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.     

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 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.     

滇东南都龙超大型锡锌多金属矿床黄铁矿LA-ICPMS微量元素组成研究

滇东南马关都龙是一个以锡锌为主,共-伴生铟、铜、铅、钨、铁、银等多种元素的锡锌多金属超大型矿床。虽然前人从矿物学、矿床地球化学、年代学等不同角度开展了较多的研究,该矿床锡锌多金属矿化为燕山晚期岩浆热液活动的产物已是不争的事实,但关于该矿床是否存在热水沉积作用及其与锡锌多金属成矿作用的关系依然存在较大争议。本文选取都龙矿区广泛存在的黄铁矿作为主要研究对象,在矿相学基础上利用LA-ICPMS对不同阶段黄铁矿的微量元素组成开展了系统的研究。野外及显微鉴定结果表明,矿区存在四种类型(期次)的黄铁矿,即:鲕状黄铁矿Py1;穿切或交代Py1的细脉状黄铁矿Py2;与闪锌矿等硫化物共生的自形黄铁矿Py3;包裹早期黄铁矿或闪锌矿等硫化物的他形黄铁矿Py4。LA-ICPMS分析结果表明,该矿床黄铁矿中富集多种微量元素,其中Co、Ni、As、Ge等元素以类质同象的形式存在黄铁矿晶格中,而其余元素多以显微矿物包体形式赋存于黄铁矿中。上述四期黄铁矿微量元素组成存在较大差别,Py1相对富集Zn和As,而其余微量元素含量较低,Co与Ni含量较低,Co/Ni比值远低于1.00,其微量元素组成与典型沉积作用形成黄铁矿基本一致; Py2与Py1具有相似的微量元素组成特征,其Co/Ni比值接近Py1变化范围; Py3和Py4除富集Zn、As外,Mn、Co、Ni、Cu、Sb、Pb、Bi元素含量也相对较高,其Co/Ni比值相对较高,多大于1,与典型岩浆热液型黄铁矿微量元素组成相似,而与沉积型黄铁矿差异明显。结合各阶段黄铁矿产出地质特征,对比不同类型黄铁矿微量元素组成,本研究认为:Py1鲕状黄铁矿为热水沉积作用形成; Py2为Py1变质改造形成的细脉状黄铁矿,其微量元素继承了Py1; Py3为岩浆热液活动形成的自形黄铁矿; Py4为岩浆热液活动晚期形成的他形黄铁矿,Ag和Bi组成作为区分不同成因类型黄铁矿的化学指标的潜力。矿区早期沉积作用形成鲕状黄铁矿过程可能为后期成矿作用提供了部分硫源及少量Zn等成矿物质,海西-印支期区域变质改造作用对矿区成矿作用影响不大,而燕山晚期岩浆热液活动才是矿区锡多金属大规模成矿作用的主导因素。     

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.     

Geochemistry and mineralogy of marine and non-marine Namurian black shales from the Tansley Borehole, Derbyshire

The Namurian black shales studied have a good palaeontological control. Pyrite, illite and organic matter are higher in the marine shales, and siderite and kaolinite are higher in the non-marine shales. The distribution of the diagenetic iron minerals is attributed to anionic activities controlled by salinity. The same control could account for the observed clay-mineral distribution by differential flocculation. The major element geochemistry closely reflects the above mineral variation. Mn and Zr are higher in the non-marine shales due to siderite and zircon respectively. Co, Cr, Rb, Y and Ba are not significantly different and a detrital source, mainly clay minerals, is suggested. In the marine shales the elements Pb, Cu, V, Ni, Sr and Zn are significantly higher. Using a discriminant function analysis the palaeosalinity groups are separated and the contribution of each element to the separation is calculated. The present element locations are thought, from correlation analysis, to be pyrite and organic matter. By analogy with experimental work and modern environments, the element enrichment is mainly attributed to reactions involving organic matter and oxyhydroxide material in environments in which salinity and slow rates of sedimentation were important factors. The element enrichment cannot be related directly to seawater concentrations, unlike some black shales, and the accumulation rates for Pb and Cu are thought to be unusually high.     

Determination of elemental affinities by density fractionation of bulk coal samples from the Chongqing coal district, Southwestern China

The occurrence and distribution of major and trace elements have been investigated in two coal-bearing units in the Chonqing mining district (South China): the Late Permian and Late Triassic coals.The Late Permian coals have higher S contents than the Late Triassic coals due to the fixation of pyrite in marine-influenced coal-forming environments. The occurrence of pyrite accounts for the association of a large number of elements (Fe, S, As, Cd, Co, Cu, Mn, Mo, Ni, Pb, Sb, Se, and Zn) with sulphides, as deduced from the analysis of the density fractions. The marine influence is probably also responsible for the organic association of B. The REEs, Zr, Nb, and Hf, are enriched by a factor of 2–3 with respect to the highest levels fixed for the usual worldwide concentration ranges in coal for these elements. The content of these elements in the Late Permian coal is higher by a factor of 5–10 with respect to the Late Triassic coal. Furthermore, other elements, such as Cu, P, Th, U, V, and Y, are relatively enriched with respect to the common range values, with maximum values higher than the usual range or close to the maximum levels in coal. The content of these elements in the Late Permian coal is higher than the Late Triassic coal. These geochemical enrichments are the consequence of the occurrence, in relatively high levels, of phosphate minerals, such as apatite, xenotime, and monazite, as deduced from the study of the density fractions obtained from the bulk coal.The Late Triassic coal has a low sulphur content with a major organic affinity. The trace element contents are low when compared with worldwide ranges for coal. In this coal, the trace element distribution is governed by clay minerals, carbonate minerals, and to a lesser extent, by organic matter and sulphide minerals.Major differences found between late Permian and Triassic coals are probably related to the source rocks, given that the main source rock of the late Permian epicontinental marine basin is the Emeishan basalt formation, characterised by a high phosphate content.     

Trace-element distribution and ore formation in vein-metasomatised peridotite at Kalskaret,near Tafjord,South Norway

The concentration profiles of the trace elements, S, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Sr, and Y have been determined across a metasomatic vein in peridotite. The introduced elements Ti, V, Sr, and Y show specific enrichment in particular silicate phases in accordance with the availability of suitable lattice sites. In contrast, the other introduced trace elements (Cu and S) behave more like the redistributed elements, Cr, Ni, Mn, and Co which do not show concentration ‘fronts’ that can be simply related to the silicate minerals. Concentration of pentlandite, chalcopyrite, and Cr-magnetite near the boundary between the enstatite and anthophyllite zones gives rise to maxima in the Ni, Cu, S, and Cr distributions, while in the chlorite zone significant concentrations of Cr and Ni occur in the chlorite itself. Control of the distribution of Ni, Cu, and Cr is ascribed to the oxidation/reduction reactions involved in the formation of pentlandite, chalcopyrite and Cr-magnetite, together with the critical role of Al in limiting chlorite formation during metasomatism.     

The determination of minor and trace element associations in coal using a sequential microwave digestion procedure

A sequential extraction procedure, using acid digestion in a CEM MDS-81D® microwave system, is reported for the investigation of trace and minor element associations in coal in (1) mineral phases other than pyrite, (2) pyrite and (3) the organic matrix. The concentrations of sulphate, pyrite and organic sulphur can also be determined by this method. The extract solutions from each stage are rapidly analysed by ICP-AES. The association of major, minor and trace elements with mineral and organic phases is suggested for a suite of certified reference coal samples. In stage 1, a significant percentage of the total Ba, Co, Cr, Cu, Mn, Ni, Pb and Sr was extracted suggesting an association with silicate, carbonate, sulphate and phosphate minerals for these elements. In stage 2, a proportion of the Cu, Mn, Ni, Pb and Zn was dissolved implying the occurrence of these elements in pyrite. An association with the organic matrix is suggested for Cr and also for Ba and Sr in lower rank coals.     

Trace Element Geochemistry of Magnetite from the Fe(-Cu) Deposits in the Hami Region, Eastern Tianshan Orogenic Belt, NW China

Laser ablation–inductively coupled plasma–mass spectrometry(LA–ICP–MS) was used to determine the trace element concentrations of magnetite from the Heifengshan, Shuangfengshan, and Shaquanzi Fe(–Cu) deposits in the Eastern Tianshan Orogenic Belt. The magnetite from these deposits typically contains detectable Mg, Al, Ti, V, Cr, Mn, Co, Ni, Zn and Ga. The trace element contents in magnetite generally vary less than one order of magnitude. The subtle variations of trace element concentrations within a magnetite grain and between the magnetite grains in the same sample probably indicate local inhomogeneity of ore–forming fluids. The variations of Co in magnetite between samples are probably due to the mineral proportion of magnetite and pyrite. Factor analysis has discriminated three types of magnetite: Ni–Mn–V–Ti(Factor 1), Mg–Al–Zn(Factor 2), and Ga– Co(Factor 3) magnetite. Magnetite from the Heifengshan and Shuangfengshan Fe deposits has similar normalized trace element spider patterns and cannot be discriminated according to these factors. However, magnetite from the Shaquanzi Fe–Cu deposit has affinity to Factor 2 with lower Mg and Al but higher Zn concentrations, indicating that the ore–forming fluids responsible for the Fe–Cu deposit are different from those for Fe deposits. Chemical composition of magnetite indicates that magnetite from these Fe(–Cu) deposits was formed by hydrothermal processes rather than magmatic differentiation. The formation of these Fe(–Cu) deposits may be related to felsic magmatism.     

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.     

Behaviour of the trace elements in a front of metasomatic-metamorphism in the Dalradian of Co. Donegal

The epidioritc and quartzite of the Malin Head district, (Ireland) are considered by Holmes and Reynolds [7] to be metasomatically transformed into skarn-rocks and mica-schist respectively. The trace element contents of these rocks were investigated using semi-quantitative methods in order to study the behaviour of the different trace elements during the metasomatic changes which have taken place. The elements which have been determined are Rb, Ba, Ag and Pb; Sr, Y and La; Li, Cr, Ni, Co, V, Cu, Sc, Sn and Mo; Ga; Zr, Be, Tl, Ge and In. The trace elements follow the major elements for which they can substitute in favourable crystal lattices, the substitution being in accord with Goldschmidts rules. Rb, Ba and probably Pb and Ag follow and substitute for K; Sr and Y for Ca and probably K; Li, Cr, Ni, Co, V, Cu, Sc, Sn and Mo for Mg, Fe² and Fe³; and Ga for Al.     

Abundance, Sources and Speciation of Trace Elements in Humus-Rich Streams Affected by Acid Sulphate Soils

The behaviour of trace elements (Al, As, Cd, Co, Cr,Cu, Fe, Mn, Ni, V, Zn) was studied in five humus-richstreams (dissolved organic carbon = 14–40 mg/L)impacted by acid sulphate soils developed in marinesulphide-bearing fine-grained sediments. During heavyrainfalls in autumn, on which the study focusses, themetals Al, Cd, Co, Cu, Mn, Ni and Zn are extensivelyleached from these acidic soils (pH = 2.5–4.5), whileAs, Cr, Fe and V are not leached more strongly fromthis soil type than from areas of till and peat. Aspeciation experiment, based on anion and cationexchange of the stream waters in the field, showedthat (1) the metals Al, Cd, Co, Mn, Ni and Zn aretransported in the streams mainly as inorganiccations, (2) Cu exists mainly in cationic form but isalso to a significant extent associated with dissolvedhumic substances, (3) Fe occurs mainly in the anionicfraction explained by organic coating on colloidal Feoxyhydoxides and (4) the hydrochemistry of As, Cr andV is complex as these elements may exist in severalunquantified anionic fractions and to a minor extentin cationic species/forms. Whereas the proportion ofacid sulphate soils in the catchments had a largeimpact on concentrations levels of several elements inthe stream waters, these soils did not have a largeaffect on the speciation of elements in water.     

湛江市菠萝主产区基岩-土壤-菠萝元素迁聚特征

为研究元素在基岩-土壤-作物系统的迁聚特征,选取湛江市徐闻县菠萝主产区为研究区,采集土壤和菠萝样品,结合元素迁移系数、生物富集系数评价了基岩-土壤-菠萝系统元素的分布和迁聚特征。结果表明: 研究区土壤含富磷(TP)、土壤全铁(TFe₂O₃)、Co、Ge、S、Se含量丰富,土壤全氮(TN)含量中等,有机质含量以中等—较丰富为主,土壤全钾(TK)含量缺乏。基岩风化成土过程中,土壤中Pb、Cr、TFe₂O₃、Ni相对基岩表现为富集,Al₂O₃、Cu、Zn、Co、Mn、TP、K₂O相对基岩表现为流失; 土壤中Co、Cr、Cu、Ge、Mn、Ni、Zn主要来源于磁铁矿风化蚀变,Se主要来源于黄铁矿风化蚀变。菠萝果实对Cd、Hg为微弱吸收,Cd相对其他元素更容易在菠萝果实中富集。Ge、As、Cd、Se、Ni在菠萝根部最为富集,Pb、Hg、Cr、Cu、Zn在菠萝叶片最为富集,菠萝果实对Cu、Pb、Cr、Hg的吸收存在协同作用。研究成果可为当地菠萝产业发展提供依据。     

云南富乐铅锌矿床黄铁矿微量(稀散)元素组成及成因信息:LA-ICPMS研究

川滇黔铅锌矿集区是华南大面积低温成矿域的重要组成部分,区内铅锌矿床是否属于MVT型矿床长期存在争议。该区铅锌矿床以富集Ge等稀散元素为特征,闪锌矿是其主要载体矿物,但稀散元素在黄铁矿中是否富集、赋存状态及微量元素组成特征等研究基本属于空白。本文通过LA-ICPMS研究富乐黄铁矿中微量元素(尤其是稀散元素)的富集特征,发现黄铁矿中也相对富集Ge。本研究样品选自富乐矿床的富乐和富盛两个矿段,包括1350、1410和1536三个中段(由深到浅),LAICPMS分析结果表明,该矿床黄铁矿以富集Cu、As、Co、Ni为特征,局部富集Pb(Sb)和Zn(以方铅矿和闪锌矿显微包裹体形式赋存于黄铁矿中),该类黄铁矿富集的稀散元素主要为Se、Ge及少量Tl、Te,而Cd和In以类质同象形式赋存于含Zn的显微包裹体(闪锌矿)中,类质同象是其余稀散元素主要赋存形式,且黄铁矿中Ge与Cu存在较好相关关系,可能存在Cu~(2+)+Ge~(2+)?2Fe~(2+)耦合置换方式。此外,黄铁矿中稀散元素的富集与成矿元素(特别是Cu)的富集密切相关,随着成矿作用的进行,从矿体深部到浅部,成矿温度逐渐降低,Se/Te比值逐渐升高,且稀散元素与成矿元素呈逐渐增加趋势。研究表明,该矿床黄铁矿的Co/Ni比值基本都小于1. 00,暗示其属于沉积改造型黄铁矿,在Co-Ni和稀散元素Se-Tl含量投影图上,富乐矿床黄铁矿的投影点与MVT型矿床投影区基本一致,而明显有别于SEDEX、VMS和矽卡岩型矿床中黄铁矿的投影区,结合富乐矿床类似于MVT型的地质特征,我们认为富乐矿床属于MVT型铅锌矿床。     

Concentration and association of minor and trace elements in Mukah coal from Sarawak, Malaysia, with emphasis on the potentially hazardous trace elements

The ash yield and concentrations of twenty-four minor and trace elements, including twelve potentially hazardous trace elements were determined in Mukah coal from Sarawak, Malaysia. Comparisons made to the Clarke values show that Mukah coal is depleted in Ag, Ba, Be, Cd, Co, Mn, Ni, Se, U, and V. On the other hand, it is enriched in As, Cr, Cu, Pb, Sb, Th, and Zn. Among the trace elements studied, V and Ba are associated predominantly with the clay minerals. Manganese, Cr, Cu, Th, and Ni are mostly bound within the aluminosilicate, sulphide and/or carbonate minerals in varying proportions, though a portion of these elements are also organically bound. Arsenic, Pb and Sb are mostly organically bound, though some of these elements are also associated with the sulphide minerals. Zinc is associated with both the organic and inorganic contents of the coal. Among the potentially hazardous trace elements, Be, Cd, Co, Mn, Ni, Se, and U may be of little or no health and environmental concerns, whereas As, Cr, Pb, Sb and Th require further examination for their potential health and environmental concerns. Of particular concern are the elements As, Pb and Sb, which are mostly organically bound and hence cannot be removed by physical cleaning technologies. They escape during coal combustion, either released as vapours to the atmosphere or are adsorbed onto the fine fly ash particles.     

广东三水盆地古近系心组生油层的元素地球化学特征

沉积物的元素地球化学特征是对沉积盆地水体环境以及古气候条件变化的响应。本文根据元素（Al、Fe、Mg、Ca、K、Na、P、V、Ni、Co、Cr、Cu、Zn、Sr、Ba、Cd、Li、Mn、Pb、Ti）的含量及其比值（Al/Ti、Fe/Mn、Sr/Ba、Mg/Ca、Sr/Ca、Na/Ca、V/Cr、Ni/Co、Ni/V）的变化，对三水盆地古近系心组红岗段生油层的沉积条件进行了系统分析。心组红岗段下部（亚段A）表现为较稳定的地球化学特征。各元素丰度及其比值指示这一时期陆源输入持续较高、且物源组成变化不大。由于海水入侵的影响，湖盆水体盐度相对较高，底部水体以弱氧化条件为主，O₂-H₂S界面位于水/沉积物界面附近。红岗段中上部（亚段B、C）的元素地球化学特征变化较为频繁且幅度很大，反映古气候和湖盆沉积条件的迅速变迁。在潮湿气候条件下，沉积物的地球化学特征表现为以Al、Ti为代表的外源元素含量及其比值较高，而Mg、Ca等盆内化学沉积元素含量较低。古氧气指标指示底部水体为还原环境，有利于有机质保存。因而，相应于较高的有机碳含量。在间歇性干旱时期，陆源输入减少，外源元素含量及其比值显著降低。随着蒸发作用的加强，水体盐度加大，内源元素丰度以及Mg/Ca、Sr/Ba、Sr/Ca和Na/Ca比值大幅度上升。底部水体为氧化环境，O₂-H₂S界面多位于水/沉积物界面或沉积物中。上述两种气候条件在红岗段中上部沉积时期交替出现。红岗段沉积后期由于淡水的长期输入，湖水出现逐渐淡化趋势。     

Geochemistry and origin of elements in some UK coals

Twenty-four UK coals ranging in rank with 4.6%–37.6% volatile matter were analysed for 46 major and trace elements. The samples were obtained from the UK Coal Bank and are representative of the major UK coal fields. The major element distributions are interpreted in terms of the mineralogical variations—quartz and kaolinite are largely responsible for the Si and Al, carbonates for Ca and Mg and pyrite for Fe. Also exerting an influence in some samples are siderite, Al-phosphate minerals and illite. Based on statistical relationships with the major elements, Rb, Cr, Th, Ce, Zr, Y, Ga, La, Ta, Nb and V are thought to be mainly present in the clay minerals, and As, Mo, Sb, Tl, Se and Bi and Pb are probably present in pyrite. Strontium and Ba are concentrated in a restricted number of samples related to the phosphate minerals. Germanium is the only element for which a major organic association can be demonstrated. Elements with an indirect association with the organic matter are Na, Cl, and Br in porefluids and possibly Te. The ash content is controlled mainly by the detrital input and the trace elements related to the ash content are therefore those elements associated with the clay minerals. Variations with rank would appear to be mainly related to the moisture content (porefluids). The trace elements associated with the quartz and clay minerals are thought to be dominantly detrital in origin. The non-detrital elements, essentially those contained in pyrite, are thought to have been incorporated in the depositional environment from waters with enhanced salinities through seawater ingress, hence there are positive relationships between S and trace element concentrations.     

Spatial trends and losses of major and trace elements in agricultural acid sulphate soils distributed in the artificially drained Rintala area,W. Finland

Acid sulphate soils, common in the coastal areas of Finland, contribute strongly to high acid, S and metal loadings on adjacent surface waters. This, in turn, is causing significant harm to the aquatic ecology. There is, however, limited knowledge on the total amounts of acidity and chemical elements leached from these soils. The overall objective of this study was to determine geochemical patterns in acid sulphate soils and their parent sediments and, based on the identified patterns assess the extent, mechanisms and present state of leaching of major and trace elements from these soils. The distribution of pH, aqua regia extractable concentrations of P and metals (Al, Ba, Ca, Co, Cr, Cu, Fe, K, La, Mg, Mn, Na, Ni, Sr, Th, Ti, V, Zn) and total concentrations of S and C were determined in 30 vertical profiles collected in the 23 km² large Rintala agricultural area (mid-western Finland) underlain largely with S-rich sediments. It was found that approximately 70% of the area consists of acid sulphate soils with a minimum pH<4.0, an average depth of 1.8 m, and S concentrations in the parent sediments varying from 0.24 to 1.04%. Acid sulphate soils have not developed where the S concentrations in the sediments are ⩽0.10% or where the concentrations of organic C in the soil zones are >4%. Four different methods were used to estimate the losses of chemical elements from the acid sulphate soils: (1) the concentrations in the soil were compared with those in the parent sediments, (2) due to indicated heterogeneities in several profiles, the vertical changes of the immobile Ti was used to re-calculate element losses, (3) element depletions in the acid sulphate soils (as compared to those in the parent sediments) were compared to the corresponding depletions in the non acid sulphate soils, (4) element concentrations in drainage waters were compared with those in the parent sediments. Based on these calculations, it was assessed that the percentual leaching of the aqua regia extractable fraction (total for S) has been as follows: S (40–50%), Na (30–50%), Mn (25–35%), Sr (15–20%), Ca–Ni–Co (approximately 10%), Mg–K–Zn (5–10%), Th–La–Cu–Al–P–Ti–Fe (<5%), and Ba–Cr–V (<1%). While it was possible to quite accurately estimate the percentages and thus the amounts of elements lost, it was not possible to estimate the rate of leaching as there is no available detailed information on dates when ditching activities and thus oxidation-acidification processes started. Other calculations indicated that the mobile S reservoir is still some 15 ton/hectare, which is huge but still smaller than the losses that have occurred since the area was drained (23–28 ton/hectare).     

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.