浙江省下寒武统荷塘组黑色页岩系地球化学特征

首次根据浙江省西北部荷塘组岩石样品的实测数据,提出了浙江省荷塘组黑色岩系6个岩性层的Pt、Pd、Au、Ag、Cu、As、Sb、Pb、Mo、Ni、V、P、U、B、Cd、Tl、Se、Zn元素的平均值,运用微量元素和稀土元素的配分模式探讨了成岩环境及元素高含量对环境的影响.荷塘组富集元素较多,富集程度高的有Mo、Se、Cd、Ag、Sb、U、As、P;较富集的有V、B、Cu、Tl、Zn,弱富集的为Au、Pt、Pb、Ni.综合地质地球化学特征研究认为,荷塘组黑色岩系具有寻找含钼、磷、矾和有色金属矿产的潜力.     

湘西北早寒武世黑色岩系微量元素地球化学特征

对湘西北杆子坪剖面牛蹄塘组黑色岩系进行了系统的微量元素地球化学研究，结果表明：牛蹄塘组底部黑色岩系Ni、Mo、V、U、Cu、Pb、Zn、Cd、Tl、Ba等亲硫元素与过渡元素高度富集，U／Th大于1，稀土元素具有明显的正Eu异常与正Y异常，是海底热水沉积作用的结果。牛蹄塘组上部碳质页岩与泥质页岩亲硫元素与过渡元素明显降低，而Nb、Ta、Zr、Hf、Rb等高场强与大离子元素明显增高，表明陆源碎屑来源越来越多。     

黔北地区下寒武统底部黑色页岩沉积环境条件与源区构造背景分析

为了深入探讨黔北地区下寒武统底部黑色页岩的沉积环境条件和源区构造背景,对黔北地区下寒武统牛蹄塘组黑色页岩进行系统采样,对其微量元素和稀土元素地球化学特征进行了系统分析。研究表明,微量元素中高的WV/(WNi+WV)和U/Th比值等反映该区黑色页岩形成于海域开阔的还原环境。区内黑色页岩样品中Mo、Sb、U、Cd、 V、Ba、Tl、Ni、W、 Cr、Cs、Cu、Zn、Bi等元素的高富集以及正Eu异常和较低的Co/Zn比值均反映了黔北下寒武统底部黑色页岩受到深部热液活动的影响。根据主、微量和稀土元素组合及比值特征可以看出黔北地区下寒武统底部黑色页岩的源岩具有花岗岩、沉积岩和玄武岩等多成因性质。源区构造背景以被动大陆边缘为主,由于受深部热液活动的影响,也显示大陆岛弧构造背景的特征。     

黑色页岩与土壤重金属污染

本文利用ICP—MS等技术分析了湘中地区黑色页岩及其相应土壤的重金属含量,在对分析结果进行统计分析的基础上,探讨了黑色页岩与土壤重金属污染的关系。研究表明,黑色页岩是富集多种重金属元素的特殊岩石。以黑色页岩岩系为母岩的土壤,不仅明显富集Cu、Cd、Cr、Co、Pb、Zn、Mo、Ni、V、U、Sn、Sb、T1、Th等多种重金属元素,而且受到Mo、Sb、Cd、U、Tl、Cu、V、Sn、Th等重金属的污染,其中以Mo、Cd、Sb、U、Tl等的污染尤为严重。黑色页岩土壤重金属污染在一些地方已产生明显的负面环境效应,值得关注。     

遵义牛蹄塘组黑色岩系中多元素富集层的主要矿化特征

在对大量数据进行系统分析的基础上，将贵州遵义下寒武牛蹄塘组黑色岩系中多元素富集层矿化元素按富集系数分为三组。超富集元素：富集系数大于1000，包括Mo、As、Se、Re等；强富集元素：富集系数介于100～1000，包括Ni、U、Au、Ag、Pt、Pd、Tl等；弱富集元素：富集系数近于5～100，包括V、Co、Cu、Pb、Zn、Y、Cd等。结合上述元素的地球化学性质和矿化岩石类型，指出贵州牛蹄塘组多元素富集层综合了岩浆作用、热水沉积和机械沉积作用的特点，是深部岩浆活动强烈喷发期的产物，提出了可能的成矿模式：早期岩浆(火山)活动伴随热水沉积，形成磷块岩(和硅质岩)；中期岩浆活动减弱，表现为剥蚀沉积；晚期火山爆发，除大量射气元素的富集，还带出深部的成矿物质，然后通过水流机械富集成矿。     

广西373铀矿床微量元素地球化学特征及其成因探讨

373铀矿床是我国南方典型碳硅泥岩型铀矿床之一,主要发育一套黑色弱硅化泥岩、粉砂岩,硅化生屑灰岩及其过渡型岩类地层,矿床明显受断裂发育影响,铀矿化于次级断裂带中.通过系统地球化学研究表明:3组不同期次脉体普遍亏损过渡元素Ti、Sc、Cr、Cu、Zn和高场强元素Nb、Ta、Zr和Hf;相对较富集Mn、Ni、As、Sr、Mo、Sb、Tl和U等微量元素.后期热液活动使脉体Ba、Sb、As和Mo等元素异常富集.后期热液叠加改造,使得岩石普遍亏损过渡元素Sc、Ti、Cr和高场强元素Nb、Ta、Zr、Hf,普遍富集Co、Ni、Zn、As、Sb、Mo、Cd、W、Tl、Pb、Bi和U,其中As、Sb、Mo、Tl和U尤为富集,富集系数平均达到100左右,U与W、As、Sb和Pb相关系数都在0.9左右,具有高度同源性,铀成矿与热液活动有关.典型剖面微量元素富集与硅化密切相关,当硅化达到一定程度后微量元素富集出现反转,即随着硅化强度增加而富集能力反而降低.V/Cr、V/Sc、Ni/Co、V/(V+Ni)、U/Th、δU、δEu和δCe等特征元素比值反应铀预富集形成于缺氧的古海洋环境.高丰度的As、Sb和Ba等元素,以及U-Th关系图解和Zn-Ni-Co三元图解均显示热水沉积成因.微量元素特征表明碳硅泥岩形成于缺氧的还原环境,铀预富集与热水沉积有关,铀成矿与热液叠加改造有关,后期热液沿运移通道上升进入储集空间,与铀预富集地层热液叠加成矿.     

贵州开阳磷矿地区下寒武统牛蹄塘组地层层序及其As、Sb、Au、Ag丰度异常与赋存状态研究

贵州开阳磷矿地区出露较为完整的下寒武统黑色岩系层序,这套黑色岩系中富含多种金属元素,但目前对岩系中主要低温成矿元素As、Sb、Au、Ag的地球化学背景异常与分布规律了解极少,对其形成背景与赋存状态无法进行深入讨论。本文以开阳磷矿地区下寒武统牛蹄塘组黑色岩系剖面作为研究对象,通过详细的野外地质调查、系统采样并进行地球化学分析、全岩硫同位素分析及黄铁矿电子探针分析,划分了详细的牛蹄塘组地层层序,对主要低温成矿元素(As、Sb、Au、Ag)的丰度异常、富集特征及赋存状态进行了研究,结果表明,黑色岩系中普遍富集As、Sb、Ag三种主要低温成矿元素,Au也在大部分层位富集。四种元素具有层控性的特点,在牛蹄塘组下部有机质含量较高的黑色白云质粉砂质页岩和黑色页岩层位中具有较高的元素丰度异常,在泥岩和粉砂岩混合层位元素丰度异常较低,钙质成分含量较高的层位元素含量较低。黄铁矿是黑色页岩中金的主要赋存矿物,也是Sb的重要赋存矿物,同时是Ag和As的次要赋存矿物;不同类型的黄铁矿,元素富集规律也不相同:As、Ag更容易富集在不规则集合体和草莓状黄铁矿中,Sb和Au则在散布的单颗粒黄铁矿中富集系数最高。     

湘中安化黑色页岩土壤玉米的元素地球化学分析

利用等离子质谱(ICP-MS)等分析技术,对产于安化东坪、烟溪黑色页岩土壤上的玉米进行元素地球化学分析.结果.表明:尽管东坪、烟溪黑色页岩土壤重金属元素富集的程度及其元素组合特征明显不同,但生长在其上的玉米有相似的主量元素和重金属元素的富集特征.玉米中Cd、Cr、Sc、Tl、Zn等重金属相对富集,以Cd的富集尤为明显;而Ba、Co、Cu、Fe、Mo、Ni、Pb、Sb、U、V等重金属相对亏损.黑色页岩土壤重金属污染的环境地球化学效应表现为Sc、Cr、Cd、Tl等生物毒性重金属元素在玉米中富集,而Ba、V、Co、Ni、Mo、Rb、Sr等生物必需微量金属在玉米中亏损.     

云南德泽下寒武统黑色岩系中Ni-Mo-V-PGE多金属矿化

云南省德泽地区筇竹寺组黑色岩系位于扬子陆块南缘下寒武统黑色页岩分布带的西端, 不同于该带中段湘黔地区的牛蹄塘组, 它发育有两个多金属富集层位, 其中, 石岩头段黑色碳质粉砂岩底部富集V、U、Ag和Pd, 玉案山段黑色页岩底部富集Mo、Ni、Pt和Pd.筇竹寺组黑色岩系整体上富集V-Ni-Mo-U-Ag-Pt-Pd, 而牛蹄塘组黑色岩系则富Ni-Zn-Co-Pt-Pd-Ag-Pb, 但它们都经历了相似的缺氧环境, 且具有相同的PGE和Ni、Mo富集机制, 是一种重要的非传统矿产资源类型.      

湘中HJC铀矿区黑色页岩土壤重金属污染地球化学分析

本文以湘中HJC铀矿区黑色页岩土壤为研究对象,对黑色页岩土壤重金属污染进行了地球化学分析。通过测制A、B、C、D等土壤剖面并系统取样,借助ICPMS等分析技术,对土壤、成土母岩、玉米等进行了系统的主量元素、重金属和其他微量元素（稀土元素）分析。结果表明,矿区黑色页岩土壤具富Al2O3、Fe2O3,而贫CaO、Na2O的化学组成特征,其化学风化指数CIA值在79~84之间。土壤因继承成土母岩的元素富集特征而富集V、Cr、Co、Ni、Cu、Zn、Mo、Cd、Sn、Sb、Tl、Pb、Th、U等多种重金属,其中Mo、Cd、Sb、U的富集最强。土壤重金属综合富集指数（EI值）在3~9之间,各剖面EI值大小顺序是：D>A>B>C, 以D剖面土壤重金属综合富集最强。土壤重金属污染富集因子（F）评价结果显示：矿区土壤普遍存在Cd、Mo、Sn、Sb、U等重金属污染,其中Mo、Cd、Sb等的污染最强,达显著（3级,2 < F < 20）污染程度以上。重金属污染效应既表现为Sc、Cd、Sn、Sb、U、Tl、Pb等生物毒性重金属在玉米中的富集,又表现为Mo、Co、Ni、Cu、Zn等生物有用金属在玉米中的明显亏损。黑色页岩即为土壤重金属污染的污染源。土壤重金属污染与重金属在成土母岩和土壤中的富集程度(Ks、EI、F)、重金属的活动性（Change%）等多种因素有关。重金属污染主影响因子的Pearson相关系数分析显示：Cd对土壤构成持久性污染,Mo、Sn、Sb、U等的污染程度可随土壤风化的进行因淋失而趋于降低,而Zn、Mn、Ba、Co、Ni、Th等目前未达到污染水平的重金属则可因次生富集而在未来引发污染。     

The Trace Element Distribution Patterns of Ediacaran-Early Cambrian Black Shales and the Origin of Selenium in the Guangning Area, Western Guangdong Province, South China

The Ediacaran and early Cambrian black shales are widespread across the South China Craton (Yangtze and Cathaysia blocks). However, the trace element distribution patterns of the Ediacaran and early Cambrian black shales in the Cathaysia Block are still unclear. In this study, thirty-four black shale samples in the Lechangxia Group (Ediacaran) and thirteen black shale samples in the lower Bacun Group (early Cambrian) from Guangning area, western Guangdong Province, South China, were analyzed for major and trace elements concentrations. Compared to the upper continental crust, the Ediacaran black shales exhibit strongly enriched Se, Ga, and As with enrichment factor values (EF) higher than 10, significantly enriched Bi and Rb (10>EF>5), weakly enriched Mo, Ba, Cs, V, In, Be, Tl, and Th (5>EF>2), normal U, Cr, Cd, Sc, Pb, Cu, and Li (2>EF>0.5), and depleted Ni, Zn, Sr, and Co. Early Cambrian black shales display strongly enriched Se, Ga, and As, significantly enriched Ba, Bi, and Rb, weakly enriched Mo, Cs, Cd, V, U, Be, In, and Tl, normal Sc, Th, Cr, Li, Cu, Ni, and Pb and depleted Co, Zn, and Sr. Moreover, Se is the most enriched trace element in the Ediacaran and early Cambrian black shales: concentrations vary from 0.25 to 30.09 ppm and 0.54 to 5.01 ppm, and averaging 4.84 and 1.72 ppm, with average EF values of 96.87 and 34.32, for the Ediacaran and early Cambrian shales respectively. The average concentration of Se in the Ediacaran black shales is 2.8 times higher than that of early Cambrian black shales. Se contents in the Ediacaran and early Cambrian black shales exhibit significant variation (P = 0.03). Provenance analysis showed that Se contents of both the Ediacaran and early Cambrian black shales were without detrital provenance and volcanoclastic sources, but of hydrothermal origin. The deep sources of Se and the presence of pyrite may explain the higher Se contents in the Ediacaran black shales. Similar with the Se-rich characteristics of the contemporaneous black shales in the south Qingling Mountain and Yangtze block, the Ediacaran and early Cambrian black shales in Guangning area, Cathaysia, are also enriched in Se, which may provide a clue for looking for the selenium-rich resources in western Guangdong Province.     

Chemistry and Sulfur Isotopes in a Chert-dominant Sequence around the Stratiform Manganese Deposit of the Noda-Tamagawa Mine, Northern Kitakami Terrane, Northeast Japan: Implication for Paleoceanographic Environmental Setting

Abstract. Chemistry and sulfur isotopes are analyzed for a series of rocks in the chert‐dominant sequence around the stratiform manganese ore deposit of the Noda‐Tamagawa mine in the northern Kitakami Terrane, northeast Japan. The sequence is litholog‐ically classified into six units in ascending order: lower bedded chert, lower black shale, massive chert, manganese ore, upper black shale, and upper bedded chert. The rocks around the manganese ore deposit exhibit anomalous enrichment in Ni (max. 337 ppm), Zn (102) and U (30) in the upper part of lower bedded chert, Mo (122), Tl (79) and Pb (33) in the lower black shale, MnO, Cu (786) and Co (62) in the manganese ore, and As (247) and Sb (17) in the upper black shale. The aluminum‐normalized profiles reveal zonal enrichment of redox‐sensitive elements around the manganese bed: Zn‐Ni‐Fe‐Mo‐U(‐Co), Tl‐Pb(‐Mo), Mn‐Fe‐Cu‐V‐Cr‐Co(‐Zn) and As‐Sb in ascending order. The uppermost part of the lower bedded chert and black shale exhibit negative Ce/Ce* values, whereas the massive chert, manganese ore and lower part of the upper bedded chert display positive values. The isotopic δ³⁴S values are 0±6 % in the lower part of the lower bedded chert, ‐19 to ‐42 % in the upper part of the lower bedded chert, ‐36 to ‐42 % in the lower black shale, ‐28 to ‐35 % in the massive chert, manganese ore and upper black shale, and ‐23±5 % in the upper bedded chert. Thus, there is a marked negative shift in δ³⁴S values in the lower bedded chert, and an upward‐increasing trend in δ³⁴S through the manganese ore horizon. The present data provide evidence for a change in the paleoceanographic environmental resulting from inflow of oxic deepwater into the stagnant anoxic ocean floor below the manganese ore horizon. This event is likely to have triggered the precipitation of manganese oxyhydroxides. The redistribution of redox‐sensitive elements through the formation of metalliferous black shale and manganese carbonate ore may have occurred in association with bacterial decomposition of organic matter during early diagenesis of initial manganese oxyhydroxides.     

Metal sources for the polymetallic Ni–Mo–PGE mineralization in the black shales of the Lower Cambrian Niutitang Formation,South China

Total organic carbon content (TOC), trace element and platinum-group element (PGE) concentrations were determined in the black shales of the Lower Cambrian Niutitang Formation in the Nayong area, Guizhou Province, South China, in order to study the polymetallic Ni–Mo–PGE mineralization. The results demonstrate that numerous elements are enriched in the polymetallic ores compared to those of the nearby black shale, particularly Ni, Mo, Zn, TOC and total PGE, which can reach up to 7.03 wt.%, 8.49 wt.%, 11.7 wt.%, 11.5 wt.% and 943 ppb, respectively. The elemental enrichment distribution patterns are similar to those in the Zunyi and Zhangjiajie areas except that the Nayong location is exceptionally enriched in Zn. Whereas positive correlations are observed between the ore elements of the polymetallic ores, no such correlations are observed in the black shale. These positively correlated metallic elements are classified into three groups: Co–Ni–Cu–PGE, Zn–Cd–Pb and Mo–Tl–TOC. The geological and geochemical features of these elements suggest that Proterozoic and Early Palaeozoic mafic and ultramafic rocks, dolomites and/or Pb–Zn deposits of the Neoproterozoic Dengying Formation and seawater could be the principal sources for Co–Ni–Cu–PGE, Zn–Cd–Pb, and Mo–Tl–TOC, respectively. Furthermore, the chondrite-normalized patterns of PGEs with Pd/Pt, Pd/Ir and Pt/Ir indicate that PGE enrichment of the polymetallic ores is most likely related to hydrothermal processes associated with the mafic rocks. In contrast, PGE enrichment in the black shale resembles that of the marine oil shale with terrigenous and seawater contributions. Our investigations of TOC, trace elements and PGE geochemistry suggest that multiple sources along with submarine hydrothermal and biological contributions might be responsible for the formation of the polymetallic Ni–Mo–PGE mineralization in the black shales of the Lower Cambrian Niutitang Formation across southern China.     

湘西北下寒武统黑色岩系钒镍钼矿微量元素地球化学

湘西北下寒武统黑色岩系是中国南方下寒武统黑色岩系的重要组成部分,富含钒镍钼等多金属元素。文中对湘西北下寒武统黑色岩系钒镍钼矿进行了微量元素研究,研究区内Ni、Cd、Mo、Sb、V、Zn、W、Ba等元素特别富集,高含量的Sb和Ba表明其为热水沉积;Mo含量极高说明其为缺氧的还原环境;高的V/（V+Ni）、V/Cr、Ni/Co以及δU值表明其沉积环境为缺氧环境;高的 U/Th表明本区有热水沉积作用;稀土元素配分模式、Ce和Eu异常及La/Yb Ce/La和La/Yb ΣREE图解投点表明其沉积环境为还原环境,并有热水沉积作用。可见黑色岩系形成于缺氧环境,热液活动为其提供了丰富的热液来源。     

Trace Elements and Rare Earth Elements of Sulfide Minerals in the Tianqiao Pb-Zn Ore Deposit, Guizhou Province, China

Trace elements and rare earth elements (REE) of the sulfide minerals were determined by inductively-coupled plasma mass spectrometry. The results indicate that V, Cu, Sn, Ga, Cd, In, and Se are concentrated in sphalerite, Sb, As, Ge, and Tl are concentrated in galena, and almost all trace elements in pyrite are low. The Ga and Cd contents in the light-yellow sphalerites are higher than that in the brown and the black sphalerites. The contents of Ge, Tl, In, and Se in brown sphalerites are higher than that in light-yellow sphalerites and black sphalerites. It shows that REE concentrations are higher in pyrite than in sphalerite, and galena. In sphalerites, the REE concentration decreases from light-yellow sphalerites, brown sphalerites, to black sphalerites. The ratios of Ga/In are more than 10, and Co/Ni are less than 1 in the studied sphalerites and pyrites, respectively, indicating that the genesis of the Tianqiao Pb–Zn ore deposit might belong to sedimentary-reformed genesis associated with hydrothermal genesis. The relationship between LnGa and LnIn in sphalerite, and between LnBi and LnSb in galena, indicates that the Tianqiao Pb–Zn ore deposit might belong to sedimentary-reformed genesis. Based on the chondrite-normalized REE patterns, δEu is a negative anomaly (0.13–0.88), and δCe does not show obvious anomaly (0.88–1.31); all the samples have low total REE concentrations (<3 ppm) and a wide range of light rare earth element/high rare earth element ratios (1.12–12.35). These results indicate that the ore-forming fluids occur under a reducing environment. Comparison REE compositions and parameters of sphalerites, galenas, pyrites, ores, altered dolostone rocks, strata carbonates, and the pyrite from Lower Carboniferous Datang Formation showed that the ore-forming fluids might come from polycomponent systems, that is, different chronostratigraphic units could make an important contribution to the ore-forming fluids. Combined with the tectonic setting and previous isotopic geochemistry evidence, we conclude that the ore-deposit genesis is hydrothermal, sedimentary reformed, with multisources characteristics of ore-forming fluids.     

贵州省白马洞铀矿床地球化学特征及成因

白马洞铀矿床是一个铀、汞、钼多金属热液矿床,处于黔中侏罗山式褶皱带,近EW向白马洞深断裂上盘。区内热液活动明显,围岩蚀变强烈,铀、汞、钼矿体赋存在中寒武统高台组页岩上、下层间角砾岩带中。本文简要介绍地质背景、成矿特征,重点论述了地球化学特征及成因,为今后在省内深入研究碳硅泥岩型铀矿成矿规律和指导深部找矿起帮助作用。     

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

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

Multiple Sources of Metals of Mineralization in Lower Cambrian Black Shales of South China: Evidence from Geochemical and Petrographic Study

Black shales of the Lower Cambrian Niutitang Formation in southern China (Huangjiawan mine, Zunyi region, northern part of the Guizhou Province) host regionally distributed stratiform polymetallic Ni‐Mo‐platinum group elements (PGE)‐Au phosphate‐ and sulfide‐rich ores. These are confined to a ≥0.2‐m thick ore horizon composed of mineralized bodies of algal onkolites, phosphate nodules, and sulfide and shale clasts in a mineralized phosphate‐ and organic matter‐rich matrix. Compared to footwall and hanging wall shales, the ore bed is strongly enriched in Ni (up to 100‐fold), As (up to 97‐fold), Mo (up to 95‐fold), Sb (up to 67‐fold), Rh (up to 49‐fold), Cu (up to 37‐fold), Pd (up to 33‐fold), Ru (up to 24‐fold), Zn (up to 23‐fold), Pt (up to 21‐fold), Ir (up to 15‐fold), Co (up to 14‐fold), and Pb (up to 13‐fold). Even footwall and hanging wall black shales are significantly enriched by Mo (21‐fold) and Ni (12‐fold) but depleted in Cr in comparison to average Cambrian black shale. Organic matter is represented by separate accumulations dispersed in the rock matrix or as biotic bitumen droplets and veinlets in ore clasts. Similar organic carbon (C_org) values in an ore bed and enclosing footwall and hanging wall shales of little mineralization indicate that metal accumulation was not controlled only by biogenic productivity and organic matter accumulation rate. Evaporitic conditions during sedimentation of the basal part of the Niutitang Formation were documented by an occurrence of preserved Ni‐, V‐, Cr‐, and Cu‐enriched phosphate‐rich hardground with halite and anhydrite pseudomorphs on the paleosurface of the underlying Neoproterozoic carbonates. Neoproterozoic black shales of the Doushantuo Formation are characterized by increased metal concentrations. Comparison of metal abundances in both hardground and Doushantuo black shales indicate that black shales could have become a source of metal‐rich hardground during weathering. The polymetallic Ni‐Mo‐PGE sulfide‐rich ore bed is interpreted to represent a remnant of shallow‐water hardground horizon rich in metals, which originated in a sediment‐starved, semi‐restricted, seawater environment. During the Early Cambrian transgression an influx of fresh seawater and intensive evaporation, together with the hydrothermal enrichment of seawater in a semi‐restricted basin, resulted in the formation of dense metalliferous brines; co‐precipitation of metals together with phosphates and sulfides occurred at or above the oxic–anoxic sediment interface. Metal‐enriched hardground was disintegrated by the action of waves or bottom currents and deposited in a deeper part of the anoxic basin. Contemporaneously with the formation of a polymetallic Ni‐Mo‐PGE‐Au sulfide ore bed, economic sedimentary exhalative (SEDEX)‐type barite deposits were forming in a stratigraphically and geotectonically similar setting. The results of geochemical study at the Shang Gongtang SEDEX‐type Ba deposit indicate that concentrations of Ag, As, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V, Zn and other metals decrease from top of the barite body toward the hanging wall black shale. Lower Cambrian black shales of the Niutitang Formation above the barite body also display similar element abundances as Neoproterozoic black shales of the Doushantuo Formation, developed in the footwall of the barite body. But the geochemical composition of the sulfide layer is different from the Ni‐Mo ore bed, showing only elevated Pb, Cu, Ni and Mo values. It is suggested that hydrothermal brines at Shang Gongtang might have leached metals from footwall Neoproterozoic sequences and became, after mixing with normal seawater, an additional source of Ag, Cr, Cu, Pb, Sb, Zn, Ni, PGE, V and other metals.     

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.