Sorption of heavy metal cations by low-temperature deposits of Pacific hydrothermal fields

Cation exchange reactions with participation of heavy metals Mn, Co, Ni, Cu, Zn, Cd, Ba, and Pb were studed in oceanic low-temperature hydrothermal deposits of various mineral compositions and in hydrogenic Fe-Mn crusts. Individual minerals and their assemblages differ significantly in absorptive capacity, which increases in the following order: hematite ? Si-protoferrihydrite < protoferrihydrite < geothite < nontronite ? Fe-vernadite + Mn-feroxyhyte < Fe-free vernadite < bernessite + Fe-free vernadite < bernessite; i.e., it successively increases from the mineral with a coordination type of lattice to minerals with a layer-type structure. The exchange complex of all minerals includes Na⁺, K⁺, Ca²⁺, and Mg²⁺, i.e., the main cations of seawater. In Mn minerals, Mn²⁺ is the main exchange component. The contribution of all the mentioned cations to the exchange capacity of minerals is as high as 90–98%. The highest absorptive capacity among the examined low-temperature oceanic deposits is characteristic of hydrothermal Mn minerals. Their capacity exceeds substantially that of hydrothermal oxides, hydroxides, Fe-aluminosilicates, and hydrogenic Fe-Mn minerals. The absorptive capacity of all examined Mn minerals relative to heavy metals increases in the same order: Ni < Zn < Cd < Mn < Co < Pb < Cu.     

PGE distribution in massive sulfides from the P<Emphasis Type="SmallCaps">ACMANUS</Emphasis> hydrothermal field,eastern Manus basin,Papua New Guinea: implications for PGE enrichment in some ancient volcanogenic massive sulfide deposits

The distribution of platinum group elements (PGE) in Cu- and Zn-rich samples from the Roman Ruins and Satanic Mills vent sites in the PACMANUS hydrothermal field (Papua New Guinea) was studied and compared to that from selected ancient volcanogenic massive sulfide (VMS) deposits. Samples from the Satanic Mills site are enriched in Pd and Rh when compared to samples from Roman Ruins and reach highest values in active and inactive Cu-rich black smoker chimneys and chalcopyrite-cemented dacite breccias (up to 356 ppb Pd and up to 145 ppb Rh). A significant positive correlation was established between Cu and Pd and Rh in samples from both vent sites. Comparisons of chondrite normalized patterns and values of Pd/Pt and Pd/Ir ratios in Cu-rich sulfides and probable source rocks (felsic volcanic rocks/MORB) along with the evidence for a magmatic component in the PACMANUS hydrothermal system indicate that leaching of back-arc volcanic rocks together with addition of magmatic volatiles to the convecting hydrothermal system was the most important factor for PGE enrichment at PACMANUS and likely at some PGE-enriched ancient VMS deposits.An erratum to this article can be found at Editorial handling: B. Lehmann     

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.     

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。     

Formation of Fe-Mn-Si oxide and nontronite deposits in hydrothermal fields on the Valu Fa Ridge, Lau Basin

Hydrothermal Fe-Mn-Si oxides and nontronite are pervasive in the Hine Hina, Vai Lili and Mariner hydrothermal fields along the central Valu Fa Ridge, Lau Basin. Morphometric and mineralogical analyses reveal that the iron-rich filaments are the most important constituents of these Fe-Mn-Si oxide deposits. Both the morphologies and chemical composition of the filaments indicate that neutrophilic Fe-oxidizing bacteria have played a key role in the formation of these deposits. A key process of the formation of these deposits is the creation of a complicated filamentous network in which a series of metabolic activities and passive sorption and nucleation processes occur. The precipitation of dissolved Si in unsaturated and saturated states leads to a “two-generation” growth model in the hydrothermal vents. The precipitation of amorphous opal occurs in a relatively narrow temperature range (41.1-42.9 °C) based on oxygen isotope analyses, indicating a fast precipitation rate of opal-A when conductive cooling of the hydrothermal fluid occurrs. Patchy nontronite in the Mariner fields is a product of the direct precipitation from hydrothermal fluids at a temperature of ∼87.9 °C, whereas the scattered nontronite at the Hine Hina field is the product of the replacement of hydrothermal Fe-Si oxides at a temperature of ∼46.2 °C.     

Geochemistry of a sediment push-core from the Lucky Strike hydrothermal field,Mid-Atlantic Ridge

Hydrothermal sediment mineralogy and geochemistry can provide insights into seafloor mineralization processes and changes through time. We report a geochemical investigation of a short (22 cm) near-vent hydrothermal metalliferous sediment core from the Lucky Strike site (LS), on the Mid-Atlantic Ridge (MAR). The sediment was collected from the base of an active white smoker vent and comprises pure hydrothermal precipitates, mainly chalcopyrite, sphalerite, pyrite and barite, with negligible detrital and biogenic inputs. Geochemically, the core is enriched in elements derived from high-temperature hydrothermalism (Fe, Cu, Zn and Ba) and depleted in elements derived from low-temperature hydrothermalism (Mn), and metasomatism (Mg). The U/Fe content ratio is elevated, particularly in the deeper parts of the core, consistent with uptake from seawater associated with sulphide alteration. Rare earth elements (REE) concentrations are low and chondrite-normalized patterns are characteristic of high-temperature vent fluids with an enrichment in light REE and a pronounced positive Eu anomaly. A stronger positive Eu anomaly associated with higher La_n/Sm_n at the core top is controlled by barite precipitation. The hydrothermal influence on the REE decreases downcore with some evidence for a stronger seawater influence at depth. Nd isotopes also exhibit an increased detrital/seawater influence downcore. Pb isotope ratios are uniform and plot on the Northern Hemisphere Reference Line in a small domain defined by LS basalts and exhibit no detrital or seawater influence. Lucky Strike sediments are derived from high-temperature mineralization and are overprinted by a weak seawater–sediment interaction when compared with other Atlantic hydrothermal sites such as TAG. The larger seawater input and/or a larger detrital contribution in deeper layers can be explained by variable hydrothermal activity during sediment formation, suggesting different pulses in activity of the LS hydrothermal system.     

Platinum-group element distribution in base-metal sulfides of the Merensky Reef from the eastern and western Bushveld Complex, South Africa

Base-metal sulfides in magmatic Ni-Cu-PGE deposits are important carriers of platinum-group elements (PGE). The distribution and concentrations of PGE in pentlandite, pyrrhotite, chalcopyrite, and pyrite were determined in samples from the mineralized portion of four Merensky Reef intersections from the eastern and western Bushveld Complex. Electron microprobe analysis was used for major elements, and in situ laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) for trace elements (PGE, Ag, and Au). Whole rock trace element analyses were performed on representative samples to obtain mineralogical balances. In Merensky Reef samples from the western Bushveld, both Pt and Pd are mainly concentrated in the upper chromitite stringer and its immediate vicinity. Samples from the eastern Bushveld reveal more complex distribution patterns. In situ LA-ICP-MS analyses of PGE in sulfides reveal that pentlandite carries distinctly elevated PGE contents, whereas pyrrhotite and chalcopyrite only contain very low PGE concentrations. Pentlandite is the principal host of Pd and Rh in the ores. Palladium and Rh concentrations in pentlandite reach up to 700 and 130 ppm, respectively, in the samples from the eastern Bushveld, and up to 1,750 ppm Pd and up to 1,000 ppm Rh in samples from the western Bushveld. Only traces of Pt are present in the base-metal sulfides (BMS). Pyrrhotite contains significant though generally low amounts of Ru, Os, and Ir, but hardly any Pd or Rh. Chalcopyrite contains most of the Ag but carries only extremely low PGE concentrations. Mass balance calculations performed on the Merensky Reef samples reveal that in general, pentlandite in the feldspathic pyroxenite and the pegmatoidal feldspathic pyroxenite hosts up to 100 % of the Pd and Rh and smaller amounts (10–40 %) of the Os, Ir, and Ru. Chalcopyrite and pyrrhotite usually contain less than 10 % of the whole rock PGE. The remaining PGE concentrations, and especially most of the Pt (up to 100 %), are present in the form of discrete platinum-group minerals such as cooperite/braggite, sperrylite, moncheite, and isoferroplatinum. Distribution patterns of whole rock Cu, Ni, and S versus whole rock Pd and Pt show commonly distinct offsets. The general sequence of “offset patterns” of PGE and BMS maxima, in the order from bottom to top, is Pd in pentlandite?→?Pd in whole rock?→?(Cu, Ni, and S). The relationship is not that straightforward in general; some of the reef sequences studied only partially show similar trends or are more complex. In general, however, the highest Pd concentrations in pentlandite appear to be related to the earliest, volumetrically rather small sulfide liquids at the base of the Merensky Reef sequence. A possible explanation for the offset patterns may be Rayleigh fractionation.     

Mineralogy and chemistry of ferromanganese crusts from the Atlantic Ocean

The mineral and chemical compositions of a set of crust samples collected from the North, Central and South Atlantic were examined by means of analytical electron microscopy and ICP-MS, chemical, and microchemical elemental analysis. The dominant mineral phases of the crusts are vernadite, asbolane, and goethite, with minor ferrihydrite, and rare hematite and feroxyhyte. The samples show wide variability in major and trace elements; however, their characteristic geochemical signatures indicate hydrogenetic origin. A comparison between the compositions of oceanic hydrogenetic and hydrothermal crusts and metalliferous hydrothermal sediments from different ocean areas suggests that the geochemical approach may be insufficient in some cases and fail to identify a hydrothermal input in ferromanganese crusts of a mixed composition.     

Gold and platinum group elements in cobaltarsenide ores: Hydrothermal concentration from a serpentinite source-rock (Bou Azzer,Morocco)

Summary The cobalt-arsenide ores of Bou Azzer are located along the borders of serpentinite massifs (Upper Proterozoic ophiolite complex) in carbonate-quartz lenses resulting from hydrothermal carbonate alteration of serpentinite. The cobalt ores contain an average gold content of 5–20 ppm; gold is mainly located in skutterudite (120 ppm av.), whereas the Fe-arsenide (loellingite) contains < 1 ppm Au. Similarly the highest PGE contents are found in skutterudite (up to 2 ppm total PGE). All the arsenide ores of Bou Azzer exhibit the same chondrite normalized PGE pattern displaying positive Rh and negative Pt anomalies, and a slight positive slope (Pd/Ir = 1 to 2). This uncommon PGE pattern closely resembles to that of sulphides of komatiites.In serpentinite, the PGE patterns are typical of slightly depleted mantle rocks, and the associated podiform chromitites are within the range of ophiolitic chromitites, except for Pd and Au enrichment.Horizons of sulphide-bearing serpentinites show relatively high contents of noble metals and display PGE patterns which closely resemble those of the Co-arsenide ores, although an order of magnitude lower. These sulphides probably correspond to the remobilization during serpentinization of primary magmatic sulphides. The sulphiderich horizons are a possible source-rock for the noble metals of the Bou Azzer cobaltarsenide ores.

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Gold und Platingruppen-Elemente in Kobalt-Arsenid Erzen: Hydrothermale Anreicherung aus einem Serpentinit (Bou Azzer, Marokko)

Zusammenfassung Die Kobalt-Arsenid Erze von Bou Azzer kommen entlang den Grenzen eines Serpentinit-Massifs (Oberproterozoischer Ophiolit-Komplex) in Karbonat-Quarz-Linsen vor, die auf hydrothermale Umwandlung des Serpentinits zurückgehen.Die Kobalt-Erze enthalten 5–20 ppm Gold; dieses kommt hauptsächlich in Skutterudit (120 ppm) vor, während die Fe-Arsenide (Loellingit) weniger als 1 ppm Gold enthalten. Die höchsten PGE Gehalte kommen ebenso in Skutterudit vor (bis zu 2 ppm PGE). Alle Arsenid-Erze zeigen das gleiche Verteilungsbild mit positiven Rh und negativen Pt Anomalien, und eine leicht positive Neigung (Pd/Ir = 1 bis 2). Diese ungewöhnlichen PGE Verteilungsbilder erinnern an die von Sulfiden aus Komatiiten.Die PGE Verteilung in Serpentiniten ist typisch für leicht verarmte Mantelgesteine, und die assoziierten podiformen Chromitite liegen innerhalb des Bereiches für ophiolitische Chromitite, mit Ausnahme der Anreicherung in Pd und Au.Lagen von Sulfid-führenden Serpentiniten zeigen relativ hohe Gehalte an Edelmetallen, und PGE-Verteilungsmuster die denen von Co-Arseniderzen sehr ähnlich sind, obwohl sie um eine Größenordnung niedriger liegen. Diese Sulfide dürften Produkte der Remobilisierung primärer magmatischer Sulfide während der Serpentinisierung sein. Die Sulfid-reichen Lagen sind als ein mögliches Ursprungsgestein für die Edelmetalle der Kobalt-Arsenid-Erze von Bou Azzer zu sehen.

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With 8 Figures     

东太平洋海盆内多金属结核中的铁矿物

东太平洋海盆内多金属结核中的铁矿物萧绪琦郭立鹤（中国地质科学院矿床地质研究所，北京１０００３７）１前言早在五十年代人们就已注意到，大洋多金属结核含铁量较高，由于结核中矿物颗粒细小，结晶程度低，使得铁矿物的确定很困难，通常称之为铁的氧化物和氢氧化物。在...     

磁铁矿中微量元素和铂族元素的组成特征

文章分析了磁铁矿中铂族元素(PGE)含量的特征,发现磁铁矿中铂族元素富集为10-9级,主要为PPGE(即Pd,Pt,Rh)。富集PPGE的主要原因是其在热液活动的晚期阶段可以被轻微的再分配和富集,其含量的高低严格受岩浆结晶过程中氧逸度的控制。磁铁矿的结晶程度直接影响岩浆体系的氧逸度,控制了PGE的含量分布,进而影响成矿。     

Geochemistry of S,Cu, Ni,Cr and Au-PGE in the garnet amphibolites from the Akom II area in the Archaean Congo Craton,Southern Cameroon

The fresh and weathered garnet amphibolites, from the Akom II area in the Archaean Congo Craton, were investigated to determine the S, Cu, Ni, Cr, and Au-PGE values. The garnet amphibolites are composed of amphibole, plagioclase, garnet, quartz, and accessory apatite, spinel, sericite, pyrite, chalcopyrite and non-identified opaque minerals. The presence of apatite, sericite, and two generations of opaque minerals suggests that they might be affected by hydrothermal alteration. They are characterized by moderate Al₂O₃, Fe₂O₃, CaO, V, Zn, and Co contents with negative Eu- and Ce-anomalies. The sulfur concentrations are variable (380–1710 ppm). According to the sulfur contents, amphibolites can be grouped into two: amphibolites with low contents, ranging between 380 and 520 ppm (av. = 457 ppm); and amphibolites with elevated contents, varying from 1140 to 1710 ppm (av. = 1370 ppm). Amphibolites contain contrast amounts of Cu (∼ 1800 to 5350 ppm) while nickel contents attain 121 ppm. Chromium contents vary from 43 to 194 ppm. Sulfur correlates positively with Cu and Cr, but negatively with Ni and Ni/Cr ratio. The total Au-PGE contents attain 59 ppb.The presence of amphibole and feldspars confirms the low degree of amphibolite weathering. The secondary minerals are constituted of kaolinite, gibbsite, goethite and hematite. Despite the accumulation of some elements, the major and trace element distribution is quite similar to that of fresh amphibolites. Nevertheless, the weathering processes lead to the depletion of several elements such as S (239–902 ppm), Cu (520–2082 ppm), and Ni (20–114 ppm). Chromium and Au-PGE show an opposite trend marked by a slight enrichment in the weathered amphibolites. Amidst the Au-PGE, Pd (60 ppb) and Pt (23 ppb) have elevated contents in the fresh rocks as well as in the weathered materials. The PPGE contents are much higher than IPGE contents in both types of materials. The Pd/Pt, Pd/Rh, Pd/Ru, Pd/Ir, Pd/Os, and Pd/Au values indicate that Pt, Rh, Ru, Ir, Os and Au are more mobile than Pd. Chondrite-normalized base metal patterns confirm the abundance of Pd and the slight enrichment of Au-PGE in weathered rocks. Palladium, Rh and Ir are positively correlated with S. Conversely Pt and Ru are negatively correlated with S and Au is not correlated with S. Despite the high and variable S and Cu contents, the garnet amphibolites possess low Au-PGE and other base metals contents.     

滇西金宝山富铂钯岩体岩浆源区研究：铂族元素和Sr-Nd同位素约束

金宝山杂岩体位于扬子板块西缘,毗邻哀牢山造山带北段,岩体中蕴含丰富的铂钯资源,是峨眉山大火成岩省(ELIP)中大型岩浆型铂族元素矿床。岩体的主要组成为辉石橄榄岩,矿体以似层状、透镜状产出于辉石橄榄岩中。地幔是镍矿床和铂族元素矿床最重要的源区,因而对Ni、Cu及PGE等元素行为的研究,是剖析岩浆型Ni-Cu-PGE矿床源区特征的一个重要研究方向。该研究获得金宝山岩体中辉橄岩铂族元素及Sr-Nd同位素数据,结合前人对ELIP中不同类型岩石系列PGE成分研究及Ni、Cu、PGE等元素在岩浆和硫化物中的分配系数,半定量模拟得到金宝山原始岩浆的形成源于地幔中高度部分熔融(25%~40%)形成的富PGE岩浆(含12.8×10-9 Pd,9.8×10-9 Pt,0.6×10-9 Rh和0.7×10-9 Ir),其铂族元素成分与ELIP苦橄岩成分相当,并且岩浆在演化的过程中遭受了10%~20%地壳混染作用。利用批式部分熔融公式及各铂族元素在硅酸盐矿物和熔体之间的分配系数反演计算得到产生金宝山熔体的地幔约含有5.3×10-9 Pd,7.5×10-9 Pt,0.75×10-9 Rh和1.5×10-9 Ir,相比原始地幔而言并没有表现出明显富集PGE的特征。这表明地幔中高度部分熔融+大量岩浆与硫化物的充分反应是形成大型岩浆型铂族元素矿床的一种可具备的条件。     

金川铜镍硫化物矿床岩浆通道型矿体地质地球化学特征

金川铜镍硫化物矿床6行富铜（铂族）矿体曾因Cu、Pt、Pd等含量明显高于相邻其它矿体而被认为是岩浆期后热液叠加作用的产物,研究发现,空间上该矿体受断层构造控制,在矿石组构、矿物组成和硫同位素组成方面与相邻岩浆融离型1号矿体一致,显示了该矿体岩浆成矿作用的特征。在元素地球化学方面,6行富铜（铂族）矿体的Cu、Ni、Pt、Pd含量及Cu/Ni比值明显高于1号主矿体,而Os、Ir、Rh、Ru却明显低于后者,同时,前者相对富含LREE,轻、重稀土分异程度高于后者。根据硫化物结晶分异过程中金属元素分配规律及稀土元素特征,阐明了6行富铜（铂族）矿体为岩浆通道型矿体,是岩浆硫化物晚期结晶的产物。矿区中西部存在的Cu、Ni、Pt、Pd、Au等含量高,而Os、Ir、Rh、Ru含量低的部位,是寻找岩浆通道型矿体的有利部位。     

铂族元素矿物共生组合(英文)

由于铂族元素能有效地降低汽车尾气的污染 ,其需求量日益增加 ,对铂族元素矿床的寻找已是当务之急。着重从矿物矿床学角度对铂族元素的矿物共生特点进行了探讨。铂族元素可呈独立矿床产出 ,主要产于基性超基性层状侵入体、蛇绿岩套及阿拉斯加式侵入体中。铂族元素也伴生于铜镍矿床中 ,该类铜镍矿床主要与苏长岩侵入体、溢流玄武岩及科马提岩有关。产于基性超基性层状侵入体中的铂族矿物有铂钯硫化物、铂铁合金、钌硫化物、铑硫化物、铂钯碲化物、钯砷化物及钯的合金。这些铂族矿物可与硫化物矿物共生 ,也可与硅酸盐矿物共生 ,还可与铬铁矿及其他氧化物矿物共生。产于蛇绿岩套中的铂族矿物主要是钌铱锇的矿物 ,而铂钯铑的矿物则较少出现 ,这些铂族矿物可呈合金、硫化物、硫砷化物以及砷化物 4种形式出现。产于阿拉斯加式侵入体中的铂族矿物主要有铂铁合金、锑铂矿、硫铂矿、砷铂矿、硫锇矿及马兰矿等少数几种 ,其中铂铁合金与铬铁矿及与其同时结晶的高温硅酸盐矿物共生 ,而其他的铂族矿物则与后来的变质作用及蛇纹岩化作用中形成的多金属硫化物及砷化物共生。产于铜镍矿床中的铂族矿物主要是铂和钯的矿物。产于基性超基性层状侵入体、蛇绿岩套及阿拉斯加式侵入体中的铂族矿物的共同特点是它们均与铬铁矿?     

Platinum-group elements distribution and spinel composition in podiform chromitites and associated rocks from the upper mantle section of the Neoproterozoic Bou Azzer ophiolite, Anti-Atlas, Morocco

The distribution of platinum-group elements (PGEs), together with spinel composition, of podiform chromitites and serpentinized peridotites were examined to elucidate the nature of the upper mantle of the Neoproterozoic Bou Azzer ophiolite, Anti-Atlas, Morocco. The mantle section is dominated by harzburgite with less abundant dunite. Chromitite pods are also found as small lenses not exceeding a few meters in size. Almost all primary silicates have been altered, and chromian spinel is the only primary mineral that survived alteration. Chromian spinel of chromitites is less affected by hydrothermal alteration than that of mantle peridotites. All chromitite samples of the Bou Azzer ophiolite display a steep negative slope of PGE spidergrams, being enriched in Os, Ir and Ru, and extremely depleted in Pt and Pd. Harzburgites and dunites usually have intermediate to low PGE contents showing more or less unfractionated PGE patterns with conspicuous positive anomalies of Ru and Rh. Two types of magnetite veins in serpentinized peridotite, type I (fibrous) and type II (octahedral), have relatively low PGE contents, displaying a generally positive slope from Os to Pd in the former type, and positive slope from Os to Rh then negative from Rh to Pd in the latter type. These magnetite patterns demonstrate their early and late hydrothermal origin, respectively. Chromian spinel composition of chromitites, dunites and harzburgites reflects their highly depleted nature with little variations; the Cr# is, on average, 0.71, 0.68 and 0.71, respectively. The TiO₂ content is extremely low in chromian spinels, <0.10, of all rock types. The strong PGE fractionation of podiform chromitites and the high-Cr, low-Ti character of spinel of all rock types imply that the chromitites of the Bou Azzer ophiolite were formed either from a high-degree partial melting of primitive mantle, or from melting of already depleted mantle peridotites. This kind of melting is most easily accomplished in the supra-subduction zone environment, indicating a genetic link with supra-subduction zone magma, such as high-Mg andesite or arc tholeiite. This is a general feature in the Neoproterozoic upper mantle.     

Platinum-group elements in porphyry copper deposits: a reconnaissance study

Summary Sulphide and flotation concentrates from 33 porphyry copper deposits have been investigated for platinum-group elements (PGE), Au, Cu and platinum-group minerals (PGM). The major sulphides in the samples studied are chalcopyrite and pyrite. Bornite is less frequent and molybdenite occurs in traces only. PGM (merenskyite, sperrylite and an unidentified Pd-Sb telluride) have been found as inclusions in chalcopyrite.Pd and Pt are present in concentrations above the analytical detection limit (> 8 ppb) in 70% respectively 30% of the deposits studied. The contents of Os, Ir, Ru and Rh are below detection limits in all samples. The analytical results show that 7 deposits (six of island arc and one of continental margin setting) reveal relatively high Pd contents (130–1900 ppb) which are associated with high Au contents (1–28 ppm). In five of them discrete PGM can be identified in accordance with elevated levels of Pd. Correlations of Au, Pd and Pt point towards a common origin.Even though the data base is relatively small, a trend is obvious, suggesting that Au-rich island arc porphyry copper deposits might host more Pd and Pt than the continental margin type ones. Other aspects of intrusive rocks, such as geological age, chemical composition and magma type do not seem to influence PGE contents.

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Platingruppen-Elemente in porphyrischen Kupfer Lagerstätten: eine Überblicksstudie

Zusammenfassung Es wurden Sulfid- und Flotationskonzentrate aus 33 Porphyry Kupfer Lagerstätten: auf Platingruppenelemente (PGE), Au, Cu and Platingruppenminerale (PGM) untersucht. Die Hauptsulfide im untersuchten Probenmaterial sind Chalkopyrit und Pyrit. Bornit ist weniger häufig and Molybdänit tritt nur in Spuren auf. An PGM wurden Merenskyit (in den Lagerstätten: Elacite, Majdanpek and Skouries), Sperrylith und ein nicht näher identifizierbares Pd-Sb- Tellurid (in der Lagerstätte Mamut) als Einschlüsse in Chalkopyrit festgestellt.Pd ist in 70% and Pt in 30% der untersuchten Lagerstätten: nachweisbar (> 8 ppb), während die Gehalte von Os, Ir, Ru and Rh in allen Proben unterhalb der Nachweisgrenze liegen. In 7 Lagerstätten: (davon sechs vom Inselbogen- und eine vom Kontinentalrandtyp) wurden relativ hohe Pd-Konzentrationen (130–1900 ppb) festgestellt, die auch durch hohe Au-Gehalte (1–28 ppm) gekennzeichnet sind. In 5 Lagerstätten: sind entsprechend den hohen Pd-Gehalten PGM nachweisbar.Geochemische Korrelationen zwischen Au, Pd and Pt weisen auf eine gemeinsame Herkunft dieser Metalle hin. Obwohl der Datenbestand noch relativ klein ist, ist ein Trend bereits sichtbar, daß Au-reiche Inselbogenporphyries Where Pd- und Pt- Gehalte erwarten lassen als der Kontinentalrand-Typ. Andere Aspekte wie geologisches Alter, Magmentyp and Chemismus der betreffenden Intrusivgesteine spielen bei der PGEFührung offensichtlich keine Rolle.

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With 8 Figures     

Subsurface processes at the lucky strike hydrothermal field, Mid-Atlantic ridge: evidence from sulfur, selenium, and iron isotopes

At Lucky Strike near the Azores Triple Junction, the seafloor setting of the hydrothermal field in a caldera system with abundant low-permeability layers of cemented breccia, provides a unique opportunity to study the influence of subsurface geological conditions on the hydrothermal fluid evolution. Coupled analyses of S isotopes performed in conjunction with Se and Fe isotopes have been applied for the first time to the study of seafloor hydrothermal systems. These data provide a tool for resolving the different abiotic and potential biotic near-surface hydrothermal reactions. The δ³⁴S (between 1.5‰ and 4.6‰) and Se values (between 213 and 1640 ppm) of chalcopyrite suggest a high temperature end-member hydrothermal fluid with a dual source of sulfur: sulfur that was leached from basaltic rocks, and sulfur derived from the reduction of seawater sulfate. In contrast, pyrite and marcasite generally have lower δ³⁴S within the range of magmatic values (0 ± 1‰) and are characterized by low concentrations of Se (<50 ppm). For ⁸²Se/⁷⁶Se ratios, the δ⁸²Se values range from basaltic values of near −1.5‰ to −7‰. The large range and highly negative values of hydrothermal deposits observed cannot be explained by simple mixing between Se leached from igneous rock and Se derived from seawater. We interpret the Se isotope signature to be a result of leaching and mixing of a fractionated Se source located beneath hydrothermal chimneys in the hydrothermal fluid. At Lucky Strike we consider two sources for S and Se: (1) the “end-member” hydrothermal fluid with basaltic Se isotopic values (−1.5‰) and typical S isotope hydrothermal values of 1.5‰; (2) a fractionated source hosted in subsurface environment with negative δ³⁴S values, probably from bacterial reduction of seawater sulfate and negative δ⁸²Se values possibly derived from inorganic reduction of Se oxyanions. Fluid trapped in the subsurface environment is conductively cooled and has restricted mixing and provide favorable conditions for subsurface microbial activity which is potentially recorded by S isotopes. Fe isotope systematic reveals that Se-rich high temperature samples have δ⁵⁷Fe values close to basaltic values (∼0‰) whereas Se-depleted samples precipitated at medium to low temperature are systematically lighter (δ⁵⁷Fe values between −1 to −3‰). An important implication of our finding is that light Fe isotope composition down to −3.2‰ may be explained entirely by abiotic fractionation, in which a reservoir effect during sulfide precipitation was able to produce highly fractionated compositions.     

Hydrothermal sulfide deposits of the Lucky Strike vent field, Mid-Atlantic Ridge

Several hydrothermal sulfide structures were sampled using Mir manned submersibles in the relatively shallow Lucky Strike vent field, Mid-Atlantic Ridge; the bathymetric position of these structures varies by approximately 100 m. The investigation of the chemical and mineral compositions of hydrothermal ore occurrences led to the conclusion that the initial high-temperature ore-bearing solution ascending toward the surface became unstable and experienced phase separation beneath the ocean floor. The phase separation was responsible for the bathymetric control of hydrothermal ore formation in the ocean.     

Genesis of PGE mineralization in the Wengeqi mafic–ultramafic complex, Guyang County, Inner Mongolia, China

The Wengeqi complex in Guyang County, Inner Mongolia, is one of several Pd–Pt-mineralized Paleozoic mafic–ultramafic complexes along the north-central margin of the North China. The complex comprises pyroxenites, biotite pyroxenites, amphibole pyroxenites, gabbros, and amphibolites. Zircons extracted from a pyroxenite yield a U–Pb SHRIMP age of 399?±?4?Ma. Several 2–6-m wide syngenetic websterite dikes contain 1–3?ppm Pd?+?Pd and are dominated by pyrite–chalcopyrite–pyrrhotite–magnetite–(pentlandite) assemblages with minor sperrylite, sudburyite, and kotuskite. Textural relationships indicate that pyrite has replaced magmatic chalcopyrite and that magnetite has replaced magmatic pyrrhotite. The mineralization is enriched in Pd–Pt–Cu > Au >> Rh–Ir–Os–Ni > Ru, similar to other occurrences of hydrothermally modified magmatic mineralization, but very different from the much less fractionated compositions of magmatic PGE mineralization. Textural, mineralogical, and geochemical relationships are consistent with alteration of an original magmatic Fe–Ni–Cu sulfide assemblage by a S-rich oxidizing high-temperature (deuteric) hydrothermal fluid.