主编絮语

自2011年第2期起,我刊推出"主编絮语"这个栏目,目的在于及时表达我刊的办刊思想和办刊动态,推介重点文章,加强与读者、作者和各位编委的信息沟通和交流。正如在本卷卷首语中指出的,文章质量是刊物的生命线。因此,如何提高发表在我刊文章的质量,是本届编委会的第一要务和工作重点。编委会将通过多种途径,从     

硫化物矿物中痕量元素的激光剥蚀-电感耦合等离子体质谱微区分析进展

第一行过渡金属元素及痕量贵金属元素高度富集在硫化物矿物中,常形成具有工业意义的矿床,使得硫化物具有重大的经济价值。对天然硫化物矿物中的这些痕量金属元素丰度及其分布的研究,在矿石成因学、经济地质学、环境地球化学等领域具有重要的应用价值。激光剥蚀-电感耦合等离子体质谱(LA-ICP-MS)微区分析技术是一种强大的痕量元素分析工具,非常适合直接分析硫化物矿物中痕量元素的浓度及其空间分布。由于硫化物的激光剥蚀特性与硅酸盐及氧化物不同,分析校准用的标准物质又极度缺乏,严重阻碍了这一技术在硫化物矿物微区分析中的应用。本文评述了硫化物简介、硫化物中痕量金属元素分析的意义、LA-ICP-MS微区分析技术在硫化物矿物痕量元素分析中的优势及近年来的应用进展、硫化物分析中的干扰与校准、包含铂族元素及金的硫化物标准物质的研制进展及合成硫化物标准物质最有应用前景的方法。     

Massive sulfide deposition and trace element remobilization in the Middle Valley sediment-hosted hydrothermal system, northern Juan de Fuca Rdge

The Bent Hill massive sulfide deposit and ODP Mound deposit in Middle Valley at the northernmost end of the Juan de Fuca Ridge are two of the largest modern seafloor hydrothermal deposits yet explored. Trace metal concentrations of sulfide minerals, determined by laser-ablation ICP-MS, were used in conjunction with mineral paragenetic studies and thermodynamic calculations to deduce the history of fluid-mineral reactions during sulfide deposition. Detailed analyses of the distribution of metals in sulfides indicate significant shifts in the physical and chemical conditions responsible for the trace element variability observed in these sulfide deposits. Trace elements (Mn, Co, Ni, As, Se, Ag, Cd, Sb, Pb, and Bi) analyzed in a representative suite of 10 thin sections from these deposits suggest differences in conditions and processes of hydrothermal alteration resulting in mass transfer of metals from the center of the deposits to the margins. Enrichments of some trace metals (Pb, Sb, Cd, Ag) in sphalerite at the margins of the deposits are best explained by dissolution/reprecipitation processes consistent with secondary remineralization. Results of reaction-path models clarify mechanisms of mass transfer during remineralization of sulfide deposits due to mixing of hydrothermal fluids with seawater. Model results are consistent with patterns of observed mineral paragenesis and help to identify conditions (pH, redox, temperature) that may be responsible for variations in trace metal concentrations in primary and secondary minerals. Differences in trace metal distributions throughout a single deposit and between nearby deposits at Middle Valley can be linked to the history of metal mobilization within this active hydrothermal system that may have broad implications for sulfide ore formation in other sedimented and unsedimented ridge systems.     

Rapid detection of bioavailable heavy metals in sediment porewaters using acid-volatile sulfide gel probes

The acid-volatile sulfide (AVS) pool in anoxic sediments is believed to play an important role in the sequestration of heavy metals, forming less soluble mineral sulfides via replacement and coprecipitation reactions. In this study, novel sediment gel probes containing immobilized FeS or MnS particles were evaluated for their ability to concentrate and detect reactive heavy metals in solution. MnS-containing gels were more effective than FeS gels at concentrating most metals in solution external to the gels, but they were more difficult to prepare and use. Copper reacted with FeS in gel probes to form one or more secondary sulfide minerals insoluble in 1 N HCl. The pixel density of digital images of these gels was highly correlated with the concentration of copper in gels and total copper in solution, suggesting a method for rapid screening of bioavailable heavy metals. Copper added to Youghiogheny River (PA, USA) sediments could be detected using this approach.     

Textural,mineralogical and stable isotope studies of hydrothermal alteration in the main sulfide zone of the Great Dyke,Zimbabwe and the precious metals zone of the Sonju Lake Intrusion,Minnesota, USA

Stratigraphic offsets in the peak concentrations of platinum-group elements (PGE) and base-metal sulfides in the main sulfide zone of the Great Dyke and the precious metals zone of the Sonju Lake Intrusion have, in part, been attributed to the interaction between magmatic PGE-bearing base-metal sulfide assemblages and hydrothermal fluids. In this paper, we provide mineralogical and textural evidence that indicates alteration of base-metal sulfides and mobilization of metals and S during hydrothermal alteration in both mineralized intrusions. Stable isotopic data suggest that the fluids involved in the alteration were of magmatic origin in the Great Dyke but that a meteoric water component was involved in the alteration of the Sonju Lake Intrusion. The strong spatial association of platinum-group minerals, principally Pt and Pd sulfides, arsenides, and tellurides, with base-metal sulfide assemblages in the main sulfide zone of the Great Dyke is consistent with residual enrichment of Pt and Pd during hydrothermal alteration. However, such an interpretation is more tenuous for the precious metals zone of the Sonju Lake Intrusion where important Pt and Pd arsenides and antimonides occur as inclusions within individual plagioclase crystals and within alteration assemblages that are free of base-metal sulfides. Our observations suggest that Pt and Pd tellurides, antimonides, and arsenides may form during both magmatic crystallization and subsolidus hydrothermal alteration. Experimental studies of magmatic crystallization and hydrothermal transport/deposition in systems involving arsenides, tellurides, antimonides, and base metal sulfides are needed to better understand the relative importance of magmatic and hydrothermal processes in controlling the distribution of PGE in mineralized layered intrusions of this type.     

Trace metal behaviour in riverine sediments: Role of organic matter and sulfides

Three sediment cores were collected in the Scheldt, Lys and Spiere canals, which drain a highly populated and industrialized area in Western Europe. The speciation and the distribution of trace metals in pore waters and sediment particles were assessed through a combination of computational and experimental techniques. The concentrations of dissolved major and trace elements (anions, cations, sulfides, dissolved organic C, Cd, Co, Fe, Mn, Ni, Pb and Zn) were used to calculate the thermodynamic equilibrium speciation in pore waters and to evaluate the saturation of minerals (Visual Minteq software). A sequential extraction procedure was applied on anoxic sediment particles in order to assess the main host phases of trace elements. Manganese was the most labile metal in pore waters and was mainly associated with carbonates in particles. In contrast, a weak affinity of Cd, Co, Ni, Pb and Zn with carbonates was established because: (1) a systematic under-saturation was noticed in pore waters and (2) less than 10% of these elements were extracted in the exchangeable and carbonate sedimentary fraction. In the studied anoxic sediments, the mobility and the lability of trace metals, apart from Mn, seemed to be controlled through the competition between sulfidic and organic ligands. In particular, the necessity of taking into account organic matter in the modelling of thermodynamic equilibrium was demonstrated for Cd, Ni, Zn and Pb, the latter element exhibiting the strongest affinity with humic substances. Consequently, dissolved organic matter could favour the stabilization of trace metals in the liquid phase. Conversely, sulfide minerals played a key role in the scavenging of trace metals in sediment particles. Finally, similar trace metal lability rankings were obtained for the liquid and solid phases.     

Post-depositional redistribution of trace metals in reservoir sediments of a mining/smelting-impacted watershed (the Lot River,SW France)

Mining/smelting wastes and reservoir sediment cores from the Lot River watershed were studied using mineralogical (XRD, SEM–EDS, EMPA) and geochemical (redox dynamics, selective extractions) approaches to characterize the main carrier phases of trace metals. These two approaches permitted determining the role of post-depositional redistribution processes in sediments and their effects on the fate and mobility of trace metals. The mining/smelting wastes showed heterogeneous mineral compositions with highly variable contents of trace metals. The main trace metal-bearing phases include spinels affected by secondary processes, silicates and sulfates. The results indicate a clear change in the chemical partitioning of trace metals between the reservoir sediments upstream and downstream of the mining/smelting activities, with the downstream sediments showing a 2-fold to 5-fold greater contribution of the oxidizable fraction. This increase was ascribed to stronger post-depositional redistribution of trace metals related to intense early diagenetic processes, including dissolution of trace metal-bearing phases and precipitation of authigenic sulfide phases through organic matter (OM) mineralization. This redistribution is due to high inputs (derived from mining/smelting waste weathering) at the water–sediment interface of (i) dissolved SO₄ promoting more efficient OM mineralization, and (ii) highly reactive trace metal-bearing particles. As a result, the main trace metal-bearing phases in the downstream sediments are represented by Zn- and Fe-sulfides, with minor occurrence of detrital zincian spinels, sulfates and Fe-oxyhydroxides. Sequestration of trace metals in sulfides at depth in reservoir sediments does not represent long term sequestration owing to possible resuspension of anoxic sediments by natural (floods) and/or anthropogenic (dredging, dam flush) events that might promote trace metal mobilization through sulfide oxidation. It is estimated that, during a major flood event, about 870 t of Zn, 18 t of Cd, 25 t of Pb and 17 t of Cu could be mobilized from the downstream reservoir sediments along the Lot River by resuspension-induced oxidation of sulfide phases. These amounts are equivalent to 13-fold (Cd), ∼6-fold (Zn), 4-fold (Pb) the mean annual inputs of the respective dissolved trace metals into the Gironde estuary.     

Structure and reactivity of zinc sulfide precipitates formed in the presence of sulfate-reducing bacteria

The biologically mediated formation of metal sulfide precipitates in anoxic sediments represents a potentially important mechanism for the sequestration of toxic metals. Current knowledge of the structure and reactivity of these biogenic metal sulfides is scarce, limiting the ability to effectively assess contaminant sequestration in, and remobilization from, these solids. In this study, SO₄-reducing bacteria (Desulfovibrio sp.) were grown for 5 days in a high-SO₄, minimal metal media amended with Zn at either 30 or 300 micromolar. Zinc speciation in the reactor solids was determined using X-ray absorption spectroscopy, and the results compared to spectra of known metal sulfide mineral phases and freshly formed metal sulfides synthesized through purely chemical processes. Biogenically mediated Zn sulfides showed significantly more short range crystallographic order than the abiotically prepared amorphous precipitates. The presence of dissolved Fe²⁺ at similar concentrations did not affect the nature of the Zn precipitates formed. The biogenic ZnS solids were also more resistant to re-oxidation than the chemical precipitates but more soluble than sphalerite mineral samples. These results suggest that Zn sulfides formed in anaerobic sediments are likely to be more resistant to re-oxidation than would be expected based on dissolution of Fe sulfides and/or sediment acid volatile sulfides.     

Dissolved sulfides in the oxic water column of San Francisco Bay,California

Trace contaminants enter major estuaries such as San Francisco Bay from a variety of point and nonpoint sources and may then be repartitioned between solid and aqueous phases or altered in chemical speciation. Chemical speciation affects the bioavailability of metals as well as organic ligands to planktonic and benthic organisms, and the partitioning of these solutes between phases. Our previous, work in south San Francisco Bay indicated that sulfide complexation with metals may be of particular importance because of the thermodynamic stability of these complexes. Although the water column of the bay is consistently well-oxygenated and typically unstratified with respect to dissolved oxygen, the kinetics of sulfide oxidation could exert at least transient controls on metal speciation. Our initial data on dissolved sulfides in the main channel of both the northern and southern components of the bay consistently indicate submicromolar concenrations (from <1 nM to 162 nM), as one would expect in an oxidizing environment. However, chemical speciation calculations over the range of observed sulfide concentrations indicate that these trace concentrations in the bay water column can markedly affect chemical speciation of ecologically significant trace metals such as cadmium, copper, and zinc.     

Precious metal and telluride mineralogy of large volcanic-hosted massive sulfide deposits in the Urals

Summary The study focuses on the mode of occurrence of Au, Ag and Te in ores of the Gaisk, Safyanovsk, Uzelginsk and other volcanic-hosted massive sulfide (VHMS) deposits in the Russian Urals. Minerals containing these elements routinely form fine inclusions within common sulfides (pyrite, chalcopyrite and sphalerite). Gold is mostly concentrated as ‘invisible’ gold within pyrite and chalcopyrite at concentrations of 1–20 ppm. Silver mainly occurs substituted in tennantite (0.1–6 wt.% Ag). In the early stages of mineralization, gold is concentrated into solid solution within the sulfides and does not form discrete minerals. Mineral parageneses identified in the VHMS deposits that contain discrete gold- and gold-bearing minerals, including native gold, other native elements, various tellurides and tennantite, were formed only in the latest stages of mineralization. Secondary hydrothermal stages and local metamorphism of sulfide ores resulted in redistribution of base and precious metals, refining of the common sulfides, the appearance of submicroscopic and microscopic inclusions of Au–Ag alloys (fineness 0.440–0.975) and segregation of trace elements into new, discrete minerals. The latter include Au and Ag compounds combined with Te, Se, Bi and S. Numerous tellurides (altaite, hessite, stützite, petzite, krennerite etc.) are found in the massive sulfide ores of the Urals and appear to be major carriers of gold and PGE in VHMS ores.     

Fate and transport of metals in H2S-rich waters at a treatment wetland

The aqueous geochemistry of Zn, Cu, Cd, Fe, Mn and As is discussed within the context of an anaerobic treatment wetland in Butte, Montana. The water being treated had a circum-neutral pH with high concentrations of trace metals and sulfate. Reducing conditions in the wetland substrate promoted bacterial sulfate reduction (BSR) and precipitation of dissolved metal as sulfide minerals. ZnS was the most common sulfide phase found, and consisted of framboidal clusters of individual spheres with diameters in the submicron range. Some of the ZnS particles passed through the subsurface flow, anaerobic cells in suspended form. The concentration of "dissolved" trace metals (passing through a 0.45 μm filter) was monitored as a function of H₂S concentration, and compared to predicted solubilities based on experimental studies of aqueous metal complexation with dissolved sulfide. Whereas the theoretical predictions produce "U-shaped" solubility curves as a function of H₂S, the field data show a flat dependence of metal concentration on H₂S. Observed metal concentrations for Zn, Cu and Cd were greater than the predicted values, particularly at low H₂S concentration, whereas Mn and As were undersaturated with their respective metal sulfides. Results from this study show that water treatment facilities employing BSR have the potential to mobilize arsenic out of mineral substrates at levels that may exceed regulatory criteria. Dissolved iron was close to equilibrium saturation with amorphous FeS at the higher range of sulfide concentrations observed (>0.1 mmol H₂S), but was more likely constrained by goethite at lower H₂S levels. Inconsistencies between our field results and theoretical predictions may be due to several problems, including: (i) a lack of understanding of the form, valence, and thermodynamic stability of poorly crystalline metal sulfide precipitates; (ii) the possible influence of metal sulfide colloids imparting an erroneously high "dissolved" metal concentration; (iii) inaccurate or incomplete thermodynamic data for aqueous metal complexes at the conditions of the treatment facility; and (iv) difficulties in accurately measuring low concentrations of dissolved sulfide in the field.     

南天山沙里塔什铅锌矿床地质特征及S、Pb同位素特征研究

沙里塔什铅锌矿床是新疆南天山多金属成矿带内重要的铅锌矿床。矿床位于南天山造山带迈丹-阔克萨勒古生代陆缘盆地,含矿层位为中泥盆世托格买提组,单个矿体呈透镜状、巢状和筒状分布在白云岩构造破碎带内,围岩蚀变较弱。矿石中金属矿物以闪锌矿、方铅矿为主。矿石金属硫化物的δ34S=-3.6‰~-12.0‰,指示硫主要来自海相硫酸盐的还原作用。矿石金属硫化物的²⁰⁶Pb/²⁰⁴Pb比值范围为17.8979~17.9625,²⁰⁷Pb/²⁰⁴Pb为15.5981~15.6023,²⁰⁸Pb/²⁰⁴Pb为38.1863~38.1971,结合矿石、围岩的微量及稀土元素特征判断,铅主要来自古生代沉积盆地高金属背景值的中泥盆世托格买提组。综合沙里塔什铅锌矿床的地质、地球化学特征,判定其为MVT型铅锌矿床。     

Magmatic Cu-Ni-PGE-Au sulfide mineralisation in alkaline igneous systems: An example from the Sron Garbh intrusion,Tyndrum, Scotland

Magmatic sulfide deposits typically occur in ultramafic-mafic systems, however, mineralisation can occur in more intermediate and alkaline magmas. Sron Garbh is an appinite-diorite intrusion emplaced into Dalradian metasediments in the Tyndrum area of Scotland that hosts magmatic Cu-Ni-PGE-Au sulfide mineralisation in the appinitic portion. It is thus an example of magmatic sulfide mineralisation hosted by alkaline rocks, and is the most significantly mineralised appinitic intrusion known in the British Isles. The intrusion is irregularly shaped, with an appinite rim, comprising amphibole cumulates classed as vogesites. The central portion of the intrusion is comprised of unmineralised, but pyrite-bearing, diorites. Both appinites and diorites have similar trace element geochemistry that suggests the diorite is a more fractionated differentiate of the appinite from a common source that can be classed with the high Ba-Sr intrusions of the Scottish Caledonides. Mineralisation is present as a disseminated, primary chalcopyrite-pyrite-PGM assemblage and a blebby, pyrite-chalcopyrite assemblage with significant Co-As-rich pyrite. Both assemblages contain minor millerite and Ni-Co-As-sulfides. The mineralisation is Cu-, PPGE-, and Au-rich and IPGE-poor and the platinum group mineral assemblage is overwhelmingly dominated by Pd minerals; however, the bulk rock Pt/Pd ratio is around 0.8. Laser ablation analysis of the sulfides reveals that pyrite and the Ni-Co-sulfides are the primary host for Pt, which is present in solid solution in concentrations of up to 22 ppm in pyrite. Good correlations between all base and precious metals indicate very little hydrothermal remobilisation of metals despite some evidence of secondary pyrite and PGM. Sulfur isotope data indicate some crustal S in the magmatic sulfide assemblages. The source of this is unlikely to have been the local quartzites, but S-rich Dalradian sediments present at depth. The generation of magmatic Cu-Ni-PGE-Au mineralisation at Sron Garbh can be attributed to post-collisional slab drop off that allowed hydrous, low-degree partial melting to take place that produced a Cu-PPGE-Au-enriched melt, which ascended through the crust, assimilating crustal S from the Dalradian sediments. The presence of a number of PGE-enriched sulfide occurrences in appinitic intrusions across the Scottish Caledonides indicates that the region contains certain features that make it more prospective than other alkaline provinces worldwide, which may be linked the post-Caledonian slab drop off event. We propose that the incongruent melting of pre-existing magmatic sulfides or ‘refertilised’ mantle in low-degree partial melts can produce characteristically fractionated, Cu-PPGE-Au-semi metal bearing, hydrous, alkali melts, which, if they undergo sulfide saturation, have the potential to produce alkaline-hosted magmatic sulfide deposits.     

REGULARITIES IN THE DISTRIBUTION OF NONFERROUS AND PRECIOUS METALS IN PRINCIPAL ORE MINERALS AND SILICATES OF THE NORIL'SK DEPOSITS

The results of a study of copper, nickel, cobalt, platinum, palladium, gold, and rhodium distribution in basic ore-forming sulfide minerals (chalcopyrite and pyrrhotites) as well as in the silicate portion of the host rocks of the Noril'sk deposit, are given. Interrelations between metals in different sulfide minerals and silicates are characterized. It has been established that palladium, platinum, and gold are concentrated in chalcopyrite while cobalt and rhodium are concentrated in pyrrhotite. The cobalt and precious metal content in sulfides grows with the increase of their nickel content. The relative content, however, of all these elements estimated for 1% of nickel is different in chalcopyrites and pyrrhotites. The former show a high platinum, palladium, and gold content and the latter--cobalt and rhodium. Ratios of these elements in sulfides and silicates are different. The relative platinum content increases in silicates due to a considerably greater content of mineralized platinum. Both nickel and cobalt form silicate compounds the latter to a much greater extent than the former. The relative cobalt content is therefore higher in silicates than in sulfides. In descending order, the element concentrations in sulfides range as follows: copper, nickel, palladium, gold, cobalt, platinum. — Auth. English Summ.     

Chemical influences on trace metal-sulfide interactions in anoxic sediments

Interactions of trace metals with sulfide in anoxic environments are important in determining their chemical form and potential toxicity to organisms. In recent years, a considerable body of observational data has accumulated that indicates very different behavior for various trace metals in sulfidic sediments. These differences in behavior cannot be entirely attributed to thermodynamic relationships, but also reflect differences in ligand exchange reaction kinetics, and redox reaction pathways.Pb, Zn, and Cd, which are generally pyritized to only a few percent of the “reactive” fraction, have faster water exchange reaction kinetics than Fe²⁺, resulting in MeS phases precipitating prior to FeS formation and subsequent pyrite formation, whereas, Co and Ni, which have slower H₂O exchange kinetics than Fe²⁺, are incorporated into pyrite. Although Hg and Cu have faster reaction kinetics than Fe²⁺, both are incorporated into pyrite or leached from the pyrite fraction with nitric acid. Hg undergoes significant chloride complexation, which can retard reaction with sulfide, but can also replace Fe in FeS to form HgS, which can only be dissolved in the pyrite fraction. Cu²⁺ is reduced by sulfide and forms a variety of sulfides with and without Fe that can only be dissolved with nitric acid. Mn²⁺ does not form a MnS phase easily and is incorporated into pyrite at high iron degrees of pyritization (DOP).Oxyanions of Mo and As are first reduced by sulfide. These reduced forms may then react with sulfides resulting in incorporation into pyrite. However, the oxyanion of Cr is reduced to Cr³⁺, which is kinetically inert to reaction with sulfide and, therefore, not incorporated into pyrite.     

Trace metals in suspended particulate matter and in sediment trap material from a permanently anoxic fjord — Framvaren, South Norway

Geochemical studies of the trace metal concentrations in suspended particulate matter (SPM) and sediment trap material from a permanently anoxic fjord, Framvaren, South Norway in 1989 and 1993 indicate that extremely high concentrations of zinc (max = 183920 mg/kg), copper (max = 4130 mg/kg), lead (max = 2752 mg/kg), and cadmium (max= 8.1 mg/kg) sometimes (1993) occur in the SPM collected in the anoxic water layer. The highest concentrations of Zn occur just below the redoxcline at 22 m water depth (in 1993), and copper, lead and cadmium have maximum concentrations between 30 and 80 m depth, where the amount of total SPM is at a minimum (about 0.3 mg/L). On a mass per volume (g/L) basis, the maximum concentrations of Cd, Cu and Fe occur at the interface (21m) and those of Zn occur just below the redoxcline (22 m depth). The SPM and sediment trap data suggest that the metals are precipitated as sulfide minerals in the anoxic water. The presence of particulate sulfides was confirmed by SEM studies that show the occurrence of discrete metal (Cu, Fe, Pb, and Zn) sulfide particles in size from 10–20 m as well as framboidal pyrites (1–5 m in size). Higher levels of metal sulfides at intermediate depths rather than in the deep water of Framvaren (> 100 m), may be due to input of trace metals by water exchange over the sill in the upper part of the water column. In the deep water, less metal sulfide precipitation takes place due to depletion of trace metals, and the dilution of particulate metal concentrations by organic matter and by the chemogenic formation of calcite.     

A laser ablation inductively coupled plasma mass spectrometry study of the distribution of chalcophile elements among sulfide phases in sedimentary and magmatic rocks of the Duluth Complex,Minnesota, USA

Nickel-copper sulfide deposits occur in the basal unit of the Partridge River Intrusion, Duluth Complex (Minnesota, USA). Many lines of evidence suggest that these sulfides are formed after assimilation of the proterozoic S-rich black shales, known as the Bedded Pyrrhotite Unit. In addition to S, black shales are enriched in Te, As, Bi, Sb and Sn (TABS) and the basaltic magma of the intrusion is contaminated by the partial melt of the black shales. The TABS are chalcophile and together with the platinum-group elements, Ni and Cu partitioned into the magmatic sulfide liquid that segregated from the Duluth magma. The TABS are important for the formation of platinum-group minerals (PGM) thus their role during crystallization of the base metal sulfide minerals could affect the distribution of the PGE. However, the concentrations of TABS in magmatic Ni-Cu-PGE deposits and their distribution among base metal sulfide minerals are poorly documented. In order to investigate whether the base metal sulfide minerals host TABS in magmatic Ni-Cu-PGE deposits, a petrographic and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) study has been carried out on base metal sulfide and silicate phases of the Partridge River Intrusion, Duluth Complex.Petrographic observations showed that the proportions of the base metal sulfide minerals vary with rock type. The sulfide assemblage of the least metamorphosed Bedded Pyrrhotite Unit from outside the contact metamorphic aureole consists of pyrite with minor pyrrhotite plus chalcopyrite (<5%), whereas within the contact aureole the sulfide assemblage of the Bedded Pyrrhotite Unit rocks consists dominantly of pyrrhotite (>95%) with small amount of chalcopyrite (<2%). The sulfide mineral assemblage in the xenoliths of the Bedded Pyrrhotite Unit and in the mafic rocks of the basal unit contains two additional sulfides, pentlandite and cubanite.Our LA-ICP-MS study shows that sulfides of the Bedded Pyrrhotite Unit are rich in TABS; consistent with these S-rich black shales being the source of TABS that contaminated the mafic magma. Most of the TABS are associated with sulfides and platinum-group minerals in the rocks of the Bedded Pyrrhotite Unit from the contact aureole, the Bedded Pyrrhotite Unit xenoliths and the mafic rocks of the Duluth Complex. In addition to these phases the laser maps show that silicate phases, i.e., orthopyroxene and plagioclase contain Sn and Pb respectively. In contrast, in the least metamorphosed samples of the Bedded Pyrrhotite Unit from outside the contact aureole although the pyrite contains some TABS mass balance calculations indicates that most the TABS are contained in other phases. In these rocks, galena hosts significant amounts of Te, Bi, Sb, Sn and Ag and few very small grains of Sb-rich phases were also observed. The host phases for As were not established but possibly organic compounds may have contributed.     

Environmental magnetic studies on surface sediments: a proxy for metal and hydrocarbon contamination

Visakhapatnam is one of the major port cities, and it is developed into a hub of many large- and medium-scale industries. Due to growing industrialization and urbanization, coast is vulnerable to both organic and inorganic micro-pollutants. Twenty-five surface sediments were collected along the Visakhapatnam coast for the measurement of texture size, petroleum hydrocarbons, trace metals and environmental magnetic parameters. The percentage of coarser particles was more in the northern region, whereas the percentage of fine particles was increased toward south. Elevated levels of petroleum hydrocarbons and trace metals were attributed due to marine and land-based sources, in particular, those were due to shipping activities, treated and partially treated sewage and industrial wastes. The concentrations of trace metals, petroleum hydrocarbons and magnetic minerals were decreased from nearshore to seaward. Our results revealed that the magnetic mineralogy is dominated by magnetite with a small proportion of hematite, and the grain size of magnetic minerals was in the range of pseudo-single domain to multidomain nature with detrital origin. From the principal component analysis, the magnetic concentration and mineralogy-dependent parameters co-vary with the heavy metal and PHC concentrations, suggesting that the inputs of magnetic minerals, petroleum hydrocarbons and heavy metals in the Visakhapatnam shelf sediments were derived from the same anthropogenic sources. Thus, the large magnetic dataset can be used to reduce the number of chemical analysis; hence, environmental magnetic parameters were used as a proxy for both organic and inorganic micro-pollutants.     

Heavy metal partitioning in river sediments severely polluted by acid mine drainage in the Iberian Pyrite Belt

This study provides a geochemical partitioning pattern of Fe, Mn and potentially toxic trace elements (As, Cd, Cr, Cu, Ni, Pb, Zn) in sediments historically contaminated with acid mine drainage, as determined by using a 4-step sequential extraction scheme. At the upperstream, the sediments occur as ochreous precipitates consisting of amorphous or poorly crystalline oxy-hydroxides of Fe, and locally jarosite, whereas the estuarine sediments are composed mainly of detrital quartz, illite, kaolinite, feldspars, carbonates and heavy minerals, with minor authigenic phases (gypsum, vivianite, halite, pyrite). The sediments are severely contaminated with As, Cd, Cu, Pb and Zn, especially in the vicinity of the mining pollution sources and some sites of the estuary, where the metal concentrations are several orders of magnitude above background levels. Although a significant proportion of Zn, Cd and Cu is present in a readily soluble form, the majority of heavy metals are bonded to reducible phases, suggesting that Fe oxy-hydroxides have a dominant role in the metal accumulation. In the estuary, the sediments are potentially less reactive than in the riverine environment, because relevant concentrations of heavy metals are immobilised in the crystalline structure of minerals.     

Sulfide Remobilisation from Sulfide Ore at High Temperatures and Differential Stresses: An Experimental Approach

We conducted experiments to simulate sulfide remobilisation from sulfide ore. The starting material was from the Hongtoushan massive sulfide deposit, NE China, and is composed of pyrite, pyrrhotite, chalcopyrite, sphalerite, quartz, and silicate minerals. The ore was immersed in a solution of 20 wt.% NaCl for 260 h, and then was mounted in a Changjiang 500 triaxial rock stress machine. After the experiments were performed for 13 h at temperatures of 362, 464, 556 and 682°C, with corresponding confining and axial pressures, the samples were cooled at room temperatures. Our results from all the runs indicate that sulfides can be remobilised both mechanically and chemically, and that remobilisation is enhanced at higher temperatures. Mechanical remobilisation can only take place over limited distances and results in minor differentiation between various sulfide minerals. Distant external remobilisation to form new orebodies is most likely caused by chemical remobilisation. In contrast to plastically deformed areas, space resulting from cataclastic deformation could provide conduits for fluid transport and space for metal precipitation. Remobilised iron sulfides will precipitate as pyrrhotite at high temperatures, but as pyrite when temperature decreases. Furthermore, chalcopyrite is more easily remobilised than sphalerite under the conditions of the present experiments. Remobilisation accompanying deformation and metamorphism may add epigenetic features to syngenetic deposits.