涡阳花沟西10号煤中微量元素的有机亲和性

为研究淮北矿区涡阳花沟西勘查区10号煤中微量元素的有机亲和性,共采集10个勘探钻孔煤样品,采用电感耦合等离子质谱仪ICP-MS分析了12种微量元素的含量;应用LECO碳硫分析仪测定了煤的总有机碳TOC,并通过两者的相关关系分析了元素的有机亲和性,结合元素的地球化学特征和煤样XRD物相鉴定结果,通过聚类分析进一步推断元素的赋存状态。结果表明:V、Cr、Co、Ni、Mo、Cd、Sb、Pb和Zn元素含量低于全国均值,没有异常富集,Be、Cu和Tl略高于全国均值;Cd具有较强的有机亲和性,Co、Zn、Be和Cr的有机亲和性较弱,V、Ni、Cu、Mo、Sb、Pb和Tl不具有机亲和性;V、Sb、Cu、Cr、Pb、Co和Ni主要以铝硅酸盐吸附态赋存,Cd主要以有机结合态赋存。      

Concentration distribution and assessment of several heavy metals in sediments of west-four Pearl River Estuary

Grain size parameters, trace metals (Co, Cu, Ni, Pb, Cr, Zn, Ba, Zr and Sr) and total organic matter (TOM) of 38 surficial sediments and a sediment core of west-four Pearl River Estuary region were analyzed. The spacial distribution and the transportation procession of the chemical element in surficial sediments were studied mainly. Multivariate statistics are used to analyses the interrelationship of metal elements, TOM and the grain size parameters. The results demonstrated that terrigenous sediment taken by the rivers are main sources of the trace metal elements and TOM, and the lithology of parent material is a dominating factor controlling the trace metal composition in the surficial sediment. In addition, the hydrodynamic condition and landform are the dominating factors controlling the large-scale distribution, while the anthropogenic input in the coastal area alters the regional distribution of heavy metal elements Co, Cu, Ni, Pb, Cr and Zn. The enrichment factor (EF) analysis was used for the differentiation of the metal source between anthropogenic and naturally occurring, and for the assessment of the anthropogenic influence, the deeper layer content of heavy metals were calculated as the background values and Zr was chosen as the reference element for Co, Cu, Ni, Pb, Cr and Zn. The result indicate prevalent enrichment of Co, Cu, Ni, Pb and Cr, and the contamination of Pb is most obvious, further more, the peculiar high EF value sites of Zn and Pb probably suggest point source input.     

Trace metals in acid sediments and waters, Pimpama catchment, southeast Queensland, Australia

The Pimpama River floodplain has developed over the last several thousand years as a result of sea-level fluctuations that shaped the lower catchment and enabled the formation of sedimentary pyrite. The subsequent production of sulfuric acid due to the oxidation of this pyrite enhances the breakdown of metal-bearing sediments and can lead to leaching of major and trace metals into the waters of the region. The seasonal pattern of rainfall and current land-use activities are important aspects that intensify the natural production of acid and influence the release and distribution of metals. To identify the source and migration of metals in the Pimpama catchment and to understand the impact of pyrite oxidation on the distribution of metals in sediments and waters, several components of the drainage system were analyzed: bedrock, sediments from river bed and bank, and water. The elements analyzed in this study (V, Cr, Co, Ni, Cu, Zn and Pb) are all present in the bedrock material which explains their occurrence in the unconsolidated sediments of the floodplain. These metals concentrate in the upper section of the sedimentary sequence and their presence is related to clay minerals such as smectite, organic matter and iron phases. However, Zn, Mo and Co occur in higher amounts than the local background and within standard shale. This comparison suggests that the diagenetic processes alone cannot explain the higher concentrations and it is concluded that these metals also have an anthropogenic source. The formation of sulfuric acid creates conditions for higher mobility of some metals, such as Cr, Co, Ni, Cu, Zn, but does not affect less mobile ones such as Mo and Pb. Over the longterm, the production of acid influences the breakdown of mineral phases and enhances the process of weathering. Over the short term, every rain event leaches acid from sediments and mobilizes metals resulting in a substantial reduction in the quality of river water. Received: 2 October 1998 · Accepted: 16 February 1999     

Deciphering factors controlling trace element distribution in the soils of Karaduvar industrial-agricultural area (Mersin,SE Turkey)

In this study, 30 topsoil samples were collected from Karaduvar area (Mersin, SE Turkey) where at present various industrial and agricultural activities are occurring. Using a five-step ultrasound-assisted sequential extraction (UASE) procedure, trace elements in soil samples were partitioned into the following: (1) soluble-exchangeable; (2) bound to carbonates; (3) bound to Fe- and Mn-oxides; (4) bound to organic matter and sulfide compounds, and (5) residual fraction. Concentrations of 11 trace elements in the extracts were determined using ICP-MS. Total concentrations ranged between (in mg kg⁻¹) 3.35 and 7.26 for As; 1.18 and 3.96 for Cd; 10.76 and 20.26 for Co; 37.99 and 63.48 for Cr; 18.55 and 243.1 for Cu; 338.7 and 565.6 for Mn; 4.42 and 6.44 for Mo; 148 and 279.3 for Ni; 10.12 and 73.71 for Pb; 17.93 and 36.55 for V, and 25.46 and 331.7 for Zn. Factor analysis was applied to dataset in order to discriminate between natural and anthropogenic pollution sources and factors controlling the spatial distribution of trace elements in the area. Results suggest that distributions of Co, Cr, Mn, and Ni are mainly controlled by lithological factors, whereas, distributions of Cu, Pb, and Zn can be attributed to agricultural activities such as pesticide/herbicide use and fertilizer application, as well as irrigation with petroleum hydrocarbon-contaminated groundwater. Highest concentrations of Cd and Mo are generally observed around the diesel-fired thermal power plant and ATAŞ refinery. Highest concentrations of As and V are generally observed at the NW sector of the area; however, no definitive source can be designated for both of these elements.     

Mineral and inorganic chemical composition of the Pernik coal, Bulgaria

The mineral and inorganic chemical composition of five types of samples from the Pernik subbituminous coals and their products generated from the Pernik preparation plant were studied. They include feed coal, low-grade coal, high-grade coal, coal slime, and host rock. The mineral matter of the coals contains 44 species that belong mainly to silicates, carbonates, sulphates, sulphides, and oxides/hydroxides, and to a lesser extent, chlorides, biogenic minerals, and organic minerals. The detrital minerals are quartz, kaolinite, micas, feldspars, magnetite, cristobalite, spessartine, and amphibole. The authigenic minerals include various sulphides, silicates, oxihydroxides, sulphates, and carbonates. Several stages and substages of formation were identified during the syngenetic and epigenetic mineral precipitations of these coals. The authigenic minerals show the greatest diversity of mineral species as the epigenetic mineralization (mostly sulphides, carbonates, and sulphates) dominates qualitatively and quantitatively. The epigenetic mineralization was a result of complex processes occurring mostly during the late development of the Pernik basin. These processes indicate intensive tectonic, hydrothermal and volcanic activities accompanied by a change from fresh to marine sedimentation environment. Thermally altered organic matter due to some of the above processes was also identified in the basin. Most of the trace elements in the Pernik coals (Mo, Be, S, Zr, Y, Cl, Ba, Sc, Ga, Ag, V, P, Br, Ni, Co, Pb, Ca, and Ti) show an affinity to OM and phases intimately associated with OM. Some of the trace elements (Sr, Ti, Mn, Ba, Pb, Cu, Zn, Co, Cr, Ni, As, Ag, Yb, Sn, Ga, Ge, etc.) are impurities in authigenic and accessory minerals, while other trace elements (La, Ba, Cu, Ce, Sb, Bi, Zn, Pb, Cd, Nd, etc.) occur as discrete phases. Elements such as Sc, Be, Y, Ba, V, Zr, S, Mo, Ti, and Ga exceed Clarke concentrations in all of the coal types studied. It was also found that a number of elements in the Pernik coals (F, V, As, Pb, Mo, Li, Sr, Ti, Ga, Ni, Ge, Cr, Mn, etc.) reveal mobility in water and could have some environmental concerns.     

Concentration and distribution of trace elements in some coals from Northern China

The concentration, distribution and modes of occurrence of trace elements in thirty coals, four floors and two roofs from Northern China were studied. The samples were collected from the major coalfields of Shanxi Province, Shaanxi Province, Inner Mongolian Autonomous Region, and Ningxia Hui Autonomous Region. The concentrations of seventeen potential hazardous trace elements, including Hg, As, Se, Pb, Cd, Br, Ni, Cr, Co, Mo, Mn, Be, Sb, Th, V, U, Zn, and five major elements P, Na, Fe, Al, and Ca in coals were determined.Compared with average concentration of trace elements in Chinese coal, the coals from Northern China contain a higher concentration of Hg, Se, Cd, Mn, and Zn. They may be harmful to the environment in the process of combustion and utilization. Vertical variations of trace elements in three coal seams indicated the distributions of most elements in coal seam are heterogeneous. Based on statistical analyses, trace elements including Mo, Cr, Se, Th, Pb, Sb, V, Be and major elements including Al, P shows an affinity to ash content. In contrast, Br is generally associated with organic matter. Elements As, Ni, Be, Mo, and Fe appear to be associated with pyrite. The concentrations of trace elements weakly correlate either to coal rank or to maceral compositions.     

Temporal Trends of Dissolved Trace Metals in Jamaica Bay,NY: Importance of Wastewater Input and Submarine Groundwater Discharge in an Urban Estuary

Jamaica Bay, NY, is a highly urbanized estuary within the boroughs of New York City conspicuously lacking published information on dissolved trace metal concentrations. The current study examines the distribution and cycling of trace metals in that embayment with data gathered during cruises in November 2004, April 2005, and June 2006. Most of the metal distributions (Fe, Zn, Co, Ag, Cu, Pb, Ni) in the water column are explained by the input of substantial volumes of treated wastewater effluent. However, several lines of evidence suggest that submarine groundwater discharge (SGD) is also an important source of dissolved Fe, Zn, Co, Ni, and isotopically distinct stable Pb ratios (²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) in the Bay. Conversely, the recirculated seawater component of SGD is an apparent sink for dissolved Mo. This study provides the first measurements of dissolved trace metals in the Jamaica Bay water column and subterranean estuary and provides evidence for trace metal input due to SGD.     

Organic matter-metal interactions in Recent sediments: the role of humic substances

Atomic emission spectrographic analysis of the trace inorganic constituents of marine humic substances gave the following range of concentrations: Si, 200 ppm to > 2%; Al, 400 ppm to ~ 1%; Fe, 600–3000 ppm; Ca, 600 ppm to > 2%; Mg, 20–6000 ppm; Na, 600 ppm to > 2%; Ag, < 6–600 ppm; B, < 60–1000 ppm; Cu, 600–4000 ppm; Mn, 8–100 ppm; Mo, <20–3000 ppm; Ni, 100–1000 ppm; Pb, < 40–600 ppm; Sn, 40–600 ppm; Ti, < 20–2500 ppm; V, 20–200 ppm; Zn, 350–4500 ppm; Zr, < 60–500 ppm.Humic substances contain a sizeable portion of the Cu, Mo and Zn found in sediments, but are less important for Ni, Co and Pb, and are insignificant for the Mn, V and Fe content. The metals are mostly introduced into the humates during their diagenetic formation in sediment by dissolution of metals from various mineralogical phases. A precursor of the sedimentary humates, the polymeric organic material dissolved in interstitial water, contains most of the Cu and Zn, about half of the Ni, Fe and Co, and very little of the Mn found in interstitial water. Comparison of the data on humates with that obtained by H₂O₂ treatment of sediments indicates that Cu, Zn and possibly most of the Mo are associated with organic matter, but that Ni and Co are associated with sulfides.     

Distribution of major and trace elements in La Luna Formation, Southwestern Venezuelan Basin

The La Luna Formation (Maraca section), Maracaibo Basin, was studied by means of V and Ni analysis of the bitumen, total organic carbon (TOC), total sulfur (St), major elements (Si, Al, Fe, Mg, Mn, Ca, Ti, Na, K, P), trace elements (V, Ni, Co, Cr, Cu, and Zn), and electron microprobe analysis (EPMA) of the whole rock, and St, major elements (Si, Al, Fe, Mg, Mn, Ca, Ti, Na, K, P), trace elements (V, Ni, Co, Cr, Cu, Zn, Mo, Ba, U, Th) and rare earth elements (La, Ce, Nd, Sn, Eu, Th, Yb, Lu) of the carbonate-free fraction. The results are discussed based on the organic and inorganic association of trace elements and their use as paleoenvironmental indicators of sedimentation. An association between V and organic matter is suggested by means of correlation between V and Ni vs. TOC, the use of EPMA (whole rock) and V and Ni concentrations (carbonate-free fraction), whereas Ni is found in the organic matter and the sulfide phase. Fe is present as massive and framboidal pyrite, whereas Zn precipitates into a separate phase (sphalerite), and Ni, Cu and, in some cases, Zn, can be found as sulfides associated with pyrite. Concentrations of V and Ni (bitumen), TOC, St, V, Ni, Cr, Cu and Zn (whole rock), U, Th, Mo (carbonate-free fraction) are indicative of changes in the dysoxic sedimentation conditions in the chert layers (TOC, St, V, Ni, Cu and low Zn and V/Cr <4) to euxinic anoxic conditions in the argillaceous limestone (TOC, St, V, Ni, Cu and high Zn and V/Cr >4). In the sequence corresponding to the argillaceous limestone, variations in the concentrations of TOC, St, V, Ni, Zn, Cu and Cr (whole rock) can be observed, also suggesting variable sedimentation conditions. The following is proposed: (i) sedimentation intervals under euxinic conditions associated with high contribution and/or preservation of organic matter, allowing a high concentration level of V and Ni in the organic phase and the accumulation of Cu, Zn and Ni (in a smaller proportion) in the sulfide phase; (ii) sedimentation intervals under anoxic conditions and in the presence of relatively lower H₂S, which allowed lower concentrations of V and Ni in the organic phase and higher concentrations of Cu, Zn, and Ni in the sulfide phase. Rare earth elements (REE) concentrations exhibit a marked increase in Ce, Nd, Sm, Eu, Y and Lu for the QM-3 interval, relative to Post-Archean Average Shale (PAAS). REE enrichment in shales has been related to the presence of phosphate minerals such as monazite or apatite. However, these minerals were not detected through XRD or EPMA in the whole rock or in the carbonate-free fraction. The association of REE with organic matter is suggested due to the absence of phosphate minerals, although assessment of these elements require further analysis.     

New operational method of testing colloid complexation with metals in natural waters

A dialysis procedure was used to assess the distribution coefficients of ∼50 major and trace elements (TEs) between colloidal (1 kDa–0.22 μm) and truly dissolved (<1 kDa) phases in Fe- and organic-rich boreal surface waters. These measurements allowed quantification of both TE partitioning coefficients and the proportion of colloidal forms as a function of solution pH (from 3 to 8). Two groups of elements can be distinguished according to their behaviour during dialysis: (i) elements which are strongly associated with colloids and exhibit significant increases of relative proportion of colloidal forms with pH increase (Al, Ba, Cd, Co, Cr, Cu, Fe, Ga, Hf, Mn, Ni, Pb, rare earth elements (REEs), Sr, Th, U, Y, Zn, Zr and dissolved organic C) and (ii) elements that are weakly associated with colloids and whose distribution coefficients between colloidal and truly dissolved phases are not significantly affected by solution pH (As, B, Ca, Cs, Ge, K, Li, Mg, Mo, Na, Nb, Rb, Sb, Si, Sn, Ti, V). Element speciation was assessed using the Visual MINTEQ computer code with an implemented NICA-Donnan humic ion binding model and database. The model reproduces quantitatively the pH-dependence of colloidal form proportion for alkaline-earth (Ba, Ca, Mg, Sr) and most divalent metals (Co, Cd, Mn, Ni, Pb, Zn) implying that the complexation of these metals with low molecular weight organic matter (<1 kDa fraction) is negligible. In contrast, model prediction of colloidal proportion (fraction of 1 kDa–0.22 μm) of Cu²⁺ and all trivalent and tetravalent metals is much higher than that measured in the experiment. This difference may be explained by (i) the presence of strong metal-binding organic ligands in the <1 kDa fraction whose stability constants are several orders of magnitude higher than those of colloidal humic and fulvic acids and/or (ii) coprecipitation of TE with Fe(Al) oxy(hydr)oxides in the colloidal fraction, whose dissolution and aggregation controls the pH-dependent pattern of TE partitioning. Quantitative modeling of metal – organic ligand complexation and empirical distribution coefficients corroborate the existence of two colloidal pools, formerly reported in boreal surface waters: “classic” fulvic or humic acids binding divalent transition metals and alkaline-earth elements and large-size organo-ferric colloids transporting insoluble trivalent and tetravalent elements.     

Geology,geochemistry and mineralogy of the lignite-hosted Ambassador palaeochannel uranium and multi-element deposit,Gunbarrel Basin,Western Australia

The Ambassador U and multi-element deposit occurs on the SW margin of the Gunbarrel Basin, Western Australia. Low-grade, flat-lying U mineralization averaging about 2 m thick at 0.03% U occurs in lignites at the redox front at the base of the weathering profile within a laterally extensive palaeochannel network. Uranium is principally associated with organic matter within the lignitic matrix, although rare discrete U minerals, such as coffinite and uraninite, are also present. The lignite is also enriched in a suite of other elements, principally base metals and sulphur, with concentrations of 0.3 ≥ 1% Cu, Pb, Ni, Co, Zn and total rare earth elements (REE) in some samples. Other element enrichments include: Cr, Cs, Sc, Se, Ta, Ti, Th, V and Zr as detrital heavy minerals of Zr, Ti and REE (oxides and silicates) or authigenic minerals of Cu, Bi, Pb, Zn, Ni, Se, Hg, Ti, Cr, Tl, V, U and REE (sulphides, vanadates, selenides, oxides, chlorides and native metals) and diffuse lignite impregnations. The Ambassador deposit probably formed from the convergence of redox-active weathering processes to unique source/host rocks, constrained within the palaeochannel. A proximal source of U and trace elements of lamproite/carbonatite origin is probable, as constrained by U–Pb isotope and U–Th disequilibria studies. Uranium and other metals were precipitated syngenetically with organic matter as it was deposited during a humid phase in the Late Eocene. Remobilization subsequently concentrated the metals in the upper 2 m of the lignite. This may have occurred during one or more periods of weathering and associated diagenesis, with the latest episode in the last 300,000 years.     

Trace elements in high-S subbituminous coals from the teruel Mining District, northeast Spain

The elemental composition of high temperature ash (750°C) and forms of S were studied in 25 coal seams from the Escucha Formation (Middle Albian) in the Teruel Mining District, northeast Spain. The principal analytical method was ICP-MS, but ICP-ES was also used in the determination of some trace elements. The analytical data show wide ranges of trace element cotnents among the coal seams studied, even in the vertical profile of a single coal seam. These wide ranges of the trace element concentrations are attributed to both syngenetic and epigenetic processes.When a comparison was made between the average trace element contents of the Teruel Mining District coals, and those of the average content in worldwide coals, the Teruel coals show slightly higher concentrations of Be and U, and lower concentrations of Ba, Cd, Mn, Pb, Sr and Zr. Further, three main groups of trace elements were differentiated on the basis of the inorganic/organic association: (1) trace elements with inorganic affinity; Ba, Ce, Co, Cr, La, Mn, Ni, Rb and Zr. Between these, Ba, Ce, Cr and Rb show a well defined correlation with the clay mineral content, and Co and Ni with pyritic-S content; (2) trace elements with an intermediate (mixed) affinity; As, Cd, Cu, Dy, Er, Eu, Gd, Ge, Ho, Lu, Mo, Nd, Pb, Pr, Sb, Sm, Sr, Tb, Th, Tm, U, Yb and Zn. In this group, As, Cd, Cu, Ge, Mo, Th, U and Zn show a weak trend associated with the mineral matter and Sr with the organic matter; and (3) Be shows an organic affinity. The high mineral matter content (21.3% HTA) of the Teruel coals may account for the great number of elements with inorganic affinity. This classification represents a general trend, but the results show that the affinities of some trace elements (e.g. As, Sb and Zn) may vary from one coal seam to another in the Teruel Mining District.     

Pyrite geochemistry in the Toarcian Posidonia Shale of south‐west Germany: Evidence for contrasting trace‐element patterns of diagenetic and syngenetic pyrites

Authigenic pyrite grains from a section of the Lower Toarcian Posidonia Shale were analysed for their trace‐element contents and sulphur‐isotope compositions. The resulting data are used to evaluate the relationship between depositional conditions and pyrite trace‐element composition. By using factor analysis, trace‐elements in pyrite may be assigned to four groups: (i) heavy metals (including Cu, Ni, Co, Pb, Bi and Tl); (ii) oxyanionic elements (As, Mo and Sb); (iii) elements partitioned in sub‐microscopic sphalerite inclusions (Zn and Cd); and (iv) elements related to organic or silicate impurities (Ga and V). Results indicate that trace‐element contents in pyrite depend on the site and mechanism of pyrite formation, with characteristic features being observed for diagenetic and syngenetic pyrites. Diagenetic pyrite formed within anoxic sediments generally has a high heavy metals content, and the degree of pyritization of these elements increases with increasing oxygen deficiency, similar to the degree of pyritization of reactive Fe. The highest gradient in the increase of the degree of trace element pyritization with bottom‐water oxygenation was found for the elements Ni < Cu < Mo = As < Tl. In contrast, syngenetic pyrite formed within a euxinic water column typically is enriched in As, Mo and Sb, but is low in heavy metals, and the geochemical variation reflects changes in sea water composition.     

Comparison of organic geochemistry and metal enrichment in two black shales: Cambrian Alum Shale of Sweden and Devonian Chattanooga Shale of United States

In most black shales, such as the Chattanooga Shale and related shales of the eastern interior United States, increased metal and metalloid contents are generally related to increased organic carbon content, decreased sedimentation rate, organic matter type, or position in the basin. In areas where the stratigraphic equivalents of the Chattanooga Shale are deeply buried and and the organic material is thermally mature, metal contents are essentially the same as in unheated areas and correlate with organic C or S contents. This paradigm does not hold for the Cambrian Alum Shale Formation of Sweden where increased metal content does not necessarily correlate with organic matter content nor is metal enrichment necessarily related to land derived humic material because this organic matter is all of marine source. In southcentral Sweden the elements U, Mo, V, Ni, Zn, Cd and Pb are all enriched relative to average black shales but only U and Mo correlate to organic matter content. Tectonically disturbed and metamorphosed allochthonous samples of Alum Shale on the Caledonian front in western Sweden have even higher amounts for some metals (V, Ni, Zn and Ba) relative to the autochthonous shales in this area and those in southern Sweden.     

淮南煤田山西组泥页岩微量元素地球化学特征及其意义

泥页岩中微量元素特征对反演泥页岩形成时的沉积和古地理气候条件具有重要意义。采集淮南煤田山西组泥页岩样品,利用ICP-MS对泥页岩中微量元素进行了测试分析,探讨了研究区山西组泥页岩中微量元素的地球化学特征及其意义。结果表明,B、Cr、U、Ga、Li、Sn、Pb、Mo、Th、W等元素富集,Cd、Co、Cu、Ti、Zn、Sc、Ba、Mn、Ni、Sr等元素亏损;揭示淮南煤田山西组形成于温暖湿润和半咸水-高咸水的沉积环境中,沉积体系为开放型,体系内为弱氧化-还原环境,其中以弱还原-还原环境为主,且表现出从早期弱氧化到中后期的还原环境的演化特征;依据U/Th、Ni/Co、Sr/Cu、B/Ga、Sr/Ba、TOC等地球化学参数结果推测,盐度和氧化还原条件受到多种因素的影响,有机质的原始堆积量是影响山西组泥页岩中有机质含量的主要因素,而盐度和氧化还原条件影响有机质中各显微组分含量。研究区温暖湿润的气候和较为还原的环境为有机质的堆积和保存提供了有利条件,为页岩气的成藏提供了物质基础。      

Trace-element study of manganese ores of the Barbil area,Keonjhar district Orissa,India

An attempt has been made to study the distribution pattern and concentration trends of eight significant metallic trace elements in the manganese ores of a few opencast workings of Barbil, Keonjhar district, Orissa, India. Cu, Pb, Zn, Co, Ni, Sr, Mo, and V are the trace elements that were chemically determined from 60 samples of manganese ores collected from the study area. Since the mean concentrations of most of the trace elements concerned in the Barbil manganese ores are generally lower than those found in the manganese ores known to be volcanogenic origin, the manganese was probably derived from some nonvolcanogenic terrestrial rock source.     

Abundances and modes of occurrence of trace elements in the Çan coals (Miocene), Çanakkale-Turkey

This study presents the concentrations and modes of occurrence of trace elements in 81 coal samples from the Çan basin of northwestern Turkey. The concentration of trace elements in coal were determined by inductively coupled plasma-mass spectrometry and inductively coupled plasma-atomic emission spectrometry. Additionally, traditional coal parameters were studied by proximate, ultimate, X-ray diffraction, and petrographic analyses. Twenty trace elements, including As, B, Ba, Be, Cd, Cu, Co, F, Hg, Mo, Ni, Pb, Sb, Se Sn, Th, Tl, U, V, and Zn, receive much attention due to their related environmental and human health concerns. The Çan coals investigated in this study are lignite to sub-bituminous coal, with a broad range of ash yields and sulphur contents. The trace element concentrations show variety within the coal seams in the basin, and the affinities vary among locations. The concentrations of B, Ba, Be, Cd, Cu, Co, F, Hg, Mo, Ni, Pb, Sb, Se, Sn, Tl, and Zn in Çan coals are within the Swaine's worldwide concentration range, with the exception of As, Th, U, and V. On the other hand, compared with world coals, the Çan basin coals have higher contents of As, B, Cu, Co, Mo, Pb, Th, U, V, and Zn. Based on statistical analyses, most of the trace elements, except for U, show an affinity to ash yield. Elements including As, Cd, Hg, Se, Cu, Mo, Ni, and Zn, show a possible association with pyrite; however, the elements Se, B, and Mo can be have both organic and inorganic associations.     

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.     

Dissolved Trace Metal–Organic Complexes in the Lot–Garonne River System Determined Using the C18 Sep-Pak System

An 11-month observation of dissolved and particulate organic matter, chlorophyll a(Chl a), C18 Sep-Pak extractable hydrophobic dissolved organic matter (hDOM) fraction and associated dissolved trace metals (Cd, Cu, V, Co, Ni, Mo, U) was performed in the Lot–Garonne River system. This system includes the Riou Mort, the Lot River and the downstream reaches of the Garonne River and represents the fluvial transport path of trace metals between the major point source of polymetallic pollution, located in the Riou Mort watershed and the Gironde estuary. Spatial and temporal variations of dissolved and particulate organic carbon and Chl areflect the presence of different types of organic matter and their relation with the hDOM fraction. Maximum Chl a/POC ratios (up to 0.03), indicate intense phytoplankton production from March to May. In the Lot River (Temple), DOC and POC concentrations were clearly higher and mean Chl a concentration (2.8 mg g⁻¹) was about three times higher than those of the other sites. High Chl a/POC ratios suggest high phytoplankton activity with maxima in spring and late summer. In the Riou Mort River, very high POC concentrations of up to 40 (mean: 20) occurred, whereas Chl a concentrations were relatively low indicating low phytoplankton activity. High, strongly variable DOC and POC concentrations suggest important natural (Carboniferous soils, forests) or anthropogenic (e.g., former coal mines, waste areas, agriculture, sewage) carbon sources within the small Riou Mort watershed. Despite high DOC concentrations in the Riou Mort River, hDOM metal fractions were generally lower than those at the other sites. The general order of decreasing binding strength between metals and the organic hydrophobic phase (Cu, U > Co, Ni > V, Mo > Cd) at all four sites was in good agreement with the Irving–William series of transition element affinity towards organic ligands. Accordingly, the role of the hydrophobic phase in dissolved Cd transport appeared to be negligible, whereas the hDOM–Cu fraction strongly contributed to dissolved Cu transport.     

Geochemical Record of the Cenomanian–Turonian Anoxic Event in Tunisia: Is it Correlative and Isochronous to the Biotic Signal?

In Tunisia, five Bahloul spaced sections, Bargou, Jerisa, Guern Halfaya, Kherij and Gafsa were analyzed for biostratigraphy (foraminifera and radiolarians) and major and trace elements. This high-resolution biostratigraphic and chemostratigraphic integrated analyses for the Late Cenomanian–Early Turonian Bahloul Formation provide new insight into the palaeoceanographic evolution of the southern Tethyan margin. Relative low abundance of related terrigenous Ti/Al and K/Al ratios and enrichment of some productivity proxies such as Ba, Cu, and Ni (organic matter related trace elements) suggests that the Bahloul, deposited during a relatively short period (0.5 Ma), was of relatively elevated primary productivity and minimal detrital input. While higher D* values concurrent with lower Ti/Al ratios are interpreted as caused by enhanced fluvial material contribution, due to more humid climate during the OAE-2. Enhanced humidity triggered probably fluvial influxes, resulted in a sluggish water circulation and consequent anoxic/euxinic conditions favoring the preservation of organic matter at the bottom. Enrichments in redox-sensitive trace metals U, V, and Mo in the Bahloul Formation deposits and redox indices, such as V/(V+Ni), U/Th, V/Cr, and Ni/Co, indicate that oxygen-restricted conditions prevailed during the Late Cenomanian to earliest Turonian times and correlate well with relative abundances of some foraminiferal and radiolarian paleo-environmental relevant indicators. High Baxs values and Uauth may indicate anoxic conditions at least at the water–sediment interface during the Bahloul Formation deposition and provide information about low to moderate sulfate-reduction reactions.