Trace element distribution in uraninite from Mesoarchaean Witwatersrand conglomerates (South Africa) supports placer model and magmatogenic source

The first systematic analyses of the trace and rare earth element (REE) distribution in uraninite from various gold-bearing conglomerates of the Mesoarchaean Central Rand Group in South Africa’s Witwatersrand Basin by in situ laser ablation-inductively coupled plasma-mass spectrometry confirms a placer origin for the uraninite and a magmatogenic provenance thereof. The chemistry of commonly rounded to sub-rounded uraninite is highly variable from grain to grain but generally marked by elevated Th, W, Bi, Mo, Ta, Y, REE contents and unusually high Au concentrations. Especially, the high Th contents and the chondrite-normalised REE patterns are incompatible with post-sedimentary hydrothermal genetic models for the U mineralisation and point to derivation of the detrital uraninite from a high-temperature, magmatogenic, presumably granitic to pegmatitic source. The elevated Au concentrations (of as much as 67 ppm) in this uraninite are unique to the Witwatersrand and hint at a granitic hinterland that was enriched in both U and Au, thus presenting a potential source domain for some of the detrital gold in the Witwatersrand conglomerates. Minute fracture fills of brannerite in close proximity to the larger, rounded uraninite grains are devoid of detectable Bi, Mo, REE and Au and have only very low concentrations of Th, W, Ta and Y. This is explicable by crystallisation from a low-temperature hydrothermal fluid. Thus, Witwatersrand U phases show, analogous to many other ore constituents, such as pyrite and gold, clear evidence of partial, short-range mobilisation of originally detrital particles by post-sedimentary fluids.     

Palaeoenvironmental significance of rounded pyrite in siliciclastic sequences of the Late Archaean Witwatersrand Basin: oxygen‐deficient atmosphere or hydrothermal alteration?

Petrographic and sulphur isotope studies support the long‐held contention that rounded grains of pyrite in siliciclastic sequences of the Late Archaean Witwatersrand Supergroup originated as placer grains. The grains are concentrated at sites where detrital heavy minerals are abundant within quartz‐pebble conglomerates and quartzose sandstones. Depositional sites with abundant pyrite are: (1) within the matrix of bar‐type, clast‐supported conglomerates; (2) on scoured or winnowed surfaces; and (3) on stratification planes. The grains are internally compact or porous, with truncation of internal structure at outer margins indicating fragmentation and rounding of pyritic source‐rocks during erosion and sediment transport. A large range in textures reflects source‐rock lithologies, with known varieties linked to sedimentary‐hosted diagenetic pyrite, volcanic‐hosted massive sulphide deposits and hydrothermal pyrite. Laser ablation sulphur isotope analysis of pyrite reveals a broader range in δ³⁴S values (? 5·3 to + 6·7‰) than that of previously reported conventional bulk‐grain analyses (? 1 to + 4‰). Rounded pyrite from the Steyn Reef has significant variation in δ³⁴S values (? 4·7 to + 6·7‰) that establishes heterogeneous sulphur compositions, with even adjacent grains having diverse isotopic signatures. The heterogeneity supports a placer origin for rounded pyrite. Euhedral pyrite and pyrite overgrowths which are undoubtedly authigenic have restricted δ³⁴S values (? 0·5 to + 2·5‰), are chemically distinct from rounded pyrite and are probably the products of metamorphism or hydrothermal alteration. The placer origin of rounded pyrite indicates that pyrite was a stable heavy mineral during erosion and transport in the early atmosphere. Its distribution in three sequences (Witwatersrand Supergroup, Ventersdorp Contact Reef and Black Reef), and in other sequences not linked to Witwatersrand‐type Au‐U ore deposits, implies deposition of redox‐sensitive detrital heavy minerals during the Late Archaean. Consequently, rounded grains of detrital pyrite are strong indicators of an oxygen‐poor atmosphere. While not confirming a placer origin for gold in Witwatersrand Au‐U ore deposits, the palaeoenvironmental significance of rounded pyrite negates its link to hydrothermal mineralization.     

Detrital pyrite in Witwatersrand gold reefs: X-ray diffraction evidence and implications for atmospheric evolution

Pyrite is easily oxidized, and therefore unambiguous evidence of detrital pyrite grains in metasediments is a significant constraint on when an oxygenated atmosphere developed. Compact rounded pyrite in the Witwatersrand gold reefs of South Africa has a detrital habit and is texturally equivalent to and spatially associated with detrital zircon and chromite. X-ray precession photography reveals that petrographically featureless As-poor grains are untwinned single crystals of high diffraction quality. This new evidence from crystallography is consistent with mechanically abraded pyrite from primary lode gold deposits, and excludes an origin by replacement of a pre-existing detrital phase. Further evidence of a detrital origin for the compact rounded pyrite is afforded by isolated grains of arsenian pyrite displaying truncated As-rich growth bands. The geographically extensive Witwatersrand fluvial conglomerates evidently had a matrix of quartz and pyrite sand and pyritic mud in their unconsolidated state and, thus, the late Archean atmosphere of Earth was likely essentially anoxic.     

白银厂铜多金属矿田微量元素和稀土元素地球化学研究

与日本黑矿及现代海底火山岩为主岩矿床相比，白银厂矿田各类矿石，尤其是块状Ｚｎ－Ｐｂ－Ｃｕ矿石具有最高的Ａｓ和Ｂｉ含量，比较高的Ｇａ、Ｃｄ和Ａｕ含量，以及较高的Ａｕ／Ａｇ和Ｃｏ／Ｎｉ比值。该矿田矿石的Ａｕ含量与闪锌矿中铁含量呈负相关关系。小铁山矿床闪锌矿与日本黑矿的闪锌矿微量元素特征很相似。矿田各类矿石ＲＥＥ型式与细碧角斑岩类岩石基体相似，这说明矿石与岩石的物质来源基本一致。研究和对比表明，火山成因     

浙江火山岩区金矿床黄铁矿的找矿矿物学研究

论文给出了中国浙江火山岩区金矿床中黄铁矿的微量元素、形态和物理性质找矿标型特征.例如.(在许多)浙江火山岩区重要金-银矿床中黄铁矿相对富含铅、锌、钼、锡、砷、锑、铋而贫钴,镍、硒、碲:并且S/Se、Ag/Au、Pb/Ni、Se/Te、(As+sb+Bi)/(Se+Te)比值较高,Co/Nj、Ag/Pb、Ag/Zn、Cu/Zn和(Co+Ni)/(Pb+Zn)比值较低,再如含金黄铁矿比不含金黄铁矿的反射率低.总之,黄铁矿的标型性研究对于寻找金矿具有重大的理论意义和实际意义.     

Alteration and mineralization styles of the orogenic disseminated Zhenyuan gold deposit,southeastern Tibet: Contrast with carlin gold deposit

Orogenic disseminated and Carlin gold deposits share much similarity in alteration and mineralization.The disseminated orogenic Zhenyuan Au deposit along the Ailaoshan shear zone,southeastern Tibet,was selected to clarify their difference.The alteration and mineralization from the different lithologies,including meta-quartz sandstone,carbonaceous slate,meta-(ultra)mafic rock,quartz porphyry and lamprophyre were researched.According to the mineral assemblage and replacement relationship in all types of host rocks,two reactions show general control on gold deposition:(1)replacement of earlier magnetite by pyrite and carbonaceous material;(2)alteration of biotite and phlogopite phenocrysts in quartz porphyry and lamprophyre into dolomite/ankerite and sericite.Despite the lamprophyre is volumetrically minor and much less fractured than other host rocks,it contains a large portion of Au reserve,indicating that the chemically active lithology has played a more important role in gold precipitation compared to structure.LA-ICP-MS analysis shows that Au mainly occurs as invisible gold in fine-grained pyrite disseminated in the host rocks,with Au content reaching to 258.95 ppm.The diagenetic core of pyrite in meta-quartz sandstone enriched in Co,Ni,Mo,Ag and Hg is wrapped by hydrothermal pyrite enriched in Cu,As,Sb,Au,Tl,Pb and Bi.Different host rock lithology has much impact on the alteration and mineralization features.Carbonate and sericite in altered lamprophyre show they have higher Mg than those developed in other of host rocks denoting that the carbonate and sericite incorporated Mg from phlogopite phenocrysts in the primary lamprophyre during alteration.The ore fluid activated the diagenetic pyrite in meta-quartz sandstone leading the hydrothermal pyrite enriched in Cu,Mo,Ag,Sb,Te,Hg,Tl,Pb and Bi,but the hydrothermal pyrite in meta-(ultra)mafic rock is enriched in Co and Ni as the meta-(ultra)mafic rock host rock contain high content of Co and Ni.However,Au and As shear similar range in both types of host rocks indicating that these two elements most likely come from the deep source fluid rather than the host rocks.It was shown in the disseminated orogenic gold deposit that similar hydrothermal alteration with mineral assemblage of carbonate(mainly dolomite and ankerite),sericite,pyrite and arsenopyrite develops in all types of host rocks.This is different from the Nevada Carlin type,in which alteration is mainly dissolution and silicification of carbonate host rock.On the other hand,Au mainly occur as invisible gold in both disseminated orogenic and Carlin gold deposits.     

Deciphering a multistage history affecting U–Cu(–Fe) mineralization in the Singhbhum Shear Zone,eastern India,using pyrite textures and compositions in the Turamdih U–Cu(–Fe) deposit

The ～200-km-long intensely deformed Singhbhum Shear Zone (SSZ) in eastern India hosts India’s largest U and Cu deposits and related Fe mineralization. The SSZ separates an Archaean cratonic nucleus to the south from a Mesoproterozoic fold belt in the North and has a complex geologic history that obscures the origin of the contained iron-oxide-rich mineral deposits. This study investigates aspects of the history of mineralization in the SSZ by utilizing new petrographic and electron microprobe observations of pyrite textures and zoning in the Turamdih U–Cu(–Fe) deposit. Mineralization at Turamdih is hosted in intensively deformed quartz–chlorite schist. Sulfides and oxides include, in inferred order of development: (a) magmatic Fe(–Ti–Cr) oxide and Fe–Cu(–Ni) sulfide minerals inferred to be magmatic (?) in origin; followed by (b) uranium, Fe-oxide, and Fe–Cu(–Co) sulfide minerals that predate most or all ductile deformation, and are inferred to be of hydrothermal origin; and (c) Fe–Cu sulfides that were generated during and postdating ductile deformation. These features are associated with the formation of three compositionally and texturally distinct pyrites. Pyrite (type-A), typically in globular–semiglobular composite inclusions of pyrite plus chalcopyrite in magnetite, is characterized by very high Ni content (up to 30,700 ppm) and low Co to Ni ratios (0.01–0.61). The textural and compositional characteristics of associated chalcopyrite and rare pyrrhotite suggest that this pyrite could be linked to the magmatic event via selective replacement of magmatic pyrrhotite. Alternatively, this pyrite and associated sulfide inclusions might be cogenetic with hydrothermal Fe-oxide. Type-B pyrite that forms elongate grains and irregular relics and cores of pyrite with high Co contents (up to 23,630 ppm) and high Co to Ni ratios (7.2–140.9) are interpreted to be related to hydrothermal mineralization predating ductile deformation. A third generation of pyrite (type C) with low Co, low Ni, and moderate Co to Ni ratios (0.19–13.93) formed during and postdating the ductile deformation stage overgrowing, replacing, and surrounding type-B pyrite. The textural evolution of pyrite parallels the tectonometamorphic evolution of the shear zone demonstrating grain elongation during progressive ductile deformation and prograde metamorphism, annealing at the peak metamorphic condition, porphyroblastic growth at the retrograde path and cataclasis following porphyroblastic growth. Compositional characteristics of hydrothermal pyrite and available geological information suggest that the U–Cu(–Fe) deposit at Turamdih might be a variant of the Fe oxide (–Cu–U–rare earth elements) family of deposits.     

Metallogenic age and fluid evolution of the Kangshan Au-polymetallic deposit in the southern margin of the North China Craton: Constraints from monazite U-Pb age,and in-situ trace elements and S isotopes of pyriteSCIEI北大核心CSCD

小秦岭-熊耳山金矿集区位于华北克拉通南缘,发育众多伴生铅锌银等金属的金矿,成为揭示克拉通破坏型金矿成因的天然实验室。产于小秦岭-熊耳山金矿集区内的康山金多金属矿床受控于北东向的中生代脆性断裂,赋存于新太古代变质岩和中元古代火山岩中。成矿过程可分为4个热液阶段:石英±黄铁矿阶段、石英-黄铁矿-黄铜矿-自然金阶段、多金属硫化物-自然金-石英-铁白云石阶段、石英-方解石±萤石阶段。本文获得康山金多金属矿床金成矿阶段热液独居石LA-ICP-MS U-Pb年龄为131.7±4.6Ma,与晚中生代华北克拉通破坏有关的岩浆热液成矿作用时代一致。本次研究开展的各阶段黄铁矿原位微量元素单点和扫面分析,发现第2阶段Au与Co、Ni、As呈正相关关系,且有明显的振荡环带,Cu、Ag、Sb、Pb、Bi这几种元素从黄铁矿颗粒的核部向边缘含量逐渐降低,且黄铁矿颗粒中出现富含这些元素的矿物包裹体,说明该阶段发生流体沸腾作用;而第3阶段黄铁矿中各微量元素含量为所有阶段中最低,黄铁矿无振荡环带且裂隙中有富含各微量元素的硫化物充填,说明各种元素在该阶段均得到充分卸载,且成矿流体的化学性质较稳定。结合前人关于该矿床各阶段流体包裹体分析结果,表明流体沸腾是Au的主要沉淀机制,而流体混合是Pb、Zn、Ag的主要沉淀机制。黄铁矿中微量元素含量指示,从第1阶段到第3阶段流体温度依次降低;第2和第3阶段流体fO2比第1阶段高且后两者相差不大。根据黄铁矿Co、Ni含量及比值的计算,认为第1和第2阶段黄铁矿为岩浆热液成因,第3阶段黄铁矿受围岩物质影响。黄铁矿原位S同位素分析得到第1至第3阶段黄铁矿δ34S分别为+6.6‰-+8.9‰、+5.0‰-+7.2‰和+6.0‰-+8.7‰,均与区域花岗岩类的S同位素值类似。综上所述,本文得出康山金多金属矿床形成于早白垩世与华北克拉通破坏有关的岩浆热液成矿作用。     

新疆托里蛇绿岩型金矿床中黄铁矿的研究

在金的伴生矿物中,黄铁矿在托里金矿床中是非常丰富的矿物。它不仅在数量上占优势,而且在本矿床中黄铁矿还以部分自然金的载体出现在矿化带中,所以对黄铁矿进行较为详细的研究是有实际意义的。另外,本矿床为一新型的金矿床——蛇绿岩型金矿,就其黄铁矿来说,无论是矿物学的特点或是地球化学特点都具有本类型矿床的独特性质,例如本黄铁矿中有CO/Ni<1、Au/Ag>1的特点。再者,托里金矿有两个成矿带,而黄铁矿在这两个成矿带中又有不同的特点,这是由于这两个成矿带不同的成矿环境所造成的。     

Morphology and geochemistry of different pyrite types from the Upper Witwatersrand System of the Klerksdorp Goldfield,South Africa

The morphology of pyrites from the Proterozoic, auriferous and uraniferous conglomerates of the Upper Witwatersrand System of the Klerksdorp Goldfield (South Africa) was studied by means of scanning electron microscopy (SEM). The pyrite particles were recovered by hydrofluoric acid leaching, thus making a three-dimensional SEM examination possible. According to morphological criteria the pyrites were classified into three types. Trace-element analysis by atomic absorption spetrophotometry (Au, Co, Ni, Cu, Zn, Pb, Mn, As) and the statistical evaluation of the results confirmed the morphological classification:

Type 1: Authigenic, idiomorphic to hypidiomorphic pyrites or pyrite accumulations, which were formed in the conglomerates during diagenesis or metamorphism.

Type 2: Allogenic, rounded, compact pyrites. This type was eroded from primary deposits in the hinterland of the Witwatersrand basin and deposited with the Witwatersrand sediments. It shows the closest trace-element affinity to pyrites from the Barberton Mountain Land, the source area model for the Witwatersrand sediments. The recognition of this pyrite type from the Klerksdorp Goldfield is in agreement with observations on detrital compact pyrites described from other goldfields of the Witwatersrand.

Type 3: Allogenic, rounded, porous pyrites. These were formed from pyritic muds and iron sulfide gels existing on the surface of the alluvial fan, and later were reworked as mud balls or fragments and deposited with the conglomerates. Indentations with radial fracture patterns point to transport partly in a plastic state. The occurrence of colloform pyrites among this type supports the postulation of pyritic muds or iron sulfide gels. Only in this type of pyrite various inclusions such as gold, quartz, silicates, brannerite, copper- and titanium-bearing minerals were found. It is suggested that these inclusions were trapped as dust-like particles in the pyritic muds or iron sulfide gels on the surface of the alluvial fan. Only the presence of the allogenic, porous pyrites could be correlated with high gold values in the conglomerates.

The three-dimensional SEM examination of the pyrites has shown that the pyrite types described by previous authors from the Witwatersrand System can be classified into the three types of pyrite given here.     

Texture and chemistry of pyrite at Chah Zard epithermal gold–silver deposit,Iran

Gold mineralization at Chah Zard, Iran, is mostly concentrated in breccia and veins, and is closely associated with pyrite. Optical and scanning electron microscopy-backscattered electron observations indicate four different pyrite types, each characterized by different textures: porous and fractured py1, simple-zoned, oscillatory-rimmed, framboidal and fibrous py2, colloform py3, and inclusion-rich py4. Laser ablation ICP–MS analysis and elemental mapping reveal the presence of invisible gold in all pyrite types. The highest concentrations (161–166 ppm Au) are found in py2 and py4, which correlate with the highest As concentrations (73,000–76,000 ppm). In As-poor grains, Au concentrations decrease by about two orders of magnitude. Copper, Pb, Zn, Te, Sb, and Ag occur with invisible gold, suggesting that at least part of the gold occurs in nanoparticles of sulfosalts of these metals and metalloids. Gold distribution patterns suggest that only negligible Au was originally trapped in py1 from the initial ore fluids. However, most, if not all, Au was transported and deposited during subsequent overprinting hydrothermal fluid flow in overgrowth rims around the margins of the py2 and within microfractures of py4 grains. Oscillatory zonation patterns for Co, Ni, Sb, Cu, Pb, and Ag in pyrite reflect fluctuations in the hydrothermal fluid chemistry. The LA-ICP–MS data reveal that Cu, Pb and Ag show systematic variations between different pyrite types. Thus, Cu/Pb and Pb/Ag ratios in pyrite may provide a potentially powerful exploration vector to epithermal gold mineralization at Chah Zard district and elsewhere.     

Paragenesis and geochemistry of ore minerals in the epizonal gold deposits of the Yangshan gold belt,West Qinling,China

Six epizonal gold deposits in the 30-km-long Yangshan gold belt, Gansu Province are estimated to contain more than 300 t of gold at an average grade of 4.76 g/t and thus define one of China's largest gold resources. Detailed paragenetic studies have recognized five stages of sulfide mineral precipitation in the deposits of the belt. Syngenetic/diagenetic pyrite (Py₀) has a framboidal or colloform texture and is disseminated in the metasedimentary host rocks. Early hydrothermal pyrite (Py₁) in quartz veins is disseminated in metasedimentary rocks and dikes and also occurs as semi-massive pyrite aggregates or bedding-parallel pyrite bands in phyllite. The main ore stage pyrite (Py₂) commonly overgrows Py₁ and is typically associated with main ore stage arsenopyrite (Apy₂). Late ore stage pyrite (Py₃), arsenopyrite (Apy₃), and stibnite occur in quartz ± calcite veins or are disseminated in country rocks. Post-ore stage pyrite (Py₄) occurs in quartz ± calcite veins that cut all earlier formed mineralization. Electron probe microanalyses and laser ablation-inductively coupled plasma mass spectrometry analyses reveal that different generations of sulfides have characteristic of major and trace element patterns, which can be used as a proxy for the distinct hydrothermal events. Syngenetic/diagenetic pyrite has high concentrations of As, Au, Bi, Co, Cu, Mn, Ni, Pb, Sb, and Zn. The Py₀ also retains a sedimentary Co/Ni ratio, which is distinct from hydrothermal ore-related pyrite. Early hydrothermal Py₁ has high contents of Ag, As, Au, Bi, Cu, Fe, Sb, and V, and it reflects elevated levels of these elements in the earliest mineralizing metamorphic fluids. The main ore stage Py₂ has a very high content of As (median value of 2.96 wt%) and Au (median value of 47.5 ppm) and slightly elevated Cu, but relatively low values for other trace elements. Arsenic in the main ore stage Py₂ occurs in solid solution. Late ore stage Py₃, formed coevally with stibnite, contains relatively high As (median value of 1.44 wt%), Au, Fe, Mn, Mo, Sb, and Zn and low Bi, Co, Ni, and Pb. The main ore stage Apy₂, compared to late ore stage arsenopyrite, is relatively enriched in As, whereas the later Apy₃ has high concentrations of S, Fe, and Sb, which is consistent with element patterns in associated main and late ore stage pyrite generations. Compared with pyrite from other stages, the post-ore stage Py₄ has relatively low concentrations of Fe and S, whereas As remains elevated (2.05～3.20 wt%), which could be interpreted by the substitution of As^? for S in the pyrite structure. These results suggest that syngenetic/diagenetic pyrite is the main metal source for the Yangshan gold deposits where such pyrite was metamorphosed at depth below presently exposed levels. The ore-forming elements were concentrated into the hydrothermal fluids during metamorphic devolatilization, and subsequently, during extensive fluid–rock interaction at shallower levels, these elements were precipitated via widespread sulfidation during the main ore stage.     

Geochemistry of Archean Radioactive Quartz Pebble Conglomerates and Quartzites from western margin of Singhbhum-Orissa Craton,eastern India: Implications on Paleo-weathering,provenance and tectonic setting

Lenses of radioactive Quartz Pebble Conglomerates (QPC) and associated quartzites are exposed along western margin of Archean Bonai Granite in Singhbhum-Orissa Craton, eastern India intermittently spreading over a strike length of 8–10 km. QPCs are radioactive while quartzites are mostly non-radioactive in nature. The purpose of the research is to investigate and characterize the radioactive QPC and quartzites geochemically to decipher their paleo-weathering conditions, provenance characteristics and possible tectonic setting of deposition. Geochemical data suggest moderate to high chemical weathering conditions in the provenance areas of QPC and quartzites. Major, trace and REE data indicate predominantly felsic to partly mafic-ultramafic sources for the deposition of radioactive Quartz Pebble Conglomerates from the surrounding Archean terrain.Elevated values of Th, U, Pb, La, Ce, Y and low Sc with high critical trace elemental ratios of Th/Sc, La/Sc, Th/Cr and Zr/Sc in radioactive QPC indicate their derivation from felsic igneous source. Low concentration of Th and Sc in quartzites compared to QPC and their variable Th/Sc ratios indicate both felsic and mafic sources for quartzites, albeit their preferential felsic affiliation. Higher Cr/Th ratios in quartzites (18.4), moderate Cr/Th in QPC (5.42), low to moderate Y/Ni in QPC (0.36–12.4) and quartzite (0.29–1.88), along with Au ranging from 30 to 1527 ppb, Pt up to 188 ppb and 682 ppb in QPC and quartzites respectively point towards some contribution from mafic-ultramafic source as well. REE patterns and in particular negative Eu anomalies for both QPC and quartzites further support their derivation from felsic rocks and could possibly linked to some of the phases of Archean Singhbhum Granite and Bonai Granite. Granitic to pegmatitic source for QPC is also revealed by the presence of rounded to sub-rounded monazite, zircon and thorian-uraninite grains in their matrix. Study indicates that QPC and quartzites were deposited in a passive margin tectonic setting developed during Archean between a span of 3.3 and 3.16 Ga along the western margin of Bonai Granite when the reducing condition was prevalent as indicated by their low Th/U ratios (<4.0) and presence of detrital grains of uraninite and pyrite in QPC. Radioactive QPC from western margin of Archean Singhbhum-Orissa Craton bears broad resemblance with QPC from Witwatersrand basin of South Africa and Elliot Lake, Canada and thus appears to be ideal sites for exploring QPC hosted U (+Au-PGE) mineralization in the analogous areas.     

Cu–(Ni–Co–Au)-bearing massive sulfide deposits associated with mafic–ultramafic rocks of the Main Urals Fault,South Urals: Geological structures,ore textural and mineralogical features,comparison with modern analogs

Cu-rich massive sulfide deposits associated with mafic–ultramafic rocks in the southern portion of the Main Urals Fault (MUF) are characterized by variable enrichments in Ni (up to 0.45 wt.%), Co (up to 10 wt.%) and Au (up to 16 ppm in individual hand-specimens). The Cu (Ni–Co)-rich composition of MUF deposits, as opposed to the Cu (Zn)-rich composition of more eastward massive sulfide deposits of broadly similar age along the western flank of the Magnitogorsk arc, reflects the abundance of seafloor-exposed, Ni–Co-rich ultramafic rocks in the most external portion of the Early-Devonian Magnitogorsk forearc. Morphological, textural, and compositional differences between individual deposits are interpreted to be the result of the sulfide deposition style and, in part, of the original subseafloor lithology. One deposit produced by dominantly on-seafloor hydrothermal processes is characterized by pyrite–marcasite ≫ pyrrhotite, not so low Zn grades (occasionally up to 2 wt.%), abundant clastic facies and periodical superficial oxidation. Deposits produced by dominantly subseafloor hydrothermal processes are characterized by pyrrhotite > pyrite, very low Zn (generally < to ≪ 0.1 wt.%), volumetrically minor clastic facies, and multi-layer deposit morphology. Very low Ni/Co ratios in the on-seafloor deposit may indicate a dominant metal contribution from a mafic rather than ultramafic source. The sulfide mineralization was associated with extensive hydrothermal alteration of the host ultramafic and mafic rocks, leading to formation of abundant talc, talc–carbonate and chlorite rocks. Occurrence of large volumes of such altered lithotypes in ophiolitic belts may be considered as a potential searching criteria for MUF-type (Cu, Co, Ni)-deposits. In spite of the contrasting geodynamic environment, geological, geochemical, textural and mineralogical peculiarities of the MUF deposits in many respects are similar to those of ultramafic-hosted massive sulfide deposits along the Mid-Atlantic Ridge. In geological time, supra subduction-zone settings appear to have been more effective than mid-ocean ridge settings for preservation of ultramafic-hosted massive sulfide deposits.     

广西大厂矿区黄铁矿的标型特征研究

本文从化学成分和物理性质方面对大厂黄铁矿进行了标型特征研究。指出大厂黄铁矿的标型特征是:高s/Fe值,高As、Se,低Co、Ni、Te,Co/Ni<1;热电系数高正值;晶胞参数a_0偏大;弱顺磁性。黄铁矿的微量元素特征表明矿床形成与岩浆热液有关,并反映了矿化演化的方向。应用黄铁矿的Sn/Cu比值可以区分矿区内不同的矿床类型。大厂锡矿体中锡石品位与黄铁矿含砷量呈正相关关系,因此,黄铁矿的高砷含量可作为寻找矿体内富锡地段的标志。     

Trace metal nanoparticles in pyrite

Hydrothermal pyrite contains significant amounts of minor and trace elements including As, Pb, Sb, Bi, Cu, Co, Ni, Zn, Au, Ag, Se and Te, which can be incorporated into nanoparticles (NPs). NP-bearing pyrite is most common in hydrothermal ore deposits that contain a wide range of trace elements, especially deposits that formed at low temperatures. In this study, we have characterized the chemical composition and structure of these NPs and their host pyrite with high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), analytical electron microscopy (AEM), and electron microprobe analysis (EMPA). Pyrite containing the NPs comes from two types of common low-temperature deposits, Carlin-type (Lone Tree, Screamer, Deep Star (Nevada, USA)), and epithermal (Pueblo Viejo (Dominican Republic) and Porgera (Papua New-Guinea)).EMPA analyses of the pyrite show maximum concentrations of As (11.2), Ni (3.04), Cu (2.99), Sb (2.24), Pb (0.99), Co (0.58), Se (0.2), Au (0.19), Hg (0.19), Ag (0.16), Zn (0.04), and Te (0.04) (in wt.%). Three types of pyrite have been investigated: “pure” or “barren” pyrite, Cu-rich pyrite and As-rich pyrite. Arsenic in pyrite from Carlin-type deposits and the Porgera epithermal deposit is negatively correlated with S, whereas some (colloform) pyrite from Pueblo Viejo shows a negative correlation between As + Cu and Fe. HRTEM observations and SAED patterns confirm that almost all NPs are crystalline and that their size varies from 5 to 100 nm (except for NPs of galena, which have diameters of up to 500 nm). NPs can be divided into three groups on the basis of their chemical composition: (i) native metals: Au, Ag, Ag–Au (electrum); (ii) sulfides and sulfosalts: PbS (galena), HgS (cinnabar), Pb–Sb–S, Ag–Pb–S, Pb–Ag–Sb–S, Pb–Sb–Bi–Ag–Te–S, Pb–Te–Sb–Au–Ag–Bi–S, Cu–Fe–S NPs, and Au–Ag–As–Ni–S; and (iii) Fe-bearing NPs: Fe–As–Ag–Ni–S, Fe–As–Sb–Pb–Ni–Au–S, all of which are in a matrix of distorted and polycrystalline pyrite. TEM-EDX spectra collected from the NPs and pyrite matrix document preferential partitioning of trace metals including Pb, Bi, Sb, Au, Ag, Ni, Te, and As into the NPs. The NPs formed due to exsolution from the pyrite matrix, most commonly for NPs less than 10 nm in size, and direct precipitation from the hydrothermal fluid and deposition into the growing pyrite, most commonly for those > 20 nm in size. NPs containing numerous heavy metals are likely to be found in pyrite and/or other sulfides in various hydrothermal, diagenetic and groundwater systems dominated by reducing conditions.     

LA-ICPMS原位微区面扫描分析技术及其矿床学应用实例

LA-ICPMS原位微区面扫描技术的发展对解析具有包裹体、环带结构的矿物或受多期岩浆/热液活动影响形成的溶蚀再结晶的矿物具有重要的地质意义。黄铁矿作为最普遍的硫化物种类之一,可形成于各种类型矿床中,其微量元素组份记录了矿床形成过程的重要信息。通过LA-ICPMS原位微区面扫描技术获得的黄铁矿晶体内部结构组份信息可用来限定成矿流体的性质、厘定成矿流体的演化规律、示踪成矿物质来源、约束变形变质作用过程中元素的活化和迁移行为,以及约束矿床成因等。本次研究选取了内蒙古二连盆地中巴彦乌拉大型铀矿床、辽宁青城子地区榛子沟铅锌矿、加拿大Pardo砂金矿中的黄铁矿作为研究对象,运用原位微区LA-ICPMS元素面扫描技术揭示其内部组份及结构信息,探索该技术在不同类型矿床中的应用价值。巴彦乌拉大型砂岩型铀矿床中的黄铁矿的内部组构信息显示成矿体系的p H和Eh对硫酸盐还原细菌活动均有影响,并控制与之相关的铀矿化;且成矿体系的p H和Eh受到外界不断供给的地下水的影响,呈振荡性变化。辽宁榛子沟铅锌矿中的黄铁矿的内部组构信息显示矿化过程受到了至少两期流体活动的叠加影响,包括早期同沉积时期的流体以及晚期与燕山期岩浆活动有关的热液流体。加拿大Pardo金矿中黄铁矿的内部组构信息显示矿床中半自形-自形的黄铁矿实际包含碎屑成因的磨圆状核部及后期热液活动形成的增生边;金主要呈浸染状分布在碎屑成因的黄铁矿核部,后期热液活动对金矿化影响微弱。     

邦布造山型金矿床黄铁矿原位微量元素特征及其成矿意义数

邦布金矿床是目前在雅江缝合带研究程度最高且唯一正在开采的大型造山型金矿床.为理解邦布金矿床中金的来源及迁移沉淀机制,运用原位微区分析技术对邦布矿床中不同世代含金黄铁矿的微量元素组成进行测定.结果显示,亲铁元素Co、Ni主要以类质同象的形式进入到黄铁矿的晶格中替代Fe,As和Se呈类质同象形式替换S,Au是以纳米颗粒的形式均匀或不均匀的分布于不同产状的黄铁矿之中.邦布金矿床中的含金石英脉中三个不同世代的黄铁矿的Co/Ni比值均小于1,保存了围岩中黄铁矿的信息,显示出一种沉积或沉积改造成因.Au与As和Se具有明显的正相关关系,As和Se对Au的迁移及富集具有重要的作用.      

Microfabric analyses applied to the Witwatersrand gold- and uranium-bearing conglomerates: constraints on the provenance and post-depositional modification of rock and ore components

Microfabrics of detrital quartz grains and quartz cement of four gold- and uranium-bearing conglomerates of various goldfields of the Witwatersrand Basin, South Africa, were investigated by optical and cathodoluminescence microscopy. The study revealed that the vast majority of quartz grains (<5 mm) originate from felsic magmatic source rocks. Cherts and polymineralic mineral grains, pointing to greenschist to amphibolite facies metasedimentary rocks, follow in abundance, whereas diagenetic to weakly metamorphosed quartzites are subordinate. Material from hydrothermal vein quartz is almost completely lacking, both in the sand and in the pebble fraction. No obvious relationships are discernible between the varying proportions of detrital siliciclastic components of the different reefs and their ore grades. Assuming a sedimentological control of gold distribution, this finding supports multiple sources for the detrital components, which were thoroughly mixed during transport. The post-depositional history of the sediments is characterized by a complex polyphase succession of deformation, cementation and hydrothermal alteration events. Both fragmentation and pressure solution features within detrital quartz, quartz cement and round grains of pyrite, zircon, chromite and uraninite demonstrate that these materials were present in the conglomerates during diagenesis, and, thus, are true detrital grains with abraded, rounded grain morphologies. By analogy, it is assumed that gold is also a detrital component, although most of the gold grains display characteristics of hydrothermal overprinting. During subsequent metamorphism, micro-shear zones are developed, and brittle-ductile crystal-plastic deformation and limited quartz recrystallization occur. Maximum temperatures of about 350 °C were reached on the prograde metamorphic path. Recrystallization and redistribution of detrital siliciclastic and ore minerals took place, and various hydrothermal/metamorphic minerals including chlorite, sericite, pyrophyllite and chloritoid were formed. These redistribution processes involved existing detrital minerals only and were generally isochemical because little evidence exists for the development of a secondary porosity and permeability that would allow major external inputs into the Witwatersrand conglomerates. Most of the gold grains have hydrothermal characteristics, as evidenced by their authigenic, crystalline shapes and their chemical compositions. However, these features are regarded to result from overprinting. Most likely, the gold grains experienced more drastic modifications relative to other ore components because of the ductile and mobile nature of gold. The retrograde metamorphic path is characterized by percolating radioactive fluids at T<300 °C, recorded by radiation damage indicated by cathodoluminescence alteration rims along quartz grain boundaries and microcracks. The degrees of radiation damage observed are proportional to the uranium contents of the conglomerate ores. The collective evidence of our study supports the modified placer model for the genesis of the Witwatersrand ores. This model explains most of the observations on the detrital mineral assemblage and its post-depositional modification elegantly and in a satisfactory manner.     

A revaluation of the Co/Ni ratio in pyrite as geochemical tool in ore genesis problems

On the basis of a sound evaluation of literature's data, the Co/Ni ratio in pyrite proves a more reliable indicator in ore genesis than previously retained. This is particularly true for volcanogenic pyritic ores which are constantly characterized by Co/Ni values (>5 but more often >10) definitely higher than those attained by sedimentary or hydrothermal pyrites. Moreover, once stated that an appropriate sampling has been performed, such geochemical studies, extended to as many deposits as possible from a same area, may provide relevant insights into the metallogenic history of the given area. On the basis of their Co/Ni ratios the Southern Tuscany ores fit in a two-stage metallogenic model: a primary (Paleozoic) emplacement of volcanogenic massive-sulfide deposits, in a sub-marine volcanic-exhalative environment, followed by later (Mio-Pliocenic) deposition of smaller, prevalently replacement deposits through hydrothermal partial mobilization of the older ones. The research of new ores may benefit from these geochemical studies too.