Suspended basaltic glass–seawater interactions

The objective of this study was to quantify by experiments the initial seawater–suspended basaltic glass interactions following the 1996 outburst flood from the Vatnajökull glacier, Iceland. The altered basaltic glass dissolved in seawater as recorded by the Si release from the glass. The dissolved concentrations of Na, Ca, Si, Ba, Cd, Co, Cu, Hg, Mn, Ni and total dissolved inorganic N increased with time but the concentrations of Mg, K, S, Sr, Fe, Pb and Zn decreased. Calculated 1 to 10 day fluxes for Si range from 38,000 tons/day to 70,000 tons/10 days. The fluxes for other major elements are more uncertain, but the positive flux (release from suspended matter to seawater) of Ca and Na, and negative flux of Mg, K and S are greater than the Si flux.     

Remarks on the short-term chemical stability of primary lead smelting slag

The short-term leaching behavior of a landfilled primary Pb smelter slag from the Santo Amaro (Brazil) smelter was investigated using about 1-day contact time with acid and alkaline solutions. Strong alteration of this slag was observed only below pH 3. In this extreme environment, in addition to the previously discussed behavior of Ca, Si, Fe, Pb and Zn, the As, Cd and Cu were solubilized; however, due to the small content of these elements in the slag, the solution has low content of them. The hierarchical cluster analysis of the results of several leaching tests shows that Pb, As and Cd are part of a group related to the metallic lead phase trapped in the matrix. There is a second group related to some components of the slag matrix (Zn, Ca and Fe) likely oxides; and Si alone is part of a third group related to the slag matrix. The sequential leaching experiments indicate that the main lead solubilization is related to the oxidant environment which confirms the predominance of lead as metallic particles inside the large particles of the slag matrix. These results indicate that, despite the fact that the landfilled slag removal is needful, it is a secondary task to reduce the contamination risk of the region of the former smelter.     

A simple way to constrain the stoichiometry of secondary smectites upon aqueous glass alteration

The comparison of the stoichiometry of several nuclear waste glasses and basaltic glasses with their associated secondary smectites evidenced that Si/Al ratios of secondary smectites are nearly equal to the Si/Al ratios of parent glasses. This information may be very useful in constraining secondary smectites structure and stoichiometry in cases where other identification methods are difficult to apply.     

The Lead, Neodymium and Strontium Isotopic Structure of Ocean Ridge Basalts

Pb-, Nd- and Sr-isotope compositions and U, Pb, Sm, Nd, Rb andSr concentrations are reported for samples of basaltic glassand altered substrates from spreading centres in the Atlantic,Indian and Pacific Oceans. Correlations are shown to exist between^{208, 207, 206}Pb/²⁰⁴Pb ratios, and ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Ndratios in basaltic glasses, but they are dominated by samplesfrom the Mid-Atlantic Ridge. Whereas basaltic glasses from EastPacific spreading centres exhibit smaller variability in Pb,Sr and Nd isotope compositions than Atlantic samples, seamountsamples from the E. Pacific have a similar range of Pb-isotopecompositions as Mid-Atlantic Ridge glasses. Contamination ofbasaltic magmas by altered oceanic crust or sediments is notconsidered to be of prime importance in determining the isotopicstructures of MORB glasses. It is proposed that the isotopicheterogeneity in the mantle beneath the Pacific and Atlanticis similar, but magma generation processes associated with fastspreading ridges of the East Pacific more effectively eradicateheterogeneities in the erupted basalts. Alteration of oceanic crust is further investigated with respectto the relative response of the U–Pb, Sm–Nd andRb–Sr systems, and the role of recycled oceanic crustin producing the mantle heterogeneities is evaluated.     

Trace element mobility during sub-seafloor alteration of basaltic glass from Ocean Drilling Program site 953 (off Gran Canaria)

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.     

An Experimental Study of Water and Carbon Dioxide Solubilities in Mid-Ocean Ridge Basaltic Liquids. Part II: Applications to Degassing

Degassing processes in basaltic magmas rich in both water andcarbon dioxide can be modeled using the solubilities of theendmember systems and the assumption of Henry's law. Suitesof vapor-saturated basaltic melts having a range of initialCO₂/H₂O ratios and erupted over a narrow depth interval willdefine negatively sloped arrays on an H₂O vs CO₂ plot. It isimportant that all of the major volatile species be consideredsimultaneously when interpreting trends in dissolved volatilespecies concentrations in magmas. Based on measured concentrations of water and carbon dioxidein basaltic glasses, the composition of the vapor phase at 1200°Cthat could coexist with a basaltic melt and the pressure atwhich it would be vapor saturated can be calculated. The rangein vapor compositions in equilibrium with submarine basaltsreflects the range in water contents in the melts characteristicof each environment. The ranges in the molar proportion of CO₂in vapor phases (X_CO2) calculated to be in equilibrium withsubmarine tholeiitic glasses are 0•93–1•00 formid-ocean ridge basalts (MORB), 0•60–0•99 forglasses from Kilauea [representative of ocean island basalts(OIB)] and 0–0•94 for glasses from back-arc basins(BABB). MORB glasses from spreading centers ranging from slow(e.g. the Mid-Atlantic Ridge) to fast (e.g. East Pacific Rise,9–13°N) are commonly supersaturated with respect toCO₂-rich vapor, resulting from magma ascent rates so rapid thatmagmas erupt on the sea-floor without having been fully degassedby bubble nucleation and growth during ascent. In contrast tothe MORB glasses, volatile contents in submarine glasses fromKilauea are consistent with having been in equilibrium witha vapor phase containing 60–100 mol% CO₂ at the pressureof eruption, reflecting differences in average magma transportrates during eruptions at mid-ocean ridges and hotspot volcanoes. Degassing during decompression of tholeiitic basaltic magmais characterized by strong partitioning of CO₂ into the vaporphase. During open system degassing, CO₂ is rapidly removedfrom the melt with negligible loss of water, until a pressureis reached at which the melt is in equilibrium with nearly purewater vapor. From this pressure downward, the water contentof the melt follows the water solubility curve. During closedsystem degassing, water and CO₂ contents in vapor-saturatedbasaltic magmas will depend strongly on the vapor compositionas determined by the initial volatile concentrations. Deviationfrom open system behavior, toward lower dissolved H₂O and CO₂saturation concentrations at a given pressure, will be greatestin melts having high total volatile concentrations and highCO₂:H₂O ratios. Closed system degassing of basaltic melts havingthe low initial H₂O and CO₂ contents typical of MORB and OIB,however, are similar to the open system case. KEY WORDS: mid-ocean ridge basalts; water and carbon dioxide solubility; degassing     

元素-铅同位素示踪在云浮硫铁矿区 土壤铊污染研究中的应用

不同源区铅同位素的组成不同,因此可以利用铅同位素的这种"指纹"特征来示踪铅的不同源区。近年来铅同位素示踪在研究土壤中相关重金属来源及其运移途径起到独特的作用。由于铊和铅具有相似的地球化学性质,并且在云浮硫铁矿区污染土壤中其分布与铅有很好的相关性,笔者利用铅同位素作为示踪工具探讨了土壤中铊的污染特征,初步研究表明铊污染物主要累积在土壤深度0~16.5cm范围内,深度为16.5cm以下土壤受到废渣中铊污染的影响较小,但废渣周围土壤深度约44cm范围已经受到来自废渣中铊的影响。     

Stable Fe isotope fractionations produced by aqueous Fe(II)-hematite surface interactions

Stable Fe isotope fractionations were investigated during exposure of hematite to aqueous Fe(II) under conditions of variable Fe(II)/hematite ratios, the presence/absence of dissolved Si, and neutral versus alkaline pH. When Fe(II) undergoes electron transfer to hematite, Fe(II) is initially oxidized to Fe(III), and structural Fe(III) on the hematite surface is reduced to Fe(II). During this redox reaction, the newly formed reactive Fe(III) layer becomes enriched in heavy Fe isotopes and light Fe isotopes partition into aqueous and sorbed Fe(II). Our results indicate that in most cases the reactive Fe(III) that undergoes isotopic exchange accounts for less than one octahedral layer on the hematite surface. With higher Fe(II)/hematite molar ratios, and the presence of dissolved Si at alkaline pH, stable Fe isotope fractionations move away from those expected for equilibrium between aqueous Fe(II) and hematite, towards those expected for aqueous Fe(II) and goethite. These results point to formation of new phases on the hematite surface as a result of distortion of Fe-O bonds and Si polymerization at high pH. Our findings demonstrate how stable Fe isotope fractionations can be used to investigate changes in surface Fe phases during exposure of Fe(III) oxides to aqueous Fe(II) under different environmental conditions. These results confirm the coupled electron and atom exchange mechanism proposed to explain Fe isotope fractionation during dissimilatory iron reduction (DIR). Although abiologic Fe(II)_aq - oxide interaction will produce low δ⁵⁶Fe values for Fe(II)_aq, similar to that produced by Fe(II) oxidation, only small quantities of low-δ⁵⁶Fe Fe(II)_aq are formed by these processes. In contrast, DIR, which continually exposes new surface Fe(III) atoms during reduction, as well as production of Fe(II), remains the most efficient mechanism for generating large quantities of low-δ⁵⁶Fe aqueous Fe(II) in many natural systems.     

Evaluation of the chemical stability of a landfilled primary lead smelting slag

A primary lead smelter operating in Santo Amaro, Bahia, Brazil, from 1960 to 1993 generated a large amount of slag that was landfilled close to the former smelter and used in roads and houses as a construction material. To evaluate the stability of the slag classical leaching procedures (TCLP, SWEP and SPLP) were applied. In addition, samples of the slag were placed in contact with HCl, HNO₃, HOAc and NaOH solutions for about 24 h at room temperature to simulate acidic and alkaline environments over a wide pH range. In the acidic environment Ca, Fe and Si are strongly solubilized, and Pb and Zn solubilization was significant only below pH 3. The lead slag was also in contact with purified water for a period of 30 days. The results show that Ca and Si were solubilized and Pb, Fe, and Zn were not detected in the solution. The solubilization kinetics are second order processes for both Ca and Si. The initial solubilization rate for Ca and Si are 4.6 and 0.6 mg/L/day, respectively. The main implication of these results is that the major potentially toxic elements of the lead slag landfilled at Santo Amaro were stabilized for a short contact time with pure water and for alkaline and acidic solutions to a pH of about 3 and the groundwater and the surface water contamination found at Santo Amaro smelter region cannot be directly attributed to the landfilled lead slag.     

210Pb activities in and fluxes to sediments of the Washington continental slope and shelf

Surface sediments of the Washington coast have ²¹⁰Pb activites which average 104 ± 48dpm/g for submarine canyon and slope regimes and 18 ± 12dpm/g for the continental shelf regime. ²¹⁰Pb sedimentary fluxes are also higher in canyons, averaging 18 ± 13dpm/cm² per yr, compared to 5.2 ± 3.1 dpm/cm² per yr for slope and 4.8 ± 1.8dpm/cm² per year for shelf regions. These ²¹⁰Pb activities and fluxes are 2–7 times greater than those reported for other coastal regions. Inputs from the atmosphere and the Columbia River are not sufficient to supply the ²¹⁰Pb, but advection of seawater containing dissolved ²¹⁰Pb produced in situ from ²²⁶Ra provides an input several times larger than the sedimentary fluxes. The sedimentary ²¹⁰Pb flux is limited by scavenging reactions rather than by supply of dissolved ²¹⁰Pb.Calculations of maximum biological uptake and fluxes of ²¹⁰Pb and ‘selective’ chemical leaching experiments all show that the primary scavenging processes are due to hydrous Mn and Fe oxides rather than biological phases. The pattern of higher ²¹⁰Pb depositional fluxes in canyons than in nearby open slope areas of comparable water depth is most reasonably explained by enhanced scavenging of dissolved ²¹⁰Pb near the sea floor, rather than by processes operating throughout the water column. Relatively rapid removal of dissolved ²¹⁰Pb from the near bottom nepheloid layer to slope and canyon sediments is shown by its mean residence time of less than two years in this layer.     

Mobilization and speciation of arsenic from hydrothermally altered rock containing calcite and pyrite under anoxic conditions

The effects of water residence time and anoxic conditions on the mobilization and speciation of As in a calcite- and pyrite-bearing altered rock excavated during a road-tunnel project has been evaluated using batch and column laboratory experiments. Higher infiltration rates (i.e., shorter water residence times) enhanced the leaching of As due to the higher pH values of the effluents and more rapid transport of dissolved As through the columns. The concentration of As in the effluent also increased under anoxic conditions regardless of the water residence time. This enhanced leaching of As under anoxic conditions could be attributed to a significant pH increase and decreased Fe oxyhydroxide/oxide precipitation compared to similar experiments done under ambient conditions. Processes that controlled the evolution of pH and the temporal release mechanisms of As under anoxic conditions were identical to those previously observed under ambient conditions: the dissolution of soluble phases, pyrite oxidation, co-precipitation and/or adsorption/desorption reactions. Speciation of As in the column experiments could partly be attributed to the pH-dependent adsorption of As species onto Fe oxyhydroxide/oxide precipitates. Moreover, apparent equilibrium of the total As and As[III] concentrations was delayed under anoxic conditions in both batch and column experiments.     

Mineralogy and environmental stability of slags from the Tsumeb smelter,Namibia

Three types of smelting slags originating from historically different smelting technologies in the Tsumeb area (Namibia) were studied: (i) slags from processing of carbonate/oxide ore in a Cu–Pb smelter (1907–1948), (ii) slags from Cu and Pb smelting of sulphide ores (1963–1970) and (iii) granulated Cu smelting slags (1980–2000). Bulk chemical analyses of slags were combined with detailed mineralogical investigation using X-ray diffraction analysis (XRD), scanning electron microscopy (SEM/EDS) and electron microprobe (EPMA). The slags are significantly enriched in metals and metalloids: Pb (0.97–18.4 wt.%), Cu (0.49–12.2 wt.%), Zn (2.82–12.09 wt.%), Cd (12–6940 mg/kg), As (930–75,870 mg/kg) and Sb (67–2175 mg/kg). Slags from the oldest technology are composed of primary Ca- and Pb-bearing feldspars, spinels, complex Cu–Fe and Cu–Cr oxides, delafossite–mcconnellite phases and Ca–Pb arsenates. The presence of arsenates indicates that these slags underwent long-term alteration. More recent slags are composed of high-temperature phases: Ca–Fe alumosilicates (olivine, melilite), Pb- and Zn-rich glass, spinel oxides and small sulphide/metallic inclusions embedded in glass. XRD and SEM/EDS were used to study secondary alteration products developed on the surface of slags exposed for decades to weathering on the dumps. Highly soluble complex Cu–Pb–(Ca) arsenates (bayldonite, lammerite, olivenite, lavendulan) associated with litharge and hydrocerussite were detected. To determine the mineralogical and geochemical parameters governing the release of inorganic contaminants from slags, two standardized short-term batch leaching tests (European norm EN 12457 and USEPA TCLP), coupled with speciation-solubility modelling using PHREEQC-2 were performed. Arsenic in the leachate exceeded the EU regulatory limit for hazardous waste materials (2.5 mg/L). The toxicity limits defined by USEPA for the TCLP test were exceeded for Cd, Pb and As. The PHREEQC-2 calculation predicted that complex arsenates are the most important solubility controls for metals and metalloids. Furthermore, these phases can readily dissolve during the rainy season (October to March) and flush significant amounts of As, Pb and Cu into the environment in the vicinity of slag dumps.     

御道口汉诺坝玄武岩偏硅酸矿泉水形成机制及其地质建造制约

冀北坝上一带玄武岩地区广布富偏硅酸地下水,研究其形成机制及其水岩作用过程对矿泉水的合理开发利用与京津冀水源涵养功能具有重要意义.结合玄武岩地质建造地下水赋存特征,综合利用水化学分析,玄武岩岩石风化机制,水岩相互作用矿物平衡体系,δD、δ18O和δ13C同位素、14C放射性同位素测年等方法,剖析了汉诺坝玄武岩偏硅酸矿泉水形成的岩石地球化学风化和水文地球化学过程及地质建造制约因素.结果表明,研究区矿泉水为低矿化度的HCO₃-Ca·Mg型与HCO₃-Na·Ca型水,矿泉水形成类型有构造断裂深循环淋溶型和层状补给富集埋藏型2类.上层古风化壳地下水14C校正年龄约为4 050 a,地下水可溶性无机碳来源于土壤CO₂与幔源CO₂的混合作用.偏硅酸矿泉水的形成与分布受玄武岩地质建造制约,受岩石地球化学特征、岩石风化地表过程和水文地球化学响应过程控制.地下水中偏硅酸主要来源于玄武岩中斜长石、单斜辉石、镁橄榄石等硅酸盐矿物的风化水解;岩石矿物风化的水化学响应过程受溶滤作用控制,受阳离子交换作用影响.      

Native Sn-Pb droplets in a zeolitic amygdale (Isle of Mull, Inner Hebrides)

Despite the particular scientific interest in the elements with high affinity to S and O₂, but found in zero-valence state in nature, the origin of these native minerals has been little explored and remains obscure. Here we describe unique Sn-Pb droplets found in a closed analcime-calcite amygdale collected from a basaltic unit cropping out at Carsaig Bay (Isle of Mull, Inner Hebrides). The droplets consist of intimate intergrowths of nearly pure Sn⁰ and Pb⁰ domains in proportion 88:12 and are enveloped in a thin, brownish film of organic composition. The occurrence of the Sn-Pb droplets in a closed amygdale, their relationship with the host analcime + calcite and their Pb isotope composition (which does not match any known anthropogenic Pb source) rule out the possibility of anthropogenic contamination and support the natural origin of the Sn-Pb alloy.The variable isotope (Pb, Sr, Nd) compositions in different members of the host basaltic sequence suggest that a parent basaltic magma was modified by crustal assimilation and post-emplacement alteration processes. Considering all possible explanations, it appears that the most likely source of Pb for the Sn-Pb alloy is a discrete basaltic unit with an isotopic composition comparable to the Antrim basalts (Northern Ireland). The amygdale phases, on the other hand, show isotopic evidence for incorporation of elements from both local basaltic and sedimentary units. The apparent isotopic disequilibrium between Sn-Pb droplets and amygdale phases indicates a complex, multi-stage fluid evolution. The occurrence of Sn-Pb droplets in organic capsules suggests that the droplets and the enveloping organic substances are co-precipitates. This implies that the transportation and deposition of Sn and Pb might have occurred through organometallic compounds. We assume interaction of seawater fluids carrying metals leached from basaltic rocks with hydrocarbons from sedimentary units as a prerequisite for the formation of the organometallic complexes. The zeolites lining the basaltic vesicles might have destabilized the migrating organo-Sn and Pb compounds causing their breakdown and precipitation of Sn-Pb alloy.     

铅锌矿山开发导致的重金属在环境介质中的积累

以连续提取法和相关性分析研究了土法冶炼锌、铅锌和矿山开采导致的重金属在废渣及环境介质土壤、溪流沉积物中的积累，并分析了其环境危害性。结果显示，贵州赫章土法炼锌导致的重金属Pb、Zn、Cd在环境介质中的积累相当高。水城杉树林铅锌矿山开采引起的重金属积累则相对较低，但也明显高于背景值；土壤和沉积物中的铁矿物对重金属有强烈的固定作用。除残渣态外，Pb、Zn在土壤、炼锌废渣中主要呈铁锰氧化物结合态，沉积物中则为碳酸盐结合态。可交换态Pb、Zn含量变异较大，但在炼锌废渣、土壤中含量明显高于河流沉积物，暗示铅锌矿开发对土壤环境的潜在危害更大。     

模拟不同气候条件下碳酸盐岩风化作用的淋溶实验研究

通过模拟干热、湿热与干冷3种气候条件,以饱和CO2水作为淋溶液,对黔中岩溶区3条碳酸盐岩风化壳岩-土界面的岩粉层试样进行了淋溶实验(其中干热、湿热条件下淋溶到残余酸不溶物阶段),对淋出液的pH值以及主要造岩元素的浓度进行了动态分析。结果表明,碳酸盐岩风化壳岩-土界面由岩到土的转变过程中,伴随碳酸盐的溶蚀,酸不溶物已表现出明显的风化倾向。碳酸盐的溶蚀强度表现为干冷>干热>湿热的变化趋势。温度低,碳酸盐的溶解速率大;排水条件好,碳酸盐溶解释放的Ca、Mg易随风化流体排出体系。对于酸不溶物组分,淋溶实验中有:(1)K、Na、Mg、Si、P的载体矿物风化强度在干热条件下最大(至于Ca,由于方解石与白云石均是其主要的载体矿物,酸不溶物相中的Ca难以在淋出液中有效识别)。在干冷与湿热之间,K、Na、Mg等盐基离子的溶出能力大多表现为湿热>干冷,指示了温度对盐基离子释放强度的重要制约作用;而Si和P未表现出一致的变化趋势,可能源于淋溶体系微环境的差异。(2)Fe与Mn表现出弱迁移性。其中,Fe在干冷环境下淋出强度最弱,说明温度是制约含Fe矿物分解速率的重要因素。而Fe在干热与湿热之间,以及Mn在3种淋溶条件下,未呈现出一致的变化趋势。(3)Al和Ti在碳酸盐岩风化过程中表现出强烈的惰性。      

庐江沙溪斑岩型铜金矿床绿泥石的地球化学特征及找矿指示

文章在前人对岛弧环境斑岩型矿床绿泥石主微量元素找矿指示研究的基础上,以陆内环境的长江中下游成矿带中的沙溪斑岩型铜金矿床为对象,利用LA-ICP-MS技术对沙溪斑岩型铜金矿床中绿泥石进行了主微量元素研究。结果显示,绿泥石中Ti、Ba、Co、K、Pb、Sr、Fe、V/Ni靠近矿化中心的位置含量高,Mn、Mg元素远离矿化中心的位置含量高。沙溪斑岩型铜金矿床中绿泥石元素含量分布主要受温度、被交代矿物、流体pH值和氧化还原环境、围岩性质影响。受交代矿物的影响,绿泥石中的有些元素(Si、Na、Mg、K、Al)的含量高低不能直接对矿化中心进行指示,但沙溪斑岩型铜金矿床绿泥石部分元素(Ti、Ba、Co、Pb、Sr、Fe)和元素比值(V/Ni)具有指示矿化中心的作用。     

Geology and Geochemistry of Highly Metamorphosed Footwall Alteration Zones in the Hongtoushan Volcanogenic Massive Sulfide Deposit,Liaoning Province,China

The Hongtoushan Archean Cu–Zn volcanogenic massive sulfide (VMS) deposit, which was metamorphosed (3.0–2.8 Ga) to upper amphibolite facies at temperatures between 600 and 650°C, occurs in the Hunbei granite–greenstone terrane, Liaoning Province of NE China. Stratiform cordierite–anthophyllite gneiss (CAG) that occurs hundreds of meters below the ore horizon in the Hongtoushan district corresponds to the metamorphosed semi‐conformable alteration zone of the VMS hydrothermal system, whereas the CAG that contains abundant deformed sulfide‐bearing quartz veins immediately below the main ore layer represents the metamorphosed discordant alteration zone. Whole‐rock geochemistry indicates that stratiform CAG was derived ultimately from five lithologies (basalt, basaltic andesite, andesite, dacite, and rhyolite), while discordant CAG derived from a single lithology (rhyolite). Amphibolite and biotite‐rich gneiss are identified as a metamorphosed least‐altered precursor for these CAGs. Mass change calculation indicates that, compared to the least‐altered rocks, stratiform CAG is enriched in Fe and Mg, and depleted in Na, K, Ca, Cu, Pb and Zn, while discordant CAG is enriched in Fe, Mg, Si, Na, Pb, Cu and Zn, and depleted in K. HREE and HFSE (Zr, Ti, Nb and Ta) behaved inertly during submarine alteration, whereas Rb, Sr, Ba and LREE (especially Eu) were leached off. Both stratiform and discordant CAGs are depleted in ¹⁸O, with values up to 7‰ lower than their corresponding least‐altered precursors. Addition of Fe, Mg, and depletion of Ca, K, Sr, and ¹⁸O, indicate that hydrothermal alteration for both types of CAGs was characterized by chloritization prior to metamorphism. Stratiform CAG could be used to evaluate the mineralization potential of VMS in metamorphic terranes, while discordant CAG containing sulfide‐bearing quartz veins could be a good indication for overlying stratiform massive sulfide ores as well as an exploration target itself.     

Lead isotopes in sulfides from the Stillwater Complex, Montana: evidence for subsolidus remobilization

Isotopic ratios of Pb in sulfide minerals (primarily pyrrhotite, chalcopyrite, and pentlandite) from a suite of samples from the platiniferous J-M Reef of the Stillwater Complex were measured to elucidate the temporal and genetic relationship between sulfides and host silicate minerals. Results indicate that sulfides and coexisting plagioclases are generally not in isotopic equilibrium, that both sulfides and feldspars record highly radiogenic initial ratios at 2.7 Ga, and that a component of “post-emplacement” radiogenic Pb has mixed with common Pb in the sulfides. A model involving introduction of radiogenic Pb carried by fluids derived from sources external to the complex is favored. Analyses of the lead isotopic composition of sulfides in veins which cut the complex indicate that a significant fraction of the radiogenic lead which was added to the sulfides was externally derived during an extensive hydrothermal episode, associated with Proterozoic regional metamorphism around 1.7 Ga. The possibility that some fractions of the radiogenic Pb may have been derived from primary minerals altered during the low-grade metamorphism cannot be discounted. The amount of radiogenic lead added is variable and in some cases negligible. There is a good correlation between the lead isotope composition and the nature of the secondary mineral assemblage. Sulfides and plagioclases in samples that show little or no alteration of the primary minerals are generally in isotopic equilibrium and preserve isotope ratios consistent with magmatic crystallization at 2.7 Ga. Samples with the most radiogenic sulfides contain abundant secondary minerals (serpentine, talc, actinolite, chlorite and zoisite) associated with greenschist facies metamorphism. Some of the radiogenic Pb in the sulfides can be removed by progressive stepwise leaching. However, in most samples recrystallization of sulfides during metamorphism has mixed common Pb and radiogenic Pb throughout the crystal structure such that, in these samples, stepwise leaching does not recover initial Pb isotopic ratios. Plagioclases are much more resistant to low temperature recrystallization and in almost all cases, stepwise leaching reveals the initial lead isotopic composition. The reactivity of sulfides over a wide temperature range enhances their utility in understanding not only the processes involved in their formation at the time of magmatic emplacement but also postmagmatic processes which were important in the redistribution and enrichment of platinum group elements (PGE) within the ore zone. Received: 30 December 1998 / Accepted: 16 June 1999