Iron speciation in interaction with organic matter: Modelling and experimental approach

The present study aims to model iron speciation when interacting with natural organic matter. Experimental data for iron speciation were achieved with insolubilized humic acid as an organic matter analogue for 1.8 × 10^− 3 M and 1.8 × 10^− 4 M iron concentrations and 2–5 pH range. Combining EPR spectroscopy and chemical analysis allowed us to fit NICA-Donnan model parameters for both organic complexation of iron and oxides precipitation.     

The aquatic chemistry of rare earth elements in rivers and estuaries

Laboratory experiments were carried out to determine how pH, colloids and salinity control the fractionation of rare earth elements (REEs) in river and estuarine waters. By using natural waters as the reaction media (river water from the Connecticut, Hudson and Mississippi Rivers) geochemical reactions can be studied in isolation from the large temporal and spatial variability inherent in river and estuarine chemistry. Experiments, field studies and chemical models form a consistent picture whereby REE fractionation is controlled by surface/solution reactions. The concentration and fractionation of REEs dissolved in river waters are highly pH dependent. Higher pH results in lower concentrations and more fractionated composition relative to the crustal abundance. With increasing pH the order of REE adsorption onto river particle surfaces is LREEs > MREEs > HREEs. With decreasing pH, REEs are released from surfaces in the same order. Within the dissolved (<0.22 µm) pool of river waters, Fe-organic colloids are major carriers of REEs. Filtration through filters and ultrafilters with progressively finer pore sizes results in filtrates which are lower in absolute concentrations and more fractionated. The order of fractionation with respect to shale, HREEs > MREEs > LREEs, is most pronounced in the solution pool, defined here as <5K and <50K ultrafiltrates. Colloidal particles have shale-like REE compositions and are highly LREE enriched relative to the REE composition of the dissolved and solution pools. The addition of sea water to river water causes the coagulation of colloidal REEs within the dissolved pool. Fractionation accompanies coagulation with the order of sea water-induced removal being LREEs > MREEs > HREEs. While the large scale removal of dissolved river REEs in estuaries is well established, the release of dissolved REEs off river particles is a less studied process. Laboratory experiments show that there is both release and fractionation of REEs when river particles are leached with seawater. The order of sea water-induced release of dissolved REE(III) (LREEs > MREEs > HREEs) from Connecticut River particles is the same as that associated with lowering the pH and the same as that associated with colloidal particles. River waters, stripped of their colloidal particles by coagulation in estuaries, have highly evolved REE composition. That is, the solution pool of REEs in river waters are strongly HREE-enriched and are fractionated to the same extent as that of Atlantic surface seawater. This strengthens the conclusions of previous studies that the evolved REE composition of sea water is coupled to chemical weathering on the continents and reactions in estuaries. Moreover, the release of dissolved Nd from river particles to sea water may help to reconcile the incompatibility between the long oceanic residence times of Nd (7100 yr) and the inter-ocean variations of the Nd isotopic composition of sea water. Using new data on dissolved and particle phases of the Amazon and Mississippi Rivers, a comparison of field and laboratory experiments highlights key features of REE fractionation in major river systems. The dissolved pool of both rivers is highly fractionated (HREE enriched) with respect to the REE composition of their suspended particles. In addition, the dissolved pool of the Mississippi River has a large negative Ce-anomaly suggesting in-situ oxidation of Ce(III). One intriguing feature is the well developed maximum in the middle REE sector of the shale normalized patterns for the dissolved pool of Amazon River water. This feature might reflect competition between surface adsorption and solution complexation with carbonate and phosphate anions.     

Characteristics of trace elements in contaminated rivers and their environmental significance

Several rivers researched around Taihu Lake in Chinese eastern plain are distributed to the west of the lake. Pollutants of different types from tributaries and inlets flow directly into the main rivers and finally into the lake. They change trace elements of rivers fi＇om which we can analyze. Researches about trace elements are helpful for understanding the pollutant characteristics, industrial structure and agricultural cultivation in the area of network rivers in the plain of China. Samples of water column, suspended matter and sediment were collected fi＇om the west rivers of Taihu Lake, which represent three typical rivers. Observation in the field and the primary composition analysis showed the Caoqiao River was mainly contaminated by industrial wastewater, the Liangxi River was discharged by domestic sewage and the Dapu River was principally input by farmland runoff. REE concentrations and their normalized curves showed obvious characters for rivers discharged by different sewages. The contents of total REE in water column followed the order of the Caoqiao River, the Dapu River and the Liangxi River fi＇om high to low. TREEs in suspended matter and sediments follow the order of the Dapu River 〉 the Caoqiao River 〉 the Liangxi River. REE normalized curves （for Australia shale） suggested that significant diversities were presented in water column, suspended matter and sediments, i.e., heavy REE enrichment in water, middle REE enrichment in suspended matter, and smooth curves for sediments. But the heavy pollution resulted in several anomalous curves in the same rivers. Some element ratios were selected as indices for polluted rivers based on their geochemical properties and diversities between rivers. The results displayed the discriminative indices for water column, suspended matter and sediment. The effective indices were Pb/Fe, Cr/Fe, Ni/Fe, Pb/Ni, Zn/Ni for water column, Cu/Al, Cu/Fe, Zn/Fe, K/Ca, K/Na, Pb/Co, Zn/Co for suspend matter and Pb/Fe, K/Ca, Ca/Mg, Zn/Ni for sediment, respectively. In general, rivers mainly discharged by industrial sewage have high ratios of Pb/Ni, K/Ca, are enriched in the middle REE and have positive Gd anomaly. The domestic sewage flowing into rivers reveals high ratios of Zn/Ni, Pb/Fe, and is enriched in the heavy REE, and has the positive Eu anomaly. If runoff of farmland enters into the rivers, it will have high ratios of Ca/Mg, K/Na, high lanthanum, and show the smooth normalized curves of REE.     

Anthropogenic organic matter in the Great Marsh of the Indiana Dunes National Lakeshore and its implications

Cores from the Great Marsh area of the Indiana Dunes National Lakeshore were examined in order to document variations in concentration, type and size of anthropogenic organic matter (A_nOM—coal, coke, etc.) and discuss their relationship to the concentration of such trace elements as Pb, Zn, and Mn in the near-surface sediment section. The results indicate that the first appearance of A_nOM corresponds to the onset of industrialization in the area. There is also a general relationship between the occurrence of A_nOM and Zn, Pb, and Mn. Trace metals were likely transported from the industrial sites to the area of their deposition as sulfur-bearing coatings on small anthropogenic particles. After deposition, these sulfur-bearing compounds reacted with organic matter within the marsh. As a result of bacterial reduction, the pyrite was produced, as suggested by a close relationship between the pyrite and A_nOM. Distance from the industrial complex upwind as well as local hydrologic conditions are among the major factors controlling distribution of A_nOM and trace elements. At the same distance from the source, types and sizes of A_nOM are influenced by the duration and frequency of flooding.     

Mobilization and redistribution of major and trace elements in two weathering profiles developed on serpentinites in the Lomié ultramafic complex, South-East Cameroon

The behaviour of major and trace elements have been studied along two serpentinite weathering profiles located in the Kongo-Nkamouna and Mang North sites of the Lomié ultramafic complex.The serpentinites are characterized by high SiO₂ and MgO contents, very low trace, rare earth and platinum-group element contents. Lanthanide and PGE contents are higher in the Nkamouna sample than in Mang North. Normalized REE patterns according to the CI chondrites reveal that: (i) all REE are below chondrites abundances in the Mang North sample; (ii) the (La/Yb)_N ratio value is higher in the Nkamouna sample (23.72) than in the Mang one (1.78), this confirms the slightly more weathered nature of the Nkamouna sample. Normalized PGE patterns according to the same CI chondrites reveal a negative Pt anomaly in the Mang sample. The Nkamouna sample is characterized by a flat normalized PGE pattern.All element contents increase highly from the parent rock to the coarse saprolite.In the weathering profiles, Fe₂O₃ contents decrease from the bottom to the top contrarily to Al₂O₃, SiO₂ and TiO₂. The contents of alkali and alkaline oxides are under detection limit.Concerning trace elements, Cr, Ni, Co, Cu, Zn and Sc decrease considerably from the bottom to the top while Zr, Th, U, Be, Sb, Sn, W, Ta, Sr, Rb, Hf, Y, Li, Ga, Nb and Pb increase towards the clayey surface soil. Chromium, Ni and Co contents are high in the weathered materials in particular in the saprolite zone and in the nodules.REE contents are high in the weathered materials, particularly in Nkamouna. Their concentrations decrease along both profiles. Light REE are more abundant than heavy REE. Normalized REE patterns according to the parent rock reveal positive Ce anomalies in all the weathered materials and negative Eu anomalies only at the bottom of the coarse saprolite (Nkamouna site). Positive Ce anomalies are higher in the nodular horizon of both profiles. An additional calculation method of lanthanide anomalies, using NASC data, confirms positive Ce anomalies ([Ce/Ce^*]_NASC = 1.15 to 60.68) in several weathered materials except in nodules ([Ce/Ce^*]_NASC = 0.76) of the upper nodular horizon (Nkamouna profile). The (La/Yb)_N ratios values are lower in the Nkamouna profile than in Mang site.PGE are more abundant in the weathered materials than in the parent rock. The highest contents are obtained in the coarse saprolite and in the nodules. The elements with high contents along both profiles are Pt (63–70 ppb), Ru (49–52 ppb) and Ir (41 ppb). Normalized PGE patterns show positive Pt anomalies and negative Ru anomalies.The mass balance evaluation, using thorium as immobile element, reveals that:

– major elements have been depleted along the weathering profile, except for Fe, Mn and Ti that have been enriched even only in the coarse saprolite;

– all the trace elements have been depleted along both profiles, except for Cr, Co, Zn, Sc, Cu, Ba, Y, Ga, U and Nb that have been enriched in the coarse saprolite;

– rare earth elements have been abundantly accumulated in the coarse saprolite, before their depletion towards the top of the profiles;

– platinum-group elements have been abundantly accumulated in the coarse saprolite but have been depleted towards the clayey surface soil.

Moreover, from a pedogenetical point of view, this study shows that the weathering profiles are autochtonous, except in the upper part of the soils where some allochtonous materials are revealed by the presence of zircon grains.     

Geochemical factors controlling accumulation of major and trace elements in Greenland coastal and fjord sediments

 The major (Al, Ti, Ca, Mg, Fe, Mn, Si) and trace element (Cd, Cr, Cu, Hg, Li, Ni, Pb, V, Zn) concentrations in surficial (<20 cm) sediments from fjords and open coastal waters around Greenland have been determined. Regionally, high concentrations of Fe, Ti, Mg, Cr, Cu, Ni, and V occur in some west and east coast sediments, but they appear to be natural in origin, as there is no indication of anthropogenic influence. Chemical partition indicates that most of the heavy metals are structurally bound in various silicate, oxide, and sulfide minerals. These host minerals occur more or less equally in the coarse and fine sediment fractions (material >63 μm and <63 μm) and have accumulated at the same rate as other detrital clastic material. Provenance and glaciomarine deposition are the main factors controlling the abundance and distribution of the major and trace elements. The chemical composition reflects the mineralogical differences in the provenance of glacial marine material deposited by water and ice adjacent to Greenland. The main source of the sediments enriched in Ti, Fe, Mg, Cr, Cu, Ni, and V appears to be material derived from the volcanic rocks of the Mesozoic-Tertiary Provinces of Greenland by glacial erosion. Received: 26 June 1995 · Accepted: 11 August 1995     

中国东部部分地区新生代岩石圈地幔的成因:主量和微量元素制约

为厘定中国东部新生代岩石圈地幔的成因,进而探讨岩石圈减薄的方式,本文选择汉诺坝、女山、盘石山和方山尖晶石二辉橄榄岩作为研究对象,系统分析了其主、微量元素。结果表明,这些地区新生代岩石圈地幔具有"新生"的性质,为上涌的软流圈物质经过小于10%的部分熔融程度后的残留相形成,后又经历了类似新生代玄武岩性质的富硅熔体的交代,交代介质的物质贡献小于3%。新生代岩石圈地幔与古老克拉通岩石圈地幔在主、微量元素上的显著差异以及新生代岩石圈地幔微量元素特征的拟合,支持拆沉为华北克拉通东部减薄的主要方式。     

193nmLA-ICPMS对国际地质标准参考物质中42种主量和微量元素的分析

本文采用配备有 193nm Ar F准分子 (excimer)激光器的 Geo L as2 0 0 M剥蚀系统和 Elan6 10 0 DRC ICP- MS对 4个美国地质调查所 (USGS)玻璃标准参考物质以及 3个美国国家标准技术研究院 (NIST)人工合成硅酸盐玻璃标准参考物质中几乎覆盖整个质量数范围 (从 7L i到 2 38U)的 38个微量和 4个主量 (Na、Mg、Ti和 Mn)元素进行了分析。分析结果表明 ,无论是对 USGS还是 NIST玻璃 ,元素分析的相对标准偏差 RSDs和分析值与参考值之间的相对偏差 (RDs)一般优于 10 % ,RSD和RD较大的元素主要出现在含量很低或不均匀样品中。稀土元素的 RSD显示 ,除 AGV- 2 G可能存在不均匀现象外 ,其它所测样品在 6 0 μm尺度上 ,元素分布是均匀的。本研究证明 ,由于 ICP- MS具有 10 8cps(每秒计数 )的动态线性范围 ,本实验室的L A- ICPMS系统可定量分析含量在百分之几的主量元素及微量元素。分析精密度和准确度可与常规溶液雾化进样 ICP- MS方法相媲美     

Spatial distribution of major and trace elements in shallow reservoir sediments: an example from Lake Waco, Texas

 Sediment geochemistry of a shallow (6-m average) reservoir (Lake Waco) was evaluated for the spatial distribution of major and trace elements. Sixty bottom and core samples along a 21-km transect within the reservoir, 18 overbank sediment samples, and 8 rock types in the drainage area were collected and analyzed for major (Al, Ca, Fe) and trace elements (As, Ba, Cr, Cu, Hg, Mn, Ni, Pb, Sr, V, Zn). Elemental concentrations in the reservoir sediments closely correspond to concentrations in the regional rocks and represent a mixture of overbank sediment composition of the tributaries. Elemental concentrations were statistically regressed against Al concentrations in order to establish regional baseline levels and thereby distinguish natural from anthropogenic sources. Spatial geochemical trends, considered in terms of element-to-Al ratio versus V-to-Al ratio, relate to the natural and anthropogenic sources contributing to the elemental concentrations. The spatial elemental distribution in the reservoir, which receive sediments from two mineralogically contrasting basins, reflect textural and mineralogical transition within the reservoir and suggest a progressive mixing of sediment from the tributaries. The spatial elemental distribution and sediment texture suggest that the sediment-source, which determines the sediment-type, has a greater influence on the major- and trace-element distributions in shallow reservoir sediments than bathymetry. Received: 25 September 1997 · Accepted: 3 February 1998     

Patterns of rare earth and other trace elements in Paleogene and Miocene clayey sediments from the Mondego platform (Central Portugal)

In the present study the origin of clay deposits occurring in an inland platform, in central Portugal, was investigated by their mineralogical and chemical composition. The clay deposits, exploited for ceramic industry are composed of silt-clay facies, the Monteira Member and the Arroça Member, which are assigned to the Coja Formation (Paleogene) and the Campelo Formation (Miocene), respectively. These clayey facies show almost compositional homogeneity, especially concerning texture. The mineralogical composition of the Monteira Member displays slightly higher content in smectite and interstratified clay minerals, which is supported by the chemical composition of samples analyzed. Both members present similar REE patterns, displaying an intense weathering record and little variation in the source area composition. Minor element geochemistry suggests low content in heavy minerals and transition metals. REE patterns and ratios of geochemical parameters support the dominant metasedimentary provenance, with a granite source contribution and also mature recycled sediments of continental origin. The study results’ suggest that the clays of these two members have the same source in terms of lithology and recycled sediments from the Hesperian massif. During the deposition of the Arroça Member, a major remobilization of the Monteira Member is suggested, explaining the geochemical similarity of both facies.     

Ordinary kriging and indicator kriging in the cartography of trace elements contamination in São Domingos mining site (Alentejo, Portugal)

The abandoned pyrite mine of São Domingos, in the southeast Portugal is still an acid mine drainage generator and a source for trace elements pollution. This study aims to evaluate and map the soils and sediments chemical pollution. With this purpose three test sites located in the vicinities of the mine were sampled for soils, sediments and mining waste materials. The samples were analysed for pH, organic carbon, iron oxides and total content of As, Cu, Cr, Hg, Pb, Sb, U, Zn, Mn, S, Fe Al, Ca, K, Mg and P. The hyperspectral image of the test sites was acquired using the aero transported sensor HymapTM. Chemical analysis and hyperspectral images data were processed to estimate the contamination maps by multivariate data analysis, ordinary kriging, cokriging and indicator kriging methodologies.The test sites located downstream the mine open pit, are highly contaminated mainly in As, Hg, Pb and Sb, but no contamination was found in the third test site, upstream the mining site. The acid mining drainage seems to be the main spreading agent of chemical contaminants mostly originating from the mine waste materials. Factorial analysis and the geostatistical methodologies allowed several approaches for the contamination cartography of mining areas.     

Determination of major and trace elements in European bottled mineral water — Analytical methods

A total of 1785 European bottled water samples were analyzed using standard laboratory methods. The bottled water samples were purchased in 2008 at supermarkets throughout 40 European countries. The samples were analyzed for 71 chemical parameters (As, Al, As, B, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Hg, Ho, I, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, Pb, Pr, Rb, Sb, Sc, Se, Sm, Sn, Sr, Ta, Tb, Te, Th, Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr, Br⁻, HCO₃⁻, Cl⁻, F⁻, NH₄⁺, NO₂⁻, NO₃⁻, PO₄³⁻, SO₄²⁻, SiO₂, pH, and EC) by quadrupole inductively coupled emission spectroscopy (ICP-QMS, trace elements), inductively coupled plasma atomic emission spectroscopy (ICP-AES, major elements), ion chromatography (IC, anions), atomic fluorescence spectrometry (AFS, Hg), titration (alkalinity), photometric methods (NH₄⁺), potentiometric methods (pH), and conductometric methods (specific electrical conductivity, EC). A very strict quality control procedure was followed by analysing blanks, international reference materials, an internal project standard, and duplicate analyses, as well as by analysing 23 elements by both ICP-QMS and ICP-AES. Analysis of marketed bottled water from springs, wells or boreholes, apart from the evaluation of its quality with respect to inorganic elements, it may provide a cheap alternative to obtain a first impression about groundwater chemistry at the European scale.     

Geochemistry of organic matter and elements of black shale during weathering in Northern Guizhou,Southwestern China: Their mobilization and inter-connection

Different from previous studies on effect of weathering upon geochemical variation along a single weathered profile, this paper provides a new methodology validated by comparing a weathered outcrop samples and their stratigraphic counterpart un-weathered core samples in a nearby shallow borehole. This outcrop and borehole penetrated the Ordovician-Silurian Wufeng–Longmaxi shales, located in the same anticline structure in the northern part of Guizhou Province, Southern China. The mineral composition, major, trace and rare earth elements (REEs) composition and Rock-Eval parameters of outcrop and core samples were analyzed and compared. Organic matter (OM) was observed in the microscope and extracted for elements analysis. The results show that short-term weathering still has significant influence on OM, mineral and elemental composition of black shales. The elements composition shows the outcrop profile was moderately weathered. The REEs compositions do not alter much during weathering process and the REEs composition and their relative ratios still are valid for rock origin determination. The OM, mainly composed by graptolite and bitumen, even entering the highly-over thermal maturity, is still sensitive to the weathering with a systematic loss 30–50% of TOC along the outcrop profile, which suggests that the OM consumption is predominantly controlled by weathering duration and the distance from the weathering surface. In turn, OM has significant influence on the trace elements transportation behavior during weathering. Some trace elements associated with the OM such as V, Cr, Th, U, Ni and Co, change significantly in their absolute concentration during weathering, but their relative ratios do not necessarily change too much and might be still reliable proxies for paleo-environmental determination. The mobility of shale minerals during weathering is in the following order: plagioclase?>?potassium feldspar and dolomite >pyrite and OM. Short-term weathering can also result in considerable transportation of elements and significant variation of minerals content in black shale, which may pose potentially high environmental and engineering risk in the regions rich in black shale.     

云南中甸地区斑岩体锆石微量元素与Hf-O同位素特征及其对成岩成矿的启示

中甸铜多金属成矿带位于义敦岛弧南缘, 被分为东、西两个斑岩带。本文以东斑岩带的普朗、地苏嘎岩体, 西斑岩带的雪鸡坪岩体为研究对象, 通过锆石微量元素和Hf-O同位素特征研究, 结合所收集到的这些岩体的全岩地球化学数据, 来揭示两个斑岩带的岩浆来源与演化过程、构造背景, 并探讨造成其成矿差异的控制因素。结果表明, 3个岩体所含锆石都亏损轻稀土、富集重稀土, 具有明显的Ce正异常和Eu负异常, Th/U平均值分别为0.19、0.27、0.13, 均为岩浆锆石。普朗、地苏嘎和雪鸡坪岩体锆石ε_Hf(t)值分别为-0.31±0.6、0.0±0.6、1.71±0.7, 锆石δ¹⁸O值分别为6.2±0.3‰、6.2±0.4‰、6.1±0.4‰; 3个岩体的源区相差不大, 均为壳幔岩浆混合, 但普朗和地苏嘎岩体地壳物质贡献更多。全岩主微量元素变化特征与锆石Nb/Yb和Th/Nb与Eu/Eu^*的相关性显示东斑岩带的普朗和地苏嘎岩体比西斑岩带的雪鸡坪岩体的结晶分异程度更高。在锆石微量元素构造判别图解中, 这些岩体均落在火山弧或与弧相关的造山环境范围。结合全岩的Nb-Y和Rb-(Y+Nb)判别图解, 以及中甸地区成岩年龄的统计, 进一步判定东、西斑岩带岩体均形成于与晚三叠世甘孜-理塘洋壳西向俯冲相关的大陆弧背景。采用锆石氧逸度计估算的普朗、地苏嘎和雪鸡坪岩体的氧逸度分别为ΔFMQ+1.58、ΔFMQ+1.42、ΔFMQ+1.91(QFM为石英-铁橄榄石-磁铁矿缓冲剂)。结合Eu/Eu^*值和全岩V/Sc比值分析, 发现3个岩体均有较高氧逸度, 但普朗和地苏嘎的岩浆氧逸度略低于雪鸡坪, 说明在相对较高氧逸条件下, 氧逸度高低与成矿规模不成比例。3个岩体的锆石结晶温度分别为769±34℃、783±36℃、819±40℃。结合全岩Sr/Y比值, 发现普朗和地苏嘎岩浆含水量高于雪鸡坪。由此推断, 更高的水含量和岩浆分异度可能是东部斑岩带比西部斑岩带发育更多斑岩矿床的重要原因, 这也暗示东斑岩带具有更大的找矿潜力。

     

The role of sulphide and carbonate minerals in the concentration of chalcophile elements in the bituminous coal seams of a paralic series (Upper Carboniferous) in the Upper Silesian Coal Basin (USCB), Poland

Sulphide and carbonate minerals from nine bituminous coal seams of a Paralic Series were investigated by means of polished-section microscopy, scanning electron microscopy and absorption spectral analyses. In addition to syngenetic accumulations of kaolinite, illite and quartz, diagenetic veinlets of subhedral pyrite and marcasite most often occur in vitrinite clast fissures and in post-tectonic fissures, nests and lenses with fusinite. Epigenetic anhedral and subhedral grains of ankerite, dolomite, siderite and calcite are also frequently found in post-tectonic veins. Pyrite replaced some of the marcasite grains and it dominates in older coal seams in the Flora Beds as compared with the Grodziec Beds. Occasionally there are anhedral and subhedral galena, sphalerite and chalcopyrite grains among coal macerals as well as cerussite among post-tectonic carbonate veins. They all represent the only minerals that are abundant in definite chalcophile elements (Cd, Co, Cu, Ni, Pb, Zn). In addition to the minerals just mentioned, the elements occurred in pyrite and ankerite grains, which contained inclusions of fusinite and other minerals (among others, clay and carbonate minerals in pyrite, pyrite in carbonates). Although there is a low content of minerals accumulating Cd, Co, Cu, Ni, Pb and Zn, the minerals significantly influence the average concentration of elements in the coal seams. In the Grodziec Beds, mineral matter, especially carbonates and sulphides, determines (>50%) the concentration of Cd, Cu, Pb and Zn in coal. The basic part of Cd, Co and Ni in the coal seams of the Grodziec Beds and of Co, Cu, Ni, Pb and Zn in coal seams of the Flora Beds originates from organic matter. These regularities can be important, from an ecological perspective, in stating whether the coals investigated are useful for combustion and in chemical processing.     

新疆火烧云超大型铅锌矿床闪锌矿微量(稀散)元素组成特征与指示意义北大核心CSCD

位于青藏高原西北部的新疆和田火烧云超大型铅锌矿床是近年来我国乃至全球最重要的铅锌找矿发现之一。该矿床矿石矿物以铅锌碳酸盐为主(菱锌矿和白铅矿),同时还发育有少量的铅锌硫化物矿体,目前对于火烧云矿床的成因仍存在较大分歧。本文以矿床硫化物矿体中的闪锌矿为研究对象,通过LAICP-MS微量元素测试和Mapping分析,揭示闪锌矿中微量元素(稀散元素)的富集规律和赋存状态,为矿床成因的厘定提供依据。结果表明,火烧云铅锌矿床闪锌矿中微量元素分布不均一,含量变化较大,以富集Cd、Tl、Ge等稀散元素为特征;Cd、Tl、Ge、Mn、As、Hg等微量元素以类质同象的形式赋存在闪锌矿中,其中,Cu与Ge的含量呈现较好的线性关系,推测在闪锌矿结晶过程中存在3Zn^(2+)Ge^(4+)+2Cu^(+)的替代机制,而Cd进入闪锌矿的方式可能为Zn^(2+)Cd^(2+),且Cd的异常富集可能与闪锌矿中低Fe含量有关;闪锌矿中微量元素Ga、Ge、Fe、Mn、In的组成特征指示了硫化物矿体形成于低温环境(65~140℃),与MVT型矿床的成矿温度一致。总体上,该矿床中的闪锌矿以富集Cd、Tl、Ge,贫Fe、Mn、In为特征,这与典型的MVT型矿床基本一致,明显区别于SEDEX、VMS与矽卡岩型铅锌矿床。结合矿床地质特征,笔者认为火烧云铅锌矿床中硫化物矿体成因与金顶铅锌矿床类似,属于MVT型矿床。     

新疆富蕴县乔夏哈拉铜(铁)金矿床地质与微量元素地球化学

笔者简单介绍了乔夏哈拉铜(铁)金矿床的基本成矿及其微量元素地球化学特征,指出其主矿体具有"垂向分带"及"铜、金向下同步富集"的特点,认为其容矿火山岩与中基性侵入岩脉具有基本相似的微量元素地球化学行为,铜、金矿石同其容矿火山岩相比具有相对贫K、Rb、Th、Ba,相对富W、Ni、Co、As、Sb、Zn及明显偏低的Th/Ta、La/Yb值。研究稀土元素地球化学,发现铜、金矿石具有明显不同于其容矿火山岩的强Eu富集,后期形成的地质体一般具有相对更为偏低的ΣREE值。综合分析表明,该铜(铁)金矿床为一与"层状夕卡岩"有关的火山热液型"层控"矿床。     

Trace metals (Cd,Pb, Cu,Zn and Ni) in sediment of the submarine pit Dragon ear (Soline Bay,Rogoznica, Croatia)

Vertical profiles of trace metal (Cd, Pb, Zn, Cu, Ni) concentrations, organic matter content, carbonate content and granulometric composition were determined in two sediment cores from the submarine pit Dragon Ear (Middle Adriatic). Concentrations of the analyzed metals (Cd: 0.06–0.12 mg kg⁻¹, Pb: 28.5–67.3 mg kg⁻¹, Zn: 17.0-65.4 mg kg⁻¹, Cu: 21.1–51.9 mg kg⁻¹, Ni: 27.8–40.2 mg kg⁻¹) were in usual range for Adriatic carbonate marine sediments. Nevertheless, concentrations of Cu, Zn, and especially Pb in the upper layer of sediments (top 12 cm) were higher than in bottom layer, while Cd and Ni concentration profiles were uniform. Regression analysis and principal component analysis were used to interpret distribution of trace metals, organic matter and carbonate content in sediment cores. Results of both analysis showed that concentrations of all trace metals in the core below the entrance to the pit were significantly positively correlated with organic matter and negatively correlated with carbonate, while in the core more distant from the entrance only Pb showed significant positive correlation with organic matter. Obtained results indicated that, except for lead which was enriched in surface sediment, in the time of sampling (before the building of the nautical marina) investigated area belonged to unpolluted areas.     

Distribution of organic matter in rocks of the Bazhenov horizon (West Siberia)

We studied the distribution of organic carbon in rocks of the Bazhenov horizon, a unique object of predominantly biogenic sedimentation in the West Siberian sedimentary basin. The contents of organic carbon in the rocks were determined using the data from 4094 core analyses and core-log relationships derived from 48,500 radioactive- and electrical-log measurements. For the Bazhenov and Tutleima Formations, both approaches gave the same results. The average content of organic carbon in the rocks is 7.7%. These data were used to compile a detailed map of the distribution of organic carbon contents in sedimentary rocks of the basin. It was shown that the average organic carbon content in the rocks increases from 2-4% on the periphery of the basin to 10-12% in its central, deepest part. The distribution of C_org values in the basin is highly asymmetric. The highest C_org values are observed in the southwestern part of the basin interior, where beds with > 10% C_org range in thickness from 5 to 12-15 m. In sections, the highest C_org values are observed in their middle and upper parts, composed predominantly of silicites and mixtites enriched in biogenic silica.     

Assessment of trace metal and rare earth elements contamination in rivers around abandoned and active mine areas. The case of Lubumbashi River and Tshamilemba Canal,Katanga, Democratic Republic of the Congo

Active and abandoned mine activities constitute the sources of deterioration of water and soil quality in many parts of the world, particularly in the African Copperbelt regions. The accumulation in soils and the release of toxic substances into the aquatic ecosystem can lead to water resources pollution and may place aquatic organisms and human health at risk. In this study, the impact of past mining activity (i.e., abandoned mine) on aquatic ecosystems has been studied using ICP-MS analysis for trace metals and Rare Earth Elements (REE) in sediment samples from Lubumbashi River (RL) and Tshamilemba Canal (CT), Katanga, Democratic Republic of the Congo (DRC). Soil samples from surrounding CT were collected to evaluate trace metal and REE concentrations and their spatial distribution. The extent of trace metal contamination compared to the background area was assessed by Enrichment Factor (EF) and Geoaccumulation Index (I_geo). Additionally, the trace metal concentrations probable effect levels (PELs) for their potential environmental impact was achieved by comparing the trace metal concentrations in the sediment/soil samples with the Sediment Quality Guidelines (SQGs). Spearman's Rank-order correlation was used to identify the source and origin of contaminants. The results highlighted high concentrations of trace metals in surface sediments of CT reaching the values of 40152, 15586, 610, 10322, 60704 and 15152 mg kg⁻¹ for Cu, Co, Zn, Pb, Fe and Mn, respectively. In the RL, the concentrations reached the values of 24093, 2046, 5463, 3340, 68290 and 769 mg kg⁻¹ for Cu, Co, Zn, Pb, Fe and Mn, respectively. The ΣREE varied from 66 to 218 and 142–331 mg kg⁻¹ for CT and RL, respectively. The soil samples are characterized by variable levels of trace metals. The EF analysis showed “extremely severe enrichment” for Cu and Co. However, no enrichment was observed for REE. Except for Mo, Th, U, Eu, Mo, Ho and Tm for which Igeo is classified as “moderately polluted and/or unpolluted”, all elements in different sites are classified in the class 6, “extremely polluted”. The trace metal concentrations in all sampling sites largely exceeded the SQGs and the PELs for the Protection of Aquatic Life recommendation. Cu and Co had positive correlation coefficient values (r = 0.741, P < 0.05, n = 14). This research presents useful tools for the evaluation of water contamination in abandoned and active mining areas.