-SQUAR ED = 0o0345965 F-PROBABILITY LEVEL = 0o05 00 STANDARD ERROR SBACT = 5 8 1 0 . F-PROBABILITY = .85165947 VARIABLE COEFFICIENT STD. ERR, F-RATIO F-PROB NORM COEFF FEBACT 0.38484180E-01 0.1172 FUNGI 3. 1870208 3.871 OMBACT -0.45089007 1.187 C O N S T A N T ~ T ^ o 3 T 3 l i i 9 1 34 1. 0 .1079 0.6777 0.1443 IT095" 0.7412 0.4242 0.7072 'Q.'30:76' 0.3435 0.1765 -0.3979 672530" » » > > S T E P NUMBER 4 REGRESSION EQUATION FOR SBACT R-SQUARED = 0.0298630 F-PROBABIL ITY LEVEL = 0 .0500 S T W L T A T D E R R O R S B A C T = 5 6 9 6 c "F-PROB A BI LI TY = .70988934 VARIABLE COE F FI CT'ENT STD. ERR. F-RATIO F-PROB NORM COEFF FUNGI - 3.1625176 3.795 OMBACT. -0.69246966E-01 0.2381 CONSTANT ' 1486. 1402 129.1. 0.6945 0..8455E-01 1 .325' 0.4180 0.7657 0.2609 0.1752 -0.6112E-01 0.2679 POTENTIAL INDEPENDENT AND OTHER VARIABLES IN THE REGRESSION ANALYSIS FOR SBACT PARTIAL CORR. TOLERANCE F-RATIO F-PROB 46 3 1 . 0 0 2.020 0 .9000E-02 0 . 0 5.000 0.2800E-01 2600. 35 .54 0.2000E-02 100.0 30.00 0.0 0.0 36 .00 9.780 3.000 6.000 0 .0 1.900 6. 000 0.7000E -02 0.9000E 6. 000 0 .7400E -01 -01 1 .560 0.1980 0.1470 O.lOOOE-01 N 0.3400E-01 0.0 14 .00 0.4000E-01 0.0 0.2000 47 3.000 0.0 .2600. 16.00 0.0 2. 100 1.800 0 .3200 1.250 0.8000E-02 ? 2.040 0 . 2 0 0 0 E - 0 2 14.00 5 .700 0.4500E-01 0.5000E-01 33 .12 0.2O00E-02 0.0 30.00 0.0 0.1500 36.00 13.70 6. 000 0.2000 6. 000 0.7000E--0 2 6. 000 0.1400 0.2950 0.2130 0.5900E-01 0.0 48 0.0 2.050 0.0 6.400 2600. 36.74 10.00 .30.00 0 .0 21. 00 6. 240 6.000 1.900 5,000 0.3600 6.000 1 .300 0.4980 0. lOOOE-Ol 0.5400E-01 0.2000E-02 14. 00 0.3900E-01 0.6000E-C1 G.2000E-02 0.0 0.0 0.1400 9. 170 0.0 0.8000E--02 0.1500 0.2260 0.0 49 0.0 2.060 0 .7500 E-'Ol 0.0 7.200 0.8200E-01 2 7 0 0 . 39.82 0.0 48.00 30.00 0.0 0.0 41.00 10.20 4.280 6 .000 0.6000 3.200 5.000 . 0.8000E--02 0.5500 8.000 0.2360 1.480 0. 6380 0.1580 0.8000E-02 0.1300 0.0 14.00 0.4000E-01 0.0 0.1900 50 3.000 0 .0 25 0 0 . 0.0 0.0 1.750 4.800 0 .4200 0.5700 0.4000E-02 2.120 0.1400E-01 10.00 8.000 0.4700E-01 0.3000E-01 21 .11 0.0 0.0, 30 .00 0.0 0.6000E- 01 . 21.00 6.930 6.000 0.0 5. 000 0.6000E -02 . 6.000 0.1200 0.4770 0. 1200 0.8200E-01 0.0 51 0.0 0.0 500.0 3.000 0.0 1.120 0.8000 0.1200 0.6000 - 0.0 0.3100E-01 0.1570 10.00 0.1600E-01 0.4000E-01 0.0 0.0 0.0 0.6000E- 01 6.800 0.0 0.4500E--01 0 .5600E -01 0.1700 0.0 -52 0.0 2.370 0. 4000E-02 0.0 1 .500 0.5000E-02 250 0 . 21.91 0.2000E-02 45.00 30.00 0.0 0 .0 21.00 • 6. 710 0.8000 6. 000 0.0 0.3000 5.000. 0.6000E--02 0.3000E 8.000 0.0 -01 0.6900 0.2000E 0.1200 -02 0.0 0.4000E-02 0 . 0 10. 00 0.4000E-01 0,0 0.70Q0E-01 53 0.0 0.0 2 5 0 0 . 0.0 0.0 0.8200 0.3000 0.3000 0.6800 0.2000E-02 2. 200 0 .2100E-01 10,00 7.000 . 0.3000E-02 G.3000E-01 15.21 0.0 0.0 30.00 0.0 0 . 8 0 0 0E-01 43.00 4.470 . 6.000 0.0 5.000 0.6000E--0 2 6.000 0.5 6 00E -01 0.2700 0.1120, 0.1200 0.0 54 0 .0 2. 060 0 .0 11.60 2500. 26.90 ' 6.000 30.00 0.0 26.00 1.120 6.000 1.000 5.000 1.120 8. OOG 0.6700 2.360 0.6000E-02 0.1890 0.2600E-01 10.00 0.6000E-01 0.3000E-01 0.0 0.0 0.0 0.8000E- 01 7.530 0.0 0.2000E--01 0 .6 500E -01 0.1300 0.0 CORRELATION MATRIX FEBACT SBACT FEBACT 1.0000 0.8402 SBACT 1.0000 FUNGI OMBACT FES TOS ELEMS SS04 INSS04 OM PH FUNGI QMBACT FES -0.0863 0.0187 -0.0309 -0.1.105 0.0293 - 0 . 0 4 9 1 1 .0000 0.2801 - 0 . 0 5 5 3 1.0000 -0.032 7 1.0000 TOS ELEMS S.S04 -0.0772 - 0 . 0 6 2 9 -0 .1598 -0.0469 -0.0300 - 0 . 1 2 1 3 0.0239 - 0 . 0756 -0.4442 -0.0778 -0.1031 -0.1175 0.0287 -0.0038 0.1395 1 .0000 0.9073 - 0 . 1079 1.0000 -0.0435 1 .0000 INSS04 CM PH 0.2195 -0.. 1033 0.15 78 0.1796 -0 .1470 0.1944 0.1670 - 0 . 3 7 3 1 0.3321 -0.3274 - 0 . 1431 0.2675 -0.1122 0.0645 0.0017 0.1523 0.1121 -0.0257 0.0045 G.1842 . - 0 . 02 95 -0 0 -0 . 3 5Z 1 .5 5-J6 .3733 1.0000 - 0 . 0 3 2 8 - 0 . 1538 1.0000 -0.2811 1 . 0 0 0 0 J CONDT MOIST TEXT -0.2146 0.1088 0.0562 -0.1557 0 . 1513 -0 . 0 2 0 0 -0.3796 0.2638 0.0055 -0.3333 0.1507 -0.4461 0.2052 -0.0239 0.0916 -0.0223 0.0819 -0.3180 0.0101 U. 1257 -0.4036 0.8912 -0.1135 0. 19.35 -0.2569 0.4238 0. 1812 0.5601 0.0728 0. 01 15 - 0 , 3979 -0.1168 -0.3580 no STRUCT HUE VALUE -0.1034 -0.2594 0.180 4 -0. 2 0 3 6 -0.1788 0.2120 -0.2477 0.1436 0. 1785 -0.1067 -0.2681 0.3982 0.0143 -0.1798 -0.0511 -0.0567 0.2644 -0.1477 -0.0857 0.2745 -0.1604 0.1907 - 0 . 08b2 -0.0350 0.2025 0.0179 -0.0232 0.3149 0.0770 -0.1460 - 0,4919 0.0214 0.0303 / CHROMA SOL FE SOLAL 0.0246 -0.1451 -0.1603 0.0504 -0.18 20 0.0 375 0.3414 - 0 . 2 7 3 9 - 0 . 0014 0.026 4 -0.1630 -0.1516 0.0400 -0.0993 0.2004 -0.1424 6,0 2.31 0.0152 -0.1734 G.1049 0.0007 -0.1369 0.5210 0.4814 0.0693 - 0 . 1 8 0 5 - 0 . 2 1 4 9 -0.13 21 0.5 319 0.1707 0.258 7 -0.52,35 0.2063 S QLC A SOLMG SOLK . 0.2058 -0. 1 0 8 3 -0 .13 50 0.1776 0.0970 - 0 . 0 8 6 2 -0.1854 -0.1244 0. 1180 0.3250 -0.1528 0.5247 -0.0962 0.2128 -0.2207 -0.2758 -0.0199 -0.0968 -0.2468 -0.0259 -0.1939 0.2929 0.50t>7 - 0 . 0 6 z l -0.0904 - 0 . 1703 -0.0627 0.1439 0. 1871 -0.1890 0.2874 0.2505 0,0416 SOLNA HCLFE HCLAL 0.1422 -0. 2 0 1 3 0.0350 0.1026 - 0 . 1 4 9 2 0.1489 -0 .2165 0. 1202 -0.0610 0.1483 0.2098 -0.137 7 -0.0886 0.0510 0.1715 -0.2105 0.6 029 0. 149 7 -0.1330 0.6213 0.0946 0.08Q8 -0.182 6 0.3 41.3 -0.0797 -0.0012 -0.0642 0.17 96 0.1003 0.18 53 0.1361 0.1551 0.2363 HCLCA HCLMG HCLK 0.0611 -0.1584 0.0782 0.0 342 0.0230 0.0992 -0,1694 0. 1087 0.2562 0.0633 -0.1651 0.947 8 -0.0753 . 0,1820 -0.0043 -0.0059 0.2242 -0.1542 -U.0179 0.1832 - 0 . 1988 0.1137 0.166 6 -0.1369 0.0441 0.0409 -0.2551 0,040 2 0.0308 -0.1415 0.3853 0.3915 0.2635 HCLNA SITES KJARO 0.1963 0.0220 0.2936 0. 1786 -0.1327 0.3052 0.0150 - 0 . 2 5 8 7 -0.1451 0.7224 -0.0348 -0.1504 -0.1029 - 0 . 0526 0.1043 -0.1241 -0.3413 -0.1916 -G.1630 -0.2923 -0.2592 - 0 . 0 8 7 9 0.1765 - 0 . 155 8 - 0 . 1832 0.1455 0.2748 - 0 . 0 6 6 1 0.2783 -0.03 82 0. 1398 -0.5 1 3 9 -0,0751 NAJARO HJARO • 0.3436 0.0474 0.2283 0.0388 - 0 . 2233 0.1544 - 0 . 0433 -0,2632 -0.0928 -0.1071 -0.0161 0. 188 8 -0 . 04.91 J.0792 0.1029 -0.3 23 1 0.0228 0.8431 0.1734 -0.08 46 - 0 . 0594 -0.2096 CORRELATION MATRIX CONDT MOIST TEXT STRUCT HUE VALUE CHROMA SOLFE SOLAL SOLCA SOLMG CONDT MOIST TEXT 1.0000 -0.1780 0 .3366 1.0000 - 0 . 0 1 5 2 1.0000 STRUCT HUE VALUE 0.2175 ' 0.0864 -0.1182 0.0930 - 0 . 0 9 3 8 0.2593 0.2719 - 0 . 0000 0. 1628 1 .0000 -0.0478 -0.1518 l.OOOO -0.3661 1.0000 CHROMA SOLFE SOLAL -0.2102 0.4804 0.6188 0.1499 - 0 . 0 4 9 9 -0.1137 0.1020 0.1231 0.0455 -0.2559 0.2763 -0.2164 0.2158 0.4310 0.2156 0.0956 -0.3661 -0.0132 i .0000 -0.03 76 0.0666 1.0000 0.03t»0 1.0000 SOLCA SOLMG SOLK 0.0455 0.6239 -0.1482 - 0 . 1 2 7 9 -0.0290 0.1814 -0.1875 0.0 727 -0.0365 -0.1172 -0.2032 0.0413 -0.1804 0. 1068 -0.0338 • 0.1698 0.0323 0.0968 -G.0456 0.0379 -0.0543 - 0 i 0 1 8 3 -0 . 0 70 4 - 0 . 0 2 i 8 " 0. 1147 0.9047 - 0 . 0856 1.0000 0.1975 0.0981 1-0000 -0,0045 SOLNA HCLFE HCLAL 0.0410 -0.1486 0.4603 0.1518 0.3341 -0.0338 - 0 . 0486 -0.4910 -0.0675 0.2220 - 0 . 0 3 5 1 -0.1559 0.1478 0.3097 -0.0625 -0 .2344 -0.0103 0 .0819 -0.0212 0. 03 95 -U.0333 0,23o3 -0.08/2 -0.1647 -0,0084 -0.0018 0.7838 0.2688 -0.2506 G. 09 70 0.0922 0.0094 0.7902 HCLCA HCLMG HCLK -0 .0604 0.3699 -0.3123 - 0 . 3 3 0 9 0.0899 0.2374 -0.4588 -0.0620 -0.3372 - 0 . 2 2 6 3 -0.1543 -0.0766 -0.16.16 0.2258 -0.3798 -0.1894 -0.0419 0.4927 - 0 . 1389 - 0 . 00.50 0.0083 -0.137 8 - 0 . 1 9 8 3 . -0.262 7 0.0583 0.7535 -0.1221 0 .7019 -0.0016 0.2293 0.1476 0.7968 -0.1077 HCLNA SITES KJARO -0.2210 0.6461 -0.0858 0,1659 0.2157 0.2832 - 0 . 2 4 0 1 0.2140 0.3302 -0.018 4 0.477 9 0.0647--0.3806 -0.0000 -0.3890 0.4093 -0.0104 0.3163 -0.1583 -0.0870 G.0446 -0 .2073 . 0.4350 -0*3418 -0.2078 - 0 . 4496 - 0 . 0 9 3 5 0.2264 0.0902 - 0 . 3 0 8 3 - 0 . 1 7 7 8 -0.4294 - 0 . 0 3 4 0 NAJARO HJARO • 0 .12 73 -0.3145 0.0261 0.2980 0. 1028 0.0260 0.0629 0. 1318 -0.3332 0.2072 0.0994 -0.1896 -0.2036 0.1351 -0.137 0 0.0355 -0.0737 - 0 . 2650 -0.0423 - 0 . 0 0 1 6 -0.0288 -0.2582 CORRELAFICN MATRIX SOLK SOLNA • HCLFE HCLAL HCLCA HCLMG HCLK HCLNA SI T E S KJARO NAJARO SOLK SOLNA HCLFE 1 .0000 0.3907 0.0201 1 .0000 0.0277 - 1.0000 • HCLAL HCLCA HCLMG -0.2495 -0 .0847 - 0 . 0 7 6 9 - 0 . 1 3 7 6 0.0511 0.0924 0. 1225 -0.1172 0.2631 1.0000 0.1466 0.7586 1.0000 0.1014 .1 .0000 J HCLK HCLNA SITES KJARO NAJARO HJARO 0 .4892 0.4.155 0.0958 - i r . 13 15 -0.0016 -0.0376 0.1265 0.25 59 0.2 879 - 6 . 1300 0.1979 -0.0839 0.2101 0.1681 •0. 1470 0.0188 0.0034 •0.0133 -0.0425 -0.0559 -0.4825 6.1225 0.1233 -0.2490 -0.0363 -0.0024 -0.1514 •0.3218 -0.0569 0.1658 -0.0946 -0. 1446 -0.4927 - 6.0264 -0 .0620 -0.1165 1.0000 0.7927 -0 .0367 6 . 1 4 4 3 0.0686 -0.33 70 1.0000 0.0282 0.2 521 0.51/3 -0.3466 1.0000 0.0469 0. 0660 0.1804 1.0000 0.3942 -0.1097 1.0000 0.2952 CORRELATION MATRIX HJARO HJARO l'.0000 . NAME- MEAN STANDARD DEVIATION EE BACT 22291.8 163290. SBACT 530.185 1893.66 ' FUNGI 610.611 978.077 GMBACT 512.833 3536.43 FES 0.92 5926 E-02 0.416568 E-01 TOS 2.52852 2.78012 ELEMS 2^58519 3.27681 '' SS04 0.747037 0.3013:53 INSS64 0.804074 0.275897 OM 0.1988 89E-01 0.159736E-01 PH 2.09981 0.105714 CONDT 9.3 3519 2.86580 MOIST 24.8837 6.29588 TEXT 28.3333 4.12082 STRUCT 34.6111 11.5357 HUE 5.33333 1.78040 VALUE 5.14815 0.656101 CHROMA 5.81481 1 .04744 SOLFE 0.922222 0.784222 SOLAL . 0.148204 0.121193 SULC A 0.191611 0.178549 SOLMG 0.112333 0.938704E-01 SOLK 0.122222E-02 0.125392E-02 SOLNA 0.870370E-03 0.109968E-02 HCLFE 8.33056 3.31539 HCLAL 0.239630 0.239803 HCLCA 0.146889 0.217438 HCLMG 0.1448 70 0.126329 HCLK 0.175500 0.167920 HCLNA 0.170370E-01 0.374987E-01 S I T E S 12.6111 2. 46038 1 KJARO 0 .377778E-01 0.152547E-01 j NAJARO 0.425926E-02 0.103890E-01 HJARO 0.850000E-01 0.439876E-01 • 54 OBSERVATIONS TOTAL 54 OBSERVATIONS ARE COMPLETE 53 DEGREES OF FREEDOM CONTROL CARD NO. =** STPREG **** STPREG **** STPREG **** STPREG **** STPREG **** STPREG **** STPREG •* CONTROL CARD NO > » » > S T E P NUMBER 3 REGRESSION EQUATION FOR SBACT R-SQUARED = 0.7080667 F-PROBABILITY LEVEL = 0.0500 STANDARD ERROR SBACT = 1053. 

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