Enrichment characteristics and its geological significance of dispersed elements within sulfide minerals from the VI ore belt in the Maoping Pb-Zn deposit,Yunnan Province,ChinaSCIEI北大核心CSCD

作为华南大面积低温成矿域的重要组成部分,川滇黔铅锌矿集区是我国重要的铅锌银等资源基地之一,同时该矿集区也是Ge、Cd、Ga和In等稀散元素的超常富集区域。毛坪矿床是该矿集区内第二大铅锌矿床,累计探明铅锌金属储量超过3Mt(Pb+Zn平均品位≥18%),锗(Ge)保有储量182t。本文以新发现的Ⅵ矿带(铅锌金属已探明储量≥60万t,Pb+Zn平均品位≥20%)为研究对象,利用LA-ICPMS对主要矿石矿物闪锌矿和黄铁矿进行了微区原位微量元素组成和Mapping分析。研究结果显示Ⅵ矿带闪锌矿普遍富集Ge(最高580×10^(-6),均值81.1×10^(-6))、Cd(最高3486×10^(-6),均值1613×10^(-6))和Ga(最高190×10^(-6),均值44.4×10^(-6));黄铁矿普遍富集Mn、As、Pb、Cu、Ag和Sb。与Ⅰ和Ⅱ号矿带闪锌矿相比,Ⅵ号矿带闪锌矿更富集Ge和Ga。闪锌矿中Fe和Pb以类质同象为主,偶见黄铁矿和方铅矿显微包体;Cu、Ge、Ag和As赋存形式主要为类质同象,替代方式为Ge^(4+)+2(Cu+,Ag+,As+)↔3Zn^(2+);Cd以类质同象方式赋存为主,替代机制为Cd^(2+)↔Zn^(2+);Ga和In可能主要以类质同象方式存在。黄铁矿中Pb和Mn主要以方铅矿和碳酸盐矿物显微包体为主;Cu、As和Sb以类质同象形式存在于黄铁矿中;Ag和Zn可能以独立矿物形式赋存;Co和Ni以类质同象方式替代Fe进入黄铁矿晶格中,替代方式为Ni^(2+)+Co^(2+)↔2Fe^(2+)。毛坪矿床新发现Ⅵ矿带硫化物相比典型MVT矿床硫化物具有不同的In和Ge含量以及Cd/Fe比值,结合矿床地质特征和其他证据,表明毛坪矿床成因类型特殊,有别于经典MVT铅锌矿床,属于川滇黔型铅锌矿床。     

Geochemistry of lead contaminated wetland soils amended with phosphorus

To remediate Pb contaminated soils it is proposed that phosphorus can be amended to the soils to transform the Pb into poorly soluble Pb-phosphate mineral phases. However, remediation strategies must account for variable Pb speciation and site-specific factors. In this study soil mineralogy and Pb speciation in soils from P-amended field trials at sites within the Coeur d’Alene River Basin in Idaho, USA were investigated. The soils are contaminated from mining activities and are enriched with Fe and Mn. Selective extraction of the soils indicated that the Fe oxides are poorly crystalline. XRD of the soil clay size fractions identified quartz, muscovite, kaolinite, siderite, lepidocrocite, and chlorite minerals. Amendment with P fertilizer dissolved the siderite. No Pb–phosphate minerals were detected by XRD. Electron microprobe analysis showed direct correlations between Pb, Fe, and Mn in the unamended soils, and negative correlations between Pb and Si. Lead and Mn were strongly correlated. In the amended soils Fe and P were strongly correlated. Results indicate that the Pb is associated with poorly crystalline Fe and Mn oxides, and that added P is primarily associated with Fe oxide phases. Comparisons of pore water Pb concentrations with chloropyromorphite and plumbogummite solubility suggest that in the phosphate-amended soils the pore waters are undersaturated in these phases, whereas several of the control soil pore waters were oversaturated, indicating the added phosphate suppressed the Pb solubility. Results from this research provide insight into the geochemistry occurring in the P-remediated soils that will help in making management and remediation decisions.     

Geochemical investigations on fluvial sediments contaminated by tin-mine tailings,Cornwall, England

Tin-mine tailings containing high concentrations of Sn, Cu, Zn, Fe, Mn, As, and W are discharged into the Red River of cornwall, England and are then transported into St. Ives Bay under normal flow conditions. Most of the tin-bearing particles in the fluvial sediments are smaller than 170 μm, but tin-bearing composite grains or mineral grains with tin interspersed in the crystal lattices also occur in coarser size fractions. Tin distribution in the sediments is controlledby: (1) the distance from the source of the tailings, and (2) the concentration processes operating on the river bed. Suspended sediment and sediment transported by saltation filtered from river water samples also showed high concentrations of metals although, in contrast to the bottom sediments, they vary within a narrow range. Distributions of Cu, Zn, Fe, As, and Pb in the filtered sediments probably are related to the physical and chemical behavior of their sulphide minerals during fluvial transportation. A regional stream-sediment geochemical reconnaissance survey for tin did not show the highest concentration in the Red River; this indicated that in other rivers and streams tin reconcentration by selective removal of light minerals had taken place in the bottom sediments after mining operations had ceased. These rivers and streams also can transport large quantitiies of land-derived sediment including tin-mine tailings discharged into them when mines were operating. The minimum distance of tin transported by the Red River is at least 10 km; however, most of the tin was derived from mine tailings and is considered to be unnatural.     

The mineralized veins and the impact of old mine workings on the environment at Segura, central Portugal

At Segura, granitic pegmatite veins with cassiterite and lepidolite, hydrothermal Sn–W quartz veins and Ba–Pb–Zn quartz veins intruded the Cambrian schist–metagraywacke complex and Hercynian granites. Cassiterite from Sn–W quartz veins is richer in Ti and poorer in Nb and Nb+Ta than cassiterite from granitic pegmatite. Wolframite from Sn–W quartz veins is enriched in ferberite component. The Sn–W quartz veins contain pyrrhotite, arsenopyrite, sphalerite, chalcopyrite, stannite, matildite and schapbachite and the Ba–Pb–Zn quartz veins have cobaltite, pyrite, sphalerite, chalcopyrite, galena and barite, which were analyzed by electron microprobe. The presently abandoned mining area was exploited for Sn, W, Ba and Pb until 1953. Stream sediments and soils have higher concentrations of metals than parent granites and schists. Sn, W, B, As and Cu anomalies found in stream sediments and soils are associated with Sn–W quartz veins, while Ba, Pb and Zn anomalies in stream sediments and soils are related to Ba–Pb–Zn quartz veins. Sn, W, B, As, Cu, Ba, Pb and Zn anomalies in stream sediments and soils are also related to the respective old mining activities, which increased the mobility of trace metals from mineralized veins to soils, stream sediments and waters. Stream sediments and soils are sinks of trace elements, which depend on their contents in mineralized veins and weathering processes, but Sn, W and B depend mainly on a mechanic process. Soils must not be used for agriculture and human residence due to their Sn, B, As and Ba contents. Waters associated with mineralized veins were analyzed by flame atomic absorption spectroscopy (FAAS) and ICP-AES have high As, Fe and Mn and should not be used for human consumption and agriculture activities. The highest As values in waters were all related to Sn–W quartz veins and the highest Fe and Mn values were associated with the Ba–Pb–Zn quartz veins. No significant acid drainage was found associated with the old mine workings.     

Hydrogeochemical characteristics of acid mine drainage and water pollution at Makum Coalfield,India

Acid mine drainage (AMD) is one of the severe environmental problems that coal mines are facing. Generation of AMD in the northeastern part of India due to the coal mining activities has long been reported. However detailed geochemical characterization of AMD and its impact on water quality of various creeks, river and groundwater in the area has never been reported. Coal and coal measure rocks in the study area show finely disseminated pyrite crystals. Secondary solid phases, resulted due to oxidation of pyrite, occur on the surface of coal, and are mainly consisting of hydrated sulphate complexes of Fe and Mg (copiapite group of minerals). The direct mine discharges are highly acidic (up to pH 2.3) to alkaline (up to pH 7.6) in nature with high concentration of SO₄²⁻. Acidic discharges are highly enriched with Fe, Al, Mn, Ni, Pb and Cd, while Cr, Cu, Zn and Co are below their maximum permissible limit in most mine discharges. Creeks that carrying the direct mine discharges are highly contaminated; whereas major rivers are not much impacted by AMD. Ground water close to the collieries and AMD affected creeks are highly contaminated by Mn, Fe and Pb. Through geochemical modeling, it is inferred that jarosite is stable at pH less than 2.5, schwertmannite at pH less than 4.5, ferrihydrite above 5.8 and goethite is stable over wide range of pH, from highly acidic to alkaline condition.     

Mineralogical and geochemical signature of mine waste contamination, Tresillian River, Fal Estuary, Cornwall, UK

The mineralized district of SW England was one of the world's greatest mining areas, with mining commencing in the Bronze age, peaking in the 1850s to 1890s, but still continuing to the present day. Consequently, it is not surprising that mining has had a major impact on the environmental geochemistry of SW England. In this study, the mineralogical and geochemical signature of mine waste contamination within the Fal Estuary at Tresillian, Cornwall, has been examined. A pulse of mine waste contamination is recognized at approximately 50?cm below present day sediment surface. Sn, As, Cu, Pb, and Zn are all enriched within this contaminated interval with up to 1800 mg?kg^–1 Sn, 290 mg?kg^–1 As, 508 mg?kg^–1 Pb, 2210 mg?kg^–1 Zn, and 1380 mg?kg^–1 Cu. Within this interval, the dominant minerals present include chalcopyrite, arsenopyrite, pyrite, cassiterite, Fe–Ti oxides (ilmenite and ?rutile), wolframite, sphalerite, baryte, zircon, monazite, tourmaline and xenotime. In addition, man-made slag products commonly occur. The exact timing of the release of mine waste into the estuary is poorly constrained, but probably occurred during or immediately following the peak in mining activity in the nearby Camborne-Redruth district, which was between 1853 and 1893. The mine waste may have entered the estuary either via the Tresillian River and its tributaries or via Calenick Creek and the Truro River and/or the Carnon River which flows into Rostronguet Creek.     

Mineralogical and geochemical behavior of mill tailing material produced from lead-zinc skarn mineralization,Hanover, Grant County,New Mexico,USA

Mineral extraction and processing, especially metal mining, produces crushed and milled waste; such material, exposed to weathering, poses the potential threat of environmental contamination. In this study, mill tailings from inactive Pb-Zn mines in New Mexico, southwest USA, have been examined for their potential environmental impacts by means of detailed mineralogical and geochemical characterization. The principal ore minerals remaining in the tailings material are sphalerite, chalcopyrite, and very minor galena, smithsonite, and cerrusite, accompanied by the gangue minerals pyrite, pyrrhotite, magnetite, hematite, garnet, pyroxene, quartz, and calcite. White precipitate occurring on tailings surfaces is composed of gypsum and hydrated magnesium sulfates. Pyrite is mostly unaltered or shows only micron-scale rims of oxidation (goethite/hematite) in some surface samples. This iron oxide rim on pyrite is the only indication of weathering-derived minerals found by microscopy. There are variations in element concentrations with depth that reflect primary variations through time as the tailings ponds were filled. Cadmium and Zn concentrations increase with depth and Ag and Pb are low for the uppermost core samples, while Cu, Ni, and Co concentrations are generally high for the uppermost core samples. These elemental distributions indicate that little or no leaching has taken place since emplacement of the tailings because no accumulation or enrichment of these metals is observed in Hanover tailings, even in reducing portions of tailings piles. Element concentrations of surface samples surrounding the tailings reflect underlying mineralized zones rather than tailings-derived soil contamination. We observed no successive decreasing metal concentrations in prevalent wind directions away from the tailings. Stream sediment samples from Hanover Creek have somewhat elevated Zn, Cd, and Pb concentrations in areas that receive sediments from erosion of the tailings. However, input from tributaries downstream of the ponds appears to be principal source of heavy metals in Hanover Creek. The results of this study indicate that there is low risk for groundwater heavy-metal contamination from Hanover tailings. Tailings material do not show significant geochemical oxidation/alteration or metal leaching with depth. Our studies indicate that neutralizing minerals present in the tailings are sufficient to keep the tailings material chemically stable. Geochemically, however, tailings materials are being eroded and may pose a threat to Hanover Creek via siltation.     

The role of prokaryotes in subsurface weathering of hydrothermal sediments: A combined geochemical and microbiological investigation

A detailed geochemical and microbiological study of a ∼2 m sediment core from the inactive Alvin mounds within the TAG hydrothermal field was conducted to examine, for the first time, the role of prokaryotes in subsurface weathering of hydrothermal sediments. Results show that there has been substantial post-depositional remobilisation of metal species and diagenetic overprinting of the original high-temperature hydrothermal minerals, and aspects have involved prokaryotic processes. Prokaryotic enumeration demonstrates the presence of a population smaller than the average for deep sea sediments, probably due to the low organic carbon content, but not inhibited by (and hence adapted to) the metal rich environment. There was a small but significant increase in population size associated with the active redox boundary in an upper metal sulphide layer (50-70 cm) around which active metal remobilisation was concentrated (Cu, Au, Cd, Ag, U, Zn and Zn). Hence, subsurface prokaryotes were potentially obtaining energy from metal metabolism in this near surface zone. Close association of numbers of culturable Mn and Fe reducing prokaryotes with subsurface Fe²⁺ and Mn²⁺ pore water profiles suggested active prokaryotic metal reduction at depth in core CD102/43 (to ∼175 cm). In addition, a prokaryotic mechanism, which is associated with bacterial sulphate reduction, is invoked to explain the U enrichment on pyrite surfaces and Zn and Pb remobilisation in the upper sediment. Although prokaryotic populations are present throughout this metalliferous sediment, thermodynamic calculations indicated that the inferred low pH of pore waters and the suboxic/anoxic conditions limits the potential energy available from Fe(II) oxidation, which may restrict prokaryotic chemolithotrophic biomass. This suggests that intense prokaryotic Fe oxidation and weathering of seafloor massive sulphide deposits may be restricted to the upper portion of the deposit that is influenced by near neutral pH and oxic seawater unless there is significant subsurface fluid flow.     

黔北白云岩红色风化壳元素地球化学特征

选取贵州高原喀斯特地区典型白云岩风化剖面作为研究对象,探讨了红土剖面元素迁移特征及其影响因素,为进一步认识红色风化壳元素地球化学特征提供依据。结果表明:（1）红土剖面中土壤样品（XPS-4~XPS-25）Fe、K、Mn常量元素及Co、Pb、Zn微量元素的分布曲线相对于其他元素靠近 UCC,元素Mg、Ca、Na、Ti和 Li、Cr、Ba、V 的数据点则显著偏离了上部陆壳的平均组成。（2）元素对协变分析得出Ti与Fe、Ba和V的积累特征一致,呈增加趋势;Ti与Mg呈反向变化特征。（3）以Ti为参比元素的剖面迁移特征表明,绝大部分元素的地球化学行为表现为迁移淋失,仅 Fe 、Cr和V 富集。K、Ba总体上呈迁出趋势,个别层段有轻微富集;Na和Co在风化原岩处有一个富集端点。元素在风化过程中的迁移聚集与土壤剖面的pH值和剖面结构变化、粘土矿物和有机质等的吸附有关。      

攀枝花市大气降尘的地球化学特征

运用ICP-MS和ICP-OES分析了攀枝花市不同时段不同地点大气降尘中重金属元素含量,并对大气降尘中重金属的地球化学特征进行了分析,得出以下结论:①攀枝花市大气尘中As、Co、Mn、Pb、Ti、V的含量,与四川省其他城市相比均偏高,Zn的含量相对较低;②Cd、Mn、Pb主要分布在冶炼区和石灰石矿区,Co、Cu、Ti主要分布在石灰石矿区,Cr和V主要分布在冶炼区,As在仁和河富集较为富集,Zn集中在排土场附近,Fe集中在冶炼区和煤矿区;③除Pb外,其余十种元素旱季含量基本都高于雨季,而雨季Pb的含量却明显高于旱季。通过主成份分析,得出了在攀枝花市大气降尘中,重金属元素的来源主要为矿山污染和开采过程中产生的废水、废气。     

Geochemical stream sediment survey in Winder Valley, Balochistan, Pakistan

A pilot scale geochemical survey of sediments from the Winder Stream (SW Pakistan) and its tributaries was carried out. The Winder Stream mainly receives sediment from the southern extensions of the Mor and Pab Ranges in the District of Lasbela (Balochistan). In these two mountain ranges, rocks from Jurassic to Cretaceous age are exposed. Rocks of the Ferozabad Group comprise of carbonates and siliciclastics of Lower–Middle Jurassic age and occupy the dominant part of the Mor Range. These strata host syngenetic and epigenetic Zn–Pb–Ba mineralizations of Stratiform Sediment-Hosted (SSH) and Mississippi Valley Type (MVT) deposits.Quantitative estimates of mobile and immobile elements were made from active stream sediments of the Winder stream and its tributaries. The samples were analyzed for Ag, Zn, Pb, Cu, Ni, Co, V, Mn, Fe and Ba using atomic absorption spectroscopy. The abundance of these elements is discussed in relation to local geological conditions such as bedrock, climate, weathering, mobility and pH of the dispersing waters. A number of Zn anomalies have been distinguished in the study area. Kharrari (Zn, 360 ppm), Sand (Zn, 340 ppm) and Draber (Zn, 210 ppm) are demarcated as new areas for Zn mineralization. The present study also indicates prospects of Ag, Cu and V in the rocks of the Mor Range.Relationships between various elements have been identified from scattergrams and reflect genetic associations. Whereby the positive correlation between Cu–Zn (0.55, n=18) and Cu–Pb (0.63) is related to possible sulphide mineralization.     

Distribution and partitioning of major and trace elements in pyrite-bearing sediments of a Mediterranean coastal lagoon

The formation of iron sulphide minerals exerts significant control on the behaviour of trace elements in sediments. In this study, three short sediment cores, retrieved from the remote Antinioti lagoon (N. Kerkyra Island, NW Greece), are investigated concerning the solid phase composition, distribution, and partitioning of major (Al, Fe) and trace elements (Cd, Cu, Mn, Pb, and Zn). According to ²¹⁰Pb, the sediments sampled correspond to depositions of the last 120 years. The high amounts of organic carbon (4.1–27.5%) result in the formation of Fe sulphides, predominantly pyrite, already at the surface sediment layers. Pyrite morphologies include monocrystals, polyframboids, and complex FeS–FeS₂ aggregates. According to synchrotron-generated micro X-ray fluorescence and X-ray absorption near-edge structure spectra, authigenically formed, Mn-containing, Fe(III) oxyhydroxides (goethite type) co-exist with pyrite in the sediments studied. Microscopic techniques evidence the formation of galena, sphalerite and CuS, whereas sequential extractions show that carbonates are important hosts for Mn, Cd, and Zn. However, significant percentages of non-lattice held elements are bound to Fe/Mn oxyhydroxides that resist reductive dissolution (on average 60% of Pb, 46% of Cd, 43% of Zn and 9% of Cu). The partitioning pattern changes drastically in the deeper part of the core that is influenced by freshwater inputs. In these sediments, the post-depositional pyritization mechanism, illustrated by overgrowths of Fe monosulphides on pre-existing pyrite grains, results in relatively high degree of pyritization that reaches 49% for Cd, 66% for Cu, 32% for Zn and 7% for Pb.     

Sedex型矿床成矿系统

系统总结了Ｓｅｄｅｘ型矿床产出的构造背景、地质环境、矿床地质地球化学特征、矿化流体来源及成矿模式等问题。结合某些最新研究成果,对该类型矿床的Ｐｂ、Ｓｉ、Ｂ同位素地球化学进行了综合研究,并以加拿大科迪勒拉地区页岩容矿的Ｚｎ Ｐｂ矿床、中国大厂锡多金属矿床及澳大利亚布罗肯希尔Ｐｂ Ｚｎ Ａｇ矿床为例,深入讨论了Ｐｂ、Ｓｉ、Ｂ的来源及其对矿床成因的指示意义。对产于不同地质环境下现代海底热液成矿系统的研究证明,有沉积物覆盖和无沉积物覆盖海底成矿热流体的化学组成及Ｐｂ、Ｓｒ、Ｂ稳定同位素地球化学明显不同。前者富含与陆壳物质有关的金属组合及ＮＨ４,并富含放射成因Ｐｂ和Ｓｒ的组分,后者富含与洋壳玄武岩有关的金属组合,但特别贫ＮＨ４。这种不同与古代Ｓｅｄｅｘ型和塞浦路斯型矿床之间化学组成的差别十分相似,它意味着前者成矿物质主要来源于下伏陆壳岩石,并为其富含Ｂ,Ｂａ,Ａｇ,Ａｓ,Ｓｂ,Ｗ,Ｓｎ,Ｈｇ,Ｍｎ等元素提供了合理的解释。在此基础上,笔者指出,在特定地球化学背景下,上述那些元素也能形成独立的Ｓｅｄｅｘ型矿床,同时强调了注意寻找这种新型矿床的重要性     

黄铁矿风化过程中元素的活性及对环境的影响

在对安徽铜陵鸡冠山硫铁矿尾矿中黄铁矿风化产物组构特征研究的基础上,划分出代表不同风化程度的4种矿石组构型,并进而对不同组构型中硫和金属元素的含量、宫集系数、流失系数变化进行了研究。研究表明在风化过程中,As、Sb、Cu、Zn明显富集,其中As、Cu、Zn对环境的潜在危害较Sb大;Co、Ni、Bi明显流失或严重流失,对环境已经形成污染,其中Bi的污染程度较高。     

广东省新榕锰矿地质特征及成因探讨

新榕锰矿是广东省重要的锰矿床 ,主矿体产于地下岩溶空洞内 ,矿石中伴生银的平均含量达 10 0×10 -6以上。锰矿石中含有少量的脆银矿、溴角银矿、含锑银黝铜矿、银金矿、单斜绿铜锌矿、黄铁矿、磁黄铁矿及重晶石等矿物。据各类岩石、矿石的矿物成分 ,以及成矿元素、稀土元素地球化学特征等方面研究 ,认为Fe、Mn成矿物质主要来源于元古宇云开群和泥盆系桂头组中的富铁锰质岩层 (锰铝榴石片岩、含锰千枚岩 ) ,部分来源于矿区北部断裂带中的热液硫化物 ,伴生元素Ag、Pb、Zn等也来源于矿区北部断裂带的热液多金属硫化物。有机质 (微生物 )可能参与了成矿物质的风化淋滤、迁移、沉淀富集等成矿作用。地下岩溶空洞是最有利的成矿场所。锰矿的成矿期为新生代。矿床成因类型属迁积_岩溶堆积型锰矿     

Weathering of the Ganga alluvial plain,northern India: implications from fluvial geochemistry of the Gomati River

In the northern part of the Indian sub-continent, the Ganga alluvial plain (GAP) feeds its weathering products to the Ganga–Brahmaputra River system, one of the world’s largest fluvial systems. The authors present a geochemical study of the GAP weathering products transported by the Gomati River (the Ganga River tributary) to understand weathering processes of an alluvial plain in a humid sub-tropical climate. A total of 28 sediment samples were collected during the monsoon season and were analysed by X-ray fluorescence spectrometry for 25 major and trace elements. Bulk chemistry of the channel, flood and suspended sediments mostly consists (>90%, >80% and >75%, respectively) of three elements; Al, Si and Fe. Major element concentrations normalised with respect to upper continental crust (UCC) show strong depletion of highly mobile elements (Na, Ca) and enrichment of immobile elements (Ti, Si). Silica enrichment in the sand fraction is probably caused by chemical weathering of feldspar. Mineral sorting during fluvial transportation acts as the single important factor that controls the geochemistry of these weathering products and also strongly influences major and trace element distribution in the individual sediment samples. Trace element (Ba, Cr, Cu, Nb, Ni, Pb, V and Zn) concentrations were strongly correlated with major element (Si, Al, Fe, Mn and K) concentrations indicating that the abundance of trace elements is controlled by the same processes that control the major element distribution in these sediments.The GAP weathering products were geochemically distinguished as arkose to litharenite in rock classification. Chemical mobility, normalised with respect to TiO₂ in UCC, indicates that Si, Na, Zr, Ba and Sr, mainly derived from feldspar, muscovite and biotite, are lost during weathering. Iron and Zn remained immobile during weathering and were strongly adsorbed by phyllosilicates and concentrated in fine-grained sediment fractions. The chemical index of alteration indicates that the GAP has experienced chemical weathering of incipient to moderate intensity. The GAP weathering products also demonstrated a progressive incomplete alteration in the alluvial sequence made-up of the Himalayan-derived sediments. A model has been proposed to better understand weathering processes and products of the GAP in temporary storage of ∼50 ka in a humid sub-tropical climate.     

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.     

Hydrothermal Alteration of Limestone and Mineral Exploration of Zn-Pb Skarn Deposits in the Sako-nishi Area of the Kamioka Mine, Central Japan

Abstract: Crystalline limestone of the Sako-nishi area in the Kamioka Zn-Pb mine, central Japan, is depleted in ¹⁸O and ¹³C toward the center of mineralization due to interaction with hydrothermal fluids with a dominant meteoric water component. The relationship between isotopic composition and mineral assemblage, texture, the chemical composition of the minerals, and the bulk chemical composition in the limestone was examined. A decrease in the δ¹⁸OSMOW value correlated with: (1) increase of fine-grained calcite which is enriched in Mn and exhibits a bright cathodoluminescence, (2) progressive hy-drothermal alteration of clinopyroxene in the original limestone into tremolite within the weakly-altered zone, and into chlorite and actinolite within the strongly-altered zone, (3) dominance of hydrothermal chlorite in altered limestone having δ¹⁸O values of less than 10%. This chlorite was enriched in Fe compared to mafic minerals in the unaltered limestone. The enrichment of Fe and Mn was more conspicuous in calcite and chlorite in skarn deposits. The occurrence and chemical composition of hydrothermal minerals in the limestone, skarn, and ore indicate that the ¹⁸O–depleted zones were formed in the later stage from fluids, which were responsible for mineralization and skarnization, and for Fe and Mn enrichment. The Al, Mn, and Fe contents, and the ratios of Mg/(Mg+Mn+Fe), Al/Mg, and Mn/Sr in the hydrochloric acid leachate of limestone varied with decreasing δ¹⁸O and δ¹³C values, reflecting increases in high-Mn calcite and high-Fe chlorite. These indexes were useful for the identification of hydrothermally altered limestone. Furthermore, the potential score weighted by each index was more effective and accurate means of detecting promising mineralization zones. An anomalous potential score due to the presence of hydrothermal minerals in the outcropping limestone occurred along the Atotsu–1GO fault. This structure indicates that the skarn deposits of the Sako-nishi area belong to Mozumi-type Zn–Pb skarn deposits, in which fissures and faults served as major passages for the hydrothermal fluid. High-Mn carbonate and high-Fe chlorite widely occur in base-metal vein deposits and Zn-Pb type skarn deposits. Leaching of altered rock with hydrochloric acid in addition to stable isotope composition and cathodoluminescence imaging is effective for geochemical exploration for hydrothermal deposits because it makes possible the detection of the elemental composition of hydrothermal minerals such as chlorite and carbonate and because of the rapidity and convenience of analysis.     

Mineralogical and geochemical constraints on environmental impacts from waste rock at Taojiang Mn-ore deposit,central Hunan,China

The mineralogy and geochemistry of the waste rocks distributed at Taojiang Mn-ore deposit, central Hunan province, China, were studied using X-ray powder diffraction (XRD), electron microprobe analysis (EMPA) fitted with energy dispersive spectrometer (EDS) and inductively coupled plasma mass spectrum (atomic emission spectra) ICP-MS (AES), with the aim of predicting the environmental impacts of weathering of the waste rocks. The mineralogical results from microscope observation and XRD and EMPA studies show that the waste rock is composed of black shale and minor Mn carbonates. The oxidation of sulfide minerals such as galena, pyrite and chalcopyrite is accompanied by decomposition of Mn carbonates and K-feldspar during exposure to atmospheric O₂. The geochemical characteristics of major, rare earth elements (REE) and trace elements of the waste rocks also show that the waste rock can be divided into black shale and Mn carbonate, and both of them are currently under chemical weathering. The major alkalies and alkaline elements (Ca, Mg, Na, K, Rb, Sr and Cs) and major elements (Fe, S and P) and heavy metals (Sc, V, Cr, Th, U, Sn, Co, Ni, Cu, Zn, Pb, Mo, Cd, Sb, an Tl) are being released during weathering. The mobility of alkalis and alkaline elements Ca, Mg, Na, K, Rb, Sr and Cs is controlled by decomposition of Mn carbonates. The dispersion of Cr, Sc and Th (U) might be related to weathering of K-feldspar, and the release of the heavy metals Co, Ni, Cu, Zn, Pb, Mo, Cd Sb and Tl is dominated by the breaking of sulfide minerals. The REE of the waste rocks and surrounding soils and the spidery distribution patterns of heavy metals in the waste rocks, the surrounding soils and the surface waters show that weathering of the waste rocks and bedrock might be the sources of heavy metal contamination for the surrounding soils and surface water system for the mining area. This is predicted by the mass-balance calculation by using Zr as an immobile element. Therefore, it is urgently necessary take measures to treat the waste rocks distributed throughout the area for the local environmental protection.     

Distribution of chemical elements in calc-alkaline igneous rocks,soils, sediments and tailings deposits in northern central Chile

This study follows the paths of 32 chemical elements in the arid to semi-arid realm of the western Andes, between 27° and 33° S, a region hosting important ore deposits and mining operations. The study encompasses igneous rocks, soils, river and stream sediments, and tailings deposits. The chemical elements have been grouped according to the Goldschmidt classification, and their concentrations in each compartment are confronted with their expected contents for different rock types based on geochemical affinities and the geologic and metallogenic setting. Also, the element behavior during rock weathering and fluvial transport is here interpreted in terms of the ionic potentials and solubility products. The results highlight the similarity between the chemical composition of the andesites and that of the average Continental Crust, except for the higher V and Mn contents of the former, and their depletion in Mg, Ni, and Cr. The geochemical behavior of the elements in the different compartments (rocks, soils, sediments and tailings) is highly consistent with the mobility expected from their ionic potentials, their sulfates and carbonates solubility products, and their affinities for Fe and Mn hydroxides. From an environmental perspective, the low solubility of Cu, Zn, and Pb due to climatic, chemical, and mineralogical factors reduces the pollution risks related to their high to extremely high contents in source materials (e.g., rocks, altered zones, tailings). Besides, the complex oxyanions of arsenic get bound by colloidal particles of Fe-hydroxides and oxyhydroxides (e.g., goethite), thus becoming incorporated to the fine sediment fraction in the stream sediments.