鸡西煤的无机地球化学研究

鸡西煤田是东北地区重要的炼焦煤基地，由于受成煤环境的影响，原煤灰分较高，影响了煤炭精细加工利用和环境。采用Ｘ射线衍射、红外光谱等分析方法对鸡西煤的无机地球化学特征研究显示，煤中的主要矿物为石英、方解石、粘土矿物、黄铁矿和菱铁矿等，它们分别以不同的状态赋存于有机质中。煤灰的主要成分为ＳｉＯ２和Ａｌ２Ｏ３，其主要源自流水带入泥炭沼泽的石英和粘土等同生矿物。元素分析表明，煤中硫、磷及微量元素锗和镓等含量较低。     

Use of laser ablation ICP-MS to determine trace element distributions in coals, with special reference to V, Ge and Al

Laser ablation ICP-MS has been used to produce element profiles from polished coal samples. The elements analysed (V, Ge, Ni, Cu, Zn, Sr and Ba) were those known to have an organic association, with the addition of Al and Fe as controls on the clay and pyrite abundances. The element profiles were compared with the petrography and a statistical analysis was also carried out. Sporinite was found to have low trace element concentrations, inertinite higher concentrations of detrital elements and vitrinite higher concentrations of V, Ge and Al. The relationships between these elements are explored and all are thought to be present in the organic matter and not as minerals. It is thought that these elements became concentrated during diagenesis, with the possibility that some of the Al could be residual. The Cu/Ni ratio in the pyrite is relatively constant, suggesting constant ionic proportions during diagenesis, and possibly a seawater source.     

Mineral matter and trace elements in coals of the Gunnedah Basin, New South Wales, Australia

The concentrations of major and trace inorganic elements in a succession of Permian coals from the Gunnedah Basin, New South Wales, have been determined by X-ray fluorescence techniques applied to both whole-coal and high-temperature ash samples. The results have been evaluated in the light of quantitative data on the minerals in the same coals, determined from X-ray diffraction study of whole-coal samples using a Rietveld-based interpretation program ( ™), to determine relationships of the trace elements in the coals to the mineral species present. Comparison of the chemical composition of the coal ash interpreted from the quantitative mineralogical study to the actual ash composition determined by XRF analysis shows a high degree of consistency, confirming the validity of the XRD interpretations for the Gunnedah Basin materials. Quartz, illite and other minerals of detrital origin dominate the coals in the upper part of the sequence, whereas authigenic kaolinite is abundant in coals from the lower part of the Permian succession. These minerals are all reduced in abundance, however, and pyrite is a dominant constituent, in coals formed under marine influence at several stratigraphic levels. Calcite and dolomite occur as cleat and fracture infillings, mostly in seams near the top and bottom of the sequence. The potassium-bearing minerals in the detrital fraction are associated with significant concentrations of rubidium, and the authigenic kaolinite with relatively high proportions of titanium. Zirconium is also abundant, with associated P and Hf, in the Gunnedah Basin coal seams. Relationships exhibited by Ti, Zr, Nd and Y are consistent with derivation of the original sediment admixed with the seams from an acid volcanic source. Pyrite in the coals is associated with high concentrations of arsenic and minor proportions of thallium; no other element commonly associated with sulphides in coals, however, appears to occur in significant proportions with the pyrite in the sample suite. Small concentrations of Cl present in the coal are inversely related to the pyrite content, and appear to represent ion-exchange components associated with the organic matter. Strontium and barium are strongly associated with the cleat-filling carbonate minerals. Ge and Ga appear to be related to each other and to the coal's organic matter. Cr and V are also related to each other, as are Ce, La, Nd and Pr, but none of these show any relationship to the organic matter or a particular mineral component.     

Distribution of environmental sensitive trace elements in the Eocene Sorgun coals, Turkey

The distribution of trace elements in the lower Eocene coal seam mined in the Yeniceltek, Kucukkohne and Ayridam coal mines from the Sorgun Basin was investigated in relation to ash content and maceral composition. The coal seam is mainly composed of huminite. In the present study, 35 samples from five seam sections were collected on the basis of megascopic characteristics. Results were determined using an energy dispersive polarised X-ray fluorescence (EDP-XRF) spectrometer on a whole-coal dry basis. Most of the major and trace elements studied are enriched in high-ash samples, while Ba, Br, Mn and W show relative enrichments in low-ash samples. Most of elements studied, such as Ga, Ce, La, Th, Nb, Rb, Zr, V, Cu, U, Pb, Sb, Cs, Sn, Cr, Se, Y and Zn, are primarily associated with mineral matter (clay minerals). Arsenic and a part of Zn, Se and Sb are probably concentrated in pyrites in the samples. Element concentrations show statistically significant negative correlations with many macerals and positive relationships with only attrinite that is mainly mixed with mineral matter (clay minerals and small quartz grains) in the samples. Nine trace elements (As, Cr, Mn, Ni, Pb, Sb, Se, Th and U), considered as potentially Hazardous Air Pollutants, are present in low to moderate concentrations. The mean values of trace element concentrations display relative enrichments in Se (2.8 ppm), Th (21 ppm) and W (26 ppm) in the investigated samples in comparison with other coals in the world.     

Elemental characteristics and paleoenvironment reconstruction: a case study of the Triassic lacustrine Zhangjiatan oil shale,southern Ordos Basin,China

Using trace elements to reconstruct paleoenvironment is a current hot topic in geochemistry. Through analytical tests of oil yield, ash yield, calorific value, total sulfur, major elements, trace elements, and X-ray diffraction, the quality, mineral content, occurrence mode of elements, and paleoenvironment of the Zhangjiatan oil shale of the Triassic Yanchang Formation in the southern Ordos Basin were studied. The analyses revealed relatively high oil yield (average 6.63%) and medium quality. The mineral content in the oil shale was mainly clay minerals, quartz, feldspar, and pyrite; an illite–smectite mixed layer comprised the major proportion of clay minerals. Compared with marine oil shale in China, the Zhangjiatan oil shale had higher contents of quartz, feldspar, and clay minerals, and lower calcite content. Silica was mainly in quartz and Fe was associated with organic matter, which is different from marine oil shale. The form of calcium varied. Cluster analyses indicated that Fe, Cu, U, V, Zn, As, Cs, Cd, Mo, Ga, Pb, Co, Ni, Cr, Sc, P, and Mn are associated with organic matter while Ca, Na, Sr, Ba, Si, Zr, K, Al, B, Mg, and Ti are mostly terrigenous. Sr/Cu, Ba/Al, V/(V + Ni), U/Th, AU, and δU of oil shale samples suggest the paleoclimate was warm and humid, paleoproductivity of the lake was relatively high during deposition of the shale—which mainly occurred in fresh water—and the paleo-redox condition was dominated by reducing conditions. Fe/Ti ratios of the oil shale samples suggest clear hydrothermal influence in the eastern portion of the study area and less conspicuous hydrothermal influence in the western portion.     

Selected elements in major minerals from bituminous coal as determined by INAA: implications for removing environmentally sensitive elements from coal

The four most abundant minerals generally found in Euramerican bituminous coals are quartz, kaolinite, illite and pyrite. These four minerals were isolated by density separation and handpicking from bituminous coal samples collected in the Ruhr Basin, Germany and the Appalachian basin, U.S.A. Trace-element concentrations of relatively pure ( 99⁺%) separates of major minerals from these coals were determined directly by using instrumental neutron activation analysis (INAA). As expected, quartz contributes little to the trace-element mass balance. Illite generally has higher trace-element concentrations than kaolinite, but, for the concentrates analyzed in this study, Hf, Ta, W, Th and U are in lower concentrations in illite than in kaolinite. Pyrite has higher concentrations of chalcophile elements (e.g., As and Se) and is considerably lower in lithophile elements as compared to kaolinite and illite. Our study provides a direct and sensitive method of determining trace-element relationships with minerals in coal.Mass-balance calculations suggest that the trace-element content of coal can be explained mainly by three major minerals: pyrite, kaolinite and illite. This conclusion indicates that the size and textural relationships of these major coal minerals may be a more important consideration as to whether coal cleaning can effectively remove the most environmentally sensitive trace elements in coal than what trace minerals are present.     

淮南矿区煤中12种微量元素的赋存状态及环境效应

为研究淮南矿区煤中微量元素的赋存状态和环境效应,在淮南矿区7个矿井共采集17个样品,采用电感耦合等离子质谱仪（ICP-MS）测定了12种微量元素的含量,分别利用聚类分析和因子分析,结合其地球化学性质,讨论了它们的赋存状态,并采用静态燃烧实验研究其挥发性。结果表明:研究的元素没有异常富集;Zn和Cu赋存于闪锌矿中,Cr、Pb和Cd被粘土矿物吸附,Ba可能赋存于铁白云石和方解石中,Ni、Mo、Co和As主要赋存于黄铁矿中,Be和Se以有机结合态存在;研究的元素大多不易挥发,但Zn和Pb易挥发,且含量较高,环境危害较大,Zn和Pb分别赋存于闪锌矿和粘土矿物中,可通过洗选脱除减小其危害。      

Coal geology and coal quality of the Miocene Mugla basin, southwestern Anatolia, Turkey

This work focuses on the relationship between the coal geology and coal quality of the Miocene Mugla basin, Southwestern Anatolia, Turkey. To this end, detailed petrographical, mineralogical and geochemical studies were performed on composite profile samples from the nine coal fields in the Mugla basin (Alatepe, Bagyaka, Bayir, Çakiralan, Ekizköy, Eskihisar, Hüsamlar, Sekköy and Tinaz coal fields). The Mugla lignite is a high ash (from 16 to 56%) and sulphur (from 2.1 to 5.7%) lignite which is petrographically characterised by a high huminite content, mainly gelinite macerals. The mineral matter of the studied lignite samples is made up mainly of clay minerals and quartz, with the exception of the Sekköy and Ekizköy lignites, in which calcite is the dominant mineral phase with minor amounts of quartz, clay minerals, pyrite and gypsum and traces of aragonite. Syngenetic opal is also frequently identified in these samples. The differentiation of these two types of lignite with specific mineralogical patterns is attributed to the contemporaneous development of peatlands with a high detrital input, dominated by the quartz and clay mineral setting, and peatlands with low detrital supply and a dominant carbonate-rich lacustrine environment. The higher water table of the latter allowed the precipitation of micritic carbonates and the development of lakes with abundant mollusc fauna. This differentiation is also evidenced by the geochemical data. Thus, the Sekköy, Ekizköy, Hüsamlar, Bayir and Alatepe lignites are characterised by relatively low Al and Fe contents (<1.4%) and high sulphur contents (4.2 to 5.7%). In addition Sekköy and Ekizköy show relatively high contents of Ca (6.3–7.1% compared to 1.6–3.8% in the other lignites). All the lignite samples studied are characterised by relatively high Mo and U contents when compared with the worldwide averages of trace elements in coal. Relatively high alkaline syngenetic conditions of the peat-forming environment of the Mugla coal are deduced from the following mineralogical, petrographical and geochemical evidence: (a) the precipitation of syngenetic opal (dissolution of quartz and re-precipitation as opal) and calcite; (b) minor and very early syngenetic sulphide precipitation (only framboidal and euhedral pyrite); (c) high bacterial activity, typical of high pH conditions, inferred from low preservation of tissue structures; (d) preservation of aragonite gastropod shells; and (e) the anomalous enrichment of U, Mo and W. A key result of the study of Mugla limnic coals (at least of the Sekköy and Ekizköy coal fields) is that a major influence was exerted on the early diagenetic evolution of the coal by the hydrochemistry of the lacustrine waters. This hydrochemistry was largely linked to the lithology of the surrounding source rock areas although the final evolutionary trend of the solute composition in the lake waters, characterized by very high carbonate and sulphate contents, was largely enhanced by the endorheic river drainage system and the arid–semiarid paleoclimatic situation under which organic matter accumulation took place.     

Mineralogical and geochemical characteristics of Miocene pelitic sedimentary rocks from the south-western part of the Pannonian Basin System (Croatia): Implications for provenance studies

Fifty-two samples of Miocene pelitic sedimentary rock from outcrops on Medvednica,Moslavacka Gora and Psunj Mts.,and boreholes in the Sava Depression and the Pozega Sub-depression were investigated.These sediments formed in different marine(with normal and reduced salinity),brackish,and freshwater environments,depending on the development stage of the Pannonian Basin System.Carbonate minerals,clay minerals and quartz are the main constituents of all pelitic sedimentary rocks,except in those from Moslavacka Gora Mt in which carbonate minerals are not present.Feldspars,pyrite,opal-CT,and hematite are present as minor constituents in some rocks.Besides calcite,dependent on the sedimentary environment and diagenetic changes,high-magnesium calcite,aragonite,dolomite and ankerite/Cadolomite are also present.Smectite or illite-smectite is the main clay minerals in the samples.Minor constituents,present in almost all samples,are detrital illite and kaolinite.In some samples chlorite is also present in a low amount.Major elements,trace elements and rare earth elements patterns used in provenance analysis show that all analysed samples have a composition similar to the values of the upper continental crust(UCC).The contents of major and trace elements as well as SiO_2/Al_2O_3,K_2O/Al_2O_3,Na_2O/K_2O,Eu/Eu~*,La/Sc,Th/Sc,La/Co Th/Co,Th/Cr,Ce/Ce~* and LREE/HREE ratios,show that the analysed pelitic sedimentary rocks were formed by weathering of different types of mostly acidic(silicic),i.e.felsic rocks.     

A preliminary study on the enrichment mechanism and occurrence of hazardous trace elements in the Tertiary lignite from the Shenbei coalfield, China

The Cr and Ni contents are high in the Eocene lignite of the Shenbei coalfield, which is a small intracontinental basin located in Liaoning Province, China. In this paper, we studied the distribution, origin and occurrence of Cr, Ni and other hazardous trace elements in the Shenbei lignite on the basis of coal petrology, and geochemistry of the lignite and combustion products. The following conclusions on the Shenbei lignite can be drawn: (1) The dominant maceral group in the Shenbei coal is huminite (humodetrinite), accounting for 96%–99% of the total maceral. Inertinite content is less than 1%. Liptinite content (sporinite and cutinite) is 0.2–1.6%. Common minerals in the Shenbei lignite include clay minerals (kaolinite), pyrite and quartz, and calcite and siderite. Chromite is not present in the lignite. (2) Potentially hazardous trace elements such as Co (22 μg/g), Cr (79 μg/g), Cu (63 μg/g), Zn (93 μg/g), V (88 μg/g) and Ni (75 μg/g) are strongly enriched in the Shenbei lignite compared with average concentration of trace elements in the Chinese coal and worldwide lignite. These elements are mainly associated with fulvic acid (FA) and/or coal organic macromolecular compounds in most of the studied lignite samples, indicating an organic association and enrichment of these elements in the Shenbei lignite. (3) Unusually high trace elements contents in the Shenbei lignite are derived mainly from the olivine basalt (country rock of coal basin) that consists of 52.7% plagioclase, 17.8% pyroxene, 14% olivine and 15.5% Ti–Fe oxide minerals. These olivine basalts have higher Cr, Ni, Pb and Zn contents than other types of rock and worldwide basalts do. (4) Fly ash of the Shenbei lignite, with 90% 1–50 μm amorphous particles and 8% 1–10 μm cenosphere, has high contents of Zn (23,707 μg/g), Be (12 μg/g), Sr (1574 μg/g), Pb (486 μg/g) and Cr (349 μg/g). In particular, the ferruginous micro-cenoshperes contain 1–12.79% Zn. Fine bottom ash (<0.031mm) of the Shenbei lignite has higher contents for most of the elements with the exception of Mo, Sn and Zn. Therefore, the potentially environmental and health impact of the fly ash and fine bottom ash should constitute a major concern.     

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。     

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.     

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.     

胶东焦家金成矿带2420~3206 m垂深金矿物和黄铁矿微量元素特征

在胶东莱州吴一村地区完成的3266.06 m深钻,是目前焦家金成矿带最深见矿钻孔,研究钻孔揭露的深部矿石中金矿物及黄铁矿微量元素特征,对探讨深部成矿作用演化具有重要意义。笔者采取深钻中2420~3206 m垂深的岩（矿）芯样品进行了详细的岩相学和矿相学研究,结合扫描电镜和电子探针微区分析,研究了矿石中金矿物的赋存状态和成分。对不同成矿阶段形成的黄铁矿进行了LA-ICPMS微量元素分析。研究结果表明,深部矿石中载金矿物主要为黄铁矿,其次为石英、黄铜矿、方铅矿,可见金主要以自然金和银金矿的形式存在,以晶隙金和裂隙金为主,其次为包体金。与浅部金矿床比较,深部金的成色较高。黄铁矿分为6种类型,第Ⅰ成矿阶段形成富Co型黄铁矿Py1,第Ⅱ成矿阶段形成富Ni型黄铁矿Py2a和Py2b,第Ⅲ成矿阶段形成富Au、As型黄铁矿Py3a和富Au、Ag、Pb、Bi型黄铁矿Py3b,第Ⅳ成矿阶段形成贫微量元素黄铁矿Py4。其中,Py1和Py2a发生强烈破碎,裂隙表面对热液中的Au络合物产生吸附作用,对金沉淀富集起重要作用。黄铁矿中Co、Ni、As等微量元素主要以类质同象形式赋存,而Au、Ag、Cu、Pb、Zn、Bi等主要以纳米级、微米级矿物包体形式赋存。Pb+Bi、Cu+Pb+Zn、Te+Bi与Au+Ag呈明显正相关,而Au与As相关性较差。黄铁矿中Co、Ni含量较低,而Au+Ag+As或Au+Ag+Pb+Bi+Cu含量较高指示成矿有利。另外,黄铁矿中Co、Ni含量较高,并且破碎强烈,成矿相关元素含量较高也指示成矿有利。     

Geochemistry and Mineralogy of Paleocene Coal from the Padhrar and Darra Adam Khel Coalfields of Pakistan

Pakistan is rich in coal resources, which amount to around 186 billion tons. The Paleocene Padhrar and Darra Adam Khel coalfields are located in the Central Salt Range Punjab Province and the Khyber Pakhtunkhwa Province, Pakistan, respectively. Padhrar coal has not been studied in detail and the Darra Adam Khel coalfields are newly-discovered, so no research has been done, due to security considerations. In this study, an attempt has been made to study the geochemical and mineralogical characteristics of the Padhrar and Darra Adam Khel coals, in order to learn about the coal quality, element enrichment mechanism, sedimentary medium conditions and potentially valuable elements for coal utilization. The Padhrar and Darra Adam Khel coals are low to medium ash, low moisture content, high in volatiles and high total sulfur coal. The vitrinite reflectance in Darra Adam Khel coal is higher than in Padhrar coal, indicating either a greater burial depth or the effects of Himalayan tectonism. The vitrinite content is dominant in the Padhrar and Darra Adam Khel coals, followed by inertinite and liptinite, the major minerals including quartz, clay minerals, calcite and pyrite. The trace elements Ni, As, Be Zn, Ge, Mo, Ta, W, Co and Nb, Sn, Hf, Ta, Pb, Th, Cd, In, Be, V, Cr, Zr, Ag, Li, W and Co are concentrated in some of the Padhrar and Darra Adam Khel coal samples, respectively. The Padhrar coal shows positive Ce, Eu and Gd anomalies, with most of the Darra Adam Khel coal showing negative Ce, Eu and positive Gd anomalies with high LREE. The Al2O3/TiO2 values indicate that the sediment source of the Padhrar and Darra Adam Khel coals is mostly related to intermediate igneous rocks. The Sr/Ba, SiO2 + Al2O3, Fe2O3 + CaO + MgO/SiO2 + Al2O3 and high sulfur content in the Padhrar and Darra Adam Khel coals indicate epithermal and marine water influence with a tidal flat, coal-forming environment and a deltaic coal-forming environment, respectively.     

Rock composition and origin of the Duwi Formation calcareous rocks, Upper Egypt

Upper Cretaceous phosphorite beds of the Duwi Formation, Upper Egypt, are intercalated with limestone, sandy limestone, marl, calcareous shales, and calcareous sandstone. Calcareous intercalations were subjected to field and detailed petrographic, mineralogical and geochemical investigations in order to constrain their rock composition and origin. Mineralogically, dolomite, calcite, quartz, francolite and feldspars are the non-clay minerals. Smectite, kaolinite and illite represent the clay minerals. Major and trace elements can be classified as the detrital and carbonate fractions based on their sources. The detrital fraction includes the elements that are derived from detrital sources, mainly clay minerals and quartz, such as Si, Al, Fe, Ti, K, Ba, V, Ni, Co, Cr, Zn, Cu, Zr, and Mo. The carbonate fraction includes the elements that are derived from carbonates, maily calcite and dolomite, such as Ca, Mg and Sr. Dolomite occurs as being dense, uniform, mosaic, very fine-to-fine, non-ferroan, and non-stoichiometrical, suggesting its early diagenetic formation in a near-shore oxidizing shallow marine environment. The close association and positive correlation between dolomite and smectite indicates the role of clay minerals in the formation of dolomite as a source of Mg^2＋ -rich solutions. Calcareous rocks were deposited in marine, oxidizing and weakly alkaline conditions, marking a semi-arid climatic period. The calcareous/argillaceous alternations are due to oscillations in clay/carbonate ratio.     

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.     

云南大关新地2井奥陶—志留纪之交钾质斑脱岩岩石地球化学特征分析

扬子地台内晚奥陶世末—早志留世初五峰—龙马溪组内沉积了多层钾质斑脱岩,但对于该时期扬子地台西缘钾质斑脱岩的研究报道相对较少。本文旨在通过对云南大关地区新地2井五峰—龙马溪组内沉积的钾质斑脱岩进行矿物学及地球化学分析,进一步确定扬子西缘该时期钾质斑脱岩原始岩浆类型及其所产生的构造环境。矿物学特征表明,钾质斑脱岩主要由黏土矿物和非黏土矿物组成,其中黏土矿物由伊利石和伊蒙混层组成,非黏土矿物以石英、长石、方解石、白云石和黄铁矿等为主。钾质斑脱岩主量元素以高K_2O,低TiO_2为特征,微量元素特征表现为富集Rb、Ba、Th、U等元素,Ti、P元素相对亏损,Ti/Th值指示了酸性火山灰的性质;ΣREE在(49.86～209.43)×10~(-6);与球粒陨石相比,轻稀土轻微富集、具Eu负异常,无Ce异常;在Nb/Y-Zr/TiO_2图解中,数据点主要落在安山岩和粗面英安岩之间,表明钾质斑脱岩源岩浆性质为中酸性岩浆;依据微量元素特征和构造环境判别结果,初步认为原始岩浆可能形成于岛弧环境,其火山灰来源可能与扬子北缘早古生代秦岭洋闭合过程中的板块碰撞有关。     

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.     

Namurian bentonites in the Pennine Basin, UK – origin and magmatic affinities

Nine Namurian clay bands retrieved from boreholes in the northern part of the Pennine Basin are, on the basis of their petrography, mineralogy and geochemistry, shown to be volcanic in origin and are therefore bentonites. The bentonites, which have a fragmental texture, are normally graded and show rare preservation of shard textures, representing vitric tuff deposits that have been altered subsequently to clay-dominated horizons. Crystals are a minor component of the bentonites, but biotite, in particular, is concentrated at the base of the beds. A clay mineral assemblage of mixed-layer illite–smectite with subordinate kaolinite identifies most of the samples as K-bentonites, but kaolinite dominates two samples that can be classed as tonsteins. Temporal variation of salinity within the depositional basin is suggested to explain these different clay assemblages. The major element geochemistry of the bentonites reflects their clay mineralogy and the compositions of diagenetic minerals present, the latter including pyrite, carbonates and hydroxyapatite. Enrichment of the bentonites in some trace elements (including Ba, Sr, Pb, Cu and Ni) can be related to the presence of the diagenetic minerals, but the extent to which the elements are added from external sources as opposed to being redistributed within the ash is unclear. Immobile trace element systematics suggest a rhyodacite/dacite composition for the original ash and derivation from the collision of plates, this being supported by evidence provided by the rare earth elements (REE) in one group of samples. However, in another group of samples, variations in REE concentrations may be caused by mobility of these elements during alteration. The chemistry of the Namurian bentonites contrasts markedly with that of the local Carboniferous volcanics but is comparable, in some respects, with one group of Westphalian tonsteins, although the latter are more rhyolitic in character. It is suggested that the Namurian bentonites and the Westphalian tonsteins of acid affinities originated from volcanic activity associated with a destructive plate margin in the Variscan externides and that the observed compositional trend may reflect magma evolution possibly related to the progressive east–west closure.