新疆阿克苏地区早寒武世碳酸盐岩沉积环境:微量元素和碳同位素证据

对出露于塔里木盆地北缘阿克苏地区寒武系纽芬兰统玉尔吐斯组上部和寒武系第二统肖尔布拉克组下部海相沉积碳酸盐岩进行了氧化-还原敏感元素(Mo、V、Cd和U)及稳定C、O同位素的地球化学剖面研究,以探讨早寒武世沉积碳酸盐岩的沉积环境.研究揭示,尤尔美那克剖面肖尔布拉克组底部和下部含有两个δ13C负异常,谷值分别为-2.1‰和...     

古海洋生产力与氧化还原指标——元素地球化学综述

海洋表层初级生产力大小以及水体氧化还原条件是古海洋和古气候研究的重要内容,而元素地球化学是研究初级生产力以及氧化还原条件最常用的手段。主量元素Fe和Si是限制生物的营养元素,痕量金属元素Cu、Ni和Zn是微营养元素,而营养条件是沉积生产力的限制因素,因此这些元素的含量能反映初级生产力大小。Ba和Mo是随有机质一起沉淀下来的,与水体的有机碳通量有关,也是古生产力大小的指标。对氧化还原敏感的痕量金属元素含量（如Cr、V和U）以及元素比值（如V/（V＋Ni）、V/Cr、Ni/Co、U/Th和V/Sc）常用来重构水体的氧化还原条件。     

Paleoenvironmental conditions across the Cretaceous–Paleogene transition at the Apennines sections (Italy): An integrated geochemical and ichnological approach

Two distal Cretaceous–Paleogene (K/Pg) boundary sections in the Central Apennine region (Italy) have been studied: Bottaccione Gorge and Contessa Highway. Geochemical and carbon isotope analyses on the infilling of trace fossils and on the host sedimentary rocks were performed to determine paleoenvironmental conditions during the Cretaceous–Paleogene transition. Major and trace element contents were measured in a 63 cm-thick interval at Bottaccione Gorge (from 22 cm below to 41 cm above the K/Pg boundary) and in a 72 cm-thick interval at Contessa Highway (from 43 cm below to 29 cm above the K/Pg boundary). Even though the K/Pg ejecta layer is now depleted at these sections due to continuous oversampling, the uppermost Maastrichtian and lowermost Danian deposits record the paleoenvironmental conditions prior to and after the K/Pg event. We used redox-sensitive element ratios (V/Al, Cr/Al, Co/Al, Ni/Al Cu/Al, Zn/Al, Mo/Al Pb/Al and U/Mo) and detrital element ratios (K/Al, Rb/Al, Zr/Al and ƩREE/Al) as proxies of certain environmental parameters, used for paleoenvironmental reconstruction. In general, similar values for elemental ratios are registered within Maastrichtian and Danian deposits, which supports similar paleoenvironmental conditions prior to and after the K/Pg event as well as the rapid reestablishment of the pre-impact conditions (i.e., oxygenation, nutrient availability, and/or sedimentary input). An enrichment in certain redox-sensitive elements above the K/Pg at the Bottaccione Gorge section suggests lower oxygenation, as also evidenced by the tracemaker community. Carbon isotope composition data from the infilling material of trace fossils furthermore reveals values similar to those of the host rocks at the corresponding depth, which supports an active infilling by nearly contemporaneous bioturbation during sediment deposition.     

The Faraoni event (latest Hauterivian) in ichnological record: The Río Argos section of southern Spain

The Early Cretaceous (latest Hauterivian) Faraoni Oceanic Anoxic Event (F-OAE) in the Río Argos section (Caravaca region, southern Spain), the candidate for the Global Boundary Stratotype Section and Point (GSSP) of the Hauterivian–Barremian transition, has been studied. Its ichnological bed-by-bed analysis allows for interpretation of oxygenation changes through the Faraoni Level interval and improvement upon previous characterization of oxygen conditions prior, during and after the F-OAE. The trace fossil assemblage belongs to the Zoophycos ichnofacies and it includes Chondrites intricatus, Chondrites targionii, Halimedides isp., Palaeophycus isp., ?Patagonichnus isp., Planolites isp., Rhizocorallium isp., Taenidium isp., Thalassinoides isp., Trichichnus linearis, Zavitokichnus fusiformis, and Zoophycos isp. Their diversity in particular beds fluctuates. Beds with four to six ichnotaxa reflect a multi-tiered macrobenthic trace maker assemblage living in good oxic and trophic conditions. In one bed below and one bed above the Faraoni Level (both marls without primary lamination), there are only two or three, mostly opportunistic ichnotaxa (Trichichnus, Chondrites, Planolites). They record dysoxic conditions. At the base of the Faraoni Level, one thicker and two thinner beds of marly mudstones (21.2 and 3.5 cm thick, respectively) are characterized by primary lamination. At the top and in the basal part of the thicker bed and in the thinner beds some trace fossils are present. These beds were deposited under anoxic conditions and later colonized by trace makers either from overlying beds deposited under oxic conditions or from the level of a greenish lamina in the lower part of the thicker bed, recording short episodes of dysoxic conditions. The thinner anoxic beds are separated by marls deposited under dysoxic conditions.     

Characterization of trace elements in sulphur-rich Late Permian coals in the Heshan coal field,Guangxi, South China

The concentration of trace elements and their distribution in the late Permian coal in the Heshan coal field, Guangxi Autonomous Region, were analysed in this paper. The late Permian coal of the Heshan mining district was developed in a low energy and shallow, confined carbonate platform. Heshan coal is a low volatile bituminous coal characterized by a high sulphur content, ranging between 2.0% and 8.2%. Compared with the worldwide average content of the trace elements in coal, the content of some trace element in the study coal is markedly high (Bi, Ce, Cr, Cs, Cu, Ga, Hf, Sr, Ta, Th, U, V, W, Y, Zr, La, Mo, Nb and Sc).The trace element associations were investigated by means of intracorrelation analysis. Some elements, such as Cl, F and Sr are found in coal in association with the carbonate minerals. V, Cr, Zn, Mo, Ni and As contents in coal vary significantly amongst the coal samples. They are mainly concentrated in the lower part of the coal #4 upper of Suhe and Lilan mines and the coal #4 lower of Dong mine, and these possibly occurring in minerals such as arsenide and sulphide. The content of U in Heshan coal is high and is mainly concentrated at the upper and the lower parts of the coal seam and it is associated with mineral assemblages with Ba, Mo, V, Ni, Zn, Rb and Cr. Furthermore, La and Ce are highly correlated with those found in phosphate minerals and Pb, Sc, Ga, Th, Y and Sn to those in aluminosilicate minerals. The enrichment of some elements such as V, Cr, Zn, Mo, Ni, Rb as well as total sulphur and iron in the lower part of most coal seams might be associated with the formation of soil horizon before the accumulation of peat in the basin. Some other elements such as Cl, F, Sr and Ca are locally concentrated in the top of specific coal seams as a result of the leaching from overlying carbonates.     

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.     

Early diagenesis of redox-sensitive trace metals in the Peru upwelling area - response to ENSO-related oxygen fluctuations in the water column

Pore water and solid phase data for redox-sensitive metals (Mn, Fe, V, Mo and U) were collected on a transect across the Peru upwelling area (11°S) at water depths between 78 and 2025 m and bottom water oxygen concentrations ranging from ∼0 to 93 μM. By comparing authigenic mass accumulation rates and diffusive benthic fluxes, we evaluate the respective mechanisms of trace metal accumulation, retention and remobilization across the oxygen minimum zone (OMZ) and with respect to oxygen fluctuations in the water column related to the El Niño Southern Oscillation (ENSO).Sediments within the permanent OMZ are characterized by diffusive uptake and authigenic fixation of U, V and Mo as well as diffusive loss of Mn and Fe across the benthic boundary. Some of the dissolved Mn and Fe in the water column re-precipitate at the oxycline and shuttle particle-reactive trace metals to the sediment surface at the lower and upper boundary of the OMZ. At the lower boundary, pore waters are not sufficiently sulfidic as to enable an efficient authigenic V and Mo fixation. As a consequence, sediments below the OMZ are preferentially enriched in U which is delivered via both in situ precipitation and lateral supply of U-rich phosphorites from further upslope. Trace metal cycling on the Peruvian shelf is strongly affected by ENSO-related oxygen fluctuations in bottom water. During periods of shelf oxygenation, surface sediments receive particulate V and Mo with metal (oxyhydr)oxides that derive from both terrigenous sources and precipitation at the retreating oxycline. After the recurrence of anoxic conditions, metal (oxyhydr)oxides are reductively dissolved and the hereby liberated V and Mo are authigenically removed. This alternation between supply of particle-reactive trace metals during oxic periods and fixation during anoxic periods leads to a preferential accumulation of V and Mo compared to U on the Peruvian shelf. The decoupling of V, Mo and U accumulation is further accentuated by the varying susceptibility to re-oxidation of the different authigenic metal phases. While authigenic U and V are readily re-oxidized and recycled during periods of shelf oxygenation, the sequestration of Mo by authigenic pyrite is favored by the transient occurrence of oxidizing conditions.Our findings reveal that redox-sensitive trace metals respond in specific manner to short-term oxygen fluctuations in the water column. The relative enrichment patterns identified might be useful for the reconstruction of past OMZ extension and large-scale redox oscillations in the geological record.     

Geochemistry and Modes of Occurrence of Hazardous Trace Elements in the No. 11 Coal Seam, Antaibao Surface Mine, Shanxi Province

Concentrations of seventeen hazardous trace elements including As, Pb, Hg, Se, Cd, Cr, Co, Mo, Mn, Ni, U, V, Th, Be, Sb, Br and Zn in the No.ll coal seam, Antaibao surface mine, Shanxi Province were determined using Instrumental Neutron Activation Analysis （INAA）, Inductively Coupled Plasma Atomic Emission Spectrometry （ICP-AES）, Cold-Vapor Atomic Absorption Spectrometry （CV-AAS） and Graphite Furnace Atomic Absorption Spectrometry （GF-AAS）. Comparisons with average concentrations of trace elements in Chinese coal show that the concentrations of Hg and Cd in the No. 11 coal seam, Antaibao surface mine are much higher. They may be harmful to the environment in the process of utilization. The variations of the trace elements contents and pyritic suffur in vertical section indicated that： （a） the concentrations of As, Pb, Mn, and pyritic sulfur decrease from roof to floor; （b） the concentrations of Cr, Zn and Mo are higher in roof, floor and lower in coal seam; （c） the concentration of Br, Sb, and Hg are higher in coal seam and lower in roof and floor; （d） the concentrations of Mo, V, Th and AI vary consistently with the ash yield. Cluster analysis of trace elements, pyritic sulfur, ash yield and major elements, such as AI, Fe, P, Ca shows that： （a） pyritic sulfur, Fe, As, Mn, Ni, Be are closely associated and reflect the influence of pyrite; （b） Mo, Se, Pb, Cr, Th, Co, Ca and A! are related to clay mineral, which is the main source of ash; （c） U, Zn, V, Na, P maybe controlled by phosphate or halite; （d） Hg, Br, Sb and Cd may be mainly organic-associated elements which fall outside the three main groups. The concentration distribution characteristics of trace elements in coal seam and the cluster analysis of major and trace elements showed that the contents of trace elements in the No. 11 coal seam, Antaibao surface mine, are mainly controlled by detrital input and migration from roof and floor.     

Geological factors influencing the concentration of trace elements in the Philippi peatland, eastern Macedonia, Greece

Six peat samples obtained from the Holocene and the Weichselian of the Philippi peat deposit, eastern Macedonia, Greece, were analyzed for 48 trace elements by Inductively Coupled Plasma–Mass Spectrometry (ICP–MS). The ash contents of these samples were also determined. Most of the trace elements are associated with the minerals in the peat, while Ge, Mo, Pb, Se, Ta, Tl, U, and W display a greater affinity with the organic matter. Compared with crustal averages (Clarke concentrations), the Philippi peat is enriched in some elements (Ag, As, Au, Cd, Mo, Se, Te, U, and W) because of the respective mineralizations in the area. The Philippi peat is also enriched in Cr, Cu, Mo, Pb, Sc, Sn, T, V, Y, and Zn in comparison with typical fen peats, as well as in As, Cr, Mo, Se, and U in comparison with typical coals. Climatic and hydrogeological conditions strongly influenced the peat-forming environment resulting in a differentiation between Holocene and Weichselian peat. Generally, the Holocene peat contains lower concentrations of trace elements in the northern and southern part of the fen, than the Weichselian one. The opposite trend is observed in the fen area close to the western basin margins.     

广东三水盆地古近系(土布)心组地球化学特征及其所指示的氧化还原条件

古近系心组红岗段是广东三水盆地的主要生油层,以一套黑—灰黑色页岩沉积为主,其富含有机质、纹层理发育良好的岩层与相对贫有机质、含微体生物化石的微扰动层交替出现。根据纹层状页岩与生物扰动页岩的C-S-Fe关系以及对氧化还原条件敏感的痕量元素(Mo、U、V、Co、Ni、Pb和Cu)地球化学记录,对这两种不同岩相的地球化学特征及其所反映的水体氧化还原条件进行了分析。纹层状页岩的TOC、S含量和DOPT值均较高,TOC-S、TOC-DOPT显示较弱的相关性;而生物扰动页岩的TOC、S含量和DOPT值相对较低,TOC-S、TOC-DOPT相关性显著。痕量元素在两种岩相中的分布也有差别,各元素在纹层状页岩中的丰度均高于生物扰动页岩,尤其是Mo和U具有较高的丰度水平、且在不同岩相中显示明显差别。黑色页岩中的C-S-Fe关系和痕量元素(特别是Mo和U)分布反映了心组红岗段沉积时期湖盆水体的氧化还原条件变化。生物扰动页岩沉积期间,底部水体主要为氧化环境,间歇性出现贫氧条件,硫酸盐还原作用发生于沉积物/水界面及其以下沉积物中。纹层状页岩形成于缺氧的底部水体条件下,水体和沉积物中均可含H2S,为有机质保存以及对氧化还原条件敏感的痕量元素的富集提供了有利条件。     

The geochemistry of primary and weathered oil shale and coquina across the Julia Creek vanadium deposit (Queensland, Australia)

A significant resource of vanadium and molybdenum exists near Julia Creek, Australia, where the middle Cretaceous organic-rich Toolebuc Formation lies between 0 and 25 m of the surface. We present and discuss a comprehensive geochemical study of the Toolebuc Formation and its enclosing stratigraphy near Julia Creek to understand this ore deposit. V and Mo contents in fresh facies are strongly associated with total organic carbon (TOC) contents, but not with Al or CaCO₃; this suggests that V and Mo were originally concentrated in the organic fraction. However, chemical extractions using H₂O₂ indicate that Mo was originally concentrated in pyrite. The data also suggest that V was mobilised from organic matter during early diagenesis and became associated with clays as little V was extracted by H₂O₂ in the fresh samples. TOC contents in the Toolebuc Formation were removed during weathering, residually enriching trace metals including V and Mo, and as a result, the TOC relationship with V and Mo disintegrates. With weathering, both V and Mo predominantly became associated with iron oxide/hydroxide phases (and possibly other unidentified phases) as these elements in the weathered facies were highly soluble in the sodium citrate–sodium dithionite digestion. Large shale-hosted V and Mo deposits such as Julia Creek offer a potentially viable alternative to the currently mined magnetite-hosted deposits. A thorough understanding of the formation and host mineral phases for V and Mo of these shale deposits, however, is critical to ensure that these valuable metals can be feasibly extracted.     

A Late Hauterivian short-lived anoxic event in the Mediterranean Tethys: the ‘Faraoni Event’

A Late Hauterivian interval (127.5 Ma), called the ‘Faraoni Event’, which is characterised by the deposition of deep-marine black shales in the Mediterranean Tethys, is demonstrably of sufficient geological brevity to be qualified as an anoxic event. This event lies within the Pseudothurmannia catulloi ammonite subzone, coincides with the extinction of the calcareous nannofossil species Lithraphidites bollii, and records an increase in a globular planktonic foraminifer. High quantities of marine organic matter were preserved in pelagic successions from northern and central Italy, Switzerland, southeastern France, southern Spain and probably elsewhere in the Mediterranean Tethys and Atlantic Ocean. Carbon-isotope stratigraphy from Tethyan and Atlantic sections shows a minor positive excursion in the uppermost part of the Hauterivian and Lowermost Barremian, suggesting accelerated extraction of organic carbon from the ocean reservoir just after the ‘Faraoni Event’. The duration of this short event is less than 100 ka according to cyclostratigraphy and coincides with a third-order sea-level rise. It is likely that similar forcing mechanisms responsible for global OAEs operated during this short time interval. To cite this article: F. Baudin, C. R. Geoscience 337 (2005).     

Trace elements and their behaviour during the combustion of marine oil shale from Changliang Mountain, northern Tibet, China

The Shengli River–Changshe Mountain oil shale zone represents a potentially large marine oil shale resource in China. With the aim of better understanding the geochemistry of trace elements in marine oil shale and its combustion residues, 40 raw samples, 27 oil shale combustion residues and 29 selected minerals from Changliang Mountain oil shale are studied for geochemical analyses. The contents of Se, Cd, Mo, As, Cs, Pb, Sr and U in the oil shale samples are enriched from 1.47 to 33.91 times as compared with the Clarke values, whereas the concentrations of other elements are slightly higher/lower than the respective worldwide means. The most enriched elements in oil shale combustion residues are Se, Cd, Mo, As and U with enrichment values from 4.78 to 50.92. Trace elements with high volatile behaviour such as As, Co, Ni, Sc, Sn and V occur predominantly in organic matter and/or sulphides. Other non-volatile or slightly volatile trace elements (e.g., Be, Bi, Cs, Cu, Ga, Hf, Li, Nb, Rb, Ta, Th, W, Zr and REEs) may occur mainly in original and relatively refractory minerals in raw oil shale. The potentially hazardous trace elements in Changliang Mountain oil shale include As, Cd, Mo and Se. Arsenic and Se are controlled mainly by Fe-bearing minerals (probably pyrite) in Changliang Mountain oil shale. Cadmium is present mainly in dolomite, while Mo occurs mainly in organic matter.     

Trace elements in the Goze Delchev coal deposit, Bulgaria

The geochemistry of trace elements in the underground and open-pit mine of the Goze Delchev subbituminous coal deposit have been studied. The coals in both mines are highly enriched in W, Ge and Be, and at less extent in As, Mn and Y as compared with the world-wide Clarkes for subbituminous coals. Ni and Ti are also enhanced in the underground coals, and Zr, Cr and Mo in the open-pit mine coals.Characteristic for the trace element contents in the deposit is a regular variation with depth. The following patterns were distinguished for profile I: a — the element content decreases from the bottom to the top of the bed paralleling ash distribution (Fe, Co, As, Sb, V, Y, Mo, Cs, REE, Hf, Ta, Th, P and Au); b — Ge and W are enriched in the near-bottom and near-top coals; c — in the middle part of the bed the content of K and Rb is maximal, while that of U is slightly enriched; d — Ba content decreases from the top to the bottom of the bed. In profile II, W and Be contents decrease from the bottom to the top. The near-bottom, and especially the near-roof samples of profile IV are highly enriched in Ge, while for W the highest is the content of the near-bottom sample.Ge, Be, As, Mn, Cl and Br are mainly organically associated. The organic affiliation is still strong for Co, B, Sr, Ba, Sb, U, Th, Mo, La, Ce, Sm, Tb and Yb in the underground coals, and Fe, Co, Na, W, Sr, Y and Ag in the coals from the open-pit mine. K, Rb, Ti, Zr, Hf and Ta are of dominant inorganic affinity. The chalcophile and siderophile elements correlate positively with Fe and each other and may be bound partly with pyrite or other sulphides and iron containing minerals.Compared statistically by the t-criteria, the elements Na, Li, Cu, Zn, Pb, Cr, Ni, Co, Mo, Fe and Be are of higher content in the open-pit mine. Tungsten is the only element of higher concentration in the underground mine. The contents of Ge, As, Sr, V, Mn, Y, Zr and P are not statistically different in both mines.It was supposed that there were multiple sources of the trace elements in the deposit. The source of the highly enriched elements (W, Ge, Be, and As) most probably were the thermal waters in the source area. The contemporary mineral springs are of high content of these elements. Another source were the hosting Mesta volcanic rocks, which are enriched in Sb, Mo, Hf, U, Th, As, Li and Rb. Some of the volcanics were hydrothermally altered and enriched or depleted of many elements. Thus, the hydrothermal solutions were also suppliers of elements for the coals. It is obvious that the contents, distribution and paragenesis, of the trace elements in both Goze Delchev coals reflect the geochemical specialization of the source area, including rocks, paleo- and contemporary thermal waters.     

Trace- and rare-earth element geochemistry and Pb–Pb dating of black shales and intercalated Ni–Mo–PGE–Au sulfide ores in Lower Cambrian strata, Yangtze Platform, South China

The Lower Cambrian black shale sequence of the Niutitang Formation in the Yangtze Platform, South China, hosts an extreme metal-enriched sulfide ore bed that shows >10,000 times enrichment in Mo, Ni, Se, Re, Os, As, Hg, and Sb and >1,000 times enrichment in Ag, Au, Pt, and Pd, when compared to average upper continental crust. We report in this paper trace- and rare-earth-element concentrations and Pb–Pb isotope dating for the Ni–Mo–PGE–Au sulfide ores and their host black shales. Both the sulfide ores and their host black shales show similar trace-element distribution patterns with pronounced depletion in Th, Nb, Hf, Zr, and Ti, and extreme enrichment in U, Ni, Mo, and V compared to average upper crust. The high-field-strength elements, such as Zr, Hf, Nb, Ta, Sc, Th, rare-earth elements, Rb, and Ga, show significant inter-element correlations and may have been derived mainly from terrigenous sources. The redox sensitive elements, such as V, Ni, Mo, U, and Mn; base metals, such as Cu, Zn, and Pb; and Sr and Ba may have been derived from mixing of seawater and venting hydrothermal sources. The chondrite-normalized REE patterns, positive Eu and Y anomalies, and high Y/Ho ratios for the Ni–Mo–PGE–Au sulfide ores are also suggestive for their submarine hydrothermal-exhalative origin. A stepwise acid-leaching Pb–Pb isotope analytical technique has been employed for the Niutitang black shales and the Ni–Mo–PGE–Au sulfide ores, and two Pb–Pb isochron ages have been obtained for the black shales (531±24 Ma) and for the Ni–Mo–PGE–Au sulfide ores (521±54 Ma), respectively, which are identical and overlap within uncertainty, and are in good agreement with previously obtained ages for presumed age-equivalent strata.Editorial handling: R. Coveney Jr.     

Seasonal variations of Zn, Cu, As and Mo in arsenic-rich stream at the Mokrsko gold deposit, Czech Republic

Monthly sampling of slightly alkaline arsenic-rich stream in the Mokrsko gold deposit revealed seasonal variations in dissolved Zn, Cu, As and Mo. Concentrations of trace metal cations (Zn, Cu) increased as much as 330 and 178%, respectively, from minimum mean values at autumn to maximum mean values at spring. In contrast, concentrations of trace element oxyanions (As, Mo) revealed opposite seasonal pattern with increase to 189% (As) and 123% (Mo) during summer–autumn, indicating that in-stream biogeochemical process(es) played the main role in controlling the seasonal variations of these trace elements. The trace elements were mainly scavenged by low crystalline Mn oxyhydroxide and Fe oxyhydroxide (ferrihydrite). Results are consistent with sorption and coprecipitation processes controlling seasonal variations of dissolved Zn and Cu, while As and Mo dynamics appear linked to Mn redox reactions. The sorption processes and Mn redox processes are attributed to the changes of pH and oxic/anoxic conditions on the surface of oxyhydroxides, respectively, which are themselves controlled by the balance between photosynthesis and respiration. Under the geochemical conditions of the stream, inferred Mn redox reactions can only be explained by microbial activity.     

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.     

晋北-宁北煤中痕量元素的地球化学特征

应用仪器中子活化 (INAA)、电感耦合等离子体原子发射光谱 (ICP- AES)和原子吸收光谱 (AAS)等方法测定了晋北-宁北一线 5对矿井、 2个露天矿、 5个电厂和 3个洗煤厂煤中环境敏感性痕量元素的含量;通过与中国土壤、其他地区煤以及世界范围煤中痕量元素含量进行对比,总结了研究区痕量元素的分布、富集特征,得知部分地区煤中 Hg、 Cd和 Se的含量较高,在燃烧利用过程中可能对环境造成影响.通过分析痕量元素与灰分、挥发分的相关性以及痕量元素间、痕量元素与 Al、 Fe和 Sp的相关、聚类特性,探讨了痕量元素间及其与矿物质间的亲合性及赋存特征.     

Comparative geochemistry of shell phosphorites and dictyonema shales of the Baltic

Major and trace element composition of the Ordovician Obolus phosphorites and associated Dictyonema shales were determined by ICP-MS and chemical and microchemical elemental analyses. Relative to the phosphorites, the Dictyonema shales are substantially enriched in a variety of trace elements, except for As, Be, Co, Y, REE, Sr, and Pb. The Obolus phosphorites show enrichment of As, Bi, Hg, Mo, La, Y, Pb, and Sr and depletion of Ag, Ba, Be, Cd, Cr, Cu, Hf, Ni, Sc, Sn, U, V, Zn, and Zr relative to the world average phosphorite composition. The average trace element composition of the Dictyonema shales is close to the mean shale composition, except for higher contents of Mo, Hg, Pb, Se, Ta, Te, Th, V, and U and lower contents of Ba, Bi, Cd, Co, Re, Sr, and Zn. The results suggest that the change from phosphate sedimentation in aerated environments to anoxic carbonaceous sedimentation was accompanied by changes in the composition and concentration of trace elements in the sediment. Both facies show similar trends of trace element distribution indicative of the stability of the composition of seawater and terrigenous sediment input.