Zincian dolomite related to supergene alteration in the Iglesias mining district (SW Sardinia)

One of the main effects of supergene alteration of ore-bearing hydrothermal dolomite in areas surrounding secondary zinc orebodies (Calamine-type nonsulfides) in southwestern Sardinia (Italy) is the formation of a broad halo of Zn dolomite. The characteristics of supergene Zn dolomite have been investigated using scanning electron microscopy and qualitative energy-dispersive X-ray spectroscopy, thermodifferential analysis, and stable isotope geochemistry. The supergene Zn dolomite is characterized by variable amounts of Zn, and low contents of Pb and Cd in the crystal lattice. It is generally depleted in Fe and Mn relative to precursor hydrothermal dolomite (Dolomia Geodica), which occurs in two phases (stoichiometric dolomite followed by Fe-Mn-Zn-rich dolomite), well distinct in geochemistry. Mg-rich smithsonite is commonly associated to Zn dolomite. Characterization of Zn-bearing dolomite using differential thermal analysis shows a drop in temperature of the first endothermic reaction of dolomite decomposition with increasing Zn contents in dolomite. The supergene Zn dolomites have higher δ¹⁸O but lower δ¹³C values than hydrothermal dolomite. In comparison with smithsonite-hydrozincite, the supergene Zn dolomites have higher δ¹⁸O, but comparable δ¹³C values. Formation of Zn dolomite from meteoric waters is indicated by low δ¹³C values, suggesting the influence of soil-gas CO₂ in near-surface environments. The replacement of the dolomite host by supergene Zn dolomite is interpreted as part of a multistep process, starting with a progressive “zincitization” of the dolomite crystals, followed by a patchy dedolomitization s.s. and potentially concluded by the complete replacement of dolomite by smithsonite.     

Some aspects of the Krol formation of the Himalaya,India

The Lower Krol sediments consist of intercalations of dolomite with shales in the marginal areas (Solan and Nainital), while limestones are interbedded with marls in the central part of the basin (Massoorie). The Upper Krols are largely composed of dolomites with subordinate limestones and shales.The non-carbonate detrital fraction is dominated by quartz with minor amounts of orthoclase, microcline and plagioclase feldspars. Illite and chlorite constitute the dominant clay minerals, lesser amounts of corrensite and kaolinite are sometimes present. An eastward increase in illite and decrease in chlorite has been ascribed to the supply and distribution of the terrigenum.Zirconium, rubidium, strontium, zinc, nickel and manganese were determined by X-ray fluorescence. Early diagenetic dolomites contain Sr, Zn, Ni and Mn in trace amounts, while the late diagenetic dolomites are characterized by an absence of these elements. The posttectonic dolomites are unusually rich in iron, manganese and sometimes in zinc.Authigenic formation of alkali feldspars, chlorite, illite, quartz and pyrite is not uncommon. The feldspars appear to have formed at early and late diagenetic stages. Potash feldspars dominate over albite in association with dolomite, whereas albite tends to be more common in the limestones.The Krol sedimentation seems to have started in a shallow coastal lagoon behind a barrier beach, upwards changing into tidal-flat deposits.     

Major and trace element associations in limestones and dolomites

Selective chemical separations of mineralogical constituents of limestones (Carboniferous limestones from the Isle of Man, and Lincolnshire limestone, Middle Jurassic, Lincolnshire) and dolomites (from Carboniferous limestone, Isle of Man) using dilute acetic acid and hydrogen peroxide have been used and the fractions obtained analysed to evaluate mineralogical associations of trace and major elements. Ca, Mg, Mn and Sr are mainly restricted to the carbonate fraction. Fe is found in carbonates, particularly dolomite, and also in sulphides with Zn, Cu, Ni and Pb, and with V and Cr and other traces in “residual” silicate minerals.It is concluded that mineralogical associations of trace elements are complex, and cannot be easily determined by statistical analysis. Selective chemical-separation methods of analysis offer direct indication of element associations with no loss of data. Calculated average concentrations in various fractions of analysed rocks (58 limestones and 19 dolomites) are tabulated.     

内蒙白乃庙斑岩铜钼矿床黄铁矿中微量元素的分配特征及其意义

黄铁矿是一种分布广泛的硫化物,但不同条件下形成的黄铁矿中微量元素的分配各具特点。本文通过对黄铁矿空间分布特征及其中多种微量元素分配特点的研究,提出黄铁矿晕的概念,讨论了其地质意义,对南北两矿带成因的同一性提供了新的信息,并提出矿体不同部位黄铁矿中Co/Ni比值的差异规律可作为判断矿体剥蚀深度的标志。     

块状硫化物矿床的地球化学找矿标志

近年来国外发现了许多大型块状硫化物矿床，而我国进展还不大。原因之一是我们对这类矿床的地质特征，成矿条件尤其是找矿标志研究还不够。这是一类成矿物质通过热液作用在海底沉积而成的特殊矿床，故在找矿勘探讨既要研究沉积矿时形成的原生晕，又要研究热液经过围岩时蚀变而产生的次生晕?Ｍｎ晕，Ｔｌ，Ｈｇ，Ｂａ，Ａｓ和Ｚｎ等元素的异常，络合剂元素的富集，微量元素的分布，铅同位素，岩石化学异指数尤其是块状硫化物Ｃｕ矿中     

四川盆地东北部晚二叠世-早三叠世白云岩与同期海水锶同位素组成的对比研究

在四川盆地东北部14条野外剖面和地下钻井的二叠系长兴组、三叠系飞仙关组和嘉陵江组石灰岩和白云岩岩石学研究的基础上,对其中189个不同类型的碳酸盐样品(包括代表海水的石灰岩样品和在不同成岩阶段形成的各种白云岩样品)进行了锶同位素组成和相应的MgO、CaO和Mn、Sr元素分析,获得了系统的晚二叠-早三叠世海水的锶同位素组成数据并建立了相应演化曲线.在此基础上,对不同地层组/段和不同类型白云岩的锶同位素组成与同期海水锶同位素组成进行了对照研究,取得了如下主要认识:(1)川东北晚二叠-早三叠世白云岩的锶同位素组成与同期海水具有类似的演化趋势,结合白云岩的低锰、高锶特征,说明白云化流体与海水存在显著的亲缘关系,与铝硅酸盐地层无关;(2)白云岩的锶同位素组成与同期海水存在差别,各地层组/段白云岩的87Sr/86Sr比值都不同程度地高于同期海水,但从下往上,即从长兴组、飞2+3段、嘉2段到嘉4段,这种差值逐渐缩小,嘉4段白云岩的锶同位素组成已和同期海水基本一致;(3)川东北长兴组、飞2+3段白云岩形成的时间显著晚于同层石灰岩,白云化流体为时间上更晚的海源流体,但嘉2、嘉4段白云岩的形成时间仅略晚于同层石灰岩,白云化流体来源于非常近同期的蒸发浓缩的高Mg/Ca比值海水,一些嘉4段的白云岩的白云化流体就是同期海水,因而这些白云岩是同生或准同生的;(4)如果把白云化的时间看作白云岩的形成时间,则违背地层叠置原理是川东北长兴组和飞仙关组结晶白云岩的主要特征之一,其形成机制可用非同期海源流体的隐伏回流-对流模式来解释,嘉陵江组白云岩形成机制可用活跃回流-萨布哈模式来解释.白云岩和代表同期海水的石灰岩锶同位素组成的对比为解决白云化流体与海水之间的时间关系提供一种新的研究途径.     

福建梅仙丁家山铅锌（银）矿床磁异常特征及其找矿意义

着重论述了丁家山铅锌（银）矿床的地质地球物理特征，磁法找矿的特殊作用，总结了建筑梅仙式矿床的物化探异常标导。     

广西高龙金矿鸡公岩矿段地质特征和构造地球化学找矿

对矿区地表至960m中段共计6个中段平面系统采集构造地球化学样品,共采集地层和构造蚀变岩样品184件,测试了Au、Ag、As、Sb、Cu、Pb、Zn、Sn、Mo、Mn、Co、Ni、Cr、V、Ti 15种微量元素的含量,编制了各元素地球化学纵剖面图和单个矿脉元素含量曲线图,综合地球化学图件分析法和格里戈良分带指数法确定了元素的纵向、横向和轴向分带序列,建立了原生晕地球化学三维分带模式。综合地质地球化学资料分析得到:硅化砂泥岩、构造蚀变岩中Au、As、Sb、Ag元素含量高,是地壳的数倍到数百倍,变异系数大,表明这些元素卷入了成矿作用,硅化泥岩是主要的富矿围岩,而矿体大部分赋存于由于成矿热液多期次强烈活动而形成的石英岩和构造角砾岩中。矿区原生晕轴向分带序列为:As、Pb、Mo、Sn、Cu、Au、Ag、Mn、Zn、Sb。与矿体北西向侧伏规律一致,矿区地球化学异常体亦具向北西侧伏的趋势。根据元素地球化学纵剖面图中主成矿元素异常高值带向下延伸未封闭,矿体向下未尖灭、特征前缘晕元素Sb和成矿晕元素Zn出现在矿尾晕等特征说明,矿体向下仍有一定的延伸,已知矿体北西侧深部是下一步找矿勘探的重点区域。     

桂东北铅锌矿床银的富集规律

作者对桂东北地区铅锌矿床中银的产出特征和富集规律进行了阐述。银主要以首次发现的含银硫盐矿物（深红银矿、银黝铜矿和含银锌黝铜矿等）产出，其次呈杂质元素分散在金属硫化物中，银的含量按方铅矿、黄铜矿、闪锌矿、黄铁矿的顺序依次降低，矿体从上向下具Ｃｕ、Ｐｂ（Ａｇ），Ｚｎ→Ｐｂ，Ｚｎ→Ｚｎ的垂向变化规律，银主要富集于上部，并与方铅矿、黄铜矿紧密伴生。     

Anomaly threshold estimation and data normalization using EDA statistics: application to lithogeochemical exploration in Lower Cretaceous Zn–Pb carbonate-hosted deposits,Northern Spain

A lithogeochemical survey of Lower Cretaceous sediments (1293 samples) in the Basque–Cantabrian basin (northern Spain) was carried out in order to estimate the mean contents of major oxides and Ba, Co, Cu, Ni, Pb, Rb, S, Sr, V, Zn and Zr in different lithological subsets and to identify anomalies related with Zn–Pb carbonate-hosted mineralization.After a detailed evaluation of different anomaly recognition methods, using both real and synthetic data, the cut-off values used in the Exploratory Data Analysis (EDA) were selected as thresholds. A prior classification of the rocks (based on chemical, mineralogical and petrographical data) guarantees appropriate homogeneous (with respect to major oxides) rock-groups during the evaluation of the data. A data standardization method was developed and applied to the samples collected from the Carranza sector (n=330). Zinc and Pb values for each sample were normalized to the particular threshold and interquartile range of their corresponding rock-type. These normalized values were plotted in geochemical maps.The results reveal the presence of Zn (up to 0.6%) and Pb (max. 1380 ppm) anomalies concentrated in carbonate facies, mainly in limestones, dolostones and dolomitic limestones. Magnesium-rich carbonates host the most significant anomalies. In the Carranza area, the great majority of outliers occur around known Zn–Pb mineral occurrences and are concentrated at the edge of the carbonate platform. In some cases fault control of the anomalies is indicated.     

Statistical assessment of geochemical pattern in overbank sediments of the river Sava,Croatia

Four overbank profiles from the three terraces of different age were sampled in 10 to 20 cm intervals for the bulk content of major and minor (Ca, Mg, Fe, Ti, Al, Na, K and P) and trace (Mo, Cu, Pb, Zn, Ni, Co, Mn, As, U, Th, Sr, Cd, Sb, V, La, Cr, Ba, W, Zr, Ce, Sn, Y, Nb, Ta, Sc, Li, Rb and Hf) elements in the minus 0.125 mm fraction. Univariate statistics together with analysis of variance discriminated between the lower-lying carbonate (CA) population dominantly composed of carbonates and the overlying silicate (SI) population being dominantly of silicate mineralogy. This stratified pattern resulted from the intensive erosive action of melting glaciers exerted on limestones and dolomites in the alpine region, followed by local inputs mainly of silicate composition. Elements exhibiting the greatest between-population variability are Ca and Mg being enriched in the CA population and Fe, Mn, P, Sr, Al, Na, K, Li, Rb, Y, Zr, Ni, Cr and Ti being enriched in the SI population. Anomalously high Hg, Pb and Ba concentrations (maximum values: 6,500±2,860 ppb, 225±13 ppm and 1,519±91 ppm, respectively) in the lowermost part of the profile S7, which is nearest to the Croatian-Slovenian border, derive from the mineralized Slovenian catchment area. This profile also contains trimodal frequency distributions of Fe, Mn and P whose highest concentrations coincide with increased values of Zn and Cu which are bimodally distributed. Geochemical patterns of majority of elements in all four profiles consistently reflect the average compositions of the upstream drainage basins.     

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.     

川西地区中二叠统栖霞组中—粗晶白云岩成因

通过野外剖面、岩心、薄片的观察及地球化学分析等手段,对川西地区栖霞组中—粗晶白云岩成因进行了研究。结果表明,中—粗晶白云石晶形呈自形、半自形及他形,可见残余生物(碎屑)幻影,裂缝发育,白云石被缝合线切割,储集空间以溶蚀孔洞和晶间孔为主,孔洞内充填有自形白云石及鞍状白云石。中—粗晶白云岩的碳同位素值处于二叠系海相碳酸盐岩的范围;川西的南部地区中—粗晶白云岩氧同位素相对于川西的北部地区更偏负;川西的北部中—粗晶白云岩锶同位素比值处于二叠系海相碳酸盐岩的范围,而川西的南部则高于此范围;稀土元素配分模式显示白云岩基本继承了石灰岩特点;白云岩Ce显示正异常,Eu无明显正异常,川西的南部地区具有较明显的La负异常。综合研究得出:颗粒滩相是白云石化作用发生的有利相带,浅埋藏阶段的海水白云石化作用是中—粗晶白云岩的主要成因,后期局部遭受热液改造作用,孔洞内充填的自形白云石也为浅埋藏阶段的海水白云石化作用所形成,而鞍状白云石为后期热液成因。     

A case of successful soil geochemistry: the Rubiales Zn-Pb orebody (NW Spain)

The Rubiales Zn-Pb orebody (NW Spain) is a blind deposit developed in a vertical shear zone during the Variscan Orogenesis. It is about 1200 m long in a N-S direction, with an average thickness of 30 m, and is hosted by lower Cambrian limestones and slates, with some quartzite beds. The deposit has a large hydrothermal alteration aureole. The silicified halo contain sphalerite and galena disseminations, with grades between 0.2 and 3% Pb + Zn.The Rubiales orebody was discovered in the late 60s following a soil geochemical survey. In the regional phase of the survey, 28,622 samples were collected in 57 lines; two of the lines over the Rubiales zone yielded 1400 ppm Pb and 1550 ppm Zn. In a local phase, centred on the anomalous zone, 1716 samples were collected in 21 lines. This local survey defined the geochemical anomalies that were subsequent drill-hole targets. Based on 38 surface-holes, geological ore reserves of 18.6 million tons, with 8.6% Zn + Pb, were estimated.Residual soil geochemical anomalies of Zn and Pb were developed over the silicification zone. The Zn anomaly has a greater extent than the Pb anomaly, due to the greater Zn mobility in surficial environments. The Zn and Pb anomalies exhibit an asymmetrical morphology, with greater extent to the south, due to the down slope creep of residual anomalies. The main cross-faults present in the deposit also control the morphology of the anomalies, as a result of Zn and Pb mobilisation and transport by ground waters along the cross-faults. The Cu anomaly defines two maxima over the feeder zones to the orebody. The two feeder zones, also in the silicification zone, are extensively brecciated and contain the highest grades of the deposit (∗> 20% Zn + Pb) and disseminated chalcopyrite.     

甘肃北山金、铜矿床红沙的植物地球化学特征及其找矿意义

北山地区植被属戈壁荒漠植被类型，主要植物群落为红沙，红沙中多数元素特别是成矿元素及其伴生元素的含量和变化系数矿区大于背景区，元素含量背景区呈对数正态分布，矿区呈偏对数正态或多峰分布，红沙中的元素组合分类背景区为Au,Cu,Pb,Zn,As,Sb,Mo,V,Mn和Ag,Sn,Sr,Ba及Ti,Cr,Co,Ni,金矿区为Au,Ag,As,Sb,Mo,Mn,Sr和Cu,Pb,Zn,Sn,Ba及Co,Ni,Ti,V,Cr,铜矿区为Cu,Pb,Zn,Mo,Au,Ag,Ba和As,Sb,Sn,Mn及Ti,V,Cr,Co,Ni,Sr，矿区红沙中浓集系数较大的元素多数在矿区岩石中的浓集系统亦较大，金，铜矿床红沙和岩石中的特征元素分别都有Au,Ag,Ag,Sb,Mo,(Mn)和Cu,Pb,(Ba,Ti,Cr)。在金，铜矿床（体上方分别发育有良好的Au和Cu的生物地球化学异常和元素组合及分带，根据红沙的地球化学特征能，判断金或铜矿种类型，并能对掩埋，隐伏金，铜矿床（体）进行定位预测。     

The nappe-hosted Hoshbulak MVT Zn–Pb deposit,Xinjiang, China: A review of the geological,elemental and stable isotopic constraints

The Hoshbulak Zn–Pb deposit is located in South Tianshan, Xinjiang, China. The Zn–Pb orebody is tabular and stratoid in form and it is hosted in calcareous rocks of the Upper Devonian Tan'gaitaer Formation which were thrust over the Carboniferous system. The ores are mineralogically simple and composed mainly of sphalerite, galena, pyrite, calcite, dolomite and exhibit massive, banded, veinlets, colloidal, metasomatic, eutectic, concentric ring and microbial-like fabrics. The Co/Ni ratios of pyrite in the ores range from 0.46 to 0.90 by electron microprobe, which suggested that the Hoshbulak Zn–Pb mineralization was formed in a sedimentary environment. The REE patterns of the hydrothermal calcite coincide well with those of recrystallized micritic limestones, suggesting that the Hoshbulak Pb–Zn mineralization was closely genetically related to limestones of the Tan'gaitaer Formation. The C-, H- and O-isotopic compositions of hydrothermal calcite and dolomite in the ores yield δ¹³C(VPDB) values ranging from − 1.9‰ to + 2.6‰ (mean 0.79‰), δ¹⁸O(VSMOW) values from 22.41‰ to 24.67‰ (mean 23.04‰) and δD values from − 77‰ to − 102‰ for fluid inclusions. It is suggested that the ore-forming fluids, including CO₂, were derived from the calcareous strata of the Tan'gaitaer Formation in association with hydrocarbon brines. The δ³⁴S(VCDT) ranges from − 22.3‰ to − 8.5‰ for early ore-stage sulfides and from 5.9‰ to 24.2‰ with a cluster between 14.4‰ and 24.2‰ for the sulfides (pyrite, sphalerite, galena) in the main ore-stage. The ore sulfur may have been derived from evaporite rocks by thermochemical sulfate reduction (TSR) as the predominant mechanism for H₂S generation. The Pb-isotopic compositions of the sulfide minerals from the Hoshbulak ores yield ²⁰⁶Pb/²⁰⁴Pb ratios from 17.847 to 18.173, ²⁰⁷Pb/²⁰⁴Pb ratios from 15.586 to 15.873 and ²⁰⁸Pb/²⁰⁴Pb ratios from 37.997 to 38.905, which indicate that the metals were sourced mainly from the Tan'gaitaer Formation. We conclude that the genesis of the Hoshbulak Mississippi Valley-type deposit was closely related to thrust faulting in the South Tianshan orogen of China.     

浙江火山岩区金矿床黄铁矿的找矿矿物学研究

论文给出了中国浙江火山岩区金矿床中黄铁矿的微量元素、形态和物理性质找矿标型特征.例如.(在许多)浙江火山岩区重要金-银矿床中黄铁矿相对富含铅、锌、钼、锡、砷、锑、铋而贫钴,镍、硒、碲:并且S/Se、Ag/Au、Pb/Ni、Se/Te、(As+sb+Bi)/(Se+Te)比值较高,Co/Nj、Ag/Pb、Ag/Zn、Cu/Zn和(Co+Ni)/(Pb+Zn)比值较低,再如含金黄铁矿比不含金黄铁矿的反射率低.总之,黄铁矿的标型性研究对于寻找金矿具有重大的理论意义和实际意义.     

Dolomite textures in the Upper Cretaceous carbonate-hosted Pb–Zn deposits,Zakho, Northern Iraq

In the northeast of Zakho City, Northern Iraq, the host rocks of Pb–Zn deposits are composed predominantly of dolomites with subordinate dolomitic limestone intervals. This study is focused on the dolomites of the Bekhme Formation (Upper Campanian) carbonate-hosted Pb–Zn deposits. The amount of dolomites, however, increases toward the mineralized zone. Dolomites are dominated by replacement dolomite with minor dolomite cements. Petrography study allowed identification of six different dolomite textures. These are (1) fine crystalline, planar-s (subhedral) dolomite, RD1; (2) medium to coarse crystalline, planar-e (euhedral) to planar-s (subhedral) dolomites, RD2; (3) medium crystalline, planar-s (subhedral) to nonplanar-a (anhedral) dolomites, RD3; (4) coarse crystalline, planar-s (subhedral) to nonplanar-a (anhedral) dolomites, RD4; (5) planar (subhedral) void-filling dolomite cements, CD1; and (6) nonplanar (saddle) void-filling dolomite, CD2. The RD1, RD2, RD3, and RD4 dolomite textures are replacive in origin and are volumetrically the most important types, whereas CD1 and CD2 dolomites with sparry calcite are commonly cements that fill the open spaces. Although the dolomites of the Bekhme Formation are not macroscopically observed in the field, their different types are easily distinguished by petrographic examination and scanning electron microscopy. It was observed that the dolomites of the Bekhme Formation are formed in two different diagenetic stages: the early diagenetic from mixing zone fluids at the tidal–subtidal (reef) environments and the late diagenetic from basinal brines which partially mixed with hydrothermal fluids at the shallow-deep burial depths. The latter occurs often with sphalerite, galena, and pyrite within mineralized zone. These dolomite types are associated base-metal mineralization (Mississippi Valley type).     

Geochemistry of trace metals associated with reduced sulfur in freshwater sediments

Porewater concentration profiles were determined for Fe, trace elements (As, Cd, Co, Cu, Mn, Ni, Pb, Zn), sulfide, SO₄ and pH in two Canadian Shield lakes (Chevreuil and Clearwater). Profiles of pyrite, sedimentary trace elements associated with pyrite and AVS were also obtained at the same sites. Thermodynamic calculations are used, for the anoxic porewaters where sulfide was measured, to characterize diagenetic processes involving sulfide and trace elements and to illustrate the importance of sulfide, and possibly polysulfides and thiols, in binding trace elements. The ion activity products (IAP) of Fe sulfide agree with the solubility products (K_s) of greigite or mackinawite. For Co, Ni and Zn, IAP values are close to the K_S values of their sulfide precipitates; for Cu and Pb, IAP/K_s indicate large oversaturations, which can be explained by the presence of other ligands (not measured) such as polysulfides (Cu) and thiols (Pb). Cobalt, Cu, Ni and Zn porewater profiles generally display a decrease in concentration with increasing ΣH₂S, as expected for transition metals, whereas Cd, Pb and Zn show an increase (mobilisation). The results suggest that removal of trace elements from anoxic porewaters occurs by coprecipitation (As and Mn) with FeS(s) and/or adsorption (As and Mn) on FeS(s), and by formation of discrete solid sulfides (Cd, Cu, Ni, Pb, Zn and Co). Reactive Fe is extensively sulfidized (51–65%) in both lakes, mostly as pyrite, but also as AVS. Similarities between As, Co, Cu and Ni to Fe ratios in pyrite and their corresponding mean diffusive flux ratios suggest that pyrite is an important sink at depth for these trace elements. High molar ratios of trace elements to Fe in pyrite from Clearwater Lake correspond chronologically to the onset of smelting activities. AVS can be an important reservoir of reactive As, Cd and Ni and, to a lesser extent, of Co, Cu and Pb. Overall, the trace elements most extensively sulfidized were Ni, Cd and As (maximum of 100%, 81% and 49% of the reactive fraction, respectively), whereas Co, Cu, Mn, Pb and Zn were only moderately sulfidized (11–16%).     

Arsenic and metal mobility from Au mine tailings in Rodalquilar (Almería,SE Spain)

In the old mining area of Rodalquilar, mine wastes, soil and sediments were characterized and the results revealed high concentration of Au, Ag, As, Bi, Cu, Fe, Mn, Pb, Se, Sb and Zn in tailings and sediments. The contaminant of greatest environmental concern is As. The mean concentration in the tailings was 679.9, and 345 mg/kg in the sediments of Playazo creek. The groundwater samples from the alluvial aquifer showed high concentration of Al, As, Cd, Fe, Hg, Mn, Ni, Pb, Se, Sb and Zn and very high concentration of chloride and sulfate, which were above the concentration defined in the European standards for drinking water. The presence of As in groundwater may be caused by the oxidation of arsenian pyrite, the possible As desorption from goethite and ferrihydrite and the jarosite dissolution. Groundwater concentrations of Cd, Fe, Mn, and possibly Cu, were associated with low values of Eh, indicating the possible dissolution of oxy-hydroxides of Fe and Mn. The mobility of metals in the column experiments show the release of Al, Fe, Mn, Cr, Cu, Ni, V and Zn in significant concentrations but below the detected values in groundwater. However, As, Cd, Sb, Se Pb and Au, are generally mobilized in concentrations above the detected values in groundwater. The possible mass transfer processes that could explain the presence of the contaminants in the aquifer and the leachates was simulated with the PHREEQC numerical code and revealed the possible dissolution of the following mineral phases: jarosite, natrojarosite, arsenian pyrite, alunite, chlorite, kaolinite and calcite.