沁水盆地晚古生代煤中硫的地球化学特征及其对有害微量元素富集的影响

煤中硫是多种有害微量元素的重要载体。基于形态硫分析、电感耦合等离子质谱及X射线衍射等方法分析沁水盆地晚古生代煤中硫和有害微量元素的分布规律,探讨了煤中硫对有害微量元素富集的影响,运用带能谱的扫描电镜和光学显微镜划分煤中硫化物的微观赋存特征。结果表明,沁水盆地煤中硫整体上以有机硫为主,平均占全硫的78%,只有在太原组个别高硫煤中以黄铁矿硫为占优势。显微镜和扫描电镜下可识别出煤中黄铁矿的微观赋存状态包括莓球状、薄膜状、晶粒状、结核状、团窝状黄铁矿和细粒黄铁矿集合体,白铁矿的微观赋存特征包括聚片状、板状和矛头状白铁矿,部分白铁矿与黄铁矿共生。沁水盆地煤中有害微量元素含量整体较低,黄铁矿是有害微量元素As、Se和Hg的重要载体,而有机硫决定了煤中U的富集。研究认为,成煤时期海水对泥炭沼泽的影响导致太原组煤中全硫和黄铁矿硫较高,太原组煤中硫的来源具有多样性,煤中黄铁矿具有多阶段演化的特点。     

陶枣煤田晚古生代煤中硫及伴生有害元素分布特征

对山东陶枣煤田晚古生代洪进行了形态硫分析、煤中黄铁矿伴生无奈的探针测试及煤中微量元素中子活化分析,结果表明,高硫煤中有害物质主要来自煤中黄铁矿,黄铁矿硫占总硫的75％以上,同时黄铁矿中伴生有大量有害元素,其质量分数与种类又与其成因类型有关。黄铁矿中伴生有害元素质量分数约在0．5％至2．5％之间。太原组高硫煤中的有害元素以Cu,As,U,Ph,Mo和Co等为特征,其成因与硫的聚集密切相关。研究还发现,As与Fe存在相关关系,As主要赋存在Fe和Cu的硫化物中。U的富集与海水的影响有关,同时也受岩浆活动的影响。侵入体附近的低灰天然焦含U最高,达10×10－6。根据以上研究结果,推测对于高硫煤采用重液洗选除硫除灰时,也可同时去除大部分有害元素,应予深入研究。     

煤中有害微量元素富集的成因类型初探

媒中微量元素的富集受多种因素和多期作用控制,往往是多因素叠加的结果。文中对煤中有害微量元素富集的成因类型进行了初步探讨,根据煤中有害元素富集的主导因素,划分出5种媒中有害微量元素富集的成因类型：（1）陆源富集型;（2）沉积-生物作用富集型;（3）岩浆-热液作用富集型;（4）深大断裂-热浪作用富集型;（5）地下水作用富集型。对煤中有害微量元素的来源。运移、富集的地质地球化学背景进行深入研究,将有助于发展中国煤地球化学基础理论,也可为煤利用过程中的环境保护提供科学依据。     

贵州小牛井田煤的地球化学特征及古海平面变化

基于贵州水城小牛井田晚二叠世煤样的全硫分、微量元素、常量元素等测试数据,探讨了煤中元素富集特征及其与陆源碎屑的关系,重点是全硫分、微量元素对古海平面变化的反演。结果表明,小牛井田煤中常量元素Si、Ca、Mg、Ti、K含量高于中国煤均值,Al、Fe、Na含量低于中国煤均值;与地壳克拉克值相比,煤中微量元素只有B和Mo相对富集;煤中微量元素的富集在一定程度上受控于陆源碎屑,常量元素对陆源碎屑也有一定的继承性。煤中全硫分及微量元素B、Co、Cr、Cu、Ga、Ge、Mo、Ni、Pb、Sr、V、Zn的纵向变化规律可以用来反演古海平面变化,海退时形成的煤层全硫分及微量元素含量较低,海侵时形成的煤层全硫分及微量元素含量较高。      

河南省平顶山煤田晚石炭世太原组沉积环境和聚煤沉积特征

平顶山煤田的太原组属于混合型的碳酸盐浅海和陆源碎屑海岸沉积。下部和上部灰岩段主要形成于滨海潮间带和浅海中,并在其中发育行风暴浊流沉积。中部碎屑岩段为障壁岛-泻湖-潮坪体系沉积。太原组煤的显微组分为微镜惰煤,煤质属于低灰高硫煤。     

湖南沃溪钨-锑-金建造矿床同生成因的微量元素和硫同位素证据

对岩矿石和矿物的微量元素、稀土元素和硫同位素地球化学的研究表明,湖南沃溪钨-锑-金建造矿床系海底同生热水沉积作用的产物。矿石与围岩中微量元素和稀土元素含量的变化关系,反映了一种复杂的热液、海水以及陆源碎屑的联合影响。矿石及其中矿物(石英)的稀土元素配分模式可与许多沉积喷流型(sedex型)块状硫化物矿石及其共生的喷流岩相对比,暗示了两者具有相似的形成机理。矿石的硫同位素资料显示,生物成因硫与热液成因硫(下伏沉积柱中硫化物的溶解和/或部分海水硫酸盐的还原)共同参与了成矿作用过程。     

重庆长河碥煤矿晚三叠世2号煤中微量元素的赋存状态

为了探讨煤中微量元素的赋存状态和地质成因,本文运用电离耦合等离子体质谱(ICP-MS)、电离耦合等离子体原子发射光谱(ICP-AES)、X射线荧光光谱(XRF)、冷原子吸收光谱(CV-AAS)、离子选择性电极法(ISE)、逐级化学提取试验(SCEE)等,研究了重庆长河碥矿晚三叠世须家河组2号煤层中微量元素的含量、赋存特征及其影响因素.发现该煤层中As(12.9 μg/g)、Cu(125 μg/g)、Cr(72 μg/g)、Ni(63 μg/g)、Pb(111 μg/g)等元素富集;逐级化学提取结果显示,煤层中Pb主要赋存在低温热液成因的黄铁矿脉中;Cr主要存在于粘土矿物中,Cr可能与陆源碎屑供给有关;Cu不仅与粘土矿物有关,也与煤中黄铁矿有关.表明低温热液流体和陆源碎屑供给对该煤中主要微量有害元素的含量和赋存特征起了决定作用.     

潘集煤矿二叠纪主采煤层中微量元素亲和性研究

安徽淮南煤田位于华北地台南端 ,发育了华北地区二叠纪含煤岩系中层位最高的可采煤层。采用仪器中子活化分析法 (INAA)测试了淮南煤田潘集煤矿二叠纪主采煤层 13个样品的 36个微量元素的浓度分布 ,并对其共生组合特点、地球化学特征及稀土元素配比模式作了初步分析 ,结果表明 ,煤中不同微量元素显示出不同的亲和性质。元素Br,As ,Sb ,Ni和Co等趋于在煤中富集 ,其中Br的有机亲和性最大。元素Na ,K ,Rb ,Th ,Hf,Zr ,Ta和REE则在煤层与顶底板接触带的碳质泥岩中富集 ,表现出与细粒陆源碎屑物更强的亲和性。其它元素倾向性不甚明显 ,但Fe ,Ca ,Sr ,HREE等元素在海水影响强度增大的煤层中含量增加。元素As,Cs,Ni,Fe和Ca在煤层中含量变化较大 ,其变异系数大于 1,其它元素则相对稳定 ,表明同一矿区煤层中微量元素含量在不受其它地质作用明显叠加影响时具有一定的稳定性。本区煤层稀土元素配比模式与华北其它地区C—P纪煤基本类似 ,普遍存在Eu亏损现象。 ∑REE在煤中分布范围为30× 10 -6～ 95× 10 -6,在顶板泥岩中超过 2 0 0× 10 -6。煤层中部 ∑REE降低 ,HREE相对富集。聚类分析表明 ,元素As ,Se ,Ag和Fe关系密切 ,这与煤中黄铁矿等成岩矿物有直接关系 ,泥炭沼泽演化期间或之后海水的直接或间接影响会促使这     

太原西山矿区杜儿坪井田夹矸地球化学特征及其地质意义

为探明太原西山矿区杜儿坪井田夹矸的地球化学特征及其地质成因,用X射线衍射分析(XRD)、电感耦合等离子体质谱(ICP-MS)、电感耦合等离子体发射光谱(ICP-OES)、氢化物-原子荧光光谱(HG-AFS)、发射光谱法(ES)等方法对杜儿坪井田2号、3号和8号煤层夹矸进行了矿物学和地球化学特征研究。结果发现2号、3号和8号煤层夹矸中矿物以高岭石、石英为主;与华北上地壳相比,杜儿坪夹矸中富集有害微量元素Cd、Se、Mo、Pb、Be、Cu、Th和U,山西组夹矸中有害元素含量大于太原组(除Mo、Pb和U);所有夹矸样品中Li、Ga的含量超过了工业品位,其工业利用价值值得关注;山西组夹矸稀土元素总含量高于太原组夹矸,所有夹矸稀土元素分配模式反映其与陆源碎屑关系密切;通过分析得到该区夹矸形成期间的陆源碎屑主要来自北部的花岗岩;太原组夹矸形成过程受海水影响;稀土元素与Al和Si等造岩矿物的聚类分析表明,夹矸中稀土元素主要赋存于高岭石等黏土矿物中。     

陆相断陷盆地煤与油页岩共生组合及其层序地层特征

为了研究陆相断陷盆地煤层与油页岩共生发育的地质现象,采用沉积学、构造地质学、能源地质学和层序地层学的相关理论和方法对煤与油页岩共生发育特征进行了研究.研究发现:陆相断陷盆地煤层与油页岩主要存在5种共生组合类型;煤和油页岩的发育均需要稳定的构造和较少的陆源碎屑物质供应,共生发育的煤和油页岩中均含有高等植物和藻类;盆地基底的幕式构造活动对煤和油页岩发育的沉积环境及其转化起到主要控制作用,气候条件、陆源碎屑物质注入、有机质供应等起到次要控制作用;在层序地层格架下,各种煤与油页岩共生组合均可发育在湖扩张体系域,从体系域早期到晚期、从滨湖到湖中心,共生组合中煤层厚度逐渐减小,油页岩厚度逐渐增大;而早期高水位体系域,则主要发育厚度大、分布稳定的油页岩-煤层组合.可见,盆地基底幕式构造活动、沉积环境演化、气候条件、陆源碎屑物质注入、有机质供应等因素共同控制了陆相断陷盆地煤与油页岩的共生发育,且共生组合主要发育在湖扩张体系域和早期高水位体系域.      

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.     

贵州六枝、水城煤田晚二叠世煤的微量元素特征

通过对六枝和水城煤田 10个煤矿主要可采煤层的 45个煤样品的常量和微量元素系统研究 ,概括了这两个煤田煤中常量和微量元素的丰度和分布特征 ;阐述了煤中微量元素的亲合性。这两个煤田煤中的全硫含量在受海水影响的煤层中较高 (最高达 7.5 % ) ,而在非海水影响的煤层中较低 ( 0 .3% )。六枝煤田的全硫含量明显高于水城煤田。Ca-Mn-Ge的平均含量在六枝煤田较低 ,而在水城煤田相对较高。在这两个煤田和不同的煤层之间 ,煤中微量元素含量的变化较小。与世界烟煤中一般含量范围相比 ,这两个煤田的特征是 Mn,V,Cu,L i,Zr,Nb,Ta,Hf,T1,Th和 U的含量相对高。     

煤中有害物质及其对环境的影响研究进展

综述了煤中有害物质的种类、分布赋存特征及对环境的影响研究进展。探讨了煤中黄铁矿的形态、世代交替、有机硫的结构及煤中硫的地质成因。阐述了煤中微量元素的种类、地质分布、赋存状态、迁移聚集机制及其环境危害。并对煤及燃煤产物中多环芳烃的种类、赋存规律及对环境和人类健康的危害进行了详细阐述。最后指出了煤中有害物质研究中存在的问题与发展趋势。     

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.     

燃煤过程中有害元素转化机理研究进展

综述了煤中有毒、有害元素经燃烧之后的存在形式与去向,元素在燃烧过程中的热解释放行为及其转化机理;强调煤中无机组分为主要存在许多有毒、爱元素在燃烧过程中会释放出来,然后再分异扩散到各种燃烧产物之中,地民人体廷民危害;指出今后研究不仅限于煤中有毒、有害元素的形成机理,更应侧重对燃烧产物中毒、有害元素的分异与去除方法作进一步的研究与试验,力求使燃煤对环境与人体健康产生的危害降低到最低程度。     

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.     

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

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