Use of Cu isotopes to distinguish primary and secondary Cu mineralization in the Ca?ariaco Norte porphyry copper deposit, Northern Peru

A significant proportion of the copper in the Ca?ariaco Norte porphyry copper deposit in northern Peru occurs in chalcocite and covellite-rich veins and disseminations that exist from the surface to depths greater than 1?km. The overall range of Cu isotopic ratios of 42 mineral separates from Ca?ariaco varies from ?8.42 to 0.61?‰, with near-surface chalcocite and Fe oxides having isotopically depleted values compared to chalcocite, covellite, and chalcopyrite from deeper levels. The majority (34 of 36) of measured Cu sulfides have a typical hypogene copper isotope composition of δ⁶⁵Cu?=?0.18?±?0.38?‰, with no enriched isotopic signature existing in the Ca?ariaco Norte sulfide data. Thus, the copper isotope data indicate that most of the chalcocite and covellite formed from high-temperature hypogene mineralization processes and that only a minor portion of the deposit is enriched by supergene processes. The nonexistence of an enriched δ⁶⁵Cu reservoir suggest the presence of an undiscovered lateral/exotic Cu occurrence that enriched ⁶⁵Cu that remained in solution during weathering. Regardless of the cause, the comparative analysis of the Cu isotope dataset reveals that little exploration potential for an extensive supergene enrichment blanket exists because the weathering history at Ca?ariaco Norte was not conducive to preservation of enriched Cu at depth beneath the leach cap.     

Pleistocene recycling of copper at a porphyry system,Atacama Desert,Chile: Cu isotope evidence

We present Cu isotope data of hypogene and supergene minerals from the Late Paleocene Spence Cu-Mo porphyry in the Atacama Desert of northern Chile. Chalcopyrite displays a restricted range of δ⁶⁵Cu values within the values reported for primary porphyry Cu sulfides (+ 0.28‰ to + 0.34‰, n = 6). Supergene chalcocite samples show heavier and remarkably homogeneous δ⁶⁵Cu values, between + 3.91‰ and + 3.95‰ (n = 6), consistent with previous models of Cu leaching and enrichment in porphyry systems. Secondary Cu minerals from the oxide zone show a wider range of composition, varying from + 1.28‰ and + 1.37‰ for chrysocolla (n = 6) to very light Cu isotope signatures reported for atacamite between -5.72‰ to -6.77‰ (n = 17). These data suggest redox cycling of Cu during supergene enrichment of the Spence Cu deposit, characterized by a first stage of supergene chalcocite formation from acidic, isotopically-heavy leach fluids of meteoric origin down-flowing in a semi-arid climate (44 to ~ 15-9 Ma). Reworking of the initial supergene copper assemblage, during the Pleistocene, by rising neutral and chlorine-rich deep formation waters under well-established hyper-arid climate conditions lead to the formation of atacamite with extremely fractionated Cu compositions. Essentially coeval chrysocolla formed by dissolution of atacamite during short episodes of wetter climatic conditions occurring in the latest Pleistocene.     

Remobilisation features and structural control on ore grade distribution at the Konkola stratiform Cu–Co ore deposit,Zambia

The Konkola deposit is a high grade stratiform Cu–Co ore deposit in the Central African Copperbelt in Zambia. Economic mineralisation is confined to the Ore Shale formation, part of the Neoproterozoic metasedimentary rocks of the Katanga Supergroup. Petrographic study reveals that the copper–cobalt ore minerals are disseminated within the host rock, sometimes concentrated along bedding planes, often associated with dolomitic bands or clustered in cemented lenses and in layer-parallel and irregular veins. The hypogene sulphide mineralogy consists predominantly of chalcopyrite, bornite and chalcocite. Based upon relationships with metamorphic biotite, vein sulphides and most of the sulphides in cemented lenses were precipitated during or after biotite zone greenschist facies metamorphism. New δ³⁴S values of sulphides from the Konkola deposit are presented. The sulphur isotope values range from −8.7‰ to +1.4‰ V-CDT for chalcopyrite from all mineralising phases and from −4.4‰ to +2.0‰ V-CDT for secondary chalcocite. Similarities in δ³⁴S for sulphides from different vein generations, earlier sulphides and secondary chalcocite can be explained by (re)mobilisation of S from earlier formed sulphide phases, an interpretation strongly supported by the petrographic evidence. Deep supergene enrichment and leaching occurs up to a km in depth, predominantly in the form of secondary chalcocite, goethite and malachite and is often associated with zones of high permeability. Detailed distribution maps of total copper and total cobalt contents of the Ore Shale formation show a close relationship between structural features and higher copper and lower cobalt contents, relative to other areas of the mine. Structural features include the Kirilabombwe anticline and fault zones along the axial plane and two fault zones in the southern limb of the anticline. Cobalt and copper behave differently in relation to these structural features. These structures are interpreted to have played a significant role in (re)mobilisation and concentration of the metals, in agreement with observations made elsewhere in the Zambian Copperbelt.     

Source,transport, and fate of rhenium,selenium, molybdenum,arsenic, and copper in groundwater associated with porphyry–Cu deposits,Atacama Desert,Chile

We collected groundwaters in and around a large (313 Mt at 1.08% Cu and 0.3% cutoff) undisturbed porphyry copper deposit (Spence) in the hyperarid Atacama Desert of northern Chile, which is buried beneath 30–180 m of Miocene piedmont gravels. Groundwaters within and down-flow of the Spence deposit have elevated Se (up to 800 μg/l), Re (up to 31 μg/l), Mo (up to 475 μg/l) and As (up to 278 μg/l) concentrations compared to up-flow waters (interpreted to represent regional groundwater flow). In contrast, Cu is only elevated (up to 2036 μg/l) in groundwaters recovered from within the deposit; Cu concentrations are low down gradient of the deposit. The differential behavior of the metals/metalloids occurs because the former group dissolves as anions, enhancing their mobility, whereas the base metals dissolve as cations and are lost from solution most likely through adsorption to clay surface exchange sites and through formation of secondary copper chlorides, carbonates, and oxides. Most groundwaters within and down-flow of the deposit have Eh–pH values around the Fe^II/Fe^III phase boundary, limiting the impact of Fe-oxyhydroxides on oxyanions mobility. Se, Re, Mo, and As are all mobile (with filtered/unfiltered samples ～ 1) to the limit of sampling 2 km down gradient from the deposit. The increase in ore-related metals, metalloids, and sulfate and decrease in sulfate–S isotope ratios (from values similar to regional salars, + 4 to + 8‰ δ³⁴S_CDT to lower values closer to hypogene sulfides, + 1 to + 4‰ δ³⁴S_CDT) is consistent with active water–rock reactions between saline groundwaters and the Spence deposit. It is likely that hypogene and/or supergene sulfides are being oxidized under the present groundwater conditions and mineral saturation calculations suggest that secondary copper minerals (antlerite, atacamite, malachite) may also be actively forming, suggesting that supergene and exotic copper mineralization is possible even under the present hyperarid climate of the Atacama Desert.     

Lithogeochemistry of hypogene, supergene and leached cap samples, berg porphyry copper deposit, British Columbia

In this paper we examine the influence of the development of supergene oxide and sulphide zones on the original hypogene geochemical patterns at the Berg deposit, British Columbia.The deposit, in the alpine zone of the Tahtsa Range, was logged (GEOLOG) and sampled in fourteen diamond drill holes along a N—S section and from outcrop where possible. Anomalous populations of major and trace elements were defined using log probability graphs and a sequential extraction (10% hydrochloric acid— ammonium oxalate — potassium chlorate/hydrochloric acid — nitric/perchloric acids) was used to study the distribution of elements between carbonate, oxide, sulphide and silicate phases.Core logs and assays show that primary ore minerals (chalcopyrite—molybdenite) extend from the outer part of the porphyry intrusion into the surrounding hornfels where the best grades of copper are found close to the intrusive contact. Maximum copper grades, however, result from development of a supergene enrichment blanket. Within the hypogene zone, principal lithogeochemical patterns reflect the differences in composition of the hornfels, originally intermediate to basic volcanics, and the intrusion, as well as the introduction of F and trace metals (Cu, Mo, Pb, Zn and Ag). Distribution of Ag is broadly comparable to that of Cu and Mo whereas anomalous Pb and Zn are present as peripheral haloes around the potential ore zones.Emergence of strongly acidic ground water and precipitation of iron oxides, indicate that leaching processes are active. Furthermore, although primary sulphides, associated with both their oxidation products and secondary sulphides, can still be found in surface samples, sequential extractions on drill core clearly indicate vertical redistribution of copper between oxide, carbonate and sulphide phases. Using ratios of metal concentrations to TiO₂, the surface concentrations of trace metals can be compared with those at depth and the relative amount of enrichment or depletion can be quantified. In highly leached sites the absolute concentrations of Cu, Mn and Zn are low which is reflected in TiO₂ ratios of <1. However, Mo, Pb and Ag are enriched at the same sites (TiO₂ ratios >1). In areas where physical erosion exceeds leaching (topographic lows) primary sulphides co-exist with secondary sulphide and oxide minerals. Here Cu, Mo, Pb, Zn, Mn and Ag are enriched. Fluorine is relatively unaffected by the leaching process. It would appear signature for a cale alkaline Cu and Mo porphyry deposit in an area where outcrop was intensely leached.     

Copper isotopic compositions of the Zijinshan high-sulfidation epithermal Cu–Au deposit,South China: Implications for deposit origin

The Zijinshan high-sulfidation epithermal Cu–Au deposit is located in the Zijinshan ore field of South China, comprising porphyry–epithermal Cu–Au–Mo–Ag ore systems. The Cu ore body is more than 1000 m thick and is characterized by an assemblage of digenite–covellite–enargite–alunite. Digenite is the dominant Cu-bearing mineral, which makes this deposit unique, although the mechanisms of digenite formation remain controversial. To elucidate the genesis of digenite, this paper presents the Cu isotopic compositions of Cu-sulfides in the Zijinshan high-sulfidation Cu–Au deposit. The Cu isotopic values (⁶⁵Cu relative to NIST 976) of all samples range from −2.97‰ to +0.34‰, and most values fall in a narrow range from −0.49‰ to +0.34‰, which is similar to the Cu isotopic signature of typical porphyry systems. Copper isotope ratios of each mineral decrease with increasing depth, a trend that is also typical of porphyry deposits. The variation tendency of δ⁶⁵Cu values between sulfides is consistent with the sequence of mineral formation. These observations suggest that the Cu-sulfides in the Zijinshan Cu–Au deposit have a hypogene origin.     

Unique Origin of Skarn at the Ohori Base Metal Deposit,Yamagata Prefecture,NE Japan: C,O and S Isotopic Study

The Ohori ore deposit is one of the Cu–Pb–Zn deposits in the Green Tuff region, NE Japan, and consists of skarn‐type (Kaninomata) and vein‐type (Nakanomata) orebodies. The former has a unique origin because its original calcareous rocks were made by hydrothermal precipitation during Miocene submarine volcanism. Carbon and oxygen isotope ratios of skarn calcite and sulfur isotope ratios of sulfides were measured in and around the deposit. Carbon and oxygen isotope ratios of the skarn calcite are δ¹³C = ?15.51 to ?5.1‰, δ¹⁸O = +3.6 to +22.5‰. δ¹³C values are slightly lower than those of the Cretaceous skarn deposits in Japan. These isotope ratios of the Kaninomata skarn show that the original calcareous rocks resemble the present submarine hydrothermal carbonates at the CLAM Site, Okinawa Trough, than Cenozoic limestones, even though some isotopic shifts had occurred during later skarnization. δ³⁴S ratios of the sulfide minerals from the Kaninomata and Nakanomata orebodies are mostly in a narrow range of +4.0 to +7.0‰ and they resemble each other, suggesting the same sulfur origin for the both deposits. The magnetite‐series Tertiary Kaninomatasawa granite is distributed just beneath the skarn layer and has δ³⁴S ratios of +7.5 to 8.1‰. The heavy sulfur isotope ratio of the skarn sulfides may have been affected by the Kaninomatasawa granite.     

Genesis of the Au–Bi–Cu–As, Cu–Mo ± W, and base–metal Au–Ag mineralization at the Mountain Freegold (Yukon, Canada): constraints from Ar–Ar and Re–Os geochronology and Pb and stable isotope compositions

The genesis of mineralized systems across the Mountain Freegold area, in the Dawson Range Cu–Au?±?Mo Belt of the Tintina Au province was constrained using Pb and stable isotope compositions and Ar–Ar and Re–Os geochronology. Pb isotope compositions of sulfides span a wide compositional range (²⁰⁶Pb/²⁰⁴Pb, 18.669–19.861; ²⁰⁸Pb/²⁰⁴Pb, 38.400–39.238) that overlaps the compositions of the spatially associated igneous rocks, thus indicating a magmatic origin for Pb and probably the other metals. Sulfur isotopic compositions of sulfide minerals are broadly similar and their δ³⁴S (Vienna-Canyon Diablo Troilite (V-CDT)) values range from ?1.4 to 3.6 ‰ consistent with the magmatic range, with the exception of stibnite from a Au–Sb–quartz vein, which has δ³⁴S values between ?8.1 and ?3.1 ‰. The δ³⁴S values of sulfates coexisting with sulfide are between 11.2 and 14.2 ‰; whereas, those from the weathering zone range from 3.7 to 4.3 ‰, indicating supergene sulfates derived from oxidation of hypogene sulfides. The δ¹³C (Vienna Peedee Belemnite (VPDB)) values of carbonate range from ?4.9 to 1.1 ‰ and are higher than magmatic values. The δ¹⁸O (V-SMOW) values of magmatic quartz phenocrysts and magmatic least-altered rocks vary between 6.2 and 10.1 ‰ and between 5.0 and 10.1 ‰, respectively, whereas altered magmatic rocks and hydrothermal minerals (quartz and magnetite) are relatively ¹⁸O-depleted (4.2 to 7.9 ‰ and ?6.3 to 1.5 ‰, respectively). Hydrogen isotope compositions of both least-altered and altered igneous rock samples are D-depleted (from ?133 to ?161 ‰ Vienna-Standard Mean Ocean Water (V-SMOW)), consistent with differential magma degassing and/or post-crystallization exchange between the rocks and meteoric ground water. Zircon from a chlorite-altered dike has a U–Pb crystallization age of 108.7?±?0.4 Ma; whereas, the same sample yielded a whole-rock Ar–Ar plateau age of 76.25?±?0.53 Ma. Likewise, molybdenite Re–Os model ages range from 75.8 to 78.2 Ma, indicating the mineralizing events are genetically related to Late Cretaceous volcano-plutonic intrusions in the area. The molybdenite Re–Os ages difference between the nearby Nucleus (75.9?±?0.3 to 76.2?±?0.3 Ma) and Revenue (77.9?±?0.3 to 78.2?±?0.3 Ma) mineral occurrences suggests an episodic mineralized system with two pulses of hydrothermal fluids separated by at least 2 Ma. This, in combination with geological features suggest the Nucleus deposit represents the apical and younger portion of the Revenue–Nucleus magmatic-hydrothermal system and may suggest an evolution from the porphyry to the epithermal environments.     

H-O-S-Cu-Pb Isotopic Constraints on the Origin of the Nage Cu-Pb Deposit, Southeast Guizhou Province, SW China

The Nage Cu-Pb deposit,a new found ore deposit in the southeast Guizhou province,southwest China,is located on the southwestern margin of the Jiangnan Orogenic Belt.Ore bodies are hosted in slate and phyllite of Neoproterozoic Jialu and Wuye Formations,and are structurally controlled by EW-trending fault.It contains Cu and Pb metals about 0.12 million tonnes with grades of 0.2 wt% to 3.4 wt% Cu and 1.1 wt% to 9.27 wt% Pb.Massive and disseminated Cu-Pb ores from the Nage deposit occur as either veinlets or disseminations in silicified rocks.The ore minerals include chalcopyrite,galena and pyrite,and gangue minerals are quartz,sericite and chlorite.The H-O isotopic compositions of quartz,S-Cu-Pb isotopic compositions of sulfide minerals,Pb isotopic compositions of whole rocks and ores have been analyzed to trace the sources of ore-forming fluids and metals for the Nage Cu-Pb deposit.The δ65CuNBS values of chalcopyrite range from-0.09% to +0.33‰,similar to basic igneous rocks and chalcopyrite from magmatic deposits.δ65CuNBS values of chalcopyrite from the early,middle and final mineralization stages show an increasing trend due to63Cu prior migrated in gas phase when fluids exsolution from magma.δ34SCDT values of sulfide minerals range from 2.7‰ to +2.8‰,similar to mantle-derived sulfur(0±3‰).The positive correlation between δ65CuNBS and δ34SCDT values of chalcopyrite indicates that a common source of copper metal and sulfur from magma.δDH2OSMOW and δ18OH2O-SMOW values of water in fluid inclusions of quartz range from 60.7‰ to 44.4‰ and +7.9‰ to +9.0‰(T=260°C),respectively and fall in the field for magmatic and metamorphic waters,implicating that mixed sources for H2O in hydrothermal fluids.Ores and sulfide minerals have a small range of Pb isotopic compositions(208Pb/204Pb=38.152 to 38.384,207Pb/204Pb=15.656 to 17.708 and 206Pb/204Pb=17.991 to 18.049) that are close to orogenic belt and upper crust Pb evolution curve,and similar to Neoproterozoic host rocks(208Pb/204Pb=38.201 to 38.6373,207Pb/204Pb=15.648 to 15.673 and 206Pb/204Pb=17.820 to 18.258),but higher than diabase(208Pb/204Pb=37.830 to 38.012,207Pb/204Pb=15.620 to 15.635 and206Pb/204Pb=17.808 to 17.902).These results imply that the Pb metal originated mainly from host rocks.The H-O-S-Cu-Pb isotopes tegather with geology,indicating that the ore genesis of the Nage Cu-Pb deposit is post-magmatic hydrothermal type.     

Variation of copper isotopes in chalcopyrite from Dabu porphyry Cu-Mo deposit in Tibet and implications for mineral exploration

The study presents copper (Cu) isotope data of mineral separates of chalcopyrite from four drill core samples in the Miocene Dabu porphyry Cu-Mo deposit formed in a post-collisional setting in the Gangdese porphyry copper belt, southern Tibet. Copper isotope values in hypogene chalcopyrite range from –1.48‰ to +1.12‰, displaying a large variation of up to 2.60‰, which demonstrates Cu isotope fractionation at high-temperature during hydrothermal evolution. The majority of measured chalcopyrite isotopic compositions show a gradual increasing trend from –1.48‰ to +1.12‰ with the increase of drilling depth from 130m to 483m, as the alteration assemblages change from potassic to phyllic. Similarly, the other δ⁶⁵Cu values (δ⁶⁵Cu = ((⁶⁵Cu/⁶³Cu)_sample/(⁶⁵Cu/⁶³Cu)_standard − 1) × 1000) of the chalcopyrite show a gradual increasing trend from −1.48‰ to +0.59‰ with the decrease of drilling depth from 130 m to 57 m, as the alteration assemblages change from potassic, phyllic, through argillic to relatively fresh. These observations suggest a genetic link between Cu isotope variation and silicate alteration assemblages formed at different temperatures, indicative of a Rayleigh precipitation process resulting in the large variation of δ⁶⁵Cu values at Dabu. In general, samples closest to the center of hydrothermal system dominated by high-temperature potassic alteration are isotopically lighter, whereas samples dominated by low-temperature phyllic alteration peripheral to the center are isotopically heavier. The predicted flow pathways of hydrothermal fluids are from No. 0 to No. 3 exploration line, and the lightest δ⁶⁵Cu values are the most proximal to the hydrothermal source. Finally, we propose that the northwest side of the No. 0 exploration line has high potential for hosting undiscovered orebodies. The pattern of Cu isotope variation in conjunction with the features of silicate alteration in porphyry system can be used to trace the hydrothermal flow direction and to guide mineral exploration.     

The geochemistry of gossans associated with Sarcheshmeh porphyry copper deposit,Rafsanjan, Kerman,Iran: Implications for exploration and the environment

The Sarcheshmeh copper deposit is one of the world's largest Oligo-Miocene porphyry copper deposits in a continental arc setting with a well developed supergene sulfide zone, covered mainly by a hematitic gossan. Supergene oxidation and leaching, have developed a chalcocite enrichment blanket averaging 1.99% Cu, more than twice that of hypogene zone (0.89% Cu). The mature gossans overlying the Sarcheshmeh porphyry copper ores contain abundant hematite with variable amounts of goethite and jarosite, whereas immature gossans consist of iron-oxides, malachite, azurite and chrysocolla. In mature gossans, Au, Mo and Ag give significant anomalies much higher than the background concentrations. However, Cu has been leached in mature gossans and gives values close or even less than the normal or crustal content (< 36.7 ppm). Immature gossans are enriched in Cu (160.3 ppm), Zn (826.7 ppm), and Pb (88.6 ppm). Jarosite- and goethite-bearing gossans may have developed over the pyritic shell of most Iranian porphyry copper deposits with pyrite–chalcopyrite ratios greater than 10 and therefore, do not necessarily indicate a promising sulfide-enriched ore (Kader and Ijo). Hematite-bearing gossans overlying nonreactive alteration halos with pyrite–chalcopyrite ratios about 1.5 and quartz stringers have significant supergene sulfide ores (Sarcheshmeh and Miduk). The copper grade in supergene sulfide zone of Sarcheshmeh copper deposit ranges from 0.78% in propylitized rocks to 3.4% in sericitized volcanic rocks, corresponding to the increasing chalcopyrite–pyrite or chalcocite–pyrite ratios from 0.3 to 3, respectively. Immature gossans with dominant malachite and chrysocolla associated with jarosite and goethite give the most weakly developed enrichment zone, as at God-e-Kolvari. The average anomalous values of Au (59.6 ppb), Mo (42.5 ppm) and Ag (2.6 ppm) in mature gossans associated with the Sarcheshmeh copper mine may be a criterion that provides a significant exploration target for regional metallogenic blind porphyry ore districts in central Iranian volcano–plutonic continental arc settings. Drilling for new porphyry ores should be targeted where hematitic gossans are well developed. The ongoing gossan formation may result in natural acidic rock drainage (ARD).     

西藏甲玛铜多金属矿硫同位素地球化学研究

西藏墨竹工卡县甲玛铜多金属矿床位于冈底斯成矿带东段,Cu、Mo、Pb+Zn、Au、Ag均达大型规模,并伴生Co、Bi、W、Ni等多金属矿化。黄铜矿、斑铜矿、辉钼矿、方铅矿、闪锌矿、黝铜矿、辉铜矿等硫化物为主要的矿石矿物,硫酸盐矿物以硬石膏为主,含矿岩浆岩以花岗斑岩、二长花岗斑岩和花岗闪长斑岩为主。通过对甲玛矿区主要硫化物和硬石膏的硫同位素分析,并结合前人研究,甲玛矿区硫化物的硫同位素δ34S值变化于13.6‰～+12.5‰,平均值1.33‰(样品数86)、硬石膏δ34S值+0.5‰～+1.8‰,平均值+1.13‰(样品数3)、岩浆岩δ34S值0.7‰～0.2‰,平均值0.5‰(样品数3),与岩浆硫δ34S值0±3‰一致。闪锌矿-方铅矿-黄铜矿矿物对的硫同位素地质温度计,显示成矿温度为408～433℃,说明其形成时硫同位素处于平衡状态。冈底斯成矿带上的驱龙等斑岩型矿床中硫化物和岩浆岩硫同位素,均具有δ34S值变化范围小,平均值接近0值,与岩浆硫特征一致的特点,反映了甲玛铜多金属矿床具有矽卡岩-斑岩型矿床硫同位素地球化学特征,硫以岩浆来源为主。     

Copper isotopes trace the evolution of skarn ores: A case study from the Hongshan-Hongniu Cu deposit,southwest China

Transition metal isotopes are sensitive geochemical tracers of ore genesis. Here we present MC-ICP-MS analytical data of Cu isotope compositions from the Hongshan-Hongniu Cu deposit in Yunnan province. The δ⁶⁵Cu values (δ⁶⁵Cu = [(⁶⁵Cu/⁶³Cu)_sample/(⁶⁵Cu/⁶³Cu)_NIST976 − 1] × 1000) of seven whole-rock quartz monzonite porphyries and twenty-two chalcopyrite samples from the skarn ore-bodies display relatively narrow ranges from −0.15‰ to 0.38‰ and from −0.02‰ to 0.77‰, respectively. The overlap of δ⁶⁵Cu values indicates a genetic relationship between the quartz monzonite porphyry and skarn ore-bodies. We also evaluate the spatial and temporal variations of Cu isotope compositions in the skarn ore-bodies by comparison with some well-documented porphyry deposits in the world. The quartz monzonite porphyry shows compositional zoning with the inner domain enriched in heavy Cu isotope and the skarn related to the porphyry depleted in heavy Cu isotope. The chalcopyrites that formed during the late stage of mineralization tend to be enriched in heavy Cu isotope, and this feature is analogous to porphyry deposits. The δ⁶⁵Cu values of the quartz monzonite porphyry show typical features of hypogene mineralization, suggesting a potential scope for deep exploration and development in this deposit.     

Copper isotopes as monitors of redox processes in hydrothermal mineralization

The stable copper isotope composition of 79 samples of primary and secondary copper minerals from hydrothermal veins in the Schwarzwald mining district, South Germany, shows a wide variation in δ⁶⁵Cu ranging from −2.92 to 2.41‰. We investigated primary chalcopyrite, various kinds of fahlores and emplectite, as well as supergene native copper, malachite, azurite, cuprite, tenorite, olivenite, pseudomalachite and chrysocolla. Fresh primary Cu(I) ores have at most localities copper isotope ratios (δ⁶⁵Cu values) of 0 ± 0.5‰ despite the fact that the samples come from mineralogically different types of deposits covering an area of about 100 by 50 km and that they formed during three different mineralization events spanning the last 300 Ma. Relics of the primary ores in oxidized samples (i.e., chalcopyrite relics in an iron oxide matrix with an outer malachite coating) display low isotope ratios down to −2.92‰. Secondary Cu(I) minerals such as cuprite have high δ⁶⁵Cu values between 0.4 and 1.65‰, whereas secondary Cu(II) minerals such as malachite show a range of values between −1.55 and 2.41‰, but typically have values above +0.5‰. Within single samples, supergene oxidation of fresh chalcopyrite with a δ value of 0‰ causes significant fractionation on the scale of a centimetre between malachite (up to 1.49‰) and relict chalcopyrite (down to −2.92‰). The results show that—with only two notable exceptions—high-temperature hydrothermal processes did not lead to significant and correlatable variations in copper isotope ratios within a large mining district mineralized over a long period of time. Conversely, low-temperature redox processes seriously affect the copper isotope compositions of hydrothermal copper ores. While details of the redox processes are not yet understood, we interpret the range in compositions found in both primary Cu(I) and secondary Cu(II) minerals as a result of two competing controls on the isotope fractionation process: within-fluid control, i.e., the fractionation during the redox process among dissolved species, and fluid-solid control, i.e., fractionation during precipitation involving reactions between dissolved Cu species and minerals. Additionally, Rayleigh fractionation in a closed system may be responsible for some of the spread in isotope compositions. Our study indicates that copper isotope variations may be used to decipher details of natural redox processes and therefore may have some bearing on exploration, evaluation and exploitation of copper deposits. On the other hand, copper isotope analyses of single archeological artefacts or geological or biological objects cannot be easily used as reliable fingerprint for the source of copper, because the variation caused by redox processes within a single deposit is usually much larger than the inter-deposit variation.     

Alteration, zoning model, and mineralogical structure considering lithogeochemical investigation in Northern Dalli Cu–Au porphyry

Dalli Cu–Au porphyry deposit was occurred in the igneous diorite, quartz diorite porphyry (QDP), and volcanic rocks such as porphyritic amphibole andesite, andesite (AND), dacite, and pyroclastics during the late Miocene to Pliocene. Regolith investigations and Advanced Spaceborne Thermal Emission and Reflection Radiometer images were used to identify the anomalous areas. According to lithogeochemical survey (from boreholes and trenches) in Northern Dalli Cu–Au porphyry, the potassic, chlorite, sericite, propylitic, and argillic alterations have been found and mineralization was basically associated with potassic and quartz–sericite alterations. The alteration is dominantly moderate quartz chlorite?±?sericite magnetite with 1–10 mm wide quartz?±?magnetite veinlets. The elevated copper–gold values are correlated with density of stockworking and mineralization. The intensity of the mineralization is high in the contact of QDP and AND with increases in pyrite and chalcopyrite values. Malachite, native Cu, and bornite were used to identify supergene, transition, and hypogene zone. In addition, molybdenum increased near to the center of granodiorite intrusion. And besides, from depth to surface in DDH03 and wall rock to mineralization zones, a sequence of Mo→Cu (Au)→Au (Cu) was recorded and the mineralization temperature cooled down (from high to low). The alteration is characterized by specific pattern and structure in Dalli Cu–Au porphyry deposit. The alteration model was followed from the modified Lowell and Gilbert model. The porphyry is stockworked by quartz veins and by quartz magnetite veins. Vein distribution and ore mineralogy vary between the different alteration zones. Due to the formation of an iron cap in the supergene, especially in the southern hills, supergene grade was higher than hypogene zone. Also, hematite, as a dominant Fe oxide in DDH03 borehole with minor limonite, jarosite, and goethite created thickness about 150–270 m in supergene zone; finally, this finding show a possibility of an extensive mineralization.     

Hydrothermal Alteration and Mineralization of Middle Jurassic Dexing Porphyry Cu-Mo Deposit, Southeast China

The Dexing deposit is located in a NE‐trending magmatic belt along the southeastern margin of the Yangtze Craton. It is the largest porphyry copper deposit in China, consisting of three porphyry copper orebodies of Zhushahong, Tongchang and Fujiawu from northwest to southeast. It contains 1168 Mt of ores with 0.5% Cu and 0.01% Mo. The Dexing deposit is hosted by Middle Jurassic granodiorite porphyries and pelitic schist of Proterozoic age. The Tongchang granodiorite porphyry has a medium K cal‐alkaline series, with medium K₂O content (1.94–2.07 wt%), and low K₂O/(Na₂O + K₂O) (0.33–0.84) ratios. They have high large‐ion lithophile elements, high light rare‐earth elements, and low high‐field‐strength elements. The hydrothermal alteration at Tongchang is divided into four alteration mineral assemblages and related vein systems. They are early K‐feldspar alteration and A vein; transitional (chlorite + illite) alteration and B vein; late phyllic (quartz + muscovite) alteration and D vein; and latest carbonate, sulfate and oxide alteration and hematite veins. Primary fluid inclusions in quartz from phyllic alteration assemblage include liquid‐rich (type 1), vapor‐rich (type 2) and halite‐bearing ones (type 3). These provide trapping pressures of 20–400 ´ 10⁵ Pa of fluids responsible for the formation of D veins. Igneous biotite from least altered granochiorite porphyry and hydrothermal muscovite in mineralized granodiorite porphyry possess δ¹⁸O and δD values of 4.6‰ and ?87‰ for biotite and 7.1–8.9‰, ?71 to ?73‰ for muscovite. Stable isotopic composition of the hydrothermal water suggests a magmatic origin. The carbon and oxygen isotope for hydrothermal calcite are ?4.8 to ?6.2‰ and 6.8–18.8‰, respectively. The δ³⁴S of pyrite in quartz vein ranges from ?0.1 to 3‰, whereas δ³⁴S for chalcopyrite in calcite veins ranges from 4 to 5‰. These are similar to the results of previous studies, and suggest a magmatic origin for sulfur. Results from alteration assemblages and vein system observation, as well as geochemical, fluid inclusion, stable isotope studies indicate that the involvement of hydrothermal fluids exsolved from a crystallizing melt are responsible for the formation of Tongchang porphyry Cu‐Mo orebodies in Dexing porphyry deposit.     

Fluid inclusion and isotope geochemistry of the Yangla copper deposit,Yunnan, China

The Yangla copper deposit, with Cu reserves of 1.2 Mt, is located between a series of thrust faults in the Jinshajiang–Lancangjiang–Nujiang region, Yunnan, China, and has been mined since 2007. Fluid inclusion trapping conditions ranged from 1.32 to 2.10 kbar at 373–409 °C. Laser Raman spectroscopy confirms that the vapour phase in these inclusions consists of CO₂, CH₄, N₂ and H₂O. The gas phases in the inclusions are H₂O and CO₂, with minor amounts of N₂, O₂, CO, CH₄, C₂H₂, C₂H₄, and C₂H₆. Within the liquid phase, the main cations are Ca²⁺ and Na⁺ while the main anions are SO₄ ^2? and Cl^?. The oxygen and hydrogen isotope compositions of the ore-forming fluids (?3.05‰?≤?δ¹⁸O_H2O?≤?2.5‰; ?100‰?≤?δD?≤??120‰) indicate that they were derived from magma and evolved by mixing with local meteoric water. The δ³⁴S values of sulfides range from ?4.20‰ to 1.85‰(average on ?0.85‰), supporting a magmatic origin. Five molybdenite samples taken from the copper deposit yield a well-constrained ¹⁸⁷Re–¹⁸⁷Os isochron age of 232.8?±?2.4 Ma. Given that the Yangla granodiorite formed between 235.6?±?1.2 Ma and 234.1?±?1.2 Ma, the Cu metallogenesis is slightly younger than the crystallization age of the parent magma. A tectonic model that combines hydrothermal fluid flow and isotope compositions is proposed to explain the formation of the Yangla copper deposit. At first, westward subduction of the Jinshajiang Oceanic Plate in the Early Permian resulted in the development of a series of thrust faults. This was accompanied by fractional melting beneath the overriding plate, triggering magma ascent and extensive volcanism. The thrust faults, which were then placed under tension during a change in tectonic mode from compression to extension in the Late Triassic, formed favorable pathways for the magmatic ore-forming fluids. These fluids precipitated copper-sulfides to form the Yangla deposit.     

Cu isotopic fractionation in the supergene environment with and without bacteria

The isotopic composition of dissolved Cu and solid Cu-rich minerals [δ⁶⁵Cu (‰) = (⁶⁵Cu/⁶³Cu_sample/⁶⁵Cu/⁶³Cu_std) - 1)*1000] were monitored in batch oxidative dissolution experiments with and without Thiobacillus ferrooxidans. Aqueous copper in leach fluids released during abiotic oxidation of both chalcocite and chalcopyrite was isotopically heavier (δ⁶⁵Cu = 5.34‰ and δ⁶⁵Cu = 1.90‰, respectively, [±0.16 at 2σ]) than the initial starting material (δ⁶⁵Cu = 2.60 ± 0.16‰ and δ⁶⁵Cu = 0.58 ± 0.16‰, respectively). Isotopic mass balance between the starting material, aqueous copper, and secondary minerals precipitated in these experiments explains the heavier isotopic values of aqueous copper. In contrast, aqueous copper from leached chalcocite and chalcopyrite inoculated with Thiobacillus ferrooxidans was isotopically similar to the starting material. The lack of fractionation of the aqueous copper in the biotic experiments can best be explained by assuming a sink for isotopically heavy copper present in the bacteria cells with δ⁶⁵Cu = 5.59 ± 0.16‰. Consistent with this inference, amorphous Cu-Fe oxide minerals are observed surrounding cell membranes of Thiobacillus grown in the presence of dissolved Cu and Fe.Extrapolating these experiments to natural supergene environments implies that release of isotopically heavy aqueous Cu from oxidative leach caps, especially under abiotic conditions, should result in precipitates in underlying enrichment blankets that are isotopically heavy. Where iron-oxidizing cells are involved, isotopically heavy oxidized Cu entrained in cellular material may become associated with leach caps, causing the released aqueous Cu to be less isotopically enriched in the heavy isotope than predicted for the abiotic system. Rayleigh fractionation trends with fractionation factors calculated from our experiments for both biotic and abiotic conditions are consistent with large numbers of individual abiotic or biotic leaching events, explaining the supergene chalcocites in the Morenci and Silver Bell porphyry copper deposits.     

Geology and geochemistry of the sediment-hosted Cheshmeh-Konan redbed-type copper deposit,NW Iran

The several-hundred-m-thick Miocene Upper Red Formation in northwestern Iran hosts stratiform and fault-controlled copper mineralization. Copper enrichment in the percent range occurs in dm-thick carbonaceous sandstone and shale units within the clastic redbed sequence and consists of fine-grained disseminated copper sulfides (chalcopyrite, bornite, chalcocite) and supergene alteration minerals (covellite, malachite and azurite). The copper mineralization formed after calcite cementation of the primary rock permeability. Copper sulfides occur mainly as replacement of diagenetic pyrite, which, in turn, replaced organic matter. Electron microprobe analysis on bornite, chalcocite and covellite identifies elevated silver contents in these minerals (up to 0.12, 0.72 and 1.21 wt%, respectively), whereas chalcopyrite and pyrite have only trace amounts of silver (<0.26 and 0.06 wt%, respectively). Microthermometric data on fluid inclusions in authigenic quartz and calcite indicate that the Cu mineralization is related to a diagenetic fluid of moderate-to low temperature (Th = 96–160 °C) but high salinity (25–38 wt% CaCl₂ equiv.). The range of δ³⁴S in pyrite is −41.9 to −16.4‰ (average −31.4‰), where framboidal pyrite shows the most negative values between −41.9 and −31.8‰, and fine-grained pyrite has relatively heavier δ³⁴S values (−29.2 to −16.4‰), consistent with a bacteriogenic derivation of the sulfur. The Cu-sulfides (chalcopyrite, bornite and chalcocite) show slightly heavier values from −14.6 to −9.0‰, and their sulfur sources may be both the precursor pyrite-S and the bacterial reduction of sulfate-bearing basinal brines. Carbonates related to the ore stage show isotopically light values of δ¹³C_V-PDB from −8.2 to −5.1‰ and δ¹⁸O_V-PDB from −10.3 to −7.2‰, indicating a mixed source of oxidation of organic carbon (ca. −20‰) and HCO₃⁻ from seawater/porewater (ca. 0‰). The copper mineralization is mainly controlled by organic matter content and paleopermeability (intragranular space to large fracture patterns), enhanced by feldspar and calcite dissolution. The Cheshmeh-Konan deposit can be classified as a redbed-type sediment-hosted stratiform copper (SSC) deposit.     

江西德兴铜厂铜矿水－岩体系氢氧同位素演化

 江西铜厂铜矿床露天采场岩石76个全岩氧同位素组成表明,该超大型铜矿的形成与具有5个水-岩交换成矿体系汇集在一起有关。水-岩体系计算表明,成矿流体储库形成是大气降水与千枚岩和花岗闪长斑岩在300℃以及W/R比值为0.5左右条件下形成,而后上升进入矿化沉积体系时温度降低,W/R比值超过10.0,计算的最少水量达1.9×10¹⁰t以上。