陕西镇安丘岭卡林型金矿金的赋存状态和富集机理

丘岭金矿床是西秦岭地区重要的卡林型金矿之一, 金矿化赋存于上泥盆统南阳山组和下石炭统袁家沟组地层中, 容矿岩石的岩性为钙质粉砂岩、粉砂质页岩和泥质灰岩.金矿石中主要金属矿物为黄铁矿和毒砂, 非金属矿物则以石英、方解石和绢云母为主.通过对矿石矿物黄铁矿和毒砂的扫描电镜-能谱分析、电子探针分析和激光剥蚀电感耦合等离子体质谱分析, 对丘岭金矿床金的赋存形式和富集机理进行了较为详细的研究.结果表明, 丘岭金矿床中金主要以次显微不可见金的形式存在, 其次为显微可见金.次显微金包括: (1)固溶体金(Au+), 主要存在于环带状细粒黄铁矿的含砷增生边区域和毒砂中, 少量存在于环带状黄铁矿的核部不含砷区域; (2)纳米级自然金颗粒(Au0), 存在于粗晶黄铁矿中.环带状细粒黄铁矿核部的次显微金可能主要以胶体吸附的形式存在, 暗示容矿岩石在沉积成岩过程中有金的初步富集, 而环带状黄铁矿幔部和毒砂中的Au则主要来源于成矿流体, 以S和As的络合物形式搬运.显微可见金主要分布在细粒黄铁矿的晶体边缘和热液蚀变绢云母、石英及方解石中, 粒径通常小于3~5 μm, 其形成可能与成矿流体中金的局部过饱和及成矿流体对细粒黄铁矿和毒砂中次显微金的活化和再次富集有关.      

Copper–Gold Skarn Mineralization at the Karavansalija Ore Zone,Rogozna Mountain,Southwestern Serbia

Karavansalija ore zone is situated in the Serbian part of the Serbo‐Macedonian magmatic and metallogenic belt. The Cu–Au mineralization is hosted mainly by garnet–pyroxene–epidote skarns and shifts to lesser presence towards the nearby quartz–epidotized rocks and the overlying volcanic tuffs. Within the epidosites the sulfide mineralogy is represented by disseminated cobalt‐nickel sulfides from the gersdorfite‐krutovite mineral series and cobaltite, and pyrite–marcasite–chalcopyrite–base metal aggregates. The skarn sulfide mineralization is characterized by chalcopyrite, pyrite, pyrrhotite, bismuth‐phases (bismuthinite and cosalite), arsenopyrite, gersdorffite, and sphalerite. The sulfides can be observed in several types of massive aggregates, depending on the predominant sulfide phases: pyrrhotite‐chalcopyrite aggregates with lesser amount of arsenopyrite and traces of sphalerite, arsenopyrite–bismuthinite–cosalite aggregates with subordinate sphalerite and sphalerite veins with bismuthinite, pyrite and arsenopyrite. In the overlying volcanoclastics, the studied sulfide mineralization is represented mainly by arsenopyrite aggregates with subordinate amounts of pyrite and chalcopyrite. Gold is present rarely as visible aggregate of native gold and also as invisible element included in arsenopyrite. The fluid inclusion microthermometry data suggest homogenization temperature in the range of roughly 150–400°C. Salinities vary in the ranges of 0.5–8.5 wt% NaCl eq for two‐phase low density fluid inclusions and 15–41 wt% NaCl eq for two‐phase high‐salinity and three‐phase high‐salinity fluid inclusions. The broad range of salinity values and the different types of fluid inclusions co‐existing in the same crystals suggest that at least two fluids with different salinities contributed to the formation of the Cu–Au mineralization. Geothermometry, based on EPMA data of arsenopyrite co‐existing with pyrite and pyrrhotite, suggests a temperature range of 240–360°C for the formation of the arsenopyrite, which overlaps well with the data for the formation temperature obtained through fluid inclusion microthermometry. The sulfur isotope data on arsenopyrite, chalcopyrite, pyrite and marcasite from the different sulfide assemblages (ranging from 0.4‰ to +3.9‰ δ³⁴S_CDT with average of 2.29 δ³⁴S_CDT and standard deviation of 1.34 δ³⁴S_CDT) indicates a magmatic source of sulfur for all of the investigated phases. The narrow range of the data points to a common source for all of the investigated sulfides, regardless of the host rock and the paragenesis. The sulfur isotope data shows good overlap with that from nearby base‐metal deposits; therefore the Cu–Au mineralization and the emblematic base‐metal sulfide mineralization from this metallogenic belt likely share same fluid source.     

Polymetallic sulfide ores hosted in Late Permian carbonate at the Alanish locality,northern Iraq: petrography and mineral chemistry

Polymetallic sulfide ores (Zn, Pb, Fe, Cu, Ag, and Cd) found in the Alanish locality of northern Iraq are hosted by dolostone in the Late Permian Chia Zairi Formation. The Alanish locality is one of several Zn–Pb deposits that are widespread in northern Iraq, situated along the northern passive margin of the Arabian plate. This paper describes the ore deposit classification, mineral chemistry, and paragenetic sequence of the area and proposes an ore formation model. We report the presence of acanthite and greenockite for the first time in Iraq. A brine solution derived from the sedimentary basin formed the primary sulfide ore minerals (sphalerite, galena, acanthite, pyrite, chalcopyrite, greenockite, and marcasite). The pre-tectonic mineralization is characterized by replacement textures including (1) high-Fe, low-Zn, dark-colored, coarse-grained sphalerite; (2) deformed anisotropic coarse-grained galena; and, (3) idiomorphic cubes of crushed pyrite. Conversely, the post-tectonic mineralization is characterized by open-space filling textures, including (1) low-Fe, high-Zn, light-colored, fine aggregated sphalerite; (2) fine-grained galena; and, (3) the existence of acanthite and marcasite. Although galena is an Ag carrier, both mineralization phases contained non-argentiferous galena. Non-sulfides (smithsonite, cerussite, and goethite) have replaced older sulfides in many areas due to supergene process. Gangue minerals present are dolomite, calcite, barite, and siderite. Open spaces and cavity filling of small paleo-karsts, replacement, veins, and veinlets are common features of the ore body. Metals were sourced from brines generated in the sedimentary basin, whereas sulfur was derived from nearby evaporates. Sediment compaction and tectonic activity, probably during Late Cretaceous, were the driving forces that squeezed and moved ore-bearing fluids derived from the sedimentary basin. Multiple stages of ore-bearing fluids were epigenetically intruded into the Late Paleozoic dolostone, forming an epigenetic strata-bound Mississippi Valley-type deposit precipitated under a temperature of 120 °C, as indicated by the cadmium fractionation in sphalerite and galena. Dolomitization and tectonic activity provided the necessary permeability for accumulating ores. The main ore body is directly connected to a fault plane and to adjacent dolostone that is frequently fractured and brecciated.     

Stable isotope geochemistry and diagenetic mineralization associated with the Tono sandstone-type uranium deposit in Japan

The Tono sandstone-type uranium mine area, middle Honsyu, Japan is composed of Miocene lacustrine sedimentary rocks in the lower part (18–22 Ma) and marine facies in the upper part (15–16 Ma). Calcite and pyrite occur as dominant diagenetic alteration products in these Neogene sedimentary rocks. The characteristics of calcite and pyrite differ significantly between lacustrine and marine facies. Abundant pyrite, calcite, organic matter, and small amounts of marcasite or pyrrhotite occur in the lacustrine facies, whereas small amounts of calcite and framboidal pyrite, organic matter and no marcasite or pyrrhotite are found within the marine units. The δ¹³C values of calcite in the lacustrine deposits are low (−19 to −6‰ PDB) but those in marine formation are high (−11 to +3‰). This implies that the contribution of marine carbonate is larger in upper marine sedimentary rocks, and carbon in calcite in the lower lacustrine formation was derived both from oxidation of organic matter and from dissolved marine inorganic carbon. The δ³⁴S values of framboidal pyrite in the upper marine formation are low (−14 to −8‰ CDT), indicating a small extent of bacterial seawater sulfate reduction, whereas those of euhedral-subhedral pyrite in the lower lignite-bearing arkose sandstone are high (+10 to +43‰), implying a large extent of closed-system bacterial seawater sulfate reduction. The δ³⁴S and δ¹³C data which deviate from a negative correlation line toward higher δ¹³C values suggest methanogenic CO₂ production. During diagenesis of the lacustrine unit, large amounts of euhedral-subhedral pyrite were formed, facilitated by extensive bacterial reduction of seawater sulfate with concomitant oxidation of organic matter, and by hydrolysis reactions of organic matter, producing CH₄ and CO₂. Uranium minerals (coffinite and uraninite) were also formed at this stage by the reduction of U⁶⁺ to U⁴⁺. The conditions of diagenetic alteration within the lacustrine deposits and uranium mineralization is characterized by low Eh in which nearly equal concentrations of CH₄ and HCO₃ ⁻ existed and reduced sulfur species (H₂S, HS⁻) are predominant among aqueous sulfur species, whereas diagenetic alteration of the marine formations was characterized by a predominance of SO₄ ²⁻ among dissolved sulfur species. Modern groundwater in the lacustrine formation has a low Eh value (−335 mV). Estimated and measured low Eh values of modern and ancient interstitial waters in lacustrine environments indicate that a reducing environment in which U⁴⁺ is stable has been maintained since precipitation of uranium minerals. Received: 9 February 1996 / Accepted: 11 April 1997     

Composition of arsenopyrite from topaz greisen veins in southeastern Missouri

Arsenopyrite occurs in greisen-sulfide veins hosted by unmetamorphosed Precambrian granite and rhyolite in the Silver Mine district of southeastern Missouri, Greisenization and sulfide mineralization appear to have been a continuous depositional sequence which recorded falling temperature in a near-surface vein environment. Textural criteria imply that equilibrium existed between arsenopyrite and pyrite and that this pair crystallized in an intermediate paragenetic position between the greisen and hydrothermal stages. Thirty-eight electron microprobe spot analyses of 15 arsenopyrite crystals from the Einstein and Gabriel veins failed to disclose chemical zoning of As/S. The compositional range of the analyzed arsenopyrites is 32. 9 to 31. 0 atomic % As. A range of arsenopyrite crystallization temperature from 485°C (±15°) to 455°C (±15°) is indicated for the Gabriel vein. In contrast, arsenopyrites from the Einstein vein record a lower and broader crystallization range of 440°C (±15°) to 368°C (±15°).     

Thermal magnetic susceptibility data on natural iron sulfides of northeastern Russia

Dependences of magnetic susceptibility (MS) on the temperature of natural iron sulfide samples (pyrite, marcasite, greigite, chalcopyrite, arsenopyrite, pyrrhotite) from the deposits of northeastern Russia were studied. The thermal MS curves for pyrite and marcasite are the same: On heating, MS increases at 420–450 °C, and unstable magnetite (maghemite) and monoclinic pyrrhotite with a well-defined Hopkinson peak are produced. In oxygen-free media with carbon or nitrogen, magnetite formation is weak, whereas pyrrhotite generation is more significant. The heating curves for chalcopyrite are similar to those for pyrite. They show an increase in MS at the same temperatures (420–450 °C). However, stable magnetite is produced, whereas monoclinic pyrrhotite is absent. In contrast to that in pyrite, marcasite, and chalcopyrite, magnetite formation in arsenopyrite begins at > 500 °C. Arsenopyrite cooling is accompanied by the formation of magnetite (S-rich arsenopyrite) or maghemite (As-rich arsenopyrite) with a dramatic increase in MS. Arsenopyrite with an increased S content is characterized by insignificant pyrrhotite formation. Greigite is marked by a decrease in MS on the heating curves at 360–420 °C with the formation of unstable cation-deficient magnetite.Monoclinic pyrrhotite is characterized by a decrease in MS at ～ 320 °C, and hexagonal pyrrhotite, by a transition to a ferrimagnetic state at 210–260 °C. The addition of organic matter to monoclinic pyrrhotite stimulates the formation of hexagonal pyrrhotite, which transforms back into monoclinic pyrrhotite on repeated heating. The oxidation products of sulfides (greigite, chalcopyrite) show an increase in MS at 240–250 °C owing to lepidocrocite.     

The Existence of the Negative Charge of Gold in Sulphide Minerals and Its Formation Mechanism1;

Abstract: Through a study, particularly an X-ray photoelectron spectroscopy (XPS or ESCA) analysis, of gold-bearing arsenopyrite and pyrite in Carlin-type gold deposits of Guangxi, China, and hydrothermally synthesized gold-bearing pyrite and marcasite, the authors have found that these minerals contain “invisible gold” whose binding energy is lower than that of native gold (Au°). Therefore they suggest that gold occurs in a negative charge state in these sulphide minerals as it replaces some sulphur and is combined with sulphur with the covalent bond. This paper also preliminarily discusses the possibility of its formation from the chemistry and geochemistry of gold, crystal chemistry of arsenopyrite, pyrite and marcasite and geochemical environment.     

铜陵包村金(铜)矿床中胶状黄铁矿矿物学及成因解析

黄铁矿是安徽铜陵包村金(铜)矿床中主要硫化物,对热液成因的显晶质黄铁矿已有大量研究,而胶状黄铁矿研究较少且成因存在争议.本文以粉晶X射线衍射、扫描电镜(SEM)、透射电镜(TEM)以及拉曼光谱(RS)为主要研究方法和手段,对包村金(铜)矿床中胶状黄铁矿的矿物组成和微结构进行研究.包村胶状黄铁矿主要由黄铁矿组成,含有白铁...     

甘肃阳山金矿田载金矿物特征及金赋存状态研究

采用电子探针分析,详细研究了甘肃阳山类卡林型金矿田原生矿石中不同成矿阶段载金矿物的Au、As、S、Fe等元素含量及其分布规律,确定含砷黄铁矿和毒砂是最重要的载金矿物,发现不同成矿阶段的黄铁矿具有不同的成分特点;沉积成岩期黄铁矿为草莓状、胶状,砷和金含量最低,分别为0.10%和0.08%;热液成矿期早阶段黄铁矿粒度较粗(0.40～1.00mm),是较高温度(270～300℃)下缓慢结晶的产物,其砷和金含量较低,分别为0.27%和0.09%;热液成矿期主阶段(包括M1,M2和M3亚阶段)黄铁矿粒度微细(0.05～0.20mm),是210～270℃条件下快速结晶的产物,砷和金含量最高,M1亚阶段分别为3.45%As和0.11%Au,M2亚阶段分别为3.88%As和0.14%Au.在含砷黄铁矿中,金可能有自然金和离子金两种存在方式.沉积成岩期和热液成矿期早阶段低砷黄铁矿中金主要以纳米级自然金(Au~0)颗粒形式分布,而在热液成矿期主阶段含砷黄铁矿中金主要以Au+的形式存在.当热液中As活度高时,含砷黄铁矿在快速生长条件下,其生长面的空穴和缺陷较多,有利于热液中Au(HS)~0络合物通过吸附反应直接进入含砷黄铁矿生长表面.此外,主阶段流体的硫化和沸腾作用均可导致H_2S的减少,有利于形成砷黄铁矿和Au沉淀富集.     

滇黔桂典型锰矿床矿相学特征及其对成矿过程的指示

滇黔桂地区代表性锰矿包括贵州松桃大塘坡锰矿、广西大新下雷锰矿、遵义铜锣井锰矿和云南砚山斗南锰矿.本文利用显微镜、X衍射仪、扫描电镜等仪器,通过研究滇黔桂地区典型锰矿矿相学特征,结合碳酸盐岩研究方法,查明产于南华系大塘坡组第一段(Nh1d1)贵州松桃大塘坡锰矿矿物组合包括菱锰矿、钙菱锰矿、锰白云石、锰方解石、石英、伊利石,微相为SMF2、沉积相FZ1(盆地相),形成于沉积环境伸展阶段;产于上泥盆统五指山组(D3w)广西大新下雷锰矿矿物组合包括褐锰矿、锰钾矿、菱锰矿、钙菱锰矿、蔷薇辉石、透闪石、石英,微相为SMF2和SMF15-M、沉积相FZ7(台地相),形成于沉积环境伸展阶段;产于中二叠统茅口组第二段(P2m2)遵义铜锣井锰矿矿物组合包括菱锰矿、钙菱锰矿、锰方解石、锰白云石、硫锰矿、黄铁矿、闪锌矿、高岭石、伊利石、菱铁矿,微相为SMF15-C和SMF17、沉积相FZ7(台地相),形成于沉积环境收缩阶段;产于中三叠统法郎组(T2f)其矿物成分包括云南砚山斗南锰矿矿物组合包括褐锰矿、水锰矿、钙菱锰矿、含锰方解石、方解石、石英,微相为SMF4和SMF13、沉积相FZ4(斜坡相),形成于沉积环境伸展阶段.     

Pyrite tracks assimilation of crustal sulfur in Pyrenean peridotites

Cobalt-bearing pyrite (0.5?C2.0?wt.% Co) is abnormally abundant (up to 35?vol.% of the total volume of the sulfide phase) in some eastern Pyrenean peridotite massifs, compared to pieces of subcontinental mantle studied so far for sulfides. Pyrite occurs as vermicular intergrowths inside pentlandite and/or chalcopyrite or as coarser, blocky grains in the intergranular pores of host peridotites. Those different pyrites are characterized by different platinum-group element systematics (measured by laser ablation microprobe and ICP-MS). Vermicular pyrite intergrown with pentlandite displays Os-, Ir-, Ru- and Rh-enriched chondrite normalized PGE patterns of Monosulfide solid solution (Mss). In contrast, coarse-grained intergranular (??blocky??) pyrites, are PGE-poor. Chalcophile trace elements (i.e. Zn, Pb, Ag, Au) that are not usually concentrated in mantle-derived sulfides were commonly detected. By contrast, selenium contents are generally low, yielding thus pyrite with high S/Se ratio (>10⁵), consistent with a sedimentary sulfur source. Pyrite microtextures and chalcophile trace element contents support a process of assimilation of crustal sulfur from the metamorphosed sedimentary country rocks. These latter generated highly reactive CO₂-S fluids, which were injected into structural discontinuities of the lherzolitic bodies. Sulfur has reacted at T?=?300?C550°C with pre-existing, mantle-derived, metal-rich sulfide assemblages (pentlandite-chalcopyrite). Addition of crustal sulfur did produce Mss which, on cooling, exsolved the Os-rich pyrite in addition to pentlandite. The coarse-grained pyrite types have crystallized directly from S-rich fluids.     

Origin and diagenetic evolution of Ca–Mg–Fe carbonates in some coalfields of Japan

Carbonate concretions, lenses and bands in the Pleistocene, Palaeogene and Upper Triassic coalfields of Japan consist of various carbonate minerals with varied chemical compositions. Authigenic carbonates in freshwater sediments are siderite > calcite > ankerite > dolomite >> ferroan magnesite; in brackish water to marine sediments in the coal measures, calcite > dolomite > ankerite > siderite >> ferroan magnesite; and in the overlying marine deposits, calcite > dolomite >> siderite. Most carbonates were formed progressively during burial within a range of depths between the sediment-water interface and approximately 3 km. The mineral species and the chemical composition of the carbonates are controlled primarily by the initial sedimentary facies of the host sediments and secondarily by the diagenetic evolution of pore water during burial. Based on the regular sequence and burial depth of precipitation of authigenic carbonates in a specific sedimentary facies, three diagenetic stages of carbonates are proposed. Carbonates formed during Stage I (< 500 m) strongly reflect the initial sedimentary facies, e.g. low Ca-Mg siderite in freshwater sediments which are initially rich in iron derived from lateritic soil on the nearby landmass, and Mg calcite and dolomite in brackish-marine sediments whose pore waters abound in Ca²⁺ and Mg²⁺ originating in seawater and calcareous shells. Carbonates formed during Stage II (500–2000 m) include high Ca-Mg siderite, ankerite, Fe dolomite and Fe–Mg calcite in freshwater sediments. The assemblage of Stage II carbonates in brackish-marine sediments in the coal measures is similar to that in freshwater sediments. This suggests similar diagenetic environments owing to an effective migration and mixing of pore water due to the compaction of host sediments. Carbonates formed during Stage III (> 2000 m) are Fe calcite and extremely high Ca-Mg siderite; the latter is exclusively in marine mudstones. The supply of Ca is partly from the alteration of silicates in the sediments at elevated burial temperatures. After uplift, calcite with low Mg content precipitates from percolating groundwater and fills extensional cracks.     

Significance of the chemistry and morphology of diagenetic siderite in clastic rocks of the Mesozoic Scotian Basin

Siderite (FeCO₃) is a widespread minor diagenetic mineral in clastic sedimentary basins. Although eodiagenetic authigenesis of siderite is well-known, siderite formed during burial diagenesis shows habits and chemical compositions that are poorly understood. This study tests the hypothesis that diagenetic siderite cements in sandstones in the Scotian Basin, offshore eastern Canada, show systematic variability in chemistry and habit that is a response to recrystallization and changing composition of basinal fluids. Mineral textures were determined from backscattered electron images, and chemistry mostly from electron microprobe analyses. Five chemical types of siderite are identified using k-means cluster analysis, based on the amount of substitution of Ca, Mg and Mn for Fe. Eodiagenetic microcrystalline coated grains, concretions and intraclasts in sandstones are principally Fe-rich siderite and locally have recrystallised to blocky equant crystals. Mesodiagenetic Mg-rich siderite partly replaced these equant crystals and also framework mica and K-feldspar grains, showing textural evidence for coupled dissolution–reprecipitation. Slender Mg-rich siderite rhombs (lozenges, bladed or wheat-seed siderite) have precipitated before and after the formation of quartz overgrowths in geochemical microenvironments. Magnesium substitution reflects Mg-rich formation waters resulting from smectite to illite conversion. Equivalent Ca-rich siderite occurs where sandstones overlie a Jurassic carbonate bank. Late Mn-rich siderite has complex textures resembling those of Mississippi-Valley type ores, with spheroidal rims, a honeycomb-like mesh and concentric infill around secondary pores. It also occurs in veins or replacing intraclasts, post-dating late ferroan-calcite cements in sandstones that show strong dissolution by hot basinal brines. The Ca, Mg and Mn content of diagenetic siderite, coupled with textural evidence for recrystallization, can thus be used to track changes in ambient formation fluids. Siderite habits and chemistry described from the Scotian Basin are found in many clastic basins, suggesting that the observed recrystallization textures and variation in chemical type are of broad application.     

Yerranderie a Late Devonian Silver–Gold–Lead Intermediate Sulfidation Epithermal District, Eastern Lachlan Orogen, New South Wales, Australia

Felsic volcanic units of the Early Devonian Bindook Volcanic Complex host the Yerranderie epithermal silver–gold–lead district 94 km west–southwest of Sydney. Mineralization in the district forms part of a fault‐controlled, intermediate sulfidation, epithermal silver–gold–base metal vein system that has significant mineral and alteration zonation. Stage 1 of the mineral paragenesis in the veins developed quartz and carbonate with early pyrite, whereas stage 2 is a crustiform banded quartz–pyrite–arsenopyrite assemblage. Stage 3, the main stage of sulfide deposition, comprises early sphalerite, followed by a tetrahedrite–tennantite–gold assemblage, then a galena–chalcopyrite–native silver–pyrite assemblage, and finally a pyrargyrite–polybasite–pearceite assemblage. Stage 4 involves the deposition of quartz veins with minor (late) pyrite and stage 5 is characterized by siderite that infilled remaining voids. Mineral zonation occurs along the Yerranderie Fault, with bornite being restricted to the Colon Peaks–Silver Peak mine area, whereas arsenopyrite, which is present in both the Colon Peaks–Silver Peak and Wollondilly mine areas, is absent in other lodes along the Yerranderie Fault. The Yerranderie Fault, which hosts the major lodes, is surrounded by a zoned alteration system. With increasing proximity to the fault the intensity of alteration increases and the alteration assemblage changes from an outer quartz–muscovite–illite–(ankerite) assemblage to a quartz–illite–(pyrite–carbonate) assemblage within meters of the fault. ⁴⁰Ar/³⁹Ar dating of muscovite from the alteration zone gave a 372.1 ± 1.9 Ma (Late Devonian) age, which is interpreted to be the timing of the quartz–sulfide vein formation. Sulfur isotope values for sulfides range from 0.1 to 6.2‰ with one outlier of ?5.6 δ³⁴S‰. The results indicate that the initial ore‐forming fluids were reduced, and that sulfur was probably sourced from a magmatic reservoir, either as a direct magmatic contribution or indirectly through dissolution and recycling of sulfur from the host volcanic sequence. The sulfur isotope data suggest the system is isotopically zoned.     

Porphyry to epithermal transition in the Agua Rica polymetallic deposit, Catamarca, Argentina: An integrated petrologic analysis of ore and alteration parageneses

Agua Rica (27°26′S–66°16′O) is a world class Cu–Au–Mo deposit located in Catamarca, Argentina. In the E–W 6969400 section examined, the Seca Norte and the Trampeadero porphyries that have intruded the metasedimentary rock are cut by interfingered igneous and hydrothermal heterolithic and monolithic breccias, and sandy dikes. Relic biotite and K-feldspar of the early potassic alteration (370° to > 550 °C) with Cu (Mo–Au) mineralization are locally preserved and encapsulated in a widespread, white mica + quartz + rutile or anatase halo (phyllic alteration) with pyrite + covellite that suggests fluids with temperatures ≤ 360 °C and high f(S₂). The Trampeadero porphyry and the surrounding metasedimentary rock with phyllic alteration have molybdenite in stringers and B-type quartz veinlets and the highest Mo grades (> 1000 ppm).Multistage advanced argillic alteration overprinted the earlier stages. Early andalusite ± pyrite ± quartz is preserved in the roots of the argillic halo rimmed by an alumina–silica material and white micas. This alteration assemblage is considered to have been formed at temperatures ≥ 375 °C from condensed magmatic vapor. At higher levels, pyrophyllite replaces muscovite and illite in clasts of hydrothermal breccias in the center and east sector of the study section, suggesting temperatures of 280 to 360 °C. Clasts of vuggy silica in the uppermost levels of the central breccia, indicates that at lower temperatures (< 250 °C), fluids reached very low pH (pH < 2). In this early stage of the advanced argillic alteration, hydrothermal fluids seem to have not precipitated sulfides or sulfosalts.Hydrothermal brecciation was concurrent with fluid exsolution (↑? V), which precipitated intermediate-temperature advanced argillic alunite (svanbergite + woodhouseite) ± diaspore ± zunyite as breccia cement along with abundant covellite + pyrite + enargite ± native sulfur ± kuramite at intermediate depths and in lateral transitional zones to unbrecciated rocks. This mineral assemblage indicates temperatures near 300 °C, oxidized and silica-undersaturated hydrothermal fluids with high sulfur fugacity to prevent gold precipitation. Multiple generations of pyrite, emplectite, colusite, Pb- and Bi-bearing sulfosalts, and native sulfur with Au and Ag, accompanied by alunite introduction in the upper level breccias, probably occurred at lower temperatures, but still high sulfur and oxygen activity. An independent Zn and Pb (as galena) mineralization stage locally coincides with Au–Ag and sulfosalts, and advanced at depth, controlled by fractures and overprinting much of the previous mineralization. A later paragenesis of veinlets of alunite + woodhouseite + svanvergite + pyrite ± enargite that cut the phyllic halo suggests temperatures ~ 250 °C and without woodhouseite + svanvergite, temperatures ~ 200 °C. Kaolinite occurs in the phyllic halo as a late mineral in clots and in veinlets thus, in this zone, the fluid had cooled enough for its formation.     

First-principles calculations of the thermodynamic mixing properties of arsenic incorporation into pyrite and marcasite

The thermodynamic mixing properties of As into pyrite and marcasite have been investigated using first-principles and Monte Carlo calculations in order to understand the incorporation of this important metalloid into solid solution. Using quantum-mechanical methods to account for spin and electron transfer processes typical of sulfide minerals, the total energies of different As–S configurations were calculated at the atomic scale, and the resulting As–S interactions were incorporated into Monte Carlo simulations. Enthalpies, configurational entropies and Gibbs free energies of mixing show that two-phase mixtures of FeS₂ (pyrite or marcasite) and FeAsS (arsenopyrite) are energetically more favorable than the solid solution Fe(S,As)₂ (arsenian pyrite or marcasite) for a wide range of geologically relevant temperatures. Although miscibility gaps dominate both solid solution series, the solubility of As is favored for X_As < 0.05 in iron disulfides. Consequently, pyrite and marcasite can host up to ∼6 wt.% of As in solid solution before unmixing into (pyrite or marcasite) + arsenopyrite. This finding is in agreement with previously published HRTEM observations of As-rich pyrites (> 6 wt.% As) that document the presence of randomly distributed domains of pyrite + arsenopyrite at the nanoscale. According to the calculations, stable and metastable varieties of arsenian pyrite and marcasite are predicted to occur at low (X_As < 0.05) and high (X_As > 0.05) As bulk compositions, respectively.     

沁水盆地晚古生代煤中硫的地球化学特征及其对有害微量元素富集的影响

煤中硫是多种有害微量元素的重要载体。基于形态硫分析、电感耦合等离子质谱及X射线衍射等方法分析沁水盆地晚古生代煤中硫和有害微量元素的分布规律,探讨了煤中硫对有害微量元素富集的影响,运用带能谱的扫描电镜和光学显微镜划分煤中硫化物的微观赋存特征。结果表明,沁水盆地煤中硫整体上以有机硫为主,平均占全硫的78%,只有在太原组个别高硫煤中以黄铁矿硫为占优势。显微镜和扫描电镜下可识别出煤中黄铁矿的微观赋存状态包括莓球状、薄膜状、晶粒状、结核状、团窝状黄铁矿和细粒黄铁矿集合体,白铁矿的微观赋存特征包括聚片状、板状和矛头状白铁矿,部分白铁矿与黄铁矿共生。沁水盆地煤中有害微量元素含量整体较低,黄铁矿是有害微量元素As、Se和Hg的重要载体,而有机硫决定了煤中U的富集。研究认为,成煤时期海水对泥炭沼泽的影响导致太原组煤中全硫和黄铁矿硫较高,太原组煤中硫的来源具有多样性,煤中黄铁矿具有多阶段演化的特点。     

Gold and sulphide minerals in Tertiary quartz pebble conglomerate gold placers, Southland, New Zealand

Auriferous quartz pebble conglomerates (QPC) formed during Tertiary sedimentary recycling in the Waimumu district, Southland, New Zealand. These sediments contain fine-grained gold of detrital origin with abundant surface textures and gold-forms associated with authigenic gold remobilisation. Most authigenic gold contains no detectable silver and occurs as overgrowths on detrital Au–Ag and Au–Ag–Hg alloys that contain up to 13 wt.% Ag, and 9 wt.% Hg. Fine-grained Au–Ag and Au–Ag–Hg alloys are compositionally heterogeneous, exhibiting both well-defined silver-depleted and silver-enriched rims. Rare coarse Au–Ag alloy is intergrown with quartz and is homogenous. Discrete grains of authigenic, porous, sheet-like gold occur in carbonaceous mudstone within a QPC sequence. Some QPC contain abundant sulphide minerals. Some of these sulphides (pyrite and arsenopyrite) are of long-distance detrital origin, presumably from the Otago Schist, whereas the bulk of the sulphide suite is marcasite of variably transported diagenetic origin, derived from the erosion of QPC and underlying Tertiary sediments. There has also been authigenic deposition of sulphide minerals in the QPC themselves. These diagenetic sulphides include framboidal and anhedral marcasite, and framboidal and euhedral pyrite. Sulphur isotope data for the sulphide minerals range from − 45‰ to + 18‰ (relative to VCDT). Sulphur isotope data for euhedral detrital pyrite and arsenopyrite range from − 9‰ to − 1‰ and are most likely derived from the Otago Schist to the north. Both framboidal and anhedral marcasite have lower values (< − 20‰) reflecting microbial sulphate reduction as a source for the precursor hydrogen sulphide. Anhedral marcasite contains elevated concentrations of Ni, Co, As and Cr, commonly with compositional banding of these metals.Both the gold and diagenetic sulphides from the Belle-Brook QPC are compositionally similar to gold and sulphides from Archaean QPC. Porous, sheet-like authigenic gold is morphologically similar to gold associated with carbonaceous material in the Witwatersrand. In addition, Southland marcasite textures resemble the rounded and banded pyrite in Witwatersrand QPC placers. There is abundant evidence from these Tertiary QPC in southern New Zealand for sedimentary transport of sulphide minerals and post-depositional sulphide mineralisation in the surficial environment despite an oxygen-rich atmosphere. These young deposits thus provide an example of authigenic gold and sulphide textures formed during diagenesis in unmetamorphosed placers. Many of these textures are similar to those commonly ascribed to metamorphic processes in Archaean auriferous QPC.     

贵州天柱大河边铅锌矿床的发现及其意义

大河边重晶石矿床是一个世界级的超大型重晶石矿床。最近在该区重晶石矿床下部的震旦系陡山沱组碳酸盐岩(白云岩)和碎屑岩中,新发现一套规模较大、层位产出稳定的铅锌矿化。铅锌矿体和重晶石矿床具有"上部为重晶矿,下部为铅锌硫化物矿床"的矿化特征。铅锌矿段矿石矿物主要为闪锌矿、黄铁矿及方铅矿,含少量白铁矿、黄铜矿及磁黄铁矿;脉石矿物主要为石英和重晶石,少量白云石、热液磷灰石、炭沥青及钡冰长石。成矿流体特征类似于形成沉积喷流型铅锌矿床的流体特征。铅锌矿化中的硫源自局限海盆内早寒武世海水经硫酸盐还原作用提供。此种类似于喷流沉积型铅锌矿床在南华裂谷盆地一带矿化层位稳定、分布范围较广泛,体现早寒武世时在裂谷盆地内存在一次大规模的热液事件。天柱大河边铅锌矿床的发现具有重要的资源意义及区内该种矿床的勘查意义。     

Mineralogical, fluid inclusion, and stable isotope constraints on mechanisms of ore deposition at the Samgwang mine (Republic of Korea)—a mesothermal, vein-hosted gold–silver deposit

The Samgwang mine is located in the Cheongyang gold district (Cheonan Metallogenic Province) of the Republic of Korea. It consists of eight massive, gold-bearing quartz veins that filled NE- and NW-striking fractures along fault zones in Precambrian granitic gneiss of the Gyeonggi massif. Their mineralogy and paragenesis allow two separate vein-forming episodes to be recognized, temporally separated by a major faulting event. The ore minerals occur in quartz and calcite of stage I, associated with fracturing and healing of veins. Hydrothermal wall-rock alteration minerals of stage I include Fe-rich chlorite (Fe/(Fe+Mg) ratios 0.74-0.81), muscovite, illite, K-feldspar, and minor arsenopyrite, pyrite, and carbonates. Sulfide minerals deposited along with electrum during this stage include arsenopyrite, pyrite, pyrrhotite, sphalerite, marcasite, chalcopyrite, galena, argentite, pyrargyrite, and argentian tetrahedrite. Only calcite was deposited during stage II. Fluid inclusions in quartz contain three main types of C–O–H fluids: CO₂-rich, CO₂–H₂O, and aqueous inclusions. Quartz veins related to early sulfides in stage I were deposited from H₂O–NaCl–CO₂ fluids (1,500–5,000 bar, average 3,200) with T _htotal values of 200°C to 383°C and salinities less than about 7 wt.% NaCl equiv. Late sulfide deposition was related to H₂O–NaCl fluids (140–1,300 bar, average 700) with T _htotal values of 110°C to 385°C and salinities less than about 11 wt.% NaCl equiv. These fluids either evolved through immiscibility of H₂O–NaCl–CO₂ fluids as a result of a decrease in fluid pressure, or through mixing with deeply circulated meteoric waters as a result of uplift or unloading during mineralization, or both. Measured and calculated sulfur isotope compositions (δ³⁴S_H2S = 1.5 to 4.8‰) of hydrothermal fluids from the stage I quartz veins indicate that ore sulfur was derived mainly from a magmatic source. The calculated and measured oxygen and hydrogen isotope compositions (δ¹⁸O_H2O = −5.9‰ to 10.9‰, δD = −102‰ to −87‰) of the ore-forming fluids indicate that the fluids were derived from magmatic sources and evolved by mixing with local meteoric water by limited water–rock exchange and by partly degassing in uplift zones during mineralization. While most features of the Samgwang mine are consistent with classification as an orogenic gold deposit, isotopic and fluid chemistry indicate that the veins were genetically related to intrusions emplaced during the Jurassic to Cretaceous Daebo orogeny.