“Invisible” silver and gold in supergene digenite (Cu1.8S)

Despite its potential economic and environmental importance, the study of trace metals in supergene (secondary) Cu-sulfides has been seriously overlooked in the past decades. In this study, the concentration and mineralogical form of “invisible” precious metals (Ag, Au) and metalloids (As, Sb, Se, Te) in supergene digenite (Cu_1.8S) from various Cu deposits in the Atacama Desert of northern Chile, the world’s premier Cu province, were determined in detail using a combination of microanalytical techniques. Secondary ion mass spectrometry (SIMS) and electron microprobe analyzer (EMPA) measurements reveal that, apart from hosting up to ∼11,000 ppm Ag, supergene digenite can incorporate up to part-per-million contents of Au (∼6 ppm) and associated metalloids such as As (∼300 ppm), Sb (∼60 ppm), Se (∼96 ppm) and Te (∼18 ppm). SIMS analyses of trace metals show that Ag and Au concentrations strongly correlate with As in supergene digenite, defining wedge-shaped zones in Ag-As and Au-As log-log spaces. SIMS depth profiling and high-resolution transmission electron microscopy (HRTEM) observations reveal that samples with anomalously high Ag/As (>∼30) and Au/As (>∼0.03) ratios plot above the wedge zones and contain nanoparticles of metallic Ag and Au, while samples with lower ratios contain Ag and Au that is structurally bound to the Cu-sulfide matrix. The Ag-Au-As relations reported in this study strongly suggest that the incorporation of precious metals in Cu-sulfides formed under supergene, low-temperature conditions respond to the incorporation of a minor component, in this case As. Therefore, As might play a significant role by increasing the solubility of Ag and Au in supergene digenite and controlling the formation and occurrence of Ag and Au nanoparticles. Considering the fact that processes of supergene enrichment in Cu deposits can be active from tens of millions of years (e.g. Atacama Desert), we conclude that supergene digenite may play a previously unforeseen role in scavenging precious metals from undersaturated (or locally slightly supersaturated) solutions in near-surface environments.     

Aggregation and Differentiation of Gold and Silver during the Formation of the Gold-Bearing Weathering Crusts (on the Example of Kazakhstan Deposits)

The supergene Au in weathering crusts of both the Suzdal and Raygorodok deposits is characterized by enhanced fineness, grain size, crystallinity, and the appearance of botryoidal aggregates of crystals. In the weathering crust of the Suzdal deposit, the exogenous Au is associated primarily with scorodite and carbonates; for Raygorodok, with chalcocite, bornite, hydrocarbonates and Cu hydrosulfates. The difference in the mineral associations of supergene Au at the deposits is determined by the occurrence of various mineral concentrators of Au in the primary endogenous substrate: arsenopyrite and pyrite at the Suzdal deposit and chalcopyrite with pyrite at the Raygorodok deposit. Due to the much greater mobility of Ag in the supergene zone, the weathering crusts are likely to contain submicron microinclusions of Ag minerals beyond the zones of Au concentration.     

Behaviour of Tl relative to K,Rb, Sr and Ba in mineralized and unmineralized metavolcanics from the Dir area,northern Pakistan

Copper mineralization in the Dir area of northern Pakistan is confined to the quartz veins and associated with hydrothermally altered metavolcanics. Chalcopyrite is the main copper-bearing phase with subordinate amounts of bornite, chalcocite, covellite, malachite and azurite. Both mineralized quartz veins and associated unmineralized (least altered) and mineralized (strongly altered) metavolcanics have been analyzed for Cu, Au, Ag, Tl, K, Rb, Ba and Sr. An increase of Cu, Au, Ag, Rb/Sr and Tl/Sr, and a decrease of Sr and K/Rb is observed in both mineralized metavolcanics and mineralized quartz veins. Thallium shows lithophile behaviour in the Dir metavolcanics and no chalcophile behaviour was observed. The Tl/Sr ratio might be an indirect guide for the exploration of volcanic-hosted hydrothermal copper deposits.     

Indium Mineralization in Copper–Tin Stratiform Skarn Ores at the Saishitang–Rilonggou Ore Field,Qinghai, Northwest China

The Saishitang–Rilonggou Ore Field (SROF), which includes the Saishitang, Tongyugou, and Rilonggou ore deposits as well as other scattered occurrences, is located in the Elashan region in Qinghai Province, and is a significant Cu–Sn ore field in NW China. These ores are hosted in stratiform skarn deposits with the main metals being Cu and Sn, as well as Zn, Pb, Au, Ag, and trace elements (e.g. Ga, Ge, Se, and In). Bulk‐rock geochemical analyses of 50 ore samples from the three deposits show that In contents in the Saishitang deposit range from 0.03 to 39 ppm (average 12.7 ppm, n = 19), with 1000 In/Zn values that vary from >0.01 to 29.83 (average 4.29). Indium contents in the Tongyugou deposit vary from 7.51 to 131 ppm (average 28.37 ppm, n = 13), with 1000 In/Zn values from 0.74 to 48 (average 17.55). Finally, indium contents in the Rilonggou deposit vary from 0.73 to 120 ppm (average 36.15 ppm, n = 18), with 1000 In/Zn values from 0.33 to 47 (average 8.52). Indium is hosted mainly in sphalerite, while some other In‐bearing minerals (e.g., roquesite, stannoidite, and stannite) are present locally within the ore field. Roquesite, which replace or fill bornite, occurs in bornite‐rich ores in the Saishitang deposit. This is the first reported Chinese locality of roquesite. Based on previously reported Zn resources, a total of 136 tons of In is calculated to be hosted in the SROF, with 30, 66, and 40 tons of In attributed to the Saishitang, Tongyugou, and Rilonggou deposits, respectively. The differences in indium contents among the deposits and their respective geological histories and characteristics suggest that the origin of indium relates to volcanogenic metallogenesis in an early Permian volcano‐sedimentary basin. Based on the evaluation of In resources, future mining operations should include the recovery of indium in the Tongyugou and Rilonggou deposits.     

Distribution of noble metals in ore mineral assemblages of the Volkovsky gabbroic pluton, central Urals

Relationships between noble-metal and oxide-sulfide mineralization during the origin of the Volkovsky gabbroic pluton are discussed on the basis of geochemical data and thermodynamic calculations. The basaltic magma initially enriched in noble metals (NM) relative to their average contents in mafic rocks, except for Pt, is considered to be a source of Pd, Pt, Au, and Ag in the gabbroic rocks of the Volkovsky pluton. The ores were formed with a progressive gain of NM in the minerals during the fractionation of the basaltic magma. The active segregation of NM in the form of individual minerals (palladium tellurides and native gold) hosted in titanomagnetite and copper sulfide ore occurred during the final stage of gabbro crystallization, when the residual fluid-bearing melt acquired high concentrations of Cu, Fe, Ti, and V, along with volatile P and S. Copper sulfides—bornite and chalcopyrite—are the major minerals concentrating NM; they contain as much as 22.65–25.20 ppm Pd and 0.74–1.56 ppm Pt; 4.39–8.0 ppm Au, and 127.2–142.6 ppm Ag, respectively. The copper ore and associated NM mineralization were formed at a relatively low sulfur fugacity, which was a few orders of magnitude (attaining 5 log units) lower than that of the pyrite-pyrrhotite equilibrium. The low sulfur fugacity and the close chemical affinity of Pd and Pt to Te precluded the formation of pyrrhotite, pyrite, and PGE disulfides. The major ore minerals and NM mineralization were formed within a wide temperature range (800–570°C), under nearly equilibrium conditions. Foreign elements (Ni, Co, and Fe) affected the thermodynamic stability of Pd and Pt compounds owing to the difference in their affinity to Te and to elements of the sulfur group (S, Se, and As). The replacement of Pd with Ni and Co and, to a lesser extent, with Pt and the replacement of Te with S, As, and Se diminish the stability field of palladium telluride. Comparison of Pd tellurides from copper sulfide ores at the Volkovsky and Baronsky deposits showed the enrichment of the former in Au, Sb, and Bi, while the latter are enriched in Pt, Ni, and Ag. The enrichment of Pd tellurides at the Baronsky deposit in Ni is correlated with the analogous enrichment of the host gabbroic rocks.     

Geology, Ar-Ar Age and Mineral Assemblage of Eocene Skarn Cu-Au±Mo Deposits in the Southeastern Gangdese Arc, Southern Tibet: Implications for Deep Exploration

Abstract. Medium‐ and large‐scaled skarn Cu‐Au±Mo deposits, e.g. Kelu, Liebu, Chongmuda and Chenba among others, are distributed in Shannan area of the Gangdese Cu‐Au metallogenic belt. Intrusions‐related skarn copper mineralization belongs to high K and calc‐alkaline rock series, located in late collision volcano‐magmatic arc and formed between 20 to 30 Ma. Copper mineralization occurs at exocontact zone of the lower Cretaceous Bima Group carbonate and other calcareous‐bearing sedimentary rocks with intrusions. At present, three main mineralization types are identified, including skarn type, hydrothermal vein type and porphyry type. Mineralizing associations are Cu‐Mo, Cu‐Au and Cu. In ore districts, those mineralization types form an entire porphyry‐skarn Cu‐Au±Mo ore‐forming system. Alterations of the exocontact are mainly skarnization and hornfelsization, while the alterations of the endocontact are mainly sericitization, silicification, and chloritization of intrusion. In the study area, the endoskarn is not well developed. Copper mineralization occurs mainly in the exocontact in the form of stratoid, lenticular and pockety ore body. Veined mineralization can be seen in marblized and hornfelsed siltstone, being away from the contact zone. In the endocontact, the mineralization is mainly veinlet‐like and disseminated. In Shannan area, skarnization can be divided into early skarnization stage and late hydrous silicate stage. The early skarnization stage is featured by mainly andradite and grossular skarn, containing minor diopside, hedenbergite, magnetite and some copper minerals; and the late hydrous silicate stage is of replacement of garnet skarn by chlorite, epidote, quartz and calcite together with sulfides precipitation. The latter is the main stage of copper mineralization. Bornite is the dominant ore mineral associated with minor chalcopyrite and pyrite; and gold as well as silver are distributed in bornite and wittichenite. Results of microthermometry study of fluid inclusions in quartz of late hydrous silicate stage from different deposits show intermediate temperature and low to intermediate‐salinity features for all samples. The dominant inclusion type is composed of two phases, being about 4 to 15 % vapor and 85 to 96 % liquid at room temperature. Homogenization temperatures range from 232 to 335d?C. Salinities have been recorded between 4.2 and 15.5 wt% NaCl equivalent. Boiling fluid inclusions are not identified and it indicates that metal deposition mainly resulted from water‐rock reactions. The results of sulfur isotope analysis indicate that the sulfur isotope values (δ³⁴S 1.29–1.68 %o) of the samples collected from skarns are similar with that from the endocontact (δ³⁴S 1–1.75 %o). Both of them have very close sulfur isotope values (near δ³⁴S 0 %o), which indicate the sulfur of both the skarn type and the porphyry type mineralization was from deep sources. Ages determined on biotite from ore‐bearing intermediate porphyries by Ar‐Ar methods range from 23.77±0.29 to 29.88±0.56 Ma, showing that skarn copper mineralization in the study area evidently is older than the porphyry Cu(‐Mo) mineralization in Gangdese, and likely representing another metallogenic event. The Cu‐Au skarn deposits in the Kelu‐Liebu‐Chongmuda belt are interpreted as the shallow level, skarn‐related deposits in a porphyry‐skarn mineralization. Appearance of porphyry copper mineralization in some skarn deposits implies that skarn copper mineralization of the study area resemble to those in northern sub‐metallogenic belt, having uniform porphyry‐skarn ore‐forming system. Therefore, it is presumed there should be potential to find deep level porphyry‐type Cu‐Au mineralization targets.     

Genetic Types and Metallogenic Model for the Polymetallic Copper–Gold Deposits in the Tongling Ore District,Anhui Province,Eastern China

The Tongling ore district is one of the most economically important ore areas in the Middle–Lower Yangtze River Metallogenic Belt, eastern China. It contains hundreds of polymetallic copper–gold deposits and occurrences. Those deposits are mainly clustered(from west to east) within the Tongguanshan, Shizishan, Xinqiao, Fenghuangshan, and Shatanjiao orefields. Until recently, the majority of these deposits were thought to be skarn-or porphyry–skarn-type deposits; however there have been recent discoveries of numerous vein-type Au, Ag, and Pb-Zn deposits that do not fall into either of these categories. This indicates that there is some uncertainty over this classification. Here, we present the results of several systematic geological studies of representative deposits in the Tongling ore district. From investigation of the ore-controlling structures, lithology of the host rock, mineral assemblages, and the characteristics of the mineralization and alteration within these deposits, three genetic types of deposits(skarn-, porphyry-, and vein-type deposits) have been identified. The spatial and temporal relationships between the orebodies and Yanshanian intrusions combined with the sources of the ore-forming fluids and metals, as well as the geodynamic setting of this ore district, indicate that all three deposit types are genetically related each other and constitute a magmatic–hydrothermal system. This study outlines a model that relates the polymetallic copper–gold porphyry-, skarn-, and vein-type deposits within the Tongling ore district. This model provides a theoretical basis to guide exploration for deep-seated and concealed porphyry-type Cu(–Mo, –Au) deposits as well as shallow vein-type Au, Ag, and Pb–Zn deposits in this area and elsewhere.     

Precious metal and telluride mineralogy of large volcanic-hosted massive sulfide deposits in the Urals

Summary The study focuses on the mode of occurrence of Au, Ag and Te in ores of the Gaisk, Safyanovsk, Uzelginsk and other volcanic-hosted massive sulfide (VHMS) deposits in the Russian Urals. Minerals containing these elements routinely form fine inclusions within common sulfides (pyrite, chalcopyrite and sphalerite). Gold is mostly concentrated as ‘invisible’ gold within pyrite and chalcopyrite at concentrations of 1–20 ppm. Silver mainly occurs substituted in tennantite (0.1–6 wt.% Ag). In the early stages of mineralization, gold is concentrated into solid solution within the sulfides and does not form discrete minerals. Mineral parageneses identified in the VHMS deposits that contain discrete gold- and gold-bearing minerals, including native gold, other native elements, various tellurides and tennantite, were formed only in the latest stages of mineralization. Secondary hydrothermal stages and local metamorphism of sulfide ores resulted in redistribution of base and precious metals, refining of the common sulfides, the appearance of submicroscopic and microscopic inclusions of Au–Ag alloys (fineness 0.440–0.975) and segregation of trace elements into new, discrete minerals. The latter include Au and Ag compounds combined with Te, Se, Bi and S. Numerous tellurides (altaite, hessite, stützite, petzite, krennerite etc.) are found in the massive sulfide ores of the Urals and appear to be major carriers of gold and PGE in VHMS ores.     

Experimental replacement of chalcopyrite by bornite: Textural and chemical changes during a solid-state process

Chalcopyrite was reacted with covellite and with chalcocite, respectively, between 200°C and 500°C. The ensuing solid-state replacement of chalcopyrite by bornite was studied both texturally and chemically. The relatively oxidizing conditions of the reaction chalcopyrite+covellite result in massive replacement, lacking structural control, where bornite and pyrite form complex intergrowth textures in chalcopyrite. Bornite nucleates around growing pyrite aggregates because of the release of copper and a decrease in volume. Diffusion of sulphur along grain boundaries and fractures largely controls the textural development. Reaction under the relatively reducing conditions involving chalcopyrite+chalcocite results in replacement of chalcopyrite in the sequence where chalcopyrite is replaced by bornite, below about 355°C, and by intermediate solid solution (ISS) and later bornite, above 355°C. The textural development, changing from replacement, apparently uninfluenced by directional properties in the host, to semioriented replacement, is structurally controlled. This suggests that the process is governed by diffusion of copper and iron through a sulphur framework. It is suggested that the observed formation of oriented bornite lamellae in chalcopyrite and in ISS during the chalcopyrite+chalcocite reaction may be explained by replacement exsolution at constant temperature.     

含金夕卡岩矿床产出构造环境和地质地球化学评价标志

近十几年来,含金夕卡岩矿床的勘查与研究在国内外取得了很大的进展,发现了一批大型矿床,从而引人注目。含金夕卡岩矿床主要集中分布于环太平洋成矿带,按其产出构造环境可分为三类,即中（新）生代褶皱带、古生代褶皱带和地盾（台）区。控矿地层主要为石炭—二叠系和三叠系碳酸盐岩,次为第三系和寒武系等。有关岩浆岩大多为浅成钙碱性中酸性侵入岩,属Ⅰ型;时代以燕山期和喜山期为主,少数为华力西期、加里东期和印支期。含金夕卡岩绝大多数为钙夕卡岩,只有少数属镁夕卡岩,又可进一步划分为还原型和氧化型。金属矿物组合的特征是常有砷化物、铋化物和碲化物存在,Ｃｕ,Ａｕ,Ａｇ,Ａｓ,Ｂｉ,Ｔｅ,Ｃｏ和Ｓｅ等元素组合是含金夕卡岩特征性的地球化学标志。矿床（田）常具明显的交代矿化分带,并可构成一定成矿系列,其综合交代矿化分带模式,自岩体向碳酸盐围岩方向依次为：Ｃｕ（Ｍｏ）→Ｃｕ（Ｆｅ）→Ｃｕ（Ａｕ）→Ａｕ→Ａｕ（Ｐｂ,Ｚｎ,Ａｇ）。矿物共生组合和流体包裹体研究表明,夕卡岩矿物形成于６８０～３２０℃,盐度为ｗ（ＮａＣｌ）＝５９５％～１８６％,金的沉淀发生在夕卡岩期后的退化热液交代阶段,大致相当于温度为３５０～１５３℃,盐度ｗ（ＮａＣｌ）＝２４％～?     

Trace and minor elements in sphalerite: A LA-ICPMS study

Sphalerite is an important host mineral for a wide range of minor and trace elements. We have used laser-ablation inductively coupled mass spectroscopy (LA-ICPMS) techniques to investigate the distribution of Ag, As, Bi, Cd, Co, Cu, Fe, Ga, Ge, In, Mn, Mo, Ni, Pb, Sb, Se, Sn and Tl in samples from 26 ore deposits, including specimens with wt.% levels of Mn, Cd, In, Sn and Hg. This technique provides accurate trace element data, confirming that Cd, Co, Ga, Ge, In, Mn, Sn, As and Tl are present in solid solution. The concentrations of most elements vary over several orders of magnitude between deposits and in some cases between single samples from a given deposit. Sphalerite is characterized by a specific range of Cd (typically 0.2-1.0 wt.%) in each deposit. Higher Cd concentrations are rare; spot analyses on samples from skarn at Baisoara (Romania) show up to 13.2 wt.% (Cd²⁺ ↔ Zn²⁺ substitution). The LA-ICPMS technique also allows for identification of other elements, notably Pb, Sb and Bi, mostly as micro-inclusions of minerals carrying those elements, and not as solid solution. Silver may occur both as solid solution and as micro-inclusions. Sphalerite can also incorporate minor amounts of As and Se, and possibly Au (e.g., Magura epithermal Au, Romania). Manganese enrichment (up to ∼4 wt.%) does not appear to enhance incorporation of other elements. Sphalerite from Toyoha (Japan) features superimposed zoning. Indium-sphalerite (up to 6.7 wt.% In) coexists with Sn-sphalerite (up to 2.3 wt.%). Indium concentration correlates with Cu, corroborating coupled (Cu⁺In³⁺) ↔ 2Zn²⁺ substitution. Tin, however, correlates with Ag, suggesting (2Ag⁺Sn⁴⁺) ↔ 3Zn²⁺ coupled substitution. Germanium-bearing sphalerite from Tres Marias (Mexico) contains several hundred ppm Ge, correlating with Fe. We see no evidence of coupled substitution for incorporation of Ge. Accordingly, we postulate that Ge may be present as Ge²⁺ rather than Ge⁴⁺. Trace element concentrations in different deposit types vary because fractionation of a given element into sphalerite is influenced by crystallization temperature, metal source and the amount of sphalerite in the ore. Epithermal and some skarn deposits have higher concentrations of most elements in solid solution. The presence of discrete minerals containing In, Ga, Ge, etc. also contribute to the observed variance in measured concentrations within sphalerite.     

五台山—恒山绿岩带Au-Ag-Cu成矿作用地球化学特征

五台山—恒山绿岩带Ａｕ、Ａｇ、Ｃｕ矿床可分为二大类型：（１）再生型金银铜矿，产在包括岩浆岩在内的各类岩石断裂构造中，与岩浆期后热液有关；（２）变生型金银铜矿，产于各类变质岩中，具有层控特征（即绿岩型金矿）。在地球化学特征上，再生型矿床与变生型矿床相比，矿体及围岩中Ｍｏ、Ａｇ、Ｐｂ、Ｚｎ、Ｃｄ等成矿及伴生元素明显富集；Ｋ２Ｏ、Ｒｂ、Ｓｒ、Ｂａ、Ｔｈ、Ｕ也明显富集，是后期岩浆热液作用的结果；Ｈｇ、Ｆ的明显富集则与后期构造活动有关；Ｚｎ／Ｃｄ比值较低，说明受到后期岩浆侵入影响；Ｔｈ／Ｕ比值低，可能指示富钙的酸性岩环境。再生型Ａｕ矿化的元素组合为Ｃｄ、Ａｓ、Ｎｉ、Ａｇ、Ｓｂ、Ａｕ、Ｈｇ（Ｂｉ），再生型Ａｇ矿化的元素组合为Ａｓ、Ｓｂ、Ａｇ、Ｃｄ、Ｃｕ、Ｎｉ（Ｍｏ、Ｐｂ、Ｚｎ、Ｂｉ），变生型Ａｕ矿化的元素组合较简单，只为Ａｕ、Ｈｇ、Ａｓ或Ａｕ、Ｃｕ。上述地球化学特征不仅可以有效地区分矿化类型，而且可以作为地球化学找矿和评价的指标     

Noble-metal ore genesis and mantle–crust interaction

The mineral and geochemical compositions of noble-metal (first of all, gold) deposits of the Fennoscandian, Siberian, and Northeast Asian orogenic belts are considered. These deposits are of several types: Au (disseminated Au–sulfide and Au–quartz), Au–Bi, Au–Ag, Au–Sb, Ag–Sb, Au–Sb–Hg, and Ag–Hg. They formed in different geodynamic settings as a result of the active motion of crustal tectonic blocks of different nature. Subduction processes (both at the front and at the rear of continent-marginal and island-arc magmatic arcs) resulted in Au–Ag, Ag–Sb, Ag–Hg, Au–Sb–Hg, and Au–Bi deposits. Collision events gave rise to Au and Au–Bi deposits. Intraplate continental rifting and formation of orogenic belts along the boundaries of block (plate) sliding led to the origin of Au and Au–Bi ores in association with Au–Ag, Au–Sb–Hg, and complex ores. In all cases, the formation of noble-metal mineralization was accompanied by magmatism of different types and metamorphism. Because of this diversity of ores, there is no single concept of the genesis of noble-metal mineralization. Several competing models of genesis exist: hydrothermal-metamorphic, pluton-metamorphic, plutonic, activity of mantle fluid flows, and multistage concentration during the crust–mantle interaction with the leading role of sedimentary complexes.     

吉林省兰家金矿原生地球化学特征

兰家金矿床位于大黑山条垒的金银多金属成矿带中。具有矽卡岩型、破碎带蚀变岩型及细脉浸染型三种类型的金矿体,矿床的形成与晚三叠世泉眼沟序列南泉眼单元的石英闪长岩的多次活动有密切的关系。Ａｕ、Ａｇ、Ｂｉ是成矿元素的特征组合,其原生地球化学特征可做为矿床评价及指导找矿的依据。     

The distribution of platinum group elements (PGE) and other chalcophile elements among sulfides from the Creighton Ni–Cu–PGE sulfide deposit, Sudbury, Canada, and the origin of palladium in pentlandite

Concentrations of platinum group elements (PGE), Ag, As, Au, Bi, Cd, Co, Mo, Pb, Re, Sb, Se, Sn, Te, and Zn, have been determined in base metal sulfide (BMS) minerals from the western branch (402 Trough orebodies) of the Creighton Ni–Cu–PGE sulfide deposit, Sudbury, Canada. The sulfide assemblage is dominated by pyrrhotite, with minor pentlandite, chalcopyrite, and pyrite, and they represent monosulfide solid solution (MSS) cumulates. The aim of this study was to establish the distribution of the PGE among the BMS and platinum group minerals (PGM) in order to understand better the petrogenesis of the deposit. Mass balance calculations show that the BMS host all of the Co and Se, a significant proportion (40–90%) of Os, Pd, Ru, Cd, Sn, and Zn, but very little (<35%) of the Ag, Au, Bi, Ir, Mo, Pb, Pt, Rh, Re, Sb, and Te. Osmium and Ru are concentrated in equal proportions in pyrrhotite, pentlandite, and pyrite. Cobalt and Pd (∼1 ppm) are concentrated in pentlandite. Silver, Cd, Sn, Zn, and in rare cases Au and Te, are concentrated in chalcopyrite. Selenium is present in equal proportions in all three BMS. Iridium, Rh, and Pt are present in euhedrally zoned PGE sulfarsenides, which comprise irarsite (IrAsS), hollingworthite (RhAsS), PGE-Ni-rich cobaltite (CoAsS), and subordinate sperrylite (PtAs₂), all of which are hosted predominantly in pyrrhotite and pentlandite. Silver, Au, Bi, Mo, Pb, Re, Sb, and Te are found predominantly in discrete accessory minerals such as electrum (Au–Ag alloy), hessite (Ag₂Te), michenerite (PdBiTe), and rhenium sulfides. The enrichment of Os, Ru, Ni, and Co in pyrrhotite, pentlandite, and pyrite and Ag, Au, Cd, Sn, Te, and Zn in chalcopyrite can be explained by fractional crystallization of MSS from a sulfide liquid followed by exsolution of the sulfides. The early crystallization of the PGE sulfarsenides from the sulfide melt depleted the MSS in Ir and Rh. The bulk of Pd in pentlandite cannot be explained by sulfide fractionation alone because Pd should have partitioned into the residual Cu-rich liquid and be in chalcopyrite or in PGM around chalcopyrite. The variation of Pd among different pentlandite textures provides evidence that Pd diffuses into pentlandite during its exsolution from MSS. The source of Pd was from the small quantity of Pd that partitioned originally into the MSS and a larger quantity of Pd in the nearby Cu-rich portion (intermediate solid solution and/or Pd-bearing PGM). The source of Pd became depleted during the diffusion process, thus later-forming pentlandite (rims of coarse-granular, veinlets, and exsolution flames) contains less Pd than early-forming pentlandite (cores of coarse-granular).     

西藏甲玛铜多金属矿床斑铜矿特征及其成因意义

甲玛矿床是中国国内少见的以斑铜矿为主要含铜矿物的产于斑岩成矿系统内的铜多金属矿床.斑铜矿是该矿床内普遍存在的重要铜矿物之一,广泛分布于矽卡岩型矿石、(矽卡岩化)大理岩型矿石中,有少量产于角岩型矿石中.在硅灰石矽卡岩型矿石内,斑铜矿分布最广,含量也最高,部分矿段中斑铜矿的含量高达7596以上,并与硅灰石呈共生或伴生关系....     

The Nucleus Deposit: Superposed Au–Ag–Bi–Cu Mineralization Systems at Freegold Mountain,Yukon, Canada

In this paper we present titanite U–Pb (both single crystal CA ID‐TIMS and in situ LA ICP‐MS) data, coupled with ore and gangue mineralogy and geochemical (both lithogeochemistry and microanalysis) data from the Nucleus Au–Ag–Bi–Cu deposit, in the Yukon (Canada) portion of the Tintina Au province. Arsenic‐bearing Au–Ag–Bi–Cu mineralization at Nucleus consists of two distinct styles of mineralization including: (i) reduced Au skarn and sulfide replacement; and (ii) a relatively shallow‐emplaced (as supported by textures and temperature of formation), vein‐controlled mineralization occurring mainly as veins and veinlets of various shapes (sheeted, single, stockworks, and crustiform), breccias, and disseminations. Whereas Au, Bi, and Cu mineralization from skarn is associated with hydrous retrograde alteration phases (actinolite, ferro‐actinolite, hastingsite, cannilloite, and hornblende), numerous alteration types are associated with the vein‐controlled style of mineralization and these include: biotite, phyllic, argillic, propylitic, carbonate, and quartz (silicification) alterations. The mineralization–alteration processes took place over a wide temperature range that is bracketed between 340 and 568°C, as indicated by chlorite and arsenopyrite geothermometers. The Au‐rich Nucleus deposit is characterized by anomalously high content of As and Bi (as much as 1 %), and whereas Au moderately correlates with Bi (r = 0.40) in the skarn mineralization style (where native Au is spatially associated with native Bi and Bi‐bearing sulfides), the two elements correlate poorly (r = 0.14) in the vein‐controlled type, in which native Bi‐ and Bi‐sulfide‐bearing veins are locally observed. Sphalerite from the vein‐controlled mineralized type is Fe‐rich (9.92–10.54 mol % FeS) indicative of low sulfidation conditions, as well as high temperature, with the latter further supported by arsenopyrite geothermometry (up to 491°C), low Ag content (3–7 wt.%) in Au, and the high gold fineness (926–964). Whereas molybdenite Re–Os ages from quartz‐molybdenite veins range from 75.8 to 76.2 ± 0.3 Ma, titanite from the skarn type mineralization recorded CA ID‐TIMS and LA ICP‐MS U–Pb ages of 182.6 ± 2.4 Ma and 191.0 ± 1.5 Ma, respectively, thus precluding any genetic link between the two spatially associated styles of mineralization from the Nucleus deposit area. The Au–Ag–Bi–Cu Nucleus deposit is therefore regarded as a superposed system in which two mineralization types, without any petrogenetic relationship, overlapped, possibly with remobilization of early‐formed mineralization.     

Volcanogenic Massive Sulfide Deposits Enriched in Gold

Volcanogenic massive sulfide deposits contain not only Cu, Zn, and Pb, but Sb, Bi, Te, Se Ag, Co, other metals, and variable amounts of Ag and Au. In some of these, gold reserves exceed 100 t, while the gold grade reaches several dozens ppm. An original database was used to establish statistically meaningful criteria for identification of deposits with large gold reserves and/or that are anomalously enriched in gold. Some peculiar features of deposits with high Au grades were investigated, including their distribution in geological history and among the principal metallogenic provinces, as well as association with volcanogenic formations and paleovolcanic structures, geochemical and mineralogical features, and factors that caused enrichment in gold.     

Trace elements in pyrite from the Petropavlovsk gold–porphyry deposit (Polar Urals): Results of LA-ICP-MS analysis

The first study of the pyrite composition from gold deposit in the Urals by the LA-ICP-MS method has been carried out. In the pyrite high contents of Au (up to 49 ppm), Ag (105 ppm), and other micronutrients (As (417 ppm), Ag (105 ppm), Co (2825 ppm), Ni (75 ppm), Cu (1442 ppm), and Zn (19 ppm)) were detected. Furthermore, an increase in the concentrations of trace elements from early to later generations of pyrite (from Py-1 to Py-3) Au, Ag, Te, Sn, Te, and Bi and depletion of Co, As, and Ni have been revealed. Gold is mainly concentrated in the pyrite of the second generation (Py-2) and occurs mostly as an “invisible” form with prevalence of nano-sized particles of native Au, similar in composition to electrum AuAg, as well as Au- and Au–Ag tellurides. The presence in the pyrite of admixtures of Cu, Co, Ni, Pb, As, and Te, possibly favors the entrance of Au into it (up to 5–50 ppm), while in common pyrite, poor in the mentioned impurities, the gold content is <1 ppm.     

Ore prospecting model and targets for the Dashuigou tellurium deposit,Sichuan Province,China

The Dashuigou tellurium (Te) deposit in Shimian city, Sichuan Province is the only known independent Te ore deposit in China. Samples were collected by 1/50,000 stream sediment survey and analyzed by inductively coupled plasma–mass spectrometry, X-ray fluorescence spectrometry, emission spectrometry, and atomic absorption spectroscopy. An ore prospecting model for the Dashuigou Te deposit was then established. In the Dashuigou area, bismuth (Bi), Te, and gold (Au) concentrations in stream sediment samples displayed weak-positive anomalies, while silver (Ag) displayed a weak-negative anomaly. Bi, Te, Ag, and Au anomalies are regarded as indicators of Te deposits; the greater the ratio of Te?+?Bi/Au?+?Ag, the larger the possibility of an independent tellurobismuthite deposit. The ratio calculated from our samples is 7.288. Five locations were identified for prospecting for Te minerals by this model, including the northern part of the Dashuigou Te deposit, Majiagou, Tizigou, southeastern Miaoping, and northern Baishuihe. These five regions are within the Dashuigou dome anticline, the exposed strata of which are controlled by tracing the tensile shear fracture; the metallogenic geological conditions and geochemical characteristics are the same as those of the known Dashuigou Te deposit. Already, Te–Bi veins have been found in some of these areas.