SYLLABUS LEACHED CAPPING AND OUTCROP INTERPRETATION FOR PORPHYRY COPPER DEPOSITS BY S.R. TITLEY December, 2004 DEPARTMENT OF GEOSCIENCES LOWELL PROGRAM IN ECONOMIC GEOLOGY SHORT COURSE Chateopyrite BoxworkFrontispiece: Lavender Pit, Bisbee, Arizona, View to the west. The picture shows outcrops of Juniper Flat stock to the right (North) with the typical red “fingerprint” of mixed hematite and goethite after oxidation of chalcocite, and bland colors of Paleozoic carbonates to the left (south) from which the predominance of Bisbee Production was mined. Photo by Peter KresanTABLE OF CONTENTS INTRODUCTION PART | HYPOGENE FEATURES General Characteristics, Igneous Rocks Rock Compositions, Volcanic and Sedimentary ‘Hypogene Features in K-Al Rocks Secondary Permeability PART I SUPERGENE ENRICHMENT Overview Process in Oxidation and Leaching Zone Supergene Sulfide Enrichment Processes and Produets in Enrichment zone Cyeling of Copper Enrichment of Accessory Metals ‘Thickness of Blankets and Cycling PART III RESIDUAL CAPPING PRODUCTS OF SUPERGENE ZONE. Supergene Alteration of K-Al-Silicate Rocks "Limonite" Forming Processes Boxwork Interpretation PART IV, CAPPING STUDIES IN THE SW and CHILE North Silver Bell, Arizona Safford District, Pos Pobres Escondida PART V CAPPING OF THE HUMID TROPICS (Ok Tedi Limonites Grasherg Limonites Capping in the Biological Cycle "Atmospheric" Capping PART VI MISCELLANEOUS SUBJECTS AND SUMMARY Integration of Sulfide and Silicate Reactions Non-Sulfide Enrichment Quantitative Capping Interpretation Secondary Oxidized Minerals and Capping Types Climatic Aspects High Level Alteration and Oxidation Summary SUMMARY OF CHEMICAL REACTIONS APPENDIX I Schurmann's Series APPENDIX II List of Secondary Minerals APPENDIX III Supergene Copper Sulfide Minerals REFERENCES AND EXTENDED BIBLIOGRAPHY‘TRODUCTION ‘This manual is an annotated outline prepared to accompany lectures and field exercises for a short course in capping and outcrop interpretation in porphyry copper systems. Its focus is upon the exposures as recognized in the American southwest. However, the perspective to be developed will be that of its widespread applicability to the phenomena of oxidation and leaching and the manifestation of those processes that take place and are seen in deposits elsewhere exposed in currently different weathering environments. The diagram below in Fig. 1 fom Jerome (1966) depicts important features of alteration style that include overprinting of alteration stages, as well as the generalized geometry of enrichment blankets and capping in a generalized porphyry system. Included are the common varieties of host rocks present in many region AERATION PATTERN Figure 1. Model Cross Section of a weathered porphyry system that served as an exploration model in the southwest in the 1950s and 1960s. The model shows the characteristic overprinting of alteration types, as well as the host rock van and position of the enrichment blanket. (Jerome, 1966) A cross-section through the El Tiro complex at Silver Bell, Arizona is shown on the next page below in Fig. 2 from Graybeal (1982). The features of the hypogene system essential to consideration of enrichment are shown, as are the enriched blanket (hachured irregularly horizontal area of the El Tiro stock) and the zone of leaching. The geometrical properties of the hypogene and supergene mineralization are seen and are characterized by laterally zoned primary mineralization contrasted with the vertically zoned supergene system(rvesce sme NYY Figure 2. E-W cross section through the El Tiro -Imperial stock complex at Silver Bell, Arizona. From Graybeal (1982). The principal zone of supergene sulfide enrichment is seen as a horizontal blanket overlying unoxidized, zoned, hypogene mineralization of the El Tiro Stock. Rocks overlying the blanket compose the oxidized profile and leached outcrops of the El Tiro mineralization. The Imperial pit mineralization is localized in skarn and was enriched to Cu oxides in the upper 20 meters The subjects addressed here are as follow: consideration of the primary hypogene features of porphyry copper deposits that influence the weathering and enrichment process; the nature and path of oxidation, leaching and supergene copper enrichment; the nature and interpretation of leached cappings and boxwork, and aspects of interpretation of outerop in the weathered systems. The short course will provide an introduction to end-member oxidized mineral compositions and habits, as well as to the properties, signatures, and meaning of mixtures of these minerals, falling under the general term, "limonite." The basic premise of capping study is that of interpretation of the genesis and history of the contemporary surface and from that induction of what lies beneath. The interpretation of oxidation and capping remains an art at this writing. Concerns with the features of oxidation extend back well into the 18th and 19th centuries, but by the late 19" Century, following extensive exploration in the western hemisphere and Australia, closer attention began to be paid to weathered ores and the implications of exposures. The concerns followed two paths, one in the field where attempts at correlation of weathering and ores were suggested, and the other from growing knowledge and experimental capacity in the laboratory where the nature of iron oxides underwent investigation. The importance of understanding weathered rocks is amplified by consideration of thespecimens shown below in Fig.3. Interpretation of each of these rocks led to the discovery of major copper deposits in the 1960s and early 1970s, Figiure 3. UPPER LEFT: Cu stained quartz-gold vein from Koki, Bougainville resulting in discovery of Panguna, PNG. CENTER: Cu stained magnetite boulder from the Ok Tedi that led to the search for Mt. Fubilan (OkTedi), PNG. UPPER RIGHT: Limonite stained porphyry from the discovery site, Escondida, Chile. PART I RELEVANT HYPOGENE FEATURES ‘Two characteristics are ubiquitous and therefore definitive in the most basic way in defining and recognizing a porphyry copper system, First, copper ores are localized in a densely fractured rock volume, a stockwork, and second, copper metallization and alteration are zoned, and third, metallization and alteration are related to the shallow emplacement of a porphyritic stock somewhere in the system. The spectrum of crustal rocks influenced by events in the pluton and the accidents of its emplacement, are related to the ore-forming process. The important primary (hypogene) features are those of the ore-sulfide mineral content and of its zoning, those of inherited permeability, and those of alteration types and styles as they vary in the zoning of metal content. General Characteristics - Igneous Rock Compositions The different composition of igneous progenitors corresponds in general ways to the kinds and styles of weathering and the efficiency of the progress of supergene processes, Ores are genetically associated with intermediate composition felsic porphyritic rocks as well as less felsic rocks in the igneous suite, Whereas the genetic tie is ubiquitous, it may not always be manifest and ores are deposited in the variety of kindsof host rocks present. Porphyries may occur as isolated monolithologie bodies or as intrusion complexes containing a range of compositions, usually evolving from mafic-to- felsic lithologies. The porphyries invade all rock types from quartzites and carbonates, through granites and related volcanic strata, through basalts to rhyolites and into metamorphic lithologies. Each responds in its own way during hypogene processes, according to its composition, and to the emplacement and resulting related phenomena of cooling of a central porphyry pluton. And when weathered, these rocks respond in different ways. Consequently, knowledge of the lithologies to be encountered in specific porphyry systems is important and relevant to the interpretation of surface processes. ompositions the various igneous suites recognized are shown below in the alkali-silica variation diagram of Figure 4, from Lang and others (1995). ‘8 Gilica Under) “| Saturated Silea) | saturated) 2 Catkatic ) NagO + KoO (Wt %) 40 45 50 55 60 65 70 75 80 Sip (Wt. %) Figure 4, Alkali-Silica Variation Diagram of igneous rock compositions of porphyry copper-associated intrusions from various settings, mostly of North America from. Lang and others, 1995. The metallogenetic and some mineralogic implications of the broad suites discussed in the text. Ina very general way, the rock compositions are associated with specific economic metal suites, all containing copper. However, the sulfide mineral suite also varies in the same general ways. The alkaline suite rocks, commonly undersaturated with respect to silica, are allied with a number of deposits of a belt of ores in Canada. This suite hosts Cu-Au ores in which the total sulfide content commonly tends to be low (ie., <1% volume and the chaleopyrite (cpy) to pyrite (py) ratio is >>1. These low total sulfide ores, perhaps for a variety of reasons (including post oxidation weathering) seem rarely enriched in supergene copper at the levels present,and the deposits are vanishingly low in Mo. (Alkalic undersaturated volcanic rocks are also presumed progenitors to many Au deposits of ares and continents, e.g., Cripple Creek, Colorado and the Au ores of Fiji)On the craton and in some ores of the island ares, the igneous suite is usually siliea saturated and calc-alkalic or alkali-calcic. These are the more common igneous rocks seen occurring with the porphyry ores and give rise to the Cu-Mo and Cu-Mo-Ag ores of the southwest where Au-bearing ores, in contrast with those of arcs or oceanic crust, are uncommon at the levels of Au concentration of the arc deposits. ‘The mineralogy of the cale-alkalic suite plays an important role in the end-results of the weathering process when sulfide-bearing rocks are involved. The K-AI-Si mineralogy acts as a "slow" acid consumer and contributes its K and Al to the suite of important limonite minerals. Matic igneous rocks, likewise, are important in any setting where porphyry ores are present, because of their iron content that also may act as an important oxidant or reductant in the process, depending upon their position. Rock Compositions - Volcanic and Sedimentary Suites The host rocks to porphyry intrusions are as varied as the crust and their existence as part of porphyry metal systems is accidental. The differences are significant in addressing the effects of both hypogene and supergene systems. In most systems, significant amount of sulfides have been deposited in the K(Na,Ca)-Al-Si rocks of the intrusions or granitic crust and their response to the hypogene and supergene processes is generally consistent. However, contrasts in the chemisiry of host rocks influences the important buffering effects in both the formation of acid and its neutralizing in the oxidation and enrichment process. The uniformity of composition of igneous rocks allows a fair degree of prodiction in the evaluation of enrichment but the heterogeneity of sedimentary rock sections results in unpredictable results when fluids originating in a uniform host encounter the variable chemistry and physical properties of sedimentary columns. Carbonate strata are rarely enriched by sulfides but develop silicate and oxide/carbonate suite of their own that are, nonetheless important as (sometimes) leachable resources. And although chemically reactive, shales or other fine, laminated rocks result in permeability contrasts tha perturb flow of descending solutions. ‘The Hypogene Sulfide System in K-Silicate Rocks The hypogene system (Fig. 5) develops from the flow of hot fluids through strongly shattered rocks in proximity to a cooling magma. The mineralogy of host rocks of porphyry copper deposits is varied; two extremes are common, one of K-silicate and K- silicate-altered rocks, the other is that of carbonate hosts where ska dominates the hypogene alteration. Supergene sulfide enrichment, dominated by chalcocite and its variants, is a phenomenon of the K-silicate rocks or other non-carbonate hosts. In skarns supergene alteration is mostly non-sulfide and is characterized by chrysocolla and tenorite, mixtures of which have the miner's name of pitch or melaconite. Mafic host rocks are a special case where alteration to biotite is the dominating style.Pyrophyllite Kaolinite+ Kaolinite Serici Ores eer me cee f | ‘coe LEACHED CAPPING Y SNR SS LENRICHED = Soe Chtorite i SSH BLANKETS SO | | ( | | { \ | | | | SUPERGENE ALTERATION > se V 24 n=01-0.2 | one | i z | n=0.1-0.01 7 jSneue 1 n=03-15 i: © | vow crave !Py:coy; pyar SHELL | Low PYRITE SHELL e core |"3-5 | Py: Cpy ' : ,o%! Bulan ; sme i o.3-09 | ieee I = I'se% | 008-08 \ 0.5-2.0 e% i ¥ 1c Bent a | fauerts ~ Sericite] I 3 Pyrite alteration] 2! potassic sedate © Propylitic—— = Le Alteration ——— > Alteration * fracture obundonce (em!) ; $*% =weight percent total sulphides Figure 5. From Titley (1995). Vertical zoning of supergene effects shown overprinted on laterally zoned features of hypogene alteration and mineralogy of a cross-section from an intrusive or thermal center (left) into distal wall rocks, right. The value "n" is fracture abundance of the composite stockwork fractures. The hypogene zoning is that suggested for Kalamazoo by Lowell (1968). Significant grade supergene sulfide enrichment is commonly if not invariably found in those volumes of K-ALSi host rocks where carly "potassie" alteration is overprinted by “phyllic" alteration, a phenomenon that increases both the imposed permeability of rocks by added fracturing and the pyrite content by augmentation of that mineral. Primary hypogene alteration zoning (Fig.5) consists of zoned "potassic” and "propylitic” alteration, overprinted by "phyllic” alteration that develops synchronously with a mechanically energetic event that develops abundant fractures in the rock (Fig.6); this alteration event, almost ubiquitously, also results in addition of vein-controlled pyrite augmenting the early sulfides precipitated by factors as great as 4-10 times the original weight of sulfide, Where sedimentary rocks compose the wallrock compositions in whole or in part, especially carbonate rocks, the shape and extent of the volume is commonly highly distorted where these rocks are involved, owing to mechanical contrasts and sharp contrasts in rock reactivity.10 Figure 6a, Quartz-Sericite-Pyrite veins overprinting K-Alt and orth Veins from oxidized porphyry. Stippled dark spots along sericite veins are chalcocite replacement grains after pyrite. Morenci, Arizona Photo by SRT Figure 6b. Overprinted orthoclase and biotite vein by quartz-orthoclase- sericite vein at Sierrita, Arizona. Photo by SRT Secondary Permeability Alteration and mineralization take place in a volume of stockwork fractured rock generally surrounding but also within the center of intrusion. It is the fractured rock that creates the permeability essential to the downward flow of waters that leach and enrich the porphyry copper systems; those volumes most densely fractured and that contain pyrite and hypogene copper minerals are those in which the greatest degree of enrichment, where other processes have been optimum, ‘The abundance of fractures increases generally toward the center of intrusive activity and dies away with distance, commonly up to several km away from the center. Fracturing takes place episodically as seen in the cross-cutting relationships. Fracture abundance as an expression of em"!, determined in outcrop by measurement of fracture length in sample areas as values of "n” (Haynes and Titley, 1980; Titley et al, 1986) is mostly > 0.4 and ranges to 1.0 locally. Fracture abundance and habit are retained and even visibly enhanced in the oxidized rocks of a stockwork. A map showing the results of an areal study of fractures at Sierrita, Arizona is shown below (Fig. 1. Figure 7, Fracture abundance isopleths summarizing abundance of all fracture- alteration types at Sierrita, Arizona, from Titley and others, 1986. Fracture abundance converges on the center of intrusions (stippled) and in the orebodies attains values in excess of 0.5em™l. The most widespread vein alteration type at Sierrita is that of orthoclase-quartz, with or without sulfide minerals, that extend to the limits of the system and extending into "granitic" wall rocks far beyond the porphyry center. Similar isopleth shapes and values are inferred from traverses across and values measured in other orebodies. Reconnaissance studies of other American and Pacific systems reveal the same characteristics. Scale bar is 3km/2.51 Primary hypogene alteration zoning consists of zoned "potassic" and "propylitic" alteration, overprinted by "phyllic” alteration that develops synchronously with a mechanically energetic event that develops abundant fractures in the rock; this alteration event, almost ubiquitously, also results in addition of vein-controlled pyrite augmenting the early sulfides precipitated by factors as great as 4-10 times the original weight of sulfide, Where sedimentary rocks compose the wallrock compositions in whole or in part, especially carbonate rocks, the shape and extent of the volume is commonly highly distorted where these rocks are involved, owing to mechanical contrasts and sharp contrasts in rock reactivity.Enrichment phenomena do not take place to significant degrees in those rocks of high pyrite content without significant chalcopyrite to provide copper, although weak enrichment may be present to levels of a few tenths ofa percent in multi-eyele (see further) processes. The extent of the pyrite “halo” is significant and may give rise to false indications if the observer is not wary and aware of these habits. FRACTURES AND FRACTURE MECHANICS The Stockwork is the Defining Structural Control of the Porphyry Copper Deposit At Shallow Levels, the Stockwork is of Restricted Volume and Cross Section, Opening to Large Cross-Sections below about 2km Depth. The Stockwork Evolution May be Defined on the Basis of the Relative Abundances of Different Altered Veins in the Vein Sequence. At Shallow Depths, Hydraulic Fracturing Probably is the Dominating Mechanism of Fracture Formation. At Depths Below about 1-2km, Results of Effective Pressure (Pload - Pfluid) may be an Increasingly Important Mechanism A comment on processes is in order. Whereas there have been a few studies that address the questions of material balance in alteration, such as those reported at Butte nearly 50 years ago, we are not aware of any studies reported that concern the mass balance in systems. Consequently, the extent to which Fe, Si, Metals and Sulfur have been augmented at System scale is unknown. But these elements and components do show volume changes in space and are part of the overall Gradient-Related Properties of the porphyry copper systems and are outlined in the next two summary sheets.GRADIENTS Occur as a Result of Establishment and Demise of Pluton-Generated Thermal System in a Large Volume of Crust. Supergene Sulfide Enrichment Results from Weathering of Gradient-Dominated Hypogene Systems 1, Gradients of Age of Systems in Space 2. Gradients in Composition of Igneous Rocks in Time and Space 3. Gradients of Texture in Igneous Rocks 4. Gradients in Abundance of Fractures 5. Gradients in Composition of Alteration Minerals in Time and Space 6. Gradients in Temperatures as Seen in Minerals and Geothermometers (Zoning) 7. Gradients in Oxygen and Hydrogen Isotopes 8. Probable Expression of Gradients in Pressure (Depth) 9. Gradients in Metal Endowment in Time and Space 10. Gradients in Ore Deposit Styles 11. Gradients in Weathering Products4 PART I SUPERGENE ENRICHMENT Parts of the following sections have been taken from Titley and Marozas (1995) and Lopez and Titley (1995). Those works address the processes and results of supergene weathering and enrichment and are modified here in those ways appropriate to the presentation of this course and syllabus. The phenomenon of supergene enrichment increases the concentration of metal of ‘many kinds of ore deposits. In addition to Cu, deposits of Fe are upgraded by superficial activity to produce supergene enriched ores as are certain deposits of Pb, Zn and Al, Ti and Ni, Moreover mechanical concentrations of dense unreactive minerals takes place to produce placer deposits. In all cases the process follows from weathering, which in the context here alludes to chemical changes, and to erosion. The weathering process is enhanced in all cases by the presence of acid and by surficial and deep seated permeability that allows fluids to move down or away from the site of chemical dissolution to precipitate their products or to remove chemical components or ions leaving an enriched residual. Two kinds of supergene enrichment of copper are seen and are controlled by the nature of the hypogene occurrences and the rocks involved. They are distinguished by the resulting copper mineralogy as sulfide enrichment or oxide enrichment. In the southwest, sulfide enrichment has been historically, economically, and volumetrically the most important and the subject of its origin constitutes the basis of most of the review and discussion that follows. There is a large literature on the subject, most of it more than 50 years old. But this old literature stems from times when supergene enrichment was almost the single most important criterion on which economic assessments were made and serves as a useful platform from which to proceed. Sulfide enrichment remains important today as a topic of concer but interest in oxide enrichment has increased because of the ease and environmentally clean ways that it may be mined and processed for Cu. Stated in a very general way, hypogene sulfide copper minerals are decomposed from acid generated by pyrite. The copper and other soluble products are moved downward or laterally in the shallow crust through the stockwork, dissolving their way downward mostly through veins and veinlets, in an oxidizing environment to a level widely believed to be the water table, where non-oxidizing conditions. There, copper it is precipitated by various mechanisms as chalcocite or chalcocite-like minerals in "blankets". In this process, chemical control is exerted by the minerals of the host rock, both primary and alteration phases, and by local oxidation states. Overview of the Weathering Process ithering” of these rocks as defined here coincides with the time at which descending, oxidizing, fluids of meteoric water dominate the pattem of flow through the veins and stockworks. Definition of this time and its environment, and18 geological signatures are important as the concept of early onset of enrichment lends an important perspective to field interpretations of ore deposits and capping. Inaiedch as sulfide and sulfate minerals dominate both the hypogene and supergene processes in the near surface environment, the onset of the supergene process also may be defined chemically as that time at which the character and origin of dissolved sulfur species changed from that of oxidation of deeply-derived HS to produce sulfate, to sulfate derived from oxidation of hypogene sulfides. Supergene alteration of silicates ‘would mimic that of the stage of hypogene advanced argillic alteration (acid-sulfate). No field work, nor definitive chemical-mineralogic study of our knowledge, has yet revealed a deposit where these (topographically) high level effects are still present and recognizable as phenomena of the onset of supergene alteration. If sulfide copper were to have been deposited, conditions could have favored the precipitation of covellite; covellite with silica-alunite alteration is known at high levels in a few systems such as voleanic-rock hosted vein ores at Summitville, Colorado. There, Stevens and Ratte (1960) invoke and discuss the potential effects of supergene phenomena on mineralization and alteration; Stoffiegen (1987), however, attributes the high-level phenomena at Summitville to ascending solutions, noting only a late time in evolution of the system at which flow directions were reversed. In southern Arizona, only Red Mountain, Arizona (Com, 1975) manifests rocks of the same alteration type at high levels above an intrusion; supergene enrichment, although of high level origin, is still beneath those high levels that would have ‘manifested the first stages of enrichment. Processes in the Zone of Oxidation and Leaching A starting point for is at exposures of rock at a level within the system beneath which no enrichment has taken place. Exposure of these rocks to weathering results in "early eycle enrichment” and progresses from weathering of sulfide minerals in K-Al-Silicate host rocks. Assumptions of sulfide habit are those for characteristics of a common system (pyriteschalcopyrite greater than 3:1 and 4 wt percent total sulfide). ‘The small amount of chaleopyrite dissolves in the atmosphere slowly and with little potential for chemical transport. Equation (A) expresses the stoichiometry of a possible reaction in which chalcopyrite grains are isolated from other sulfide minerals. (A) Oxidation of Chaleopyrite (A) 12CuFeS3 + 5102 = 12CuSO4 + 4Fex(SO4)3 + 2Fe703 Copper may be transported in this process but under only under conditions of sustained low pH; examples from the field reveal hematite, as shown stoichiometrically in reaction A, is the residual iron phase. The process of solution and transportation is enhanced if sufficient pyrite is available to form acid and ferric iron to sustain the oxidation state. The need for excess pyrite to promote this process is discussed by16 Blanchard (1968) and the reactions that lead from solution of pyrite to solution of chalcopyrite are shown below as reactions (B), (C), and (D). (B,C,D) Oxidation of Pyrite and Solution of Chalcopyrite (B) 8FeS2 +2802 + 8H20 = 8FeSO4 + 8H2SO4 (C) 8FeSO4 + 412804 + 202 = 4Fe2(SO4)3 + 4H20 (D) 2CuF eS + 4Fex(SO4)3 = 2CuSO4 + 10FeSO4 + 4S Thus, 8 mols of FeS2 (reaction B) are necessary to dissolve 2 mols of chalcopyrite (CuFeS2), necessary to form 2 mols of CuSO4 (Reaction D) that are necessary in turn to form I mol Cu2S. The reaction set underscores the importance of a py:cpy ratio of 4:1 as optimum and necessary in the process to completely extract Cu. An obvious chemical condition influencing these reactions is the ratio of iron in oxidation states (Fe+3/Fe+2) as well as the Fe+3/H* ratio. Beyond the stoichiometry shown here, bench- top laboratory studies of the effect of pyrite were reported by Durek (1964) and are shown below in Figure 4 where the results of copper leaching of mixtures of different proportions of pyrite to chaleopyrite are compared; the figure includes the values of changing Fe*3/Fe*? ratios resulting from the changing starting compositions, the highest value of the ratio occurring at highest ratios of pyrite:chalcopyrite. Experimental verification of this stoichiometry is shown below in the figure from Durek (1964). Supergene Enrichment of Copper as Copper Sulfides. The formation of enriched sulfide copper ores takes place by simultaneous oxidation of sulfide minerals, their leaching and the enrichment of copper, each occupies acting in a distinct location in a (generally) vertically zoned section of the shallow crust. The zone of oxidation is uppermost and is manifested by oxidation products of rocks present; it may be linked with leaching of sulfides or with modification of material from which sulfides have already been leached. Weathering of all iron minerals results in a “cap” of oxidized minerals whose character depends upon the original mineralogy. The zone of leaching may overlap with, but generally underlies the zone of oxidation, It is an interval where waters decompose the original ore and rock mineralogy; its top may become oxidized as erosion progressively removes the surface. The zone of enrichment lies beneath the zone of leaching, and is the site where dissolved metals are precipitated, by a variety of possible processes, to form secondary enrichment. The results of experimental work by Durek (1964) is shown below where different ratios of epy (chaleopyrite) or ce (chalcocite) to pyrite were subjected to solution and the results indicated on ratio vs. composition diagrams. (The experimental methods were not described.)PRODUCTS OF LEACHING OF VARIOUS MIXTURES OF PYRITE AND Cu SULFIDES nas ae Sak <4) ds 7 a 6 4] 2 4 g 8 88s s gE . ol ok 2. k PYRITE: CHALCOPYRITE E PYRITE “CMALCOCITE & x § é from Durek (1964) Figure 8. Experimental verification of the requirements of high pyrite to chalcopyrite ratios necessary for copper leaching in K-AL-Si rocks (non-reactive). Ratios of 4:1 not reported but values of 3:1 approach those stoichiometrically determined. Copper solubility diagram for mixtures of various proportions of chalcopyrite and pyrite (left) and chalcocite and pyrite (right). Separate pH values as well as Cu concentration and % of Cu leached are shown for differing ratios. Values across the bottom of the left side of the figure are ferrous-ferrie ratios determined in leach solutions. Diagram redrafted from Durek (1964). Enrichment progresses in cycles that are episodic and result from changes in base level. Early cycle enrichment may generally be considered as resulting in some upgrading of primary copper values. Each succeeding cycle may be viewed as upgrading earlier cycles at greater depth are contrasted in feet-percent changes (the conventional way of expressing supergene enrichment values) between early and late cycle processes. Further shown in Fig. 9 below. A progressive increase in amount of copper with each stage, which is marked by the formation of'a new (deeper) blanket at the expense of destruction of an older (higher) one, results in inereasing "maturity" of supergene concentrations that began with precipitation of small amounts of copper associated with deeper hypogene sulfides. Multiple enrichment stages are interpreted in many districts of the westem hemisphere where hypogene grades of about 0.1-0.2% Cu were increased in multiple episodes by factors of up to 10x the protore grades. Moreover, geological observations from virtually all enriched ores, together with a body of consistent stoichiomentricchemistry, indicates enrichment takes place in those copper-bearing rocks where pyrite contents are also high; these conditions are realized in those rocks typified by quartz~ sericite-pyrite alteration where pyrite:chaleopyrite ratios are greater than 2:1, ideally 4:1. Processes and Products in the Zone of Enrichment Copper dissolved in the oxidation process involving break down of pyrite and chalcopyrite moves across the zone of oxidation to a level of contrasting conditions, conventionally considered the water table, or into a zone where pyrite is not undergoing oxidation, to precipitate on pyrite or, iff they are present, on other hypogene copper sulfides; This precipitation follows the principles of replacement reported by Schurmann (1888). Examination of these suites in the microscope reveals that chalcopyrite and bornite appear to be first attacked in this replacement process. The reaction that follows generation of soluble copper, (D) above, is that of precipitation of Cu on pyrite (Reaction E) Copper-bearing acid solutions move down through the zone of leaching until they encounter an environment where oxidation of pyrite no longer is operative and where copper is precipitated by pyrite following Schurmann's Series. (Appendix I) (E) Precipitation of Chaleoeite (CugS) on Pyrite (B) 5FeSz + 14CuSO4 + 12120 = 7CupS + 5FeSO4 + 127804 This is the fundamental reaction that results in sulfide enrichment of copper and is controlled by conditions favoring non-oxidation of pyrite and replacement of copper by chaleocite. Anecdotal information, together with specimens of pure chaleocite have led to the notion that chalcocite may precipitate directly at the redox interface. Were this the case, and it may be so in some instances, a chemical reduetant such as pyrite or ferrous iron in solution or in mafies remains necessary to change the solutions of oxidized copper. Chalcocite deposition takes place in an environment controlled by a (usually) horizontal redox boundary, the result of which is formation of enriched "blankets." Blankets may have extensive horizontal dimensions (100s to 1000s meters) but relatively thin (105-100 meters) vertically. The redox boundary is conventionally presumed to be the water table. Following extraction of copper and iron sulfates from superjacent rocks, the blanket may be presumed to be stable until base-level is lowered, either by direct lowering of the water table or by local or regional uplift that may result in such lowering, At this stage, the ‘weathering and enrichment process resumes and chalcocite of the enriched blanket, together with subjacent sulfide minerals are once again attacked and moved still deeply or laterally to a new position of chemical and dynamic equilibrium. These cycles of "re- enrichment" result in increasing grades of "maturity" of the enriched sulfide blankets provided no copper is lost from the system. Thus, in the ideal case, subsequent stages of moving copper commence with solution of blankets in which the chaleocite:pyrite ratio changes because progressively more primary sulfide is replaced by chalcocite in the process.19 A ° ¢ ° | jill oars sarees 7] awn] tem isa ence Supeareeett aroma Figure 9. Oxidation, leaching and enrichment in two profiles showing, diagramatically, early and late stage processes in cyclical enrichment. Generalized from characteristics observed in enriched ores of Arizona and New Mexico. The figure generalizes features of the primary assemblage (A), early stage modification (B), and the profile developed from a later stage of chalcocite formation following some change in base level brought about by uplift or by other mechanisms of lowering of the water tabl Cycling of Copper in Enrichment Relatively immature "early cycle" enrichments are shown in the photomicrograph of Figs. 10. The specimens show the way in which early or immature-stage sulfide enrichment progresses with replacement of pyrite along crack mosaic boundaries; the pyrite to chalcocite ratio is probably >> 10:1. In later stages as shown in Figure 11, the replacement is more extensive. In these examples, the pyrite:chaleocite ratio is about 2.:1 and the products of solution of enrichment are specific, contrasting with products with lowered ratios.Figure 10. Photomicrograph of early cycle enrichment where chalcocite (grey) fills and replaces walls of mosaically fractured pyrite. Width of field about 1 em, Py=pyrite; cechalcocite; sil-silicates undifferentiated, Enrichment of Accessory Metals Production figures for Arizona porphyry ores reveal significant (>2.0g/t) silver values that must reflect production from supergene enriched copper sulfide ores in the particular cases. Thus, silver must move and concentrate in the copper sulfide enrichment process. It is not known ifit is fixed in oxide copper deposits. Little is known about its behavior but it may be concentrated along the way in jarosite. The case for Au is less clear, although studies of the behavior of Au indicate its concentration with iron oxides in the weathering environment. Molybdenum is oxidized in the weathering process and in the presence of iron and across a broad range of pH, it may concentrate as ferrimolybdite; this mineral was present at Esperanza and Mineral Park and is reported elsewhere. ‘This mineralogy does not represent enrichment of any sort reported. However, there are anecdotal reports of molybdenite enrichment coincident with the position of chalcocite at Hillsboro, New Mexico and at Mineral ParkFigure 11, Later-cycle enrichment where some pyrite grains retain traces of early-cycle veinlet-chalcocite. However, much pyrite has been replaced by chalcocite working in from grain boundaries, and is present now as cores to more extensive areas (volumes) of chalcocite (lighter gray). Width of field about 0.5em. cc=chalcocite; py=pyrite; mt=magnetite (darker Figure 12. Chaleocite replacing massive pyrite, Escondida, Chile: Photo by SRT2 Enrichment Cycles and the Thickness of Blankets. The range of thicknesses of economically enriched supergene sulfide blankets is significant, from that of about 30-40 meters thickness at Silver Bell, Arizona, to those of 100s of meters as in the Globe-Miami and Morenci areas of Arizona and the great thicknesses at such places as Escondida and Chuquicamata. There is no documented explanation for the variation, especially for those of great thicknesses, Hypotheses may be advanced to account for the thick blankets that involve extreme short-term fluctuations of the water table with development of many stacked blankets from the actions of many superimposed cycles (See Fig.13 below), or that invoke very slow uplift and lowering of base level without significant erosion, a phenomenon that would explain Andean enrichment and perhaps that of the thick blankets of the southwest. Cycled enrichment with enrichment factors in deposits of theAmerican southwest are shown in Table 1 from Marozas and titley (1995). Although correlation of cause and effect in specific ways is not always possible, many thick blankets occur in down-dropped blocks, suggesting many different logical explanations related to the process or to protection. Figure 13, Covellite “stratigraphy” within a section of the Clay ore body at Morenci, Arizona. Titley and Enders (1999) have propose a “bottom to top” enrichment in a down-dropped block, with each covellite “layer” representing the upper face of enrichment at water table levels that rose, through the process of lowering of the block. Faults not shown: Width of projection to section about 100m,23 ‘enn on on we in eHD Dae pA ANS 9 NA i AYN 2} IHW PRE HoH URNA HES -toreapon x pop soup spe rma ot fom my hy per pnts beep) noma pew ae ee “Woe ana ep ao yrs men ng pnalns nme tnnpon pap ramones ane NOH A pa emir ies md syne pu rg 9 pas cdo ee ony aan ener oct NT ‘rep oo se Kral sam ep ose gr ong Pr ame tenn ny Py Tl) a ope oe A TTR rl gs a 004 ‘oma oid ogame p64 ‘une “nom ory ou “64 6 see ‘08 one (igo ob sae 198 SAE wopeany suadiodns Ting woo; = eT ceeebeomme Galego 42 sora tar nym seebeqwm STONED woe sosco ou ems wzbeqwo —aiybeg uoseoL +2 wm rote p09, soenbiog que S—YIRUID WOSt-OL 4 soso tote ranas ean mes 8 ate Laeebiogyue SOAAES USL-OL mH ro ime wwsepan to PHD HR4 WHOT-OE 3M mvt wese0end —tooe oH 010 a sooeg soorptnay Std Seni von mH Rs) HuN| amo nse pod Ea HON Table 1. Grades, enrichment cycles and characteristics of supergene sulfide enricment in SW North American Deposits. From Titley and Marozas (1995).SUPERGENE ENRICHMENT Supergene Processes Commence When Hypogene Processes Cease Enrichment is Cyclical and Cummulative Enrichment Goes Forward Where Rocks and Hypogene Minerals are Appropriate. Sulfide Enrichment is Most Common in K-AI-Si Rocks and Almost Never in Carbonate Rocks. Carbonates Ordinarily Enrich to Oxides and Silicates. Systems with High Py:Cpy Content and >3%(vol) Py with Appropriate Alteration in K-Al-Si Rocks are the Most Common Seen in Sulfide Enriched Systems. In Many Regions, Sulfide Enrichment is Cyclical. Blankets Evolve from Low-Grade Cu (Immature) to High-Grade Cu (Mature) Through a Process of Repeated Uplift and Oxidation. No Specific Climate is Recognized as Essential, Rather, the Process is Envisioned as Taking Place as a Consequence of Derivation from Response to Climatic Cycles. Climatic Cycles in Concert with Uplift or Other Geologic Phenomena that may Change Base Level are Keys to the Process.PART IIL, RESIDUAL (CAPPING) PRODUCTS ACROSS THE SUPERGENE ZONE. ‘The weathering processes affecting iron-sulfide, copper-bearing rocks result in a group of products referred to as "sulfide-copper," "oxide-copper," and "limonite." Discussion of the limonites follows here and concerns their place and origin in the leaching, and oxidation profile, and consequently their significance, as presently understood. Work reported by the Kennecott Exploration Services Group (Anderson, 1982) addresses the art and science of capping interpretation. Papers during the first half of the Century, which focused specifically on limonites and capping, include those by Blanchard (1939, 1968), Blanchard and Boswell (1925, 1928, 1930), and Boswell and Blanchard (1927,1929) described the physical nature of leached outcrops. Of these earlier works, only Locke's (1926) treatment on leached outcrops attempted to interpret capping on a quantitative basis. Supergene Alteration of the Sulfide-Bearing K-AL-Silicate Rocks. The great proportion of sulfide minerals is contained or encased in quartz-bordered veins. Consequently, the principal sulfide minerals and reactions between them are isolated from reactive gangue and may be considered in that context. However, acid products of ‘weathering not used or consumed in the process of copper mobilization and transfer react, with K-silicate minerals to produce a distinctive suite of secondary silicate minerals. Debate continues concerning the influence of silicate minerals on the secondary sulfide enrichment process, and the production of secondary silicates such as montmorillonite and sericite as a result of the flow of acid-oxidizing fluids through the host rocks, The nature and importance of these questions was recognized and stated by Sullivan (1905) in the first issue of Economic Geology. The production of clays from silicate minerals during the leaching and weathering process is an interpretation based on observations of a hundred years of study of these systems. During the last half of the century, numerous reports describe the presence of supergene silicates occurring within and above enrichment blankets. Durek (1964) reports nontronite as a product of ultimate consumption of iron-alkalis and silica at the base of supergene effects at Morenci, Arizona, Supergene silicate alteration is described in detail at Ray and Miami by Ransome (1919), at Santa Rita, New Mexico (Rose and Baltosser, 1966), at La Caridad (Saegart et al., 1974) and at Quebrada Blanca, Chile by Hunt et al. (1983). Zoning of supergene phyllosilicates has been documented at the North San Xavier deposit by Koenig (1980) and at Silver Bell by Marozas (1982) where clay-size silicates are observed to change in both composition and mineralogy in patterns that correspond with the zone of sulfide oxidation, leaching, and enrichment. At Silver Bell, hypogene alteration in the protore is mostly characterized by quartz-sericite alteration that overprints quartz-orthoclase alteration of felsic igneous26 rocks. There, Marozas carried out a detailed study of supergene silicate mineralogy associated with oxidation of these ores. Kaolinite is present in significant amounts near and at the surface in the upper oxidized zone, and is a conspicuous weathering product in the position(s) of the former enriched blanket(s) where it occurs with distinctive limonite types. Kaolinite is present in only minor amounts in the enriched and protore zones. Montmorillonite is present in the enriched and protore zones but is replaced by kaolinite in the oxidized zone. Chilorite is present only at the base of the enriched zone. Sericite is present at Silver Bell throughout all alteration zones, but exhibits gradual compositional changes from the oxidized zone to the protore zone. Electron microprobe analyses of the composition of sericite minerals across the Silver Bell supergene profile indicate that the relative amount of aluminum in the micas increases and silica, iron, and magnesium decrease as manifestations of an increasingly pronounced effects of acid leaching. The concentration of elements in the micas ranges from a celadonite-like composition in the enriched and protore zones to an ideal muscovite composition in the oxidized zone. Thus, leaching during the supergene process alters sericite by selective leaching of alkali and alkali carth cations from the mica without necessarily destroying the mineral structure as it does in the case of montmorillonite. Ina general way, silicate reactions during supergene enrichment are those of conventional acid weathering: i.e. the conversion of feldspar and/or celadonite to muscovite, and of muscovite to kaolin. These reactions release alkali and alkali-earth cations into solution while they consume acid. Reaction (F) Orthoclase to Muscovite: (E) 3KAISi30g + 2H* = KAIZSi30; 9(OH)2 +2K* + 6Si02 Reaction (F) Celadonite to Muscovite: (F) 3KAIMgSig01 9(OH)2 + 8H* = KAI3Si3019(OH)2 +2K* +2Mg*? + 98i02 + 6120 Reaction (G) Muscovite to Kaolinit (G) 2KAl;Si30}9(OH)2 + 2H* + 3H20= 3AbSi205(OH)4 + 2K* A significant effect of the weathering process is that of liberation of alumina in acid systems. The reactions shown above mostly have conserved alumina as a basis for a consistent stoichiometric direction through the weathering process and its basis is sound observationally as muscovite, smectites and kaolinite have been documented in rocks from these systems, However, in thé extreme acid environment that produces jarosite, alumina in some soluble form is put into the weathered system and is observed in arid and semi-arid climates as "alum" or some form of aluminum sulfate (aluminite). It is most commonly seen in washes that surround currently-weathering, high-pyrite systems and is the basis for the many "Alum Gulch(es)" and "Alum Wash(es)" recorded on maps. These minerals are unstable in moist climates and serve only to "whiten" flowing water where the sulfide weathering process is taking place.27 "Limonite" Mineral Forming Processes in the Zone of Oxidation and Leaching Most workers recognize contrasts in limonites to be a result of mixing of the iron products of the process. The mixtures comprise proportions of goethite, hematite and jarosite. Anderson (op.cit.) details the importance of mixtures of the oxidized products of the process and presents a basis for both interpreting limonite compositions and assigning penultimate properties to the weathered mixtures. Limonite minerals of concern are shown below in Fig. 14 on the temary diagram of hematite, water, and sulfur species published by Anderson (1982). The portion of the diagram of concem here is that of jarosite, goethite, and hematite. Other iron sulfate minerals shown in the temary diagram are soluble and rare outside of the extremely arid climates of the Andes. He0) IRON MINERALS: weMarite-reres GOETMITE- reas SonosTHOMTE® 01 re s04 ton sisecntont season el ee | GOETHITE, duanostre. \LEPDOCROCITE ALUNITE Ce) tenant Poy ago AMORPHOUS coPPER AND IRON COMPOUNDS Neovocive -eomereso. FoRoUDIsE coo aayay Sop onye 805 LEGEND COPPER MINERALS © Common Minerals BIRT Site ae 2 Projected from K-AL Compositions Bee, { H30* substitution tor K* MALACHITE—Cugio4!,¢0, x0 discredited limonite minerals Hherecesianisicagy eee Figure 14, Tabulation of secondary copper minerals and a ternary diagram of hematite, sulfur species and water showing minerals of concern. Diagram from Anderson (1982) with the author's permission.28 ‘The products of oxidation of pyrite are dissolved iron species and mobile acids. ~ The minerals formed are residual or replacement, depending chiefly upon the existing redox state and the pH (which is controlled by the amount of pyrite originally present and the reactivity of the host rocks). The principal iron oxide mineral products are either or both hematite and goethite; jarosite is a product of acid reaction with feldspar. These changes are shown at mesoscopic scale in the figure below and an Eh-pH diagram is shown below in Figure 15, GOETHITE Fe0OH Figure 15. Eh-Ph Diagram of Iron-Oxide-Sulfide-Sulfate phases in the capping environment. The broad field of Goethite is nearly co-extensive with that of Hematite. Noteworthy is the pH control of the Jarosite-Goethite equilibrium. The presences of Jarosite indicates low pH environments at the site of formation, From Lopez and Titley (1995) and Bladh (1982).‘The transitions of the products shown above are seen in localized exposures of weathering in addition to bench-face scale, as shown below in Figs.16 and 17 Figure 16, Pyrite exposed on a bench floor, oxidizing to jarosite, thence outward to goethite, and marginally to hematite. Boundary between jarosite and Goethite marks a pH boundary (measured. by SRT. Figure 17. El Tiro Stock, Silver Bell, Arizona. A Jarosite core is flanked by Goethite with Hematite on the surface. Photo by SRTThe stoichiometry of formation of these oxide minerals is shown in reactions H and J Reaction (H) Formation of Hematite (A) Fe2(S04)3 + 3H20 = 3HyS04 + Fe203 (Hematite) Reaction (J) Formation of Goethite (J) Fex(SO4)3 + 6H20 = 32804 + 2Fe(OH)3 (Goethite, Approximately) (The reactions are written to. support the inference seen in stratigraphic positions and weathered profiles that goethite is a product of more extreme hydration than that accompanying the formation of goethite.) The acids formed in the solution of pyrite react with K-AI silicate host rocks to produce alunite and jarosite, reactions that are enhanced by the acid-sulfate environment (Reaction Hi). Alunite and kaolinite, as shown below are produced from K-AL-Si rocks where these conditions are present. Reaction K. Formation of Jarosite and Kaolinite in the Zone of Leaching (K) 2K Al3Si30 9(OH)2 + 6FeSO4 + 13120 + 3/202 = 2KFe3(SO4)2(OH)g + AlySig05(OH) + H2SO4 A generalized stoichiometric reaction resulting in a combination of alunite and jarosite is shown below (L) in which Al and Og are conserved, Alunite, verified by analysis, from Silver Bell and elsewhere has a dull pale green to yellow cast and XRD determinations have shown the material to be a mixture of the two sulfates. (It is noteworthy that the mineral assemblage produced here is the same as that produced and stable in the shallow hypogene stage of advanced argillc (acid-sulfate) alteration.) Reaction L, Sulfidation of Feldspar to Produce Alunite and Jarosite (L) 4FeSO4 + 3KAISi30g + 420 + 4H* +02 = KAI3(S04)7(OH)g + KFe3(S04)2(OH)g + 98102 +Kt + Fe*3 Photographs of some common and less-common oxidation and capping products are shown below in Plates A and B, and a description of oxide and sulfide minerals of these systems is presented in Appendix31 Plate A. Photographs of selected capping samples are shown below. “Relief limonite (hematite) after chaleocite __ Hematite after chalcocite (+pyrite) Silver Bell, Arizona Photo by SRT Escondida Photo by SRT Goethite and Jarosite, Silver Bell, Ariz. Jarosite, Gross Peak, Mineral Park, Photo by SRT (Ithaca Peak) Arizona Photo by SRT Neotocite, Silver Bell, Arizona Photo by SRTPlate B. Additional, less-common oxidation and capping minerals. Scordite (FeAsO:2H20) after aspy Brochantite (CuSO,3Cu(OH):) after _—_Antlerite (CuSO) 2Cu(OH); derived from Solution of chaleocite from solution of chalcocite Exotic chrysocolla from weathered Exotic malachite and chrysocolla in Skarn, replacing carbonates in channel fill, Northwest Extension, Cemented alluvium, Twin Buttes, Morenci, Arizona3 Jarosite is stable only in an environment of low pH (<2.5), at greater pH (more alkaline), converting to goethite and a weak acid solution capable still of producing alunite if sufficient potash and alumina are available. Both alunite and jarosite are conspicuous products of the oxidation and leaching cycle in ores of the southwest, jarosite a product of immediate reaction of sulfates with K-bearing silicates, and alunite mostly a product found beneath weathered, former enriched sulfide blankets and invariably associated with transported hematite. In very arid regions, iron sulfates such as coquimbite, rhomboclase, copiapite, and Kornelite may be stable but are not widely, ifat all, reported, in the oxidation and enrichment zones of deposits of the American southwest. ‘The iron oxide signature of the former presence of chalcocite is that of hematite or hhematite-goethite mixtures. This phenomenon remains unexplained in a rigorous context ‘today but there is some basis for proposing the differences lie in the presence of iron with the enrichment. Tunnel (1930), citing his (then unpublished) work and that of Posnjak (1931) notes that with high pyrite:chalcocite ratios, chalcocite is dissolved and that there is sufficient acid to keep iron mobilized to precipitate exotic hematite upon dilution and neutralization (Reaction M). Reaction (M) Solution of a mixture of 2:1 pyrite: chalcocite (M) 2F eS + CupS + 1002 = Fep(SOg)3 + 2CuSO4. (SEE, Reaction H, previously, for the reaction producing hematite from Fe7(SO4)3) Downward movement of Cu*+ dissolved from the high blanket, augmented with copper newly extracted from uplifted rocks with hypogene copper sulfide, move to a deeper level of chemical reduction, conventionally considered to be the water table, and forms a new blanket of higher Cu grade as shown in the photomicrographs of Figures 8 and 9 16,17). Ensuing cycles of enrichment result in continuing breakdown of chaleocite and ir diminishingly smaller cores of pyrite, a result of which is the diminishment of the pytite to chalcocite ratio, as shown below in reaction (N). Reaction (N) Oxidation of a 1:2 (Pyrite to Chaleocite) Mixture. (N) 2FeS2 + 4CugS + 17.503 = Fe203 + 8CuS0434 In this reaction (N), hematite is fixed at the site of oxidation, rather than transported and usually forms to the characteristic relief boxwork of residual hematite after solution of the chaleocite-pyrite mixture. The boxwork "pseudomorphs" the grains of mixed pyrite and chalcocite (See, Figure 9). A 1:2 molecular ratio of pyrite to chalcocite is the minimum proportion of pyriite necessary to provide sufficient S to dissolve chalcocite; this reaction in air results in indigenous hematite/goethite left in place. Thus, the ratio of pyrite to chalcocite in the blanket is critical to the continued mobility of copper and the enrichment process. Pure chalcocite does not contain sufficient sulfur to mobilize both moles of copper present when weathered (In Cug§, the Cu:S is 2:1). Consequently, weathering of pure or “mature” chalcocite blankets results in fixing of haif the copper as cuprite or tenorite, the other copper molecule transportable as copper sulfate. The reaction that oxidizes and dissolves chaleocite may be generalized as shown next in reaction (P). Reaction (P) Oxidation of Chaleocite (P) Cug$ + 5/202 = Cu** + SO4= + CuO Rarely, native Cu or cuprite are products but most commonly, the weathered oxide product is a mineraloid analyzed to be (CuMnFe)Si03:nH30 or "neotocite" (Anderson, 1982), or to be copper pitch. Copper sulfates, antlerite or brochantite, are common coatings of weathering chalcocite. However, mature chaleocite blankets may, and do, ‘weather and move in response to continued acid attack from sulfates generated through oxidation of residually contained, or superjacent pyrite, above the blanket.Leached Capping Profiles Figure 18. Toquepala Profile (Oscar Damiani for Scale) Hematite cap exposed on high benches, grading downward into goethite, with a thin subjacent layer of jarosite abobe grey chalcocite enriched ores. Photo by SRT Figure 19. American Mountain, Morenci, Arizona showing profile trom hematite into jarosite from deep oxidation of pre-exzisting chalcocite blanket. Flanked to right by goethite. Much of the oxide ore at Morenci is believed to be partially decomposed supergene sulfide enrichment,A generalized capping profile across a section that involves leaching of an enriched blanket and re-enrichment at depth. Silver Bell, El Tiro, and North Silver Bell Fig. 20 | le etée a (_] SineeReano 4 (6 2614 9G 261T Figure 20. Vertical Profile of major limonite types in a second cycle of oxidation of a pre-existing blanket and deeper deposition at Silver Bell, Arizona. The color pallet is based upon finger-print "smudges” from limonites exposed on the pre-mining surface at North Silver Bell. It is common practice to prepare limonites from pure end products and mix proportionately Hematite, Goethite and Jarosite to obatain desirable ratios for mapping purposes. A further practice is carrying “smudge” golors in notebooks or on mapping ‘hosts (sometimes messy) for spt comparisons ka Profiles of capping across some Andean ores are shown below in Fig, 21, and correlatin and interpretation diagram are shown further in Fig, 22.CAPPING LIMONITE PROFILES Gintubye ~-& CHUQUICAMATA pte Arne AE > (S. Wall) M1 =B.deote B. ELSALVADOR ee (Hundido Camp) craic im in Wehirk ©, EL SALVADOR Begone (Cerro Pelado) D. ESCONDIDA z (Cerro Colorado) tiene E. ZALDIVAR (Pit) = (scondida (SR. Title July 1996) AL B. c D. E. Figure 21. Capping limonite profiles for Andean Deposits, as indicated. Unpublished data of SRT 3738 MINERAL ABBREVIATIONS Pic LiMoNITE- ANTLERITE: NeOTOCITE eRocsanrite aA oeTaiTe JAROSITE HEMATITE CAPPING CLASSIFICATION Figure 22. Capping Classification Diagram from Anderson(1982) with permission of the author. Diagram shows the range of formation of various limonite products as are related to sulfide compositions of the rock progenitor. 4.4 The Interpretation of Boxworks39 Fracture data can be accumulated in notebook fashion as shown in the example of Fig. 23. The color smudges can be preserved on various kinds of soft (notebook) paper, or on separated sheets prepared for the purpose, such in profiles as the drill log sheets shown previously. Fracture abundance numbers may be plotted directly on field sheets. as Etat aaenin) au Aaah de <9 GAs sfetight on tlh» aie Figure 23, Sample of Field Book with collection of capping colors. Whereas limonite colors and other capping minerals are potentially significant in the interpretation of weathering histories, other weathering products lend credence to the interpretation of the former presence of enriched blankets, a necessary component of increasingly mature and higher grade enrichment, These products are boxworks representing the former presence of sulfide or other minerals in the former assemblages The Interpretation of Boxworks Whereas limonite colors and other capping minerals are potentially significant in the interpretation of weathering histories, other weathering products lend credence to the interpretation of the former presence of enriched blankets, a necessary component of increasingly mature and higher grade enrichment, These products are boxworks representing the former presence of sulfide or other minerals in the former assemblages.40 Figure 24a, Boxwork after chalcocite. Typical honeycomb texture of hematite walled clusters of relief forms. From opened vein surface. Overexposure | enhancement of characteristic hematite boxwork above is shown below. leaves behind a characteristic boxwork consisting of hematite bordered cells, shown in Fig.24a above and in enhancement of the honeycomb texture in Fig 14b, below, The high hematite content of limonites derived from reasonably mature blankets is diluted by various concentrations of goethite whose quantity varies with the amount of pyrite left in the cores of chalcocite grains of the weathered blanket. eS: oid: Figure 24b. Photographically enhanced surface of 24a. showing cellular boxwok41 ‘The Hematite-Goethite mixtures give rise to the so-called "Bismarck" - brown or "Seal- Brown" limonites characteristic of this feature. The very dark brown to black limonites of this boxwork streak crims{GVhich is a standard criterion of the dominant presence of Hematite, shown below in the real colors of the hematite of the sample shown above Primary sulfides leave their own boxwork and itis “fortunate” that both chalcopyrite and bornite manifest their own distinctive geometries. These boxworks are shown below in Figure 25. The boxwork after chalcopyrite is siliceous and usually clean except for occasional hematite or brown stained surfaces and has a characteristic "laddee" geometry. Noteworthy is the fact that massive chalcopyrite left to weather breaks down first into long prisms approximating the boxwork geometry. The bornite boxwork expresses a characteristic curvature into pseudo-spherical triangles and habit. The siliceous walls of these boxworks must derive in some fashion from those supergene solutions that are precipitating quartz or silica of some type simultaneously with the solution of the sulfide of the sample. Figure 25. Boxwork after chalcopyrite (left and of bornite on the right. Seale across bottom of each rendition about 1 em. From Blanchard Collection at the University of Arizona, _ As compared with the distinctive boxworks of the copper minerals described above, the boxwork from pyrite is comparatively non-descript, chacteristic only that it reveals equant, generally straight edged, commonly rectilinear selvages. Although Blanchard describes these boxworks as well as those of other sulfide minerals, their recognition remains a high art when they are part of'a complex sulfide assemblage. PART IV FIELD STUDIES OF CAPPING IN THE AMERICAN SW AND CHILE Surface geological maps over orebodies are an essential and common product of geological studies and they have been widely shown or otherwise imported. However, ‘maps that show capping types and their distribution, although likely in existence, are extremely rare in my experience. Several good reasons for this paucity of information exist, an important one is that the caps over many systems are long gone, having been mined away in the first stages of stripping and development of open pits. A second reason42 attaches to this temporal constraint. Published works on capping go back into the 1920s with the book by Locke (1926) and the susbsequent book by Blanchard (1939, 1968) and the work of Kennecott (Anderson, 1982) provide bases for interpretation of capping at specimen scale. Unpublished maps of capping products were produced by the Asarco group, chiefly the work of Kenyon Richard and Harold Courtright, one map product of which is that showing Courtrights interpretation of the capping at Cerro Colorado Grande at Escondida, published by Ruiz (1994) ‘We started a program of capping archival in the 1990s as part ofa broader geochemical study of mine waters and mineralogy in the oxidized zones of porphyry systems in Arizona that were supplemented by the author’s sampling of capping from deposits in many regions. Archiving of capping has been completed at North Silver Bell Arizona, and over the Dos Pobres orebody in the Safford district of Arizona. The results are described in the sections that follow. Mapping of Capping Above the North Silver Bell Enriched Blanket. Lopez (1994) and Lopez and Titley (1995) have shown the distribution of limonite types above a drilled blanket at North Silver Bell (Plate C). The results of this work are shown below in Figures 26,through 32, below. The Silver Bell figures show the relationships of capping and hypogene alteration to the position of the enriched blanket. At North Silver Bell, a small intrusion to the northwest invades a thick (200-300m) suecession of a quartz-rich "dacite” which is the principal host to hypogene and supergene ores.(Fig. 26) Quartz-latite dike swarms, almost indistinet from the dacite extend ENE across the north half of the exposures. ‘Hypogene alteration comprises an early "potassic” characterized by orthoclase-quartz- sulfide veinlets in the NW quadrant that have been overprinted by quartz-sericite-pyrite alteration, affecting other rocks to a limit where propylitic alteration extends to fresh rocks ig. 27) Supergene sulfide enrichment with the thickest and richest part of the blanket is near on a N-S line through the center of the maps where its top is some 15-20m beneath ‘most closely adjacent surface and where some grades attain values in excess of 1% Cu. ‘The fracture abundance map of Fig. 28, combined with the capping map of Figure 29, shows that the dominant limonite type exposed above the blanket is goethite (with minor jarosite). ‘The hematite shown in Figure 29 is mostly exposed along high ridges and slopes where inspection reveals it to be residual after earlier (and higher) former chalcocite enrichment (Fig. 30). Its absence above the blanket is almost solely due to deeply cutting erosion that has removed most of the characteristic, former-blanket type, of capping above the current recognized blanket. Noteworthy is the fact that hematite extends as a capping product to the east, beyond the limits of the blanket as identified by drilling but above areas where there is no record of a test4B Plate C. Pre-Mining Surface Looking NNE at N. Silver Bell, and Mining as of Novenber 2004 Pre-mine North Silver Bell Surface, looking NNE at capping above the No. Silver Bell orebody. The old Railroad grade from Red Rock to Silver Bell (ca.1900) is seen in the lower left corner of the photograph. Phoro by SRT North Pit of North Silver Bell. The reference point for the top picture is the railroad grade in the SW quadrant of the photograph. Nov. 2004 Photo by SRT44 ve Te Lene [SS ow Esker Sansa SILVER BELL DISTRICT PIMA COUNTY, ARIZONA Figure 6: Index Map Showing Study Area and General Geology of the Silver Bell District. After Graybeal (1982) Figure 26, Geological Map of North Silver Bell, After Graybeal 1982 and AsarcoFiglure 27, Alteration Map at North Silver Bell, Arizona. Vertical Red bars are orthoclase, biotite and quartz veins, mostly centered over the N. Silver Bell stock. Dashed reds, blue and black are quartz-sericite (pyrite) veins of different abundance, and the vertical green bars are of epidote-chlorite veins and replacements. (From Lopez, 1995, modified from Piekenbrock, 1983) aera FIGURE 9: ALTERATION ZONES gE epidote, emerite, catcite NORTH SILVER BELL, PIMA CO, ARIZONA BB rae ats pine ira ee faa ea Cam Steg ots Sensis te G00 =——=—$$—— (women rae ment woRe%, ts FT too vere~~ 46 Froeveer 22: Fracrom= Densrrr Norra Srivee Bert, Prua Co., Amrzona op i60__ 199013902000 eer Pee snipous i Cease —— HIB 0.500 no neuen oo aoa 200 soo #00 ETERS { 0.40.en" ~ O43 en’ ELEVATIONS IN FEET 5 020 en" 0380 CONTOUR INTERVAL 100 FEET 3 000en"= 01908 “+ seoTzoN connens Figure 28. Fracture abundance map at North Silver Bell.: Values shown range from >0.5em-1 to present but <0.20em-147 An extremely important aspect of outcrop interpretation is that of integration of ‘measurement of fracture style, type, and abundance, that go along with interpretation of limonites and inferences as to that which may lie below, Examples shown below are those of the pre-ore jointing exposed at Silver Bell. Figs 29 and 30. Figure 29. Hill Slope exposures of volcanic host rocks beneath the former No. SilverBell enriched blanket. Jarosite formed from remnant domains of primary sulfides. The red limonites are a jarosite-hematite mixture Figure 30. Stockwork fractured volcanic host rocks of North Silver Bell in the zone of leaching and oxidation with jarosite “paint”on surface; black spots are neotocite, and a goethite-hematite limonite coats fracture surfaces.8 1:12000 500 1990 _1500_2000 FEET ~ DOMINANT LIMONITE aan MINERALIZATION eee cee eed reece Levarions I FET {CONTOUR INTERVAL 100 FRET ca Figure 31. Capping Map of North Silver Bell, from Lopez and Lopez and Titley 1995, Red shows areas of >50% Hematite in the limoites, Brown shows areas >50% Goethite in Limonite, and Yellow shows areas of dominant Jarosite with Goethite.49 The hematitic limonites shown in Fig, 32 are characteristic of those found at higher elevations in the ore deposit and represent remanants of the blanket from which the current mineralization is being taken, Cook (1994) dated supergene alunites from Silver Bell that revealed two stages of formation, 16.2Ma and 4.8Ma, dates related to episodes of the supergene processes Figure 32. Ridge Limonites N. AgBell Mapping of Capping at Dos Pobres (Safford district, Arizon: Under auspices of Phelps Dodge, Brant Wilson (2004) compiled a capping map above the Dos Pobres deposit. Unlike Silver Bell, where relief was significant and useful in examination of capping, relatively flat, covered surfaces had to be utilized and the capping products were determined from isolated outcrops, whose distribution is shown below in a geologic map, modified by Wilson from Phelps Dodge data Aa an K. Figure 33. Geologic Outcrop map of Dos Pobres from Wilson 2004 and Phelps Dodge hypogene mineralization and also host the products of weathering and enrichment. A consequence appears to be the development of widespread hematite, mostly transported30 and we did not discover the rich, Bismark Brown capping limonites and boxworks that are common elsewhere. A generalized capping map is shown below (from Wilson, 2004). HEB porate orcas capa Figure 34. Capping Map at Dos Pobres, Scale as shown. The Cu bearing hematites appear mostly transported, but the blue (central) area hosts hematite that is rich in Cu, up to several thousand ppm From Wilson, 2004. Figure 35. Transported hematite at Dos Pobres. Red spots are replace feldspars. Photo from Wilson, 2004,Mapping of Capping at Escondida, Chile Harold Courtright of Asarco mapped the capping at Cerro Colorado Grande at Escondida. His work is reported in Ortiz (1995) and his map, as reproduced in Ortiz (1995) is shown below as Fig. 36. Weight of spots is related to interpreted relationship to copper, as explained on the map. Courtright’s criteria are unknown, but samples taken on Cerro Colorado Grande in 1998 are shown below in Figs. 37 and aspect of the hill is shown in Fig. 38, ‘sais eee er oe —ESCONDIDA OPEN PIT ar C° Del sir LIMONITES AFTER oc/cpy © sooenare to sovounr__—— Figure 36. Capping Map at Escondida, with coding and scale as shown. Map by Harold Courtright as reproduced by Ortiz (1995)32 Figure 37. Capping Limonites from Cerro Colorado Grande, Escondida, Chile. On the left, Hematite-rich Goethite limonites, and on the right, hematite limonites stain the fractures of the host rocks. Photo by SRT Figure 38, Cerro Colorado Grande, Escondida, Chile, site of the Courtright Map and the capping samples shown above in Fig. 37. Photo faces the discovery drill site on this side of the hill. Photo by SRTPART V CAPPING AND SURFACES OF THE HUMID TROPICS Discussions and descriptions heretofore have been those of deposits where, ‘generally, arid to semi-arid climates have prevailed. The porphyry systems of islands and island ares merit further comment. In these regions of the humid tropics, rainfall is commonly heavy (>250 inches/yr) but in some regions, seasonal. Uplift rates are rapid (eg., 1km/my) and erosion rates significant, enhanced by relief and seismic activity Deposits are geologically youthful, ie., 1Ma to ca 30Ma. Nonetheless, capping is present, and oxidation and leaching, above supergene sulfide copper enrichment exists. Figure 39. Porphyry Copper Country: Left, Plesyumi, New Britain, PNG; Right, Frieda River, PNG with jarosite stained outcrops in zones of pyrite. Heavy cover to creek banks and mixed hypogene and supergene outcrops within creeks. Photos by SRT liron oxide-sulfide capping is present in these regions where acid substrates support low pH and jarosite stability. Continuous dilution of pyrite, however, results in more commonplace occurrence of goethite, that carries copper values Hall et al. (1990) report SOMt of supergene sulfide copper at Frieda River, P.N.G., together with a zone of oxidized copper minerals. ‘The enrichment of oxidized and enriched zones of copper is about 1.5x that of the hypogene grades of about 0.5%Cu with Au values of about 0.3g/t, nearly the same as that of the hypogene grades. The absence of gold enrichment is commonplace in zones of base metal enrichment, although silver is commonly enriched in chalcocite in many deposits. Photographs of selected cappings andexposures of oxidized caps of mineralized copper systems of Papua New Guinea and Borneo are in Figure 40 and 41 below Figure 40, Jarosite-coated cliff exposures at Frieda River (Left) and sample of oxidized capping from Plesyumi, New Britain. The capping sample shows oxidized, fractured fragmental volcanic rocks of capping, jarosite, and goethite surfaces. Photos by SRT Figure 41. Pit-face and track-side exposures of capping and stockwork preserved in saprolites of porphyries at Yanderra, P.N.G. (Left) and at Gunung Nungkok, Sabah, ‘Malaysia (Right). Oxide colors and capping characteristics shown in each. Brown streaks from pyrite (sericite) veins, irregular Black veins are quartz-chaleopyrite (pyrite) and straight black veins are quartz. Photos by SRTMoss is a common cover of sulfides (probably owing to the acidic nature of such a substrate, and when stripped, allows inspection of weathered outcrop. Shown in Fig. 42, below is such a comparison from Morgru Creek, Yanderra, P.N.G. Figure 42. Moss exposures along creek (left) and sub-moss capping in porphyry to the right at Yanderra, P.N.G. Capping and fracture characteristics as outlined above Photos by SRT The renditions of capping above are of rocks at some unknown but likely considerable depths beneath the original tops of the systems, At Wafi River, P.N.G., the exposures are believed to be of high level and the alteration exposed is that of alunite and silica, together with pyrite, The indicator of better news below is that of the combination of fracturing and conspicuous capping types, as shown below. Figure 43. Exposures of capping in advanced argillic(?) zone of alteration, Wafi River, P.N.G. At left is exposure of fractured and veined breccia with pronounced hematite capping, possibly after covellite-pyrite mineralization, with vertical zones of pyrite, On the right is jarositic capping in silica-alunite altered breccia. Photos by SRTOuterop and Capping Characteristics in the New Guinea Highlands OK TEDI, P.N.G. 36 Figure 44. Pre-Mine surface at Mt. Fubilan (Ok Tedi), Papua New Guine, showing drill sites (iron-stained) and Hong Kong Ridge. Figure 45. Goethite-Jarosite mixtures in capping from Hong Kong Ridge, Ok Tedi,GRASBERG, WEST PAPUA, INDONES! Figure 46, Original surface of the Grasberg orebody, West Papua, Indonesia Photograph courtesy of Freeport McMoRan Cu and Au, Inc. Figure 47. Goethitic and hematite limonites from exposures of trachyte on the high north slopes of the Grasberg. Photo by SRTCapping in the “Biological Cycle” (PLATE D) The response of plants and animals to the crustally anomalous characteristics of ores may be an integral part of surface characteristics. The geobotanical aspect of capping studies relies upon plants as indicators of the presence of mineralized systems, Much of the interpretation of plants relies almost solely upon coincidence that in most cases is poorly restrained. Many plants are indirect indicators with no reliable geochemical correlation, but reliable nonetheless in the regions where they occur Eschscholzia californica (California Poppy) SW N.America (seasonal) Copper Flower (San Manuel) Photo by SRT Impatiens. New Guinea Copper Flower. Yanderra, P.N.G. Photo By SRT To the right, copper staining on a waterfall along Morgru Creek, Yanderra, P.N.G. The staining is from copper permeating moss, below whose dry weight assay is 4% Cu, the balance silica. Photos by SRT Morgru (Copper) Creek, P.N.G.39 Regional differences exist that are related to climate and setting. In the semi-arid regions of Queensland, Australia, geologists recognize a specific weed that grows over copper- bearing rocks of many different styles of ore bodies. Copper weed is shown below Figure 50, Polycarpea burtoni, copper weed, seen in the Blue Valley Prospecting Authority, Queensland. Austraia. Photo by SRT Elsewhere, other kinds of capping manifestations are present. The termite mound is a conspicuous feature of much of the northern half of Australia, The mystery of how and why such features, shown below, occur is not known to the author. However, the color and composition of the outer covering of these mounds reflects the mineral composition of the subjacent rocks. Mapping of colored mounds correlating with isolated esposures revealed a zonal distribution of alteration and capping types that corresponded with soil geochemistry. Figure 51. Termite “mounds” on the left. On the right rock types from shallow draws and creeks with corresponding mound colors. L to R. q-sericite; goethite/hematite; hematite/jarosite; and jarosite on q-sericite-pyrite. Interior is cellular structure of digested(?) wood. Red River Prospecting Authority,Qld. Australia. Mineral were partially verified by X-Ray and hand specimen identification, Photos by SRT“Atmospheric Capping” Figure 52, Metcalf Ore body and Pit, Morenci, Arizona. Photograph by SRT,6 PART VI MISCELLANEOUS SUBJECTS AND SUMMARY Integration of Sulfide and Silicate Reactions. The fordedIng descriptions of sulfide behavior and silicate alteration were sulfide ‘weathering reactions. The model provides insights into the complex interrelationships between copper transport and weathering of felsic mineral assemblages during supergene enrichment. Computed mineral assemblages are generally in agreement with those observed in natural systems. The model also predicted the mobility of copper and sulfate between various weathering zones, as well as the mobility of gangue elements derived from the weathering of silicate minerals. It has been found that while most of the copper is fixed below the groundwater table by secondary sulfide precipitation, gangue elements such as caleium and sodium together with iron are generally transported out of the ‘weathering system. Marozas (1982) studied modem leach waters and supergene mineralogy at Silver Bell, Arizona and illustrated the important role in enrichment that is assumed by silicate reactions. Silicate minerals affect solution chemistry by contributing gangue cations and consuming hydrogen. Both of these effects can influence the efficiency of copper enrichment in the supergene environment. Copper mobility is enhanced in groundwater systems when sulfate ligands are available to improve metal stability by complexing. Copper mobility can be impaired in concentrated solutions when gangue metal cations capable of complexing with sulfate (i.e. Cu, Mg, Ca, Al, etc.) compete with copper for available ligands. The degree to which the cations are complexed can be calculated from known stability constants. Speciation analysis of acidic leach waters collected from Silver Bell illustrates how alkali and alkali-earth cations derived from silicate ‘weathering reactions can affect copper speciation, mobility, and reactivity. Variations in concentration of metal-sulfate complexes and free metal cations with sulfate are shown for the total metal concentrations measured in Silver Bell leach waters (Figure 53). At Silver Bell, a concentration of sulfate was measured at 10-0.74 ‘molarity (Value A shown in Figure 53. At this concentration Mg(SO4)0 and Al(SO4)9"! are the dominant sulfate species in solution, because of 1) the high concentration of magnesium and aluminum; and 2) the higher stability of ‘magnesium sulfate and aluminum sulfate complexes with respect to Cu Figure 53. Diagram showing the concentration of metal and alkali sulfate complexes versus sulfate concentration for a water sample at Silver Bell. The vertical line is that of the sulfate concentration of sulfate in the analysis.2 ‘The presence of sulfate-secking cations like magnesium and aluminum in solution forces copper to its free ion or hydrated state in losing in the competition for sulfate ligands. Calculations show that 53 percent of the total copper in solution is available as free copper cation in the Silver Bell leach water sample and 47 percent is complexed as Cu(SO4)9. Theoretical calculations of copper speciation in a similar system without competing cations (Al, Ca, Mg), show that only 40 percent ‘would be available as free copper and 60 percent is complexed as Cu(SO4)0. Speciation analysis such as this reveals important clues about copper behavior in supergene systems, because free copper ion is the reactive form of copper in solution. When higher concentrations of copper are available to react in the free or uncomplexed form, precipitation reactions will occur at lower pH values and/or at higher oxidation potentials than when complexed form dominate copper speciation as shown in Figure 54 During acid weathering, silicate-derived cations (Al, Ca, Mg) can hinder the transport of copper out of the oxidized zone by increasing the amount of Figure 54. Eh-pH diagram showing relevant copper species and copper n. Dashed line shows relationships at Cu molality of 0.01, solid line, the relationships at molality of 0.0001. uncomplexed copper in solution and therefore driving it into equilibrium with supergene copper minerals, even at low pH conditions (fig. 54). Although conditions in the enrichment zone are reducing, sulfate is generally unreactive because the rate of inorganic sulfate reduction is extremely slow (Ohmoto and Lasaga, 1982). Thus copper complexing, ith sulfate ligands may deter secondary sulfide enrichment reactions. Silicate derived ions may improve the efficiency of secondary copper enrichment by increasing the amount of free copper that will be available for reaction with reduced sulfide minerals, i. reaction with pyrite to produce chalcocite (Reaction E) Dilution of solutions carrying sulfuric acid and iron as well as sulfate complexes, and consumption of those substances, products of reactions (B), (C), and (D) above, results in formation of hydrated iron oxides (limonites). Non-Sulfide Enrichment in Porphyry Copper Systems ‘The development of supergene sulfide copper enrichment takes place in "non- reactive" host rock systems where seemingly, pyrite content in excess of 2 volume percent has formed and where the pyrite to chalcopyrite ratios are in the range of 3-6:1. The process proceeds where there is adequate rock permeability exists and where the sulfide minerals are exposed (in veins and veinlets) to the moving solutions. Acid (low pH) solutions and oxidizing conditions are necessary to move metals to an environment of contrasting redox states. The questions to be addressed is that of whether these conditions are attained in reactive rocks.6 Carbonate, sulfate, silicate, oxide, and chloride copper mineral species occur in some special environments where acid may not be consumed or where the oxidation state (ie. Eh) is strongly oxidizing. The most important and conspicuous environment where these mineral species are present are in calc-silicate altered portions of porphyry systems where carbonate rocks dominate compositions of pluton walls. Important to the consideration of weathering in hypogene alteration of this type is the facts that the hypogene sulfide assemblage and the acid consuming properties of the host rocks differ markedly from that in felsic igneous rocks. Hypogene cale-silicate ores are a mix of vein and pervasive alteration assemblages dominated Ca, Mg, and Fe silicates. These minerals are not significant acid consumers although calcite, which is present in some parts of such systems, is. Graybeal (1982) as attributed the absence of sulfide enrichment in skams at Silver Bell to this fact. More importantly, pethaps, and such a situation may be proposed for Silver Bell, Twin Buttes, and Mission, Arizona is the fact that skarn ores do not ordinarily contain the high pyrite contents of the typical felsic porphyry system and the pyrite to chalcopyrite ratios are ordinarily much less (i.¢. 1:2-4). (At Morenci, supergene sulfide enrichment occurs beneath calc-silicate altered Paleozoic strata, but is reported also to be in clastic rocks of the succession.) Consequently two chemical effects may be considered. Small amounts of sulfate produced in weathering are scavenged to form complexes of Mg and perhaps alkali and iron. Moreover, acid is not consumed by the rock suite, allowing transport of Cu ion until dilution takes place and the metal is precipitated as oxide (tenorite) or silicate (chrysocolla). Quantitative Capping Interpretation ‘The interpretation of the surface above an oxidized and enriched porphyry system in felsic igneous rocks (or mineralogical equivalent) concerns the interpretation of four fundamental factors. These factors are applied when other evidence such as rock types, alteration, and appropriate setting support the notion that the observer is working with a porphyry copper system. The interpretations are based upon the observation of the nature and extent of fracturing (the stockwork), upon the nature of limonites present, the presence of characteristic boxworks after sulfide minerals, and to a limited degree upon geochemistry. Secondary Oxidized Copper Minerals and "Limonite” Types Secondary oxidized copper minerals of importance in outerop interpretation are those formed in the absence of sulfur and in oxidizing environments. They are found in outcrops above or in lateral proximity to those volumes of rock through which dissolved copper has moved but was not fixed by reduced sulphur. These minerals include, importantly, chrysocolla, "neotocite," or tenorite or copper "wad." These oxides and silicates have restricted, and consequently important, characteristics of formation.ot Limonite types as considered here are various mixtures of geothite, hematite, and jarosite. The implications of those mixtures and the relative proportions of each mineral in those mixtures have been hypothesized and their meaning interpreted by many geologists, ‘going back to Tunnel (1931) whose concerns were the contrasting meanings of goethite vs hematite in outcrop (SEE Reactions H, J, M, and N). Further meaning has hen assigned in the context of the Kennecott studies (Anderson, 1982) Blanchard (1968) has given over only 3 pages to a discussion of limonite colors. Yet subsequent work by the Kennecott group (Anderson, 1982) has indicated that different limonite mixtures are critical to the interpretation and that the colors of limonite, as indicative of key characteristics of the weathering history. Diagrams showing the range of occurrence of different limonites in the framework of pyrite, chalcopyrite, and chaleocite volumes and proportions are shown below in Figure 55. In that diagram, the range of proportions of primary minerals necessary to the formation of enriched copper sulfides are in the shaded area. Shown below is a diagram showing, limonite compositions as functions of percent of goethite in limonites as related to total volume percent sulfides (as pyrite as interpreted from various cappings as noted. The diagram also shows the range of distribution of neotocite and combined pitch limonite and neotocite. Areas of weak and moderate leaching are indicated une 9h Stine anrecnt Figure 55. From Anderson (1982) with permission. Diagram of Goethite as related to primary assemblages with chaleopyrite as mole percent of the assemblages and total volume percent sulfides.65 In Figure 56 (below) the proportions of hematite and goethite in the limonite mixtures is shown as related to volume percent sulfides and mole percent of chalcocite in the original mixtures. The diagram expresses the fact that hematite or hematite-goethite mixtures are and indication of the former presence of chalcocite in the mixture. As shown in the photomicrographs of Figures 10 and 11, pyrite of immature blankets is present as cores to chalcocite grains. It is the weathering of this pyrite that gives rise to the soluble iron which ultimately produces the hematite of the blanket - and as noted earlier, the exact reactions that produce the mixtures are very poorly understood. Inthe upper portion of the diagram (high chaleocite, low pytite)are shown the products of weathering of mature (100%) chalcocite blankets to tenorite, with cooperate and native copper, and brochantite (SEE reaction P.) Tenorite is a common product of the weathering of skarn-altered assemblages where acid production is weak and reactivity of the host rock may neutralize supergene solutions, i i Figure 56. Showing Goethite and Hematite compositions of limonite as related to volume% sulfides and mole% chalcocite. From Anderson 1982 with permission. The diagrams do not express the relationship of jarosite to goethite in the limonite mixtures. The salient point about jarosite is its instability in neutral solutions. It is66 stabilized at pH lower than about 2.5 above which it transitions to geothite; in Figure 13, the range of stability of jarosite across a broad range of pyrite but restricted range of other sulfide minerals is shown, together with the range of goethite stability at only low pyrite contents bespeaking elevated pH. As noted earlier, the production of alum following the breakdown of feldspar in formation of jarosite results in solutions which can form the various aluminum sulfate compounds under appropriate conditions. Climatic Aspects A conventional view of climatic conditions in which the supergene sulfide enrichment process takes place has held that it requires, or at least takes place in an arid climate; such is the climate of regions where much sulfide enrichment is presently known, However, characteristics of capping and of the process in island arc regions reveals that the process is taking place at the present time in an environment of considerable rainfall (Titley, 1978) requiring only that there be open flow to enhance water circulation, The contrasting viewpoints and evidence may be rationalized in the suggestion that the present climate in the American southwest is conducive to removal of soils and vegetation, denuding surfaces to expose the red fingerprints of oxidation of iron. These products are also present in the youthful deposits of the humid tropics. ‘An argument commonly made is that Tertiary climates were those favorable to the process and are like those of the present time. However, the present arid climate of Arizona has been recognized as one of only recent onset and that not too long ago, arctic climates prevailed and before that, the climatic regime remains largely a matter of present research and study. What does seem likely, however, is that it is the effect of climatic cycles that may be important. Alternate wetting and drying, either seasonally or over longer terms may be the principal agent that results in water table fluctuations (that may result in very thick blankets?) and that dissolve and then move copper downward. Cook's (1994) study has found episodic changes the destruction of enriched blankets (and therefore in their formation) that are suggested (Cook, op.cit) to reflect the onset of arid climates. His diagram, shown below as Figure 57, reveals a crude correspondence to the development of region-wide tectonic and voleanic events of the Tertiary and a correlation with specific stratigraphic assemblages.o SE — OMY. Stree pend, SKN Bisbee eure ‘A SKN 30 A 10 e 162A TR ve |” mg] Se 30 L —teisn 30 Tram and Preuramie | a i seston 7 1 40 é 4 TT x 2 40 rove Figure 57. Correlation diagram across southern Arizona and contiguous New Mexico of Tertiary assemblages from Cook (1994). The triangles indicate age dates of alunite, jarosite, and illite from supergene enriched systems as named (SXN=San Xavier North) and are position laterally to correspond in general with approximate longitude as shown on inset in lower left corner of the diagram. Cook attributes the onset of much of enrichment in the Miocene following initiation of the Basin and Range orogenic eycle. Not shown is Bisbee (Jurassic in age) where dates indicate a Cretaceous age of first enrichment. Durations of events suggested are on the order of a few million years. High Level Alteration, Oxidation and Related Issues Capping products produced in the leaching and enrichment process are those resulting from acid-oxidizing, sulfate-producing reactions. These are the same conditions, albeit taking place at lower temperatures, as those that produce the advanced argillic alteration (acid-sulphate) seen at high levels in some porphyry copper systems, and certainly those of a specific genre of precious metal ores. In the American southwest, the hypogene alteration type is present at Red Mountain and at Sunnyside, Arizona. The alteration type was recognized and reported at high levels at El Salvador. It is appropriate to address these characteristics seen in both the supergene and hypogene systems. 1. Alunite, together with some silica flooding, and kaolinite are seen in both systems. Pyrophyllite may have a stability field at the low temperatures of supergene activity. In the hypogene alteration these minerals, especially alunite and silica may appear68 to"flood" the involved rocks as a manifestation of rock-pervasive hydrothermal alteration. In supergene alteration, alunite occurs mostly as a vein-forming mineral, believed to be produced where enriched blankets are oxidized and to lie below them. Anecdotal information suggests this style of occurrence because alunite of the sort considered in supergene processes is not present or is extraordinarily rare beneath existing supergene sulfide blankets. 2. One discriminant may relate to the nature of the structural control of porphyry copper systems, the stockwork. In those hypogene systems where stockwork-style fracturing overprints either a vein, vein-system, or a pervasive advanced argillic cap, such as at Red Mountain Arizona, a logical interpretation is that a stockwork-developing agent existed at depth. Outcrop study and interpretation should address that possibility. 3. The presence of pyrite and enargite in these advanced argillic systems (stockwork veins in such systems reveal them), supergene enrichment may proceed in ‘much the same way as that in non-sulphate altered systems. ‘The capping in such systems has been only poorly studied and reported although secondary arsenical minerals are known as is the boxwork from chaleocite in hematite-dominated limonite. 4, Breccias are common high-level phenomena that may occur in the acid-sulphate environment as well as manifesting themselves at deeper levels within "conventional" porphyry copper systems. At high levels, they, too, may reveal the effects of pervasive acid-sulphate alteration. But their link with a deeper source is not always conspicuous although they result from comparable energy sources. Summary ‘The process of supergene enrichment of many deposits in the American southwest has been complex and cyclic. In many deposits such as Silver Bell and at Morenci, at least two and possibly as many as four specific cycles (as remain at Red Mountain, Arizona) may have taken place as suggested from the position of relief limonites and hematitic capping. The work of Cook suggests at least 3 well-dated and identified periods of enrichment that must some way correlate with phenomena that lower base level, at least intermittently. Enriched copper ores represent an upgrade of hypogene grades (commonly in the range of 0.3-0.5% copper where affected) to values of in excess of 1.5% (In the early days of mining, porter (not hypogene necessarily) was considered anything less that 1%). In their destruction, the process leaves behind many clues as to the nature of former mineralization and alteration. However, the job of interpretation still remains in great part an art but we are gaining on it.A Summary of Chemical Reactions in the Oxidation-Enrichment Processes ‘THE SULFIDE ENRICHMENT PROCESS (A) Oxidation of Chaleopyrite (A) 12CuFeS2 + 5102 = 12CuSO4 + 4Fe2(S04)3 + 2Fe203 (B,C,D) Oxidation of Pyrite and Solution of Chalcopyrite (B) 8FeS2 + 2802 + 8H20 = 8FeSO4 + 8H2S04 (C) 8FeSOq + 4H2SO04q + 202 = 4Fe2(SO4)3 + 4H20 (D) 2CuFeS2 + 4Fe2(SO4)3 = 2CuSO4 + 10FeSO4 + 48 Thus, 8 mols of FeS2 (reaction B) are necessary to dissolve 2 mols of chalcopyrite (CuFeS 2), necessary to form _2 mols of CuSQ4 (Reaction D) that are necessary in turn to form_Lmol CugS. The reaction set underscores the importance of a py:cpy ratio of 4:1 as optimum and necessary in the process to completely extract Cit. (E) Precipitation of Chalcocite (CuS) on Pyrite ‘E) 5FeSz2 + 14CuSO4 + 12H20 = 7Cu2S + 5FeSO4 + 12H2SO04 4 2! SILICATE MINERAL WEATHERING REACTIONS Orthoclase to Muscovite (E): (E) 3KAISi30g + 2H* = KAI3Si3019(OH)2 + 2K* + 6Si02 Celadonite to Muscovite (F) (F) 3KAIMgSi4019(OH)2 + 8H* = KAI3Si30 9(OH)2 + 2Mg*? + 2K+ + 9 SiOz + 6H20Muscovite to Kaolinite (G) (G) 2KA138i3019(OH)2 + 2H* + 3H20= 3A17Si205(OH)4 + 2K+ "LIMONITE" FORMING REACTIONS IN THE ZONE OF OXIDATION AND LEACHING Reaction H, Formation of Hematite (H) Fe2(S04)3 + 3H20 = 3H2S04 + Fe203 (Hematite) Reaction J. Formation of Goethite (J) Fez(S04)3 + 6H20 = 3H2S04 + 2Fe(OH)3 (Goethite, Approximately) Reaction K. Formation of Jarosite and Kaolinite in the Zone of Leaching (K) 2KA13Si30} 9(OH)2 + 6FeSO4 + 12H20 + 3/202 = 2KFe3(SO4)2(OH)¢ + Al2Si205(OH) + H2SO4 Reaction L, Sulfidation of Feldspar to Produce Alunite and Jarosite (L) 4FeSO4 + 3KAISI30g + 4H20 + 4H* +02 = KA13(S04)2(OH)g + KFe3(SO4)2(OH)g + 9Si02 +K* + Fe*3 THE SOLUTION OF CHALCOCITE AND FORMATION OF RELATED "LIMONITE" (As Suggested by Tunell, 1931) Reaction M, Solution of a mixture of 2:1 pyrite: chaleocite (M) 2FeS2 + Cug$ + 1002 = Fe2(S04)3 + 2CuSO4. AND, from Reaction H (previously) Ferric Sulphate + Water = Acid + Goethite7 Downward movement of Cu** dissolved from the high blanket, augmented with copper newly extracted from uplifted rocks with hypogene copper sulfide, move to a deeper level of chemical reduction, conventionally considered to be the water table, and forms a new blanket of higher Cu grade as shown in the photomicrographs of Figures 8 and 9. Ensuing cycles of enrichment result in continuing breakdown of chaleocite and their diminishingly smaller cores of pyrite, a result of which is the diminishment of the pyrite to chaleocite ratio, as shown below in reaction (N). Reaction (N) Oxidation of a 1:2 (Pyrite to Chaleocite) Mixture. (N) 2FeSz + 4CugS + 17.502 = Fe203 + 8CuSO4 Reaction P, Oxidation of Chalcocite (P) CugS + 5/203 = Cu** + SO4= + CuO APPENDIX I SCHURMANN'S SERIES This old but useful notion stems initially from observations that certain metals are precipitated in the oxidizing process by other, certain, minerals, Basically, the Series predicts the order of formation of sulfide minerals, based upon their affinity for sulfur. A metal ion in solution will be precipitated at the expense of certain other sulfide minerals with which it is in contact in predictable ways. The diminishing order of affinity for sulfur is Hg, Ag, Cu, Bi, Cd, Pb, Zn, Ni, Co, Fe, and Mn. Thus the copper in a solution will be precipitated on iron sulfides (pyrite or pyrrhotite), where those minerals are stable, liberating the iron to solution and fixing the copper as CuS or Cup$. Coatings of covellite or chalcovite are also seen on sphalerite (ZnS) and galena (PbS) where they sometimes give a blue hue to the sulfide substrate. The extent to which application of the series may be applied is unknown but its application in concems with supergene copper minerals seem valid,R APPENDIX II SECONDARY "OXIDE" MINERALS "Akaganiite" (BGoethite) BHFeO2. Lustrous red-brown enamel-appearing goethite, commonly found in weathered zones above porphyry molybdenum deposits where it may contain a few percent of Mo. "Alum" (possibly Aluminite Aly(SO4)(OH)4: 7H20 or other undescribed hydrous aluminum sulfate phases). White earthy coatings developed from breakdown of feldspars, ‘micas or clays in the zone of weathering, from sulfate activity. Products of weathering seen in the many "Alum Gulches" of arid regions and a product of precipitation in drainages distal to sulfide systems where acids reaet with K-AL-Si rocks. Alunite - (Na,K) Als(SO4)2(OH)6, White to various shades of gray-green depending upon contaminants, commonly jarosite with which it is isostructural, Streak white, H=4 but commonly in the field up to (apparently) 6 because dispersionof fine grained silica within it. Crystalline to massive but usually extremely fine-grained, Conspicuous conchoidal fracture. Of hypogene origin in acid-sulfate parts of original porphyry copper systems. But also importantly a product of high sulfate alteration of feldspars during weathering. Commonly seen with hematite and just beneath former enriched blankets. In the supergene zone, it occurs most commonly in veins and veinlets; in the hypogene zones its habit is that of "flooding" with silica pyrophyllite and kaolinite mixtures. Antlerite - Cu3(OH)4SO4. Light green soft mineral occuring in lumps or rarely as poorly crystalline prismatic crystals. H=3 with a pale green streak. Formed during oxidation or partial leaching of sulfide assemblages with a high Cu-S ratio, especially in weathering of chalcocite. Azurite - Cu3(OH)2(CO3)9. Azure blue, monoclinic crystalline to massive habit, vitreous to earthy luster. Commonly occurs with malachite and tenorite. Brochantite (Cug(OH)gSOg. Monoclinic, emerald green with pale green streak Prismatic, acicular crystals commonly in clusters on veinor joint surfaces, and sometimes drusy crusts. Hardness about 3. Common as a decomposition product from oxidation of chaleocite, Stable in atmosphere. Chaleanthite - CuSO4-5H0. Blue-Vitriol, Decomposition product of copper sulfides, especially chalcocite under acid-oxidizing conditions. The blue stain on exposed sulfide in pit walls. Stalactitic, reniform, botryoidal. Unstable and hygroscopic. Chrysocolla - CuSiO3: nl120. Bluish gren to green to pale, washed out green, Cryptocrystalline, opaline with cochoidal fracture. White streak. hygroscopic with a hardness of about 4. Suggested to have formed in environments of low Mn-Cu or high silica-sulfate ratios instead of neotocite, and a product of partial leaching of Cu.Copper Cu. Metallic. A product of decomposition of pure chaleocite in which it occurs as thin plates. Cuprite Cu20. Red with adamantine, metallic, or submetallic luster and a reddish streak. ‘Cubic, less commonly octahedral in habit. Hardness about 3.5-4 with a conchoidal fracture and poor cleavage. A product of oxidation of chalcocite with which it commonly oceurs, more generally in environments of a high Cu to S ratio. Ferrimolybdite Fep(MoO,)3 + SHO. Sulfur yellow to greenish yellow, asbestosform and fibrous in masses that are very soft. Forms as an oxidation product of molybdenite in the absence of strong acids. Molybdenite commonly left in outerop and iron may be obtained from earlier formed iron oxides. Goethite Fe203 - H2O (or HFeOg, sa Lepidocrocite) Soft, earthy brown mineral with dark streak, uncommonly radial clusters of prismatic or acicular crystals. Where crystalline, H=5.5, where earthy or pulvurulent, H=3-4. "Diagnostic as representative of that amount of iron not leached from outcrop" Gypsum CaSOq - 2H 0. Crystalline, usually white mineral with hardness of 2. Seen zone of leaching in rocks of high Ca availability. Hematite Fe703. Hexagonal The varieties from weathering of rocks are usually earthy and soft with a brownish red to red to deep maroon streak, depending upon contamination as it is commonly present in mixtures of other minerals, the purer minerals of deep red streak. The hardness of the pure phases is from 5 to 6. Its color ranges from crimson to very dark brown to bluish black. Martite is a variety occurring with cubic or octohedral habit, a weathering product of cither magnetite or pyrite, which it pseudomorphs. Jarosite K(Fe,Al)3(SO4)2(OH)¢. Occasionally visibly crystalline in small masses of rhombohedral crystals with a vitreous luster, otherwise earthy, dull and compact. Light! yellow in color with a light yellow streak. It occurs intermixed with goethite or hematite in limonite mixtures of the weathered zones in sulfide bearing rock. A mineral forming and stable only at very low (<3) pH, it breaks down at higher pH ,with loss of Al and S04, (Sce "Alum") to goethite. Its presence indicates close proximity to co-existing pyrite in rocks of felsic igneous mineralogy. Lindgrenite Cu3(MoO4)2(OH)3. Rare. Orthorhombie, occurring as tabular or platy crystals rarely acicular. H=4.5 Green to yellowish green in thin plates. A secondary ‘mineral that occurs in weathering of low-iron, low sulfur mineral assemblages, that is molybdenite and chaleocite, Malachite Cup(OH)2CO3. Bright green, massive, botryoical or tuberose forms to crystalline masses. Monoclinic, erystals rare but short or long prismatic and commonly in tufis or rosettes. H=3.5-4. Light green to pale streak. Its formation is mostly in” carbonate or non K-Al mineral rocks and is analogous to that of Antlerite, occurring in environments of high Cu to $ minerals in reactive rocks, Neotocite (Cu,Fe,Mn)SiO3. A mineraloid and an iron-manganese-bearing analogue to chrysocolla. Black, amorphous with a dull, drab and rarely vitreous luster. The streak is waxy and black to dark olive in color. Identifiable by a field test using 10% acid to dissolve and plate a nail or pick point with Cu. Forms in the oxidation of chalcopyrite (cpy) or chalcocite (ce) depositswith a epy or ce to py ratio of > 0.5 or >0.3 respectively. Commonly found in the zone of leaching beneath a zone of active weathering of copper sulfides above a low total sulfide (3). Tenorite CuO Black scaly mineral with a metallic luster and a hardness of 3-4. Black streak. Common with malachite and chrysocolll in the weathered surfaces of copper skarns. Torbernite Cu(UO)2(PO4)9 - 8-12H90. Tetragonal, brittle, micaceous, grass green to emerald green crystals. ‘Turgite (See Hematite) 2Fe703 - HO. Botryoidal, reniform masses of dark to medium brown color, hardness of about 5, that display a characteristic brilliant luster and play of colors. Water content said to be variable. Its occurrence as a distinct mineral species has not been verified but the name is commonly applied to those minerals with this habit. Commonly seen as a residual product after weathering of pyrite masses. APPENDIX IIL GLOSSARY AND REVIEW OF SUPERGENE COPPER SULFIDE MINERALS. ‘The generalized and conventional composition of supergene copper sulfide mineralogy is that of "chalcocite, " a name that is used in the absence of a more detailed knowledge and analysis of a suite of similar copper minerals of similar occurrence. In addition to the chaleocite-like minerals of supergene enrichment, covellite is also present in some places and in some systems. There exist other minerals of the chaleocite-genre that have been reported and their nature and properties are briefly addressed in the tabluation that, follows. Chalcocite. (CuzS, Monoclinic) In its pure form itis a dark-blue to black mineral whose streak is shiny grey metallic and its luster varying between metallic or "steely" and "sooty", the latter term used for the mineral where itis fine-grained. lusterless, and of earthy or powdery consistency and habit. There is some evidence to suggest that the metallic or75 “steely” chalcocite is that variety more commonly seen in chalcocite of hypogene origin but polished sections of the sooty variety reveal a distinct and unequivocal metallic luster and the deep steely-bluc of the "steely" variety. Although there have been few adequate detailed study of the sulfide suites, most supergene chalcocite of the southwest is likely to be this mineral. Digenite (CugSs, Hexagonal) At the hand lens scale very similar to chalcocite in color, luster, and streak. Difficult to distinguish but likely present in some supergene sulfide systems, occurring with chalcocite. It is a hypogene mineral at Butte, Montana and at Superior, Arizona. Djurleite (Cu31S16, Monoclinic) A mineral of the same mesoscopic properties as that of chaleocite and digenite. Very slight harder than digenite with penetration determinations and about the same as chalcocite. Reported in the supergene sulfide ores of Globe Miami, Arizona and may be more widespread than now recognized. Analite (Cuz$4 Orthorhombic) Similar to the minerals above but of more restricted (as reported) occurrence. No known occurrences in porphyry ores of the southwest but may be present in Some of those of the Andes. Hardest of the group of minerals included here, about 3 (Mho) but still difficult to distinguish Covellite (CuS, Hexagonal) Very distinctive because of its blue color and sometimes leafy habit. In very rare crystals or sheets its much softer (1.5-2) than the chaleocite minerals. Its style of occurrence, as a mineral replacing hypogene copper and iron sulfides is the same as that of the chaleocite "group" but it occurrence bespeaks conditions of formation less certain than those of the more common supergene sulfide minerals. Covellite may also occur is "post-mine" oxidation of copper sulfides and is sometimes present at thin layers on other sulfides where it gives rise to iridescence. At Morenci, in a few exposures of enriched mineralization, covellte is nature's mineral of choice as the stable phase. In these exposures, covellite like chalcocite appears to replace iron sulfides and most likely chalcopyrite if it is present. Its occurrence, in this system, and in this place of otherwise chalcocite-dominant enrichment is inexplicable in the context of reality and the most that can be said stems from the Eh-pH diagram shown below of the copper phases. In this diagram, covellite may be seen to "wedge" itself into the chaleocite field under acid conditions.Diagram constructed to show phases at | atm totP, C03 = 1073 and S = 10-1 Relevant Phases CuS04:5H0: Chaleanthite Cu3(OH) 4804: Antles Cug(OH) 6804: Brochantite ‘Cup(OH)xCO3:Malachite CuO: Tenorite diagram of phases in the Cu-O- S-H system... Diagram from B.B.Hanshaw in Schmitt (1963), Collection of Equilibrium Diagrams: Harvard, University. 16 Castemsey ‘Seon 504 eustortycoy7 REFERENCES AND EXTENDED BIBLIOGRAPHY Ague, J.J., and Brimhall, G.H., 1989, Geochemical modeling of steady state fluid flow and chemical reaction during supergene enrichment of porphyry copper deposits: Economic Geology, v.84, p.506-528. ‘Anderson, C.A., 1955, Oxidation of eopper sulfides and secondary sulfide enrichment: Economic Geology, 50th Anniversary Vol., Pt. 1, p-324-340. Anderson, J.A., 1982, Leached capping and techniques of appraisal, in, Titley, S.R., ed., Advances in Geology of the Porphyry Copper Deposits, Southwestern North America: Tucson, University of Arizona Press, p.275-295. Baas Becking L.G.M., Kaplan, LR., and Moore, D., 1960, Limits of the natural environments in terms of pH and oxidation-reduction potentials: Journal of Geology, v.68, p.243-284, Bateman, A.M., 1942, Economic Mineral Deposits: New York, John Wiley & Sons, 916p., Esp. Chapter 5.8, p.245-289, Bladh, K.W., 1982, The formation of goethite, jarosite, and alunite during the weathering of sulfide- bearing felsic rocks: Economic Geology, v. 77, p.176-184, Blanchard, Roland, 1939, Interpretation of leached outcrops: Jour, Chem., Met., and Min, Soc., South Africa, v.39, 9.344.373. . 1968, Interpretation of leached outcrops: Nevada Bureau of Mines Bulletin 66, 196p. Blanchard, Roland, and Boswell,P.F., 1925, Notes on the oxidation products derived from chaloapyrite: Economie Geology, v.20, p.613-638. , 1928, Status of leached outcrops investigations: Enginering and Mining Journal, v.125, p.280-285; p.373-377. , 1930, Limonite types derived from bornite and tetrahedrite: Economic Geology v.25 357-380. Boswell, P-F., and Blanchard, Roland, 1927, Oxidation products derived from sphalerite and galena: Economie Geology, v.22, p.419-453, , 1929, Cellular structure in limonite: Beonomie Geology, v.24, p.791-796. Brown, J.B., 1971, Jarosite-goethite stabilities at 25°C, 1 atmosphere: Mineralium Deposita, v. 6, 245-252, Buehler, H.A., and Gottschalk, V.H. 1910, Oxidation of sulfides: Economic Geology, v.5, 9.28-39. Cook, §.S., 11,1994, The geologic history of supergene enrichment in the porphyry copper deposits of southwestern North America: Tucson, University of Arizona unpub. Ph.D. Disseration, 165p. Cook, S.S., 1988, Supergene copper mineralization at the Lakeshore mine, Pinal County, Arizona: Economic Geology, v. 83 p.297-309, Com, R.M., 1975, Alteration-mineralization zoning, Red Mountain, Arizona: Economic Geology, v. 70, p. 1437-1447.78 Durek, J.J., 1964, Some characteristics of weathered outcrops of disseminated copper deposits: New York, Columbia University, Unpublished Ph.D. Dissertation, 149p. Emmons, $.F., 1900, The secondary enrichment of ore deposits: American Institute of Mining EngineersTrans., v.30, p177-217 Emmons W.H.,1913, The enrichment of sulfide ores: U.S. Geological Survey Bull. 529, 260p. Emmons, W-H., 1917, The enrichment of ore deposits: U.S.Geotogieal Survey Bulletin 625, $30p Garrels, R-M., 1954, Mineral species as functions of pHi and oxidation-reduction potentials, with special reference to the zone of oxidation and secondary enrichment of sulfide ore deposits: Geochimica et Cosmochimica Acta, v.5, p.153-168, Garrels, R.M., and Thompson, M.E., 1960, Oxidation of pyrite by iron sulfate solutions: American Joumal of Science, v.258A, p.57-67. Grout, F-F., 1908, The oxidation of pyrite: Economic Geology, v.3, p.932-534. P. Hall, R., Britten, R.M., and Henry, D.D., 1990, Frieda River coper gold deosits, in, Geology of the Mineral Deposits of Australia and Papua New Guinea (Ed. F.B. Hughes,p-1709-1715.(The Australasian Institute of Mining and Metallurgy: Melbourne). Haynes, F.M., 1983, Vein densities in drill core, Sierrita porphyry copper deposit, Pima County, ‘Arizona: Economic Geology, v.79, 755-758. Hunt, 1.P., Bratt, J.A., and Marquardt L., J.C., 1983, Quebrada Blanca, Chile; an enriched porphyry copper deposit: Mining Engineering, p. 636-644. Jarrell, O.W., 1944, Oxidation at Chuquicamata, Chile: Economie Geology, v. 39, p.251-286. Kemp, J.F., 1905, Secondary enrichment in ore-deposits of copper: Economic Geology, v.1, p.11-25. Koenig, Brian, 1978, Oxidation-leaching and enrichment zones of a porphyry copper deposit a ‘mineralogical and quantitative chemical study: Tueson, University of Arizona unpub. M.S. Thesis, 7p. Livingston, D.E., Mauger, R.L., and Damon, P.E., 1968, Geochronology of the emplacement, enrichment, and preservation of Arizona porphyry copper deposits: Economic Geology, v.63, p.30-36. Locke, Augustus, 1926, Leached outcrops as guides to copper ores: Baltimore, Williams and Wilkins Co., 166p. Lopez, J. A., and Titley, S.R., 1995, Outerop and capping characteristics of the supergene sulfide enrichment at North Silver Bell, Pima County, Arizona, in, Pierce, F.W., and Bolm, J.G., eds., Porphyry Copper Deposits of the American Cordillera: Tucson, Arizona Geological Society Digest 20, 424-435, Lovering, T.S., 1948, Geothermal gradients, recent climatic changes, and rate of sulfide oxidation in the San Manuel district, Arizona: Economic Geology, v.43, p.1-20. Marozas, D.C., 1982, The role of silicate mineral alteration in the supergene enrichment process: Tucson, University of Arizona unpub. M.S. Thesis, 57p. McKinstry, H.E., 1948, Mining Geology, New York, Prentice Hall, 679p, (Esp. p. 243.276).Morse, H.W., and Locke, Augustus, 1924, Recent progress with leached ore capping: Economic Geology, v.19, p.249-258. Ney, C.S., Cathro, R.J., Panteleyev, A., and Rotherham, D.C., 1976, Supergene copper ‘mineralization, in, Sutherland Brown, A., ed., Porphyry Deposits of the Canadian Cordillera: Canadian Inst. of Mining and Metallurgical Engineers Special Volume 15, p.72-78. Ohmoto, Hiroshi, and Lasaga, A.L., 1982, Kinetics of reactions between aqueous sulfates and sulfides: Geochimica et Cosmochimica Acta, v.46, p.1727-1745. Penrose, R.A.F., Jr., 1894, Superficial alteration of ore deposits: Journal of Geology, v.2, p. 288-317. Posnjak, E., and Merwin, H.B., 1919, The hydrated ferric oxides: American Journal Science, Fourth Ser., v. 47, no. 281, p.310-347. Posnjak, E., and Merwin, H.E., 1922, ‘The system Fey03-SO3-Hy0: Journal American Chemical Society, v.44, p.1965-1994. Posnjak, E., and Tunell, 1929, The system cupric oxide-sulfur trioxide-water: American Journal of Science, Fifth Ser., v.18, no. 103, p. 1-34. Ransome, F.L., 1910, Criteria of downward sulfide entichment: Beonomie Geology, v.5, p.205-220, 1919, The copper deposits of Ray and Miami, Arizona: U.S.Geological Survey Professional Paper 115, 192p. Rose, A.W., and Baltosser, W.W., 1966, The porphyry copper deposit at Santa Rita, New Mexico, in, Titley, S.R., and Hicks, C,L,, eds., Geology of the Porphyry Copper Deposits, Southwestern North America: Tucson, University of Arizona Press, p. 205-220, Sacgart, W.E., Sell, J.D., and Kilpatrick, B.E., 1974, Geology and mineralization of La Caridad porphyry copper deposit, Sonora, Mexico: Economic Geology, v.69, p. 1060-1077. Sato, M., 1960, Oxidation of sulfide ore bodies: I, Geochemical environments in terms of Eh and pH: Economie Geology, v.55, p.928-961 . 1960b, Oxidation of sulfide ore bodies: Il. Oxidation mechanism of sulfide minerals at 25°C: Economic Geology, v. 55, p. 1202-1231 1992, Persistency-field Eh-Ph diagrams for sulfides and their application to supergene oxidation and enrichment of sulfide ore bodies: Geochimica et Cosmochimica Acta, v. 56, p.3133-3156. Sato, M., and Mooney, H.M., 1960, The electrochemical mechanism of sulfide self-potentials: Geophysics, v.25, p. 226-249, ‘Schmit, H.H., 1962, Equilibrium Diagrams for Minerals At Low Temperature and Pressure: Cambridge, Geological Club of Harvard, 199p Schurmann, E., 1888, Ueber die Verwandtschaft der Schwermetalle zum Schwefel: Justis Liebig’s Ann. Chemie, v.249, p.326-350. Schwartz, G.M., 1934, Paragenesis of the oxidi ized ores of copper: Economic Geology, v.29, p.5:80 , 1949, Oxidation and enrichment in the San Manuel copper deposit, Arizona: Economic Geology, v.44, p.253-277. Stevens, T-A., and Rate’, J.C., 1960, Geology and ore deposits ofthe Summitville district, San Juan Mountains, Colorado: U.S.Geological Survey Professional Paper 343, 70p. Stoffregen, Roger, 1987, Genesis of acid-sulfate alteration and Au-Cu-Ag mineralization at Summitville, Colorado: Economic Geology, v. 82, p. 1575- 1591, ‘Stokes, N.H., 1906, Experiments on the solution, transportation and deposition of eopper, silver and gold: Economic Geology, v.1, p.644-660. 1907, Experiments on the action of various solutions on pyrite and marcasite, Economie Geology, ¥-2, p.14-23. Sullivan, E.C., 1905, The chemistry of ore deposition - precipitation of copper by natural silicates: Economic Geology, v. 1, p.67-73. Titley, S.R., and Marozas, D.C., 1995, Processes and products of supergene copper enrichment, in, Pierce, F.W., and Bolm, J.G., eds., Porphyry Copper Deposits of the American Cordillera: Tucson, Arizona Geological Society Digest 20, p.156-168. Titley, S.R., 1978, Geologic history, hypogene features, and processes of secondary sulfide enrichment at the Plesyumi copper prospect, New Britain, papua New Guinea: Economie Geology, v. 73, p. 768 784 Tunell, George, 1930, The oxidation of disseminated copper ores in altered porphyry: Cambridge, Harvard University, Unpub. Ph.D. dissertation, 106p. Tunell, George, and Posnjak, E.W., 1931, A portion of the system, ferric oxide-cupric oxide-sulfur ttioxide-water: Journal of Physical Chemistry, v.35, p.929-946. ‘Tunell, George, and Posnjak, E.W., 1931, The stability relations of goethite and hematite: Economic Geology, v.26, p.337-343; 894.898. Van Hise, C.R., 1900, Some principles controlling the deposition of ores; American Institute of Engineers Transactions, v.30, p.27-177. Weed, W.H., 1900, Enrichment of metallic veins by leter metalic sulfides: Geological Society of America Bulletin, v.11, p.179-206, Weiss, Richard L., 1965, Outcrops as euides to copper ore - four examples: New York, Columbia University, unpub. Ph.D. Diss., 184p. White, Charles H., 1924, Prospecting for disseminated copper by a study of leached cappings: Engineering and Mining Journal, v.117, p.483-488. Whitney, J.D., 1855, Remarks on the changes which take place in the structure and composition of ‘mineral veins near the surface with particular reference to the East Tennessee Copper Mines: American Journal of Science, v.20, p.53-57. Winchell, A.N., 1907, The oxidation of pyrite: Economic Geology, v.2 p.290-294. Zies, B.G., Allen, E.T., and Merwin, H.E., 1916, Some reactions involved in secondary copper sulfide enrichment: Economic Geology, v.11, p.407-503.