Mineralogy and geochemistry of the No. 6 Coal (Pennsylvanian) in the Junger Coalfield, Ordos Basin, China

This paper discusses the mineralogy and geochemistry of the No. 6 Coal (Pennsylvanian) in the Junger Coalfield, Ordos Basin, China. The results show that the vitrinite reflectance (0.58%) is lowest and the proportions of inertinite and liptinite (37.4% and 7.1%, respectively) in the No. 6 Coal of the Junger Coalfield are highest among all of the Late Paleozoic coals in the Ordos Basin. The No. 6 Coal may be divided vertically into four sections based on their mineral compositions and elemental concentrations. A high boehmite content (mean 6.1%) was identified in the No. 6 Coal. The minerals associated with the boehmite in the coal include goyazite, rutile, zircon, and Pb-bearing minerals (galena, clausthalite, and selenio-galena). The boehmite is derived from weathered and oxidized bauxite in the weathered crust of the underlying Benxi Formation (Pennsylvanian). A high Pb-bearing mineral content of samples ZG6-2 and ZG6-3 is likely of hydrothermal origin. The No. 6 coal is enriched in Ga (44.8 μg/g), Se (8.2 μg/g), Sr (423 μg/g), Zr (234 μg/g), REEs (193.3 μg/g), Hg (0.35 μg/g), Pb (35.7 μg/g), and Th (17.8 μg/g). Gallium and Th in the No. 6 Coal mainly occur in boehmite, and the Pb-bearing selenide and sulfide minerals contribute not only to Se and Pb contents in the coal, but also probably to Hg content. A high Zr content is attributed to the presence of zircon, and Sr is related to goyazite. The REEs in the coal are supplied from the sediment-source region, and the REEs leached from the adjacent partings by groundwater.     

南秦岭山阳—柞水矿集区夏家店金矿床微量-铂族元素地球化学特征及其对矿床成因的指示

夏家店金矿床位于南秦岭造山带内,是一个受构造和地层控制的大型金矿床,矿石类型为角砾岩型、碎裂岩型和石英脉型3种类型,赋矿围岩主要为寒武系水沟口组的炭泥质板岩、炭硅质板岩、硅质岩及白云岩,次为泥盆系西岔河组的角砾岩。本文对夏家店金矿床中矿石（角砾状炭硅质板岩、碎裂硅化白云岩、碎裂炭泥质板岩和石英脉状矿化的硅质岩）和围岩（硅质岩、硅化白云岩和硅质板岩）的微量元素、铂族元素（PGE）质量分数进行测试,进而探讨成矿物质来源以及矿床成因。结果表明：不同类型的矿石与其各自的围岩具有高度的相似性,均富集Sr、Ga、Zr等元素;不同类型的矿石稀土总量均高于各类围岩,但是两者具有相似的稀土配分模式,轻稀土富集,重稀土亏损,均表现出负Eu异常（δEu值为0.51~0.63）;不同类型的矿石PGE总量（7.71×10^-9~38.30×10^-9,平均值23.00×10^-9）均明显大于各类围岩PGE总量（1.28×10^-9~2.44×10^-9,平均值1.86×10^-9）,相比上地壳,不同类型的矿石均明显富集Os、Ir、Pt和Pd,亏损Ru、Rh,而各类围岩均富集Os,亏损Pt、Ru、Rh、Pd,但两者的铂族元素配分曲线具有高度相似性,呈Ru亏损的V型,为地壳的（Os）-Pt-Pd型配分模式。以上特征表明不同类型的矿石和围岩具有明显的微量、稀土元素和PGE地球化学继承性,暗示夏家店下寒武统有可能是重要的矿源层之一。同时,所有矿石和围岩的Au/Ir值（分别为4 821~299 666）和406~8 050）及Pd/Ir值（分别为16.9~588.0和15.2~47.5）变化范围均较大,两者Au/Ir值远高于炭质球粒陨石和原始地幔值、Pd/Ir值远高于岩浆成因矿石值,且夏家店金矿床矿石和围岩的PGE配分曲线与典型热液成因矿床一致。这些特征显示夏家店金矿床具有明显的热液成因,是构造-热液流体成矿作用的产物。     

贵州普安矿区晚二叠世煤中贵金属元素的赋存状态和地质成因

运用电感耦合等离子体质谱(ICP-MS)和逐级化学提取技术(SCET)对贵州西部普安矿区晚二叠世煤中贵金属元素的含量、赋存状态和成因机理进行了研究.结果表明,贵州普安矿区2号主采煤层的矿物组成主要为低温热液流体成因的黄铁矿和陆源碎屑成因的粘土矿物;与中国煤煤相比,该煤中Rh(38 ng/g)、Pb(640 ng/g)、Ir(9 ng/g)、Pt(98 ng/g)、Au(16 ng/g)和Ag(1620 ng/g)明显富集,其中Pb、Ir、Au的含量分别是中国煤的4.3倍、9倍和5.3倍.逐级化学提取结果表     

Abundance and distribution of PGE and Au in the island-arc mantle: implications for sub-arc metasomatism

Ultramafic xenoliths from a veined mantle wedge beneath the Kamchatka arc have non-chondritic, fractionated chondrite-normalized platinum-group element (PGE) patterns. Depleted (e.g., low bulk-rock Al₂O₃ and CaO contents) mantle harzburgites show clear enrichment in the Pd group relative to the Ir group PGEs and, in most samples, Pt relative to Rh and Pd. These PGE signatures most likely reflect multi-stage melting which selectively concentrates Pt in Pt–Fe alloys while strongly depleting the sub-arc mantle wedge in incompatible elements. Elevated gold concentrations and enrichment of strongly incompatible enrichment (e.g., Ba and Th) in some harzburgites suggest a late-stage metasomatism by slab-derived, saline hydrous fluids. Positive Pt, Pd, and Au anomalies coupled with Ir depletions in heavily metasomatized pyroxenite xenoliths probably reflect the relative mobility of the Pd and Ir groups (especially Os) during sub-arc metasomatism which is consistent with Os systematics in arc mantle nodules. Positive correlations between Pt, Pd, and Au and various incompatible elements (Hf, U, Ta, and Sr) also suggest that both slab-derived hydrous fluids and siliceous melts were involved in the sub-arc mantle metasomatism beneath the Kamchatka arc.     

Mineralogical and compositional characteristics of Late Permian coals from an area of high lung cancer rate in Xuan Wei, Yunnan, China: Occurrence and origin of quartz and chamosite

Some townships in Xuan Wei County, Yunnan Province, have one of the highest lung cancer mortality rates in China and the epidemic disease in the area has generally been attributed to the polycyclic aromatic hydrocarbons (PAHs) released from domestic coal burning. However, the cancer-causing culprit is not settled as Tian [Tian, L., 2005. Coal Combustion Emissions and Lung Cancer in Xuan Wei, China. Ph.D. thesis, University of California, Berkeley.] found nanometer quartz in these coals, soot emissions, and lung cancer tissues. We have conducted mineralogical and geochemical studies of the coals from Xuan Wei for the purpose of shedding light on the minerals which may be related to the epidemic lung cancer. In this paper, abundances, modes of occurrence, and origins of minerals and elements in the coals from two mines in Xuan Wei have been studied using optical microscope, low-temperature ashing, X-ray diffraction analysis, scanning electron microscope equipped with energy-dispersive X-ray spectrometer, and inductively-coupled plasma mass spectrometry. The minerals in the coals are mainly composed of quartz, chamosite, kaolinite, and calcite. The particle size of quartz is rather small, mostly less than 20 μm and it is of authigenic origin. Chamosite occurs mainly as cell-fillings. The occurrence of quartz and chamosite indicates that they were derived from the hydrothermal fluids. Epigenetic calcite is derived from calcic fluids. Kaolinite is derived mainly from sediment source region of Kangdian Oldland to the west of coal basin. The composition of Xuan Wei coal is high in SiO₂, Fe₂O₃, TiO₂, CaO, MnO, V, Co, Ni, Cu, and Zn. The high SiO₂ content is attributed to quartz, and the Fe₂O₃ content to chamosite. The high Mn and low Mg contents in the coal indicate the inputs of hydrothermal fluids. CaO occurs mainly in epigenetic calcite. Elements Ti, Co, Ni, Cu, Zn, and rare earth elements were derived from the basaltic rocks at sediment source region.     

四川木落稀土矿床方解石铂族元素地球化学特征

方解石作为木落稀土矿床常见的脉石矿物,其中的铂族元素(简称PGE)地球化学特征有可能记录了地质流体的性质。采用ICP-MS分析木落方解石中PGE的含量,并对铂族元素的分布、相关性、成因进行了探讨。木落方解石可以分为两类:I型方解石和Ⅱ型方解石。I型方解石中∑PGE(不含Os)0.62～1.33ng/g,具相对低的Pd/Pt、Pd/Rh、Pd/Ru、Pd/Ir比值,不太显著的Pt-Pd分配模式,为岩浆成因方解石,与成矿作用密切相关;Ⅱ型方解石中∑PGE(不含Os)1.85～2.97ng/g,具相对高的Pd/Pt、Pd/Rh、Pd/Ru、Pd/Ir比值和显著的Pt-Pd分配模式,为热液成因方解石,代表了成矿作用后的一期地质流体作用,与成矿关系不大,仅局部地区存在改造前次流体作用形成的稀土矿体。富CO2热液具有携带PGE的能力,并能够导致PGE的分异,与富CO2岩浆相比,富CO2热液对铂族元素具有一定程度的富集作用。     

秦岭凤太矿田层控铅锌(铜)矿床的氧化硅产出特征及其硅质来源

秦岭凤太矿田的所有铅锌(铜)矿床中都含有大量的氧化硅，前人资料中往往以沉积或蚀变单一形成方式论其成因，非此即彼。本文提出氧化硅有三种产出类型，以同生沉积型为主，其次为成岩后生阶段交代灰岩者，第三类为造山期形成的脉体。三类氧化硅的产出特征有许多不同，但硅质来源一致，即均来自深部地层和岩石中循环的含矿热液。对矿床中氧化硅的研究不仅有助于深入探讨矿床的成因，而且对于该类矿床的勘查有较重要的意义。     

Iridium enrichment and poor fractionation from gold, platinum and palladium in clausthalite (PbSe), Tilkerode, eastern Harz, Germany

Enrichments in platinum-group elements were found in clausthalite, PbSe, which occurs in carbonate–hematite veins hosted in black shale of Upper Wenlockian age in the eastern Harz, Germany. Spot measurements by laser ablation–quadrupole inductively coupled plasma mass spectrometry (LA–QICPMS) show that the clausthalite has Pt contents that average 0.459?ppm and range from 0.003 to 2.83?ppm. Other noble metals quantified in the present work include Au (0.226?ppm, 0.109–0.451?ppm), Ru (0.061?ppm, 0.006–0.264?ppm), Ir (0.071?ppm, 0.010–0.185?ppm), Pd (0.046?ppm, 0.017–0.107?ppm) and Os (0.010?ppm, <0.003–0.024?ppm). Elemental ratios of Au/Ir, Pd/Ir and Pt/Ir, the average values of which are respectively 4.6, 0.8, and 4.9, suggest that Au, Pd and Pt are poorly fractionated from Ir. The resulting Ir enrichment is unusual and should reflect a particularly soluble (and stable) aqueous complex of Ir in a highly oxidizing, low-temperature, Se-rich solution.     

Textures, paragenesis and wall-rock alteration of lode-gold deposits in the Charters Towers district, north Queensland: implications for the conditions of ore formation

Ore deposits of the Charters Towers Goldfield (CTGF) are mainly hosted by fault-fill veins. Extensional (∼8% of all veins) and stockwork-like (∼3%) veins are less common and of little economic significance. Crosscutting relationships and published structural and geochronological data indicate a Late Silurian to Early Devonian timing of gold mineralization, coincident with regional shortening (D₄) and I-type magmatism. Paragenetic relationships, which are uniform in veins everywhere within the CTGF, suggest that vein formation commenced with the deposition of large volumes of buck quartz (stage I), followed by buck and comb quartz, and significant pyrite and arsenopyrite precipitation (stage II). Gold was introduced during stage III, after earlier sphalerite and coincident with galena and chalcopyrite. Narrow, discontinuous calcite veins of stage IV mark the waning of gold-related hydrothermal activity or a later unrelated episode. Ore zones within the veins are everywhere composed of comb and/or gray quartz, calcite and/or ankerite and bands or clusters of fractured pyrite that are spatially associated with galena, sphalerite or chalcopyrite. Low-grade or barren vein sections, on the other hand, are mainly composed of milky buck quartz with little evidence for modification, overprinting or interaction with later fluids. Gold-related hydrothermal wall-rock alteration is symmetrically zoned, displaying proximal sericite–ankerite and distal epidote–chlorite–hematite assemblages that may be taken to imply wall-rock interaction with near neutral fluids (pH 5–6). Isocon plots assuming immobile Al, P, Ti, Y and Zr consistently indicate As, K, Pb, S and Zn enrichment and Na, Si and Sr depletion in altered wall-rock specimens relative to the least altered rocks. Alteration assemblages, quartz textures, fault rocks and published fluid inclusion and stable isotope data imply that the veins were formed under conditions of episodic fluid overpressuring (∼0.9–3.8 kbar), at a depth of ∼7 km and a temperature of ∼310°C. The published fluid inclusion data also imply that gold precipitation may have been brought about by fluid mixing. However, physi- and chemisorption of gold complexes onto sulfide surfaces may have been important depositional processes and controls on gold enrichment at the millimeter to centimeter scale, given that most gold particles are attached to the surfaces of pyrite crystals of stage II or to etch-pits and fracture surfaces within the earlier pyrite.     

Siderite mineralization of the Gemericum superunit (Western Carpathians, Slovakia): review and a revised genetic model

The Gemericum is a segment of the Variscan orogen subsequently deformed by the Alpine–Carpathian orogeny. The unit contains abundant siderite–sulphide and quartz–antimony veins together with stratabound siderite replacement deposits in limestones and stratiform sulphide mineralization in volcano-sedimentary sequences. The siderite–sulphide veins and siderite replacement deposits of the Gemericum represent one of the largest accumulations of siderite in the world, with about 160 million tonnes of mineable FeCO₃. More than 1200 steeply dipping hydrothermal veins are arranged in a regional tectonic and compositional pattern, reflecting the distribution of regional metamorphic zones. Siderite–sulphide veins are typically contained in low-grade (chlorite zone) sedimentary, volcano-sedimentary or volcanic Lower and Upper Paleozoic rocks. Quartz–antimony veins are hosted by higher-grade units (biotite zone). Siderite–sulphide veins are dominated by early siderite followed by a complex set of stages, including quartz–sulphide (chalcopyrite, tetrahedrite), barite, tourmaline–quartz, and sulphide-remobilization stages. The temporal evolution of these stages is difficult to study because of the widespread and repeated tectonic processes, within-vein replacement and recrystallization. Siderite–sulphide veins show considerable vertical (up to 1200 m) and lateral (up to 15 km) extent, and a thickness typically reaching several metres. Carbonate-replacement siderite deposits of the Gemericum are hosted by a Silurian limestone belt and are similar to stratabound siderite deposits of the Eastern Alps (e.g., Erzberg, Austria).Based on a review of geological, petrological and geochronological data for the Gemericum, and extensive stable and radiogenic isotope data and fluid inclusion data on hydrothermal minerals, the siderite–sulphide veins and siderite replacement deposits are classified as metamorphogenic in a broad sense. The deposits were formed during several stages of regional crustal-scale fluid flow. Isotope (S, C, Sr, Pb) fingerprinting identifies the metamorphosed rock complexes of the Gemericum as a source of most components of hydrothermal fluids. Fluid inclusion and stable isotope data evidence the participation of several contrasting fluid types, and the existence of contrasting P–T conditions during vein evolution. A high-δ¹⁸O, medium- to high-salinity, H₂O-type fluid is the most important component during siderite deposition, whereas H₂O–CO₂-type fluid inclusion containing dense liquid CO₂ and corresponding to minimal pressures between 1 and 3 kbar were found in a younger tourmaline–quartz stage. Younger quartz–ankerite(±siderite)–sulphide stages are characterized by high-salinity (17 to 35 wt.% NaCl equivalent) and low-temperature (T_h=90 to 180 °C) H₂O-type fluids.The vein deposits are interpreted as a result of multistage hydrothermal circulation, with Variscan and Alpine mineralization phases. Based on available indirect data, the most important mineralization phase was related to regional fluid flow during the uplift of a Variscan metamorphic core complex, producing siderite–sulphide (±barite) mineralization, while tourmaline–quartz stage and sulphide remobilization stages are related to Alpine processes. Two phases of vein evolution are evident from two groups of ⁸⁷Sr/⁸⁶Sr isotope ratios of Sr-rich, Rb-poor hydrothermal minerals: 0.71042–0.71541 in older barite and 0.7190–0.7220 in late-stage celestine and strontianite.     

Platinum-group minerals in the Santo Tomas II (Philex) porphyry copper-gold deposit,Luzon Island,Philippines

Mineralized quartz diorites of the Santo Tomas II porphyry copper-gold deposit, carry high Au contents (average: 1.8 ppm) as well as 160 ppb Pd and 38 ppb Pt. Values of other platinum-group elements (PGE) and rhenium are below the analytical detection limits. There is a significant positive correlation between Au and Cu. The highest Pd values were detected in the most Au- and Cu-rich rocks. Platinum-group minerals (PGM) occur exclusively as inclusions in chalcopyrite and bornite. Potential Pd and Pt contents in sulphide concentrates are estimated at 1.5 g/t and 0.4 g/t, respectively. The precious metal assemblages consist of merenskyite (main PGM), kotulskite, moncheite, native gold, electrum, hessite and petzite. Polyphase fluid inclusions in quartz veinlets, associated with a PGM-bearing bornite-chalcopyrite-magnetite assemblage, are characterized by high salinity (35 to > 60 eq. wt% NaCl) and high trapping temperatures (between 380 and 520 °C). They may represent primary magmatic-hydrothermal fluids, which have been responsible for the transport of Pd, Pt and Au as chloride complexes.     

Platinum-group element geochemistry of peridotite xenoliths from the Sierra Nevada and the Basin and Range, California

The nature of PGE-Re (PGE = Pt, Pd, Os, Ir, Ru) behavior in subcontinental lithospheric mantle was investigated using new, high precision PGE-Re abundance measurements and previously published Re-Os isotopic analyses of peridotite xenoliths from the Sierra Nevada and Mojave Province, California. Ru/Ir ratios and Ir concentrations are constant over a wide range in S content and major-element fertility indices (e.g., Mg/(Mg+Fe)), indicating that Ru and Ir are not only compatible during partial melting, but also that their partitioning behaviors may not be controlled entirely by sulfide. Pt/Ir, Pd/Ir, Os/Ir, and Re/Ir ratios range from slightly superchondritic to distinctly subchondritic for all xenoliths except for one anomalous sample (1026V), which is characterized by radiogenic ¹⁸⁷Os/¹⁸⁸Os, low Re/Os ratio, and large enrichments in Cu, Os, Pt, Pd, and S relative to Ir (COPPS metasomatism). Assuming chondritic initial relative abundances, the magnitudes of some of the depletions in Pt, Pd, Os, and Re relative to Ir and Ru require incompatible behavior or substantial secondary loss. In detail, some samples, which are otherwise characterized by fertile major-element indices, exhibit low S contents and subchondritic Os/Ir and Pd/Ir ratios, indicating that depletions in Pd and Os relative to Ir are not simple functions of the degree of melting as inferred from major elements. Possible mechanisms for depleting Pt, Pd, Os, and Re relative to Ir and Ru include partitioning into chromian spinels and alloys, partitioning between sulfide and sulfide liquids, mobilization by aqueous fluids, or secondary loss associated with late-stage sulfide breakdown. However, it is not possible to explain all of the depletions in Pt, Pd, Os, and Re by any single mechanism.The preferential enrichment in Os over Re and Ir in sample 1026V is somewhat paradoxical because this sample’s radiogenic ¹⁸⁷Os/¹⁸⁸Os requires a metasomatic agent, originating from a source with a high time-integrated Re/Os ratio. The abundant garnet websterite xenoliths may be a suitable source because they have high Re/Os ratios, radiogenic Os, and abundant garnet, which may sequester Re over Os during partial melting. However, their extremely low Os contents require the processing of large amounts of garnet websterite to concentrate enough Os into the metasomatic sulfides needed to enrich sample 1026V in Os. The homogeneity in ¹⁸⁷Os/¹⁸⁸Os ratio in the remaining xenoliths suggest that their Os isotopic compositions were not significantly affected by PGE metasomatism. The singular nature of 1026V’s composition emphasizes the rarity of COPPS metasomatism.     

PGE fractionation in seafloor hydrothermal systems: examples from mafic- and ultramafic-hosted hydrothermal fields at the slow-spreading Mid-Atlantic Ridge

The distribution of platinum group elements (PGEs) in massive sulfides and hematite–magnetite±pyrite assemblages from the recently discovered basalt-hosted Turtle Pits hydrothermal field and in massive sulfides from the ultramafic-hosted Logatchev vent field both on the Mid-Atlantic Ridge was studied and compared to that from selected ancient volcanic-hosted massive sulfide (VHMS) deposits. Cu-rich samples from black smoker chimneys of both vent fields are enriched in Pd and Rh (Pd up to 227 ppb and Rh up to 149 ppb) when compared to hematite–magnetite-rich samples from Turtle Pits (Pd up to 10 ppb, Rh up to 1.9 ppb). A significant positive correlation was established between Cu and Rh in sulfide samples from Turtle Pits. PGE chondrite-normalized patterns (with a positive Rh anomaly and Pd and Au enrichment), Pd/Pt and Pd/Au ratios close to global MORB, and high values of Pd/Ir and Pt/Ir ratios indicate mafic source rock and seawater involvement in the hydrothermal system at Turtle Pits. Similarly shaped PGE chondrite-normalized patterns and high values of Pd/Pt and Pd/Ir ratios in Cu-rich sulfides at Logatchev likely reflect a similar mechanism of PGE enrichment but with involvement of ultramafic source rocks.     

Geochemical signature of orogenic hydrothermal activity in an active tectonic intersection zone,Alpine Fault,New Zealand

A highly faulted and fractured rock mass has developed at the intersection of the Alpine and Hope faults, two major active faults in the South Island, New Zealand. The Alpine Fault is an oblique dextral reverse fault at the late Cenozoic-Recent Pacific-Australian plate boundary. The Hope Fault is a strike-slip fault parallel to the plate convergence vector. Hydrothermal fluids driven by the active tectonic processes have passed through the fractured rock mass, causing localised rock alteration and vein formation. Mylonites in the Alpine Fault zone are crosscut by cm-scale veins of quartz and/or ankerite with minor sulphides, with cemented breccias in dilational jogs. Breccia clasts and immediate (cm-scale) host rocks have been variably impregnated with carbonates and quartz. This generation of veins, breccias and altered rocks is post-dated by cataclasite and fault gouge zones which have been cemented by calcite, illite, smectite and chamosite. Ankerite and calcite have ¹⁸O between +10 and +30, and ¹³C between 0 and –8. These minerals are inferred to have formed from water with variable components of both meteoric and crustally exchanged fluid. Rock alteration associated with ankerite–quartz veins has added arsenic (up to 200 ppm As), strontium, and some Y to the rocks. Host-rock mylonites (<2 ppm As) have been depleted in arsenic compared to their precursors (5–15 ppm As). This depletion of arsenic in the middle crust provides the source for arsenic in shallower-level vein systems.Editorial handling: N. White     

The characteristics of automobile catalyst-derived platinum group elements in road dusts and roadside soils: a case study in the Pearl River Delta region,South China

The emission of platinum group elements (PGE) from automobile catalytic converters has led to enrichment of PGE in road dusts and roadside soils in urban areas that are well above the natural background levels. This paper evaluates the source of contamination of all the PGE and Au in road dusts and roadside soils in the Pearl River Delta region, including three major cities, Shenzhen, Guangzhou and Hong Kong, South China. Samples were digested using Carius tube and analyzed by isotope dilution ICP-MS; Os was separated by distillation and other PGE by Te-coprecipitation. All samples have elevated PGE concentrations above the background values of uncontaminated soils and contain higher Pt, Pd and Rh than other PGE. The maximum values are 181 ng/g Pt, 514 ng/g Pd, 53 ng/g Rh and 1345 ng/g Au. There are clear positive correlations between Pt and Pd, Pt and Rh, and Pd and Rh, indicating that the main emitted of PGE from automobile catalyst are Pt, Pd and Rh. High concentrations of Au were also found in road dust samples from Hong Kong and Shenzhen. Dust samples with higher Os contents have lower ¹⁸⁷Os/¹⁸⁸Os ratios. Samples from Hong Kong show relatively high Pt/Rh ratios. Positive correlations between Pt and Ru, and Pt and Ir were found in Shenzhen and Hong Kong, but only positive correlations between Pt and Ir were found in Guangzhou. These different characteristics reflect different automobile catalytic systems used in Hong Kong and mainland China.     

Sulphide Segregation in Ferropicrites from the Pechenga Complex, Kola Peninsula, Russia

The Palaeoproterozoic Ni–Cu sulphide deposits of the PechengaComplex, Kola Peninsula, occur in the lower parts of ferropicriticintrusions emplaced into the phyllitic and tuffaceous sedimentaryunit of the Pilgujärvi Zone. The intrusive rocks are comagmaticwith extrusive ferropicrites of the overlying volcanic formation.Massive lavas and chilled margins from layered flows and intrusionscontain <3–7 ng/g Pd and Pt and <0·02–2·0ng/g Ir, Os and Ru with low Pd/Ir ratios of 5–11. Theabundances of platinum group elements (PGE) correlate with eachother and with chalcophile elements such as Cu and Ni, and indicatea compatible behaviour during crystallization of the parentalmagma. Compared with the PGE-depleted central zones of differentiatedflows (spinifex and clinopyroxene cumulate zones) the olivinecumulate zones at the base contain elevated PGE abundances upto 10 ng/g Pd and Pt. A similar pattern is displayed in intrusivebodies, such as the Kammikivi sill and the Pilgujärvi intrusion.The olivine cumulates at the base of these bodies contain massiveand disseminated Ni–Cu-sulphides with up to 2 µg/gPd and Pt, but the PGE concentrations in the overlying clinopyroxenitesand gabbroic rocks are in many cases below the detection limits.The metal distribution observed in samples closely representingliquid compositions suggests that the parental magma becamesulphide saturated during the emplacement and depleted in chalcophileand siderophile metals as a result of fractional segregationof sulphide liquids. Relative sulphide liquid–silicatemelt partition coefficients decrease in the order of Ir >Rh > Os > Ru > Pt = Pd > Cu. R-factors (silicate-sulphidemass ratio) are high and of the order of 10⁴–10⁵, andthey indicate the segregation of only small amounts of sulphideliquid in the parental ferropicritic magma. In differentiatedflows and intrusions the sulphide liquids segregated and accumulatedat the base of these bodies, but because of a low silicate–sulphidemass ratio the sulphide liquids had a low PGE tenor and Pt/Irand Cu/Ir ratios similar to the parental silicate melts. Duringcooling the sulphide liquid crystallized 40–50% of monosulphidesolid solution (mss) and the residual sulphide liquid becameenriched in Cu, Pt and Pd and depleted in Ir, Os and Ru. TheCu-rich sulphide liquid locally assimilated components of thesurrounding S-rich sediments as suggested by the radiogenicOs isotopic composition of some sulphide ores (     

Sulfides associated with podiform bodies of chromite at Tsangli,Eretria, Greece

Small bodies of pyrrhotite, chalcopyrite, minor pentlandite, and magnetite occur at the peripheries of podiform bodies of chromite in ultramafic ophiolitic rocks at Tsangli, Eretria, central Greece. Banding of magnetite and sulfide within the bodies is reminiscent of magmatic banding. A magmatic origin has been proposed for similar sulfide masses in the Troodos ophiolite (Panayiotou, 1980). The compositions of the host rocks, chromite, and of the sulfides have been investigated. On average, the sulfide mineralization, recalculated to metal content in 100% sulfide, contains 0.55% Ni, 5.15% Cu, 0.29% Co, 9 ppb Pd, 179 ppb Pt, 16 ppb Rh, 112 ppb Ru, 31 ppb Ir, 58 ppb Os, and 212 ppb Au. These metal contents, particularly the high Cu/(Cu+Ni) ratio of 0.78 and the Pt/(Pd+Pt) ratio of 0.95, are inconsistent with the sulfides having reached equilibrium with their Ni rich host rocks at magmatic temperatures and accordingly it is concluded that they are not of magmatic origin. The average ³⁴S value of the sulfide bodies is +2 while that of a sample of pyrite from country-rock schist is –15.6. These values are inconclusive as to the origin of the sulfur. It is suggested that the sulfides have been precipitated by hydrothermal fluids, possibly those responsible for the serpentinization of the host rocks. The source of the metals may have been the host rocks themselves.     

北京十三陵地区中侏罗统九龙山组硅质岩成因模式及地质意义

中生代晚期中国北部陆相沉积地层发育,中侏罗统九龙山组是本时期沉积的典型代表。北京十三陵地区九龙山组出露有一套硅质岩,其Ge/Si值介于热液流体(~11 μmol/mol)和河流(~0.7 μmol/mol)之间,整体为3~4 μmol/mol,少数样品的Ge/Si值较高;其REE分配具有较明显的Eu正异常(1.2~2.4,平均1.58),整体比较平稳,无明显Ce异常,兼具河流和热液的特征。通过对REE特征和Ge/Si值进行半定量分析,本研究认为九龙山组硅质岩的物源来自热液和河流的混合,其中,热液贡献约为30%。     

Highly siderophile element behaviour accompanying subduction of oceanic crust: Whole rock and mineral-scale insights from a high-pressure terrain

Highly siderophile element concentrations (HSE: Re and platinum-group elements (PGE)) are presented for gabbros, gabbroic eclogites and basaltic eclogites from the high-pressure Zermatt-Saas ophiolite terrain, Switzerland. Rhenium and PGE (Os, Ir, Ru, Rh, Pt, Pd) abundances in gabbro- and eclogite-hosted sulphides, and Re-Os isotopes and elemental concentrations in silicate phases are also reported. This work, therefore, provides whole rock and mineral-scale insights into the PGE budget of gabbroic oceanic crust and the effects of subduction metamorphism on gabbroic and basaltic crust.Chondrite-normalised PGE patterns for the gabbros are similar to published mid-ocean ridge basalts (MORB), but show less inter-element fractionation. Mean Pt and Pd contents of 360 and 530 pg/g, respectively, are broadly comparable to MORB, but gabbros have somewhat higher abundances of Os, Ir and Ru (mean: 64, 57 and 108 pg/g). Transformation to eclogite has not significantly changed the concentrations of the PGE, except Pd which is severely depleted in gabbroic eclogites relative to gabbros (∼75% loss). In contrast, basaltic eclogites display significant depletion of Pt (?60%), Pd (>85%) and Re (50-60%) compared with published MORB, while Os, Ir and Ru abundances are broadly comparable. Thus, these data suggest that only Pt, Pd and Re, and not Os, Ir and Ru, may be significantly fluxed into the mantle wedge from mafic oceanic crust. Re-Os model ages for gabbroic and gabbroic eclogite minerals are close to age estimates for igneous crystallisation and high-pressure metamorphism, respectively, hence the HSE budgets can be related to both igneous and metamorphic behaviour. The gabbroic budget of Os, Ir, Ru and Pd (but not Pt) is dominated by sulphide, which typically hosts >90% of the Os, whereas silicates account for most of the Re (with up to 75% in plagioclase alone). Sulphides in gabbroic eclogites tend to host a smaller proportion of the total Os (10-90%) while silicates are important hosts, probably reflecting Os inheritance from precursor phases. Garnet contains very high Re concentrations and may account for >50% of Re in some samples. The depletion of Pd in gabbroic eclogites appears linked, at least in part, to the loss of Ni-rich sulphide.Both basaltic and gabbroic oceanic crust have elevated Pt/Os ratios, but Pt/Re ratios are not sufficiently high to generate the coupled ¹⁸⁶Os-¹⁸⁷Os enrichments observed in some mantle melts, even without Pt loss from basaltic crust. However, the apparent mobility of Pt and Re in slab fluids provides an alternative mechanism for the generation of Pt- and Re-rich mantle material, recently proposed as a potential source of ¹⁸⁷Os-¹⁸⁶Os enrichment.