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.     

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.     

Geochemistry of environmentally sensitive trace elements in Permian coals from the Huainan coalfield, Anhui, China

To study the geochemical characteristics of 11 environmentally sensitive trace elements in the coals of the Permian Period from the Huainan coalfield, Anhui province, China, borehole samples of 336 coals, two partings, and four roof and floor mudstones were collected from mineable coal seams. Major elements and selected trace elements were determined by inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and hydride generation atomic absorption spectrometry (HAAS). The depositional environment, abundances, distribution, and modes of occurrence of trace elements were investigated. Results show that clay and carbonate minerals are the principal inorganic constituents in the coals. A lower deltaic plain, where fluvial channel systems developed successively, was the likely depositional environment of the Permian coals in the Huainan coalfield. All major elements have wider variation ranges than those of Chinese coals except for Mg and Fe. The contents of Cr, Co, Ni, and Se are higher than their averages for Chinese coals and world coals. Vertical variations of trace elements in different formations are not significant except for B and Ba. Certain roof and partings are distinctly higher in trace elements than underlying coal bench samples. The modes of occurrence of trace elements vary in different coal seams as a result of different coal-forming environments. Vanadium, Cr, and Th are associated with aluminosilicate minerals, Ba with carbonate minerals, and Cu, Zn, As, Se, and Pb mainly with sulfide minerals.     

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     

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.     

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。     

华南地区晚二叠和晚三叠世煤中稀土元素特征研究

在华南地区贵州六盘水、江西乐平、露庆和湖北黄石矿区晚二叠和晚三叠世煤层的稀土元素ICP—MS分析数据的基础上，系统研究了研究区煤中稀土元素的含萤分布特征、赋存特征、配分模式以及地质控制因素。含量分布表明晚二叠世稀土元素含量总体高于晚三叠世；煤中稀土元素与灰分成正相关关系，部分煤样品由于有富稀土元素的重矿物组合的存在而出现稀土元素的异常高值；同一矿区、同一时代煤中稀土元素的配分模式具有一定的相似性，而不同地区同一时代和同一地区不同时代煤中稀土元素的配分模式具有较大差异；煤的沉积环境，煤中无机矿物组成以及海水的影响是控制煤中稀土元素含量和配分模式的主要地质因素。     

Geochemistry of Sulfur and Hazardous Elements in Late Paleozoic Coals and Partings from Taozao Coalfield, Shandong Province, China

Intermsoftheharmfulmattersincoalandcoalminingwastes,thefirstisabouthazardouselements ,theotherin cludessulfurandhazardousorganicmatter.Muchresearchontracetoxicelementsandtheirimpactsonenvironmenthasbeeninvestigatedinmanycountries (Goodarzi,1995 ;Finkelman ,1994 ;Chouetal.,1982 ) .Althoughthere searchconcerningthisaspectwasstartedmuchlaterinChi na ,manystudieshavebeenstrengthenedsince 1980 ,andmuchprogresshasbeenmade ,alargenumberofdatahavebeencollected ,andthecomparisonshavebeenmadeforthedata…     

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。     

贵州普安矿区晚二叠世煤中贵金属元素的赋存状态和地质成因

运用电感耦合等离子体质谱(ICP-MS)和逐级化学提取技术(SCET)对贵州西部普安矿区晚二叠世煤中贵金属元素的含量、赋存状态和成因机理进行了研究.结果表明,贵州普安矿区2号主采煤层的矿物组成主要为低温热液流体成因的黄铁矿和陆源碎屑成因的粘土矿物;与中国煤煤相比,该煤中Rh(38 ng/g)、Pb(640 ng/g)、Ir(9 ng/g)、Pt(98 ng/g)、Au(16 ng/g)和Ag(1620 ng/g)明显富集,其中Pb、Ir、Au的含量分别是中国煤的4.3倍、9倍和5.3倍.逐级化学提取结果表     

中国西南地区二叠纪乐平世陆生生物大灭绝期煤中砷和硒的演化及古环境意义

为了探讨中国西南地区二叠系乐平统(上二叠统)龙潭组中下部煤系不同煤组分中砷、硒的含量和演化及古环境意义,对近10年来采集于中国西南扬子地台的二叠系乐平统龙潭组主采煤层的原煤、亮煤、煤矸石、黄铁矿结核等样品中砷、硒元素含量进行了测定和分析,并与中国华北地台一些煤矿的上石炭统-下二叠统太原组、山西组的原煤、镜煤、亮煤、煤矸石、黄铁矿结核等样品中砷、硒含量进行对比分析。结果表明：西南地区乐平统龙潭组煤的砷、硒含量变化较大,但总体高于华北晚石炭世和早二叠世煤的砷、硒含量;西南二叠系乐平统龙潭组大多数的亮煤中砷、硒含量高于原煤全煤样(刻槽样)中的砷、硒含量,也远远高于同煤层煤矸石的含量,龙潭组部分亮煤的砷含量尤其高,为55～338 mg/kg,还发现砷含量为89 mg/kg的亮煤。但华北上石炭统-下二叠统的镜煤中的砷、硒含量与之相反,低于原煤全煤样的砷、硒含量,其中砷含量非常低,为063～129 mg/kg。说明西南地区上二叠统煤中的砷和硒与煤的有机质密切相关,可能主要来源于成煤古植物。在西南乐平世早、中期第Ⅰ幕陆生生物集群灭绝事件期间,陆生动物的食物--植物中有毒有害元素砷、硒含量明显增加,陆生环境或泥炭沼泽中可溶性砷、硒含量增加。     

枣庄煤田太原组煤中微量元素地球化学特征

采用中子活化法测定了山东枣庄煤田晚古生代太原组高硫煤层中的微量元素质量分数 ,用数理统计方法取得了高硫煤中微量元素的浓度分布范围、平均值和变异系数 ,用逐步聚类分析法和相关分析法分析了微量元素的共生组合关系 ,并用扫描电镜 -能谱分析了不同煤岩组分的微量元素浓度 ,在此基础上结合形态硫分析结果和沉积相分析结果 ,讨论了高硫煤中微量元素的富集因素、聚集机理和成因背景 ,指出受海水影响的沼泽沉积环境不但对煤中形态硫的分布和含量有控制作用 ,同时对煤中微量元素的浓度和共生组合特点也有影响。太原组高硫煤中的微量元素按其成因可分成两组 ,一组是陆源碎屑富集型 ,其含量直接与煤中灰分产率呈正相关关系 ;另一组为盆地内部沉积 -生物作用富集型元素 ,海水的入侵和盆地介质的停滞还原条件和陆源碎屑物质输入量的减少最有利于沉积 -生物作用型元素的富集 ,并以有害元素 Cu、As、 U、 Pb、 Mo、 Sr和 Co的富集为特征。煤中黄铁矿及其他硫化物是许多有害元素的重要载体 ,充分凝胶化的富氢镜质体比其他组分承载和吸附有更多的有害元素。深入研究不同煤层的有害元素的有机亲和性有利于指导煤的合理利用和采用有效的有害元素的去除措施 ,以利于煤的有效和洁净利用     

Rare Earth Element Geochemistry of Late Palaeozoic Coals in North China

Instrumental Neutron Activation Analysis (INAA) was done to determine the abundances of rare earth elements (REE) of 58 samples of Late Palaeozoic Carboniferous-Permian coals and related rocks in North China. Detailed study of REE geochemistry shows that the ∑REE of most coals studied in this paper is in a normal range between 30×10-6 and 80×10-6 with a mean of 56×10-6. The REE in the Taiyuan Formation in the northern part of North China are much richer than those in the southern part. This is due to the shorter distance to the source area in the north. Moreover, the IREE is in positive correlation to coal ash, especially closely related to the content of clay minerals <2μm in size. This reveals that most REE were carried by terrigenous clastic materials, especially fine clay minerals. In the coals the light REE (LREE) are much richer than the heavy REE (HREE), and the LREE/HREE ratio in coals generally varies from 2 to 8. The LREE/HREE ratio of high-ash, low-sulphur coals is higher than that of lo     

Distribution Characteristics of Sulfur and the Main Harmful Trace Elements in China's Coal

To promote the rational development and use of clean coal resources in China,data on the regional and age distribution of sulfur,arsenic and other harmful elements in Chinese coal was broadly collected,tested for content,and analyzed.Coal in northwestern China is characterized by low to extremely low levels of sulfur;the coal of the Taiyuan Formation in northern China mainly has high-sulfur content;that of the Shanxi Formation is mainly characterized by low sulfur coal;and the Late Permian coal in southern China has overall higher sulfur content;other regions have low sulfur coal.The average content of harmful trace elements in the bulk of China's coal is similar to the corresponding content in the coal of the North America and the rest of the world,whereas the content of various elements(Hg,Sb and Se)is different in magnitude to the corresponding percentage in the crust.The average content of the elements Cr,Se,Co,Be,U,Br in Late Permian coal in S China ranks first in the country whereas the average content of Hg and Cl in the coals of Late Carboniferous to Early Permian age in N China are the highest.The average content of Mn in Early and Middle Jurassic coal is higher in NW China.The high content of harmful elements in some coal should cause particular concern both in the development and utilization of coal.     

我国煤中砷的含量赋存特征及对环境的影响

在检测了156个煤样中砷含量的基础上,收集了近2000个煤样的资料,分析了我国煤中砷元素的含量和赋存特征及砷富集的地质因素。结果表明,我国多数煤中砷含量处于0.8× 10-6~20×10-6,算术平均值为4× 10-6;砷的赋存方式主要为: a. 类质同象置换硫赋存于黄铁矿中; b. 低变质煤可赋存于有机质中; c. 以粘土矿物和稀有的含砷矿物为载体。煤中砷富集的地质因素,一是后期热液带入煤层;二是由陆源物质带入泥炭沼泽;三是同沉积时期海水的影响。燃用富砷煤是引发环境污染的基本原因,但是燃煤方式也是重要因素。多数煤中砷含量并不高,控制和预防砷的危害还是可以做到的。      

Distribution Characteristics of Sulfur and the Main Harmful Trace Elements in China’s Coal

To promote the rational development and use of clean coal resources in China, data on the regional and age distribution of sulfur, arsenic and other harmful elements in Chinese coal was broadly collected, tested for content, and analyzed. Coal in northwestern China is characterized by low to extremely low levels of sulfur; the coal of the Taiyuan Formation in northern China mainly has high-sulfur content; that of the Shanxi Formation is mainly characterized by low sulfur coal; and the Late Permian coal in southern China has overall higher sulfur content; other regions have low sulfur coal. The average content of harmful trace elements in the bulk of China＇s coal is similar to the corresponding content in the coal of the North America and the rest of the world, whereas the content of various elements （Hg, Sb and Se） is different in magnitude to the corresponding percentage in the crust. The average content of the elements Cr, Se, Co, Be, U, Br in Late Permian coal in S China ranks first in the country whereas the average content of Hg and CI in the coals of Late Carboniferous to Early Permian age in N China are the highest. The average content of Mn in Early and Middle Jurassic coal is higher in NW China. The high content of harmful elements in some coal should cause particular concern both in the development and utilization of coal.     

赣东北晚二叠和晚三叠煤的微量元素对比研究

通过对赣东北晚二叠世和晚三叠世煤的微量元素对比研究，阐述了这两种类型煤中常量和微量元素的含量和赋存特征。通过煤质特征，矿物学和元素的组相关性分析，概括了引起这两种类型煤常量和微量元素之间差弄的地质原因。     

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.     

华南湘桂粤地区煤中热液脉体的岩石学研究

煤中高含脉率脉体的出现，是煤热液变质作用的重要依据之一。本文详细讨论了湘桂粤地区早奥陶世、早石炭世、晚二叠世和晚三叠世煤中热液脉体的种类、岩石学特征及其与煤变质程度的关系。无论什么时代的无烟煤，随着其变质程度升高，煤中脉体的种类增多，矿物成分变得复杂，较高温热水矿物出现。     

电感耦合等离子体质谱-原子荧光光谱法研究上海口岸进口印度尼西亚煤炭微量元素的赋存形态特征

印度尼西亚是我国最大的煤炭进口国,本文应用电感耦合等离子体质谱、原子荧光光谱、直接测汞仪等技术分析了上海口岸31批进口印度尼西亚煤炭中的12种微量元素,结合数理统计方法研究该类煤炭中微量元素的赋存形态。结果表明,进口印尼煤炭中含有高汞煤、三级含砷煤,As、Hg的平均富集系数大于1,其迁移风险值得关注;Be、Cu、Mo、Cd、Sn、Pb含量均低于中国煤和世界煤炭的平均水平,体现出印尼煤炭低灰分的品质特征。12种微量元素和相关项目(灰分和全硫)可划分为3类:第一类归纳为黏土矿物吸附类,包括As、Be、Cr、Co、Ni、Cu、Mo、Cd、Sn、Pb、灰分;第二类归纳为硫铁矿类,包括Hg、全硫;第三类归纳为碳酸盐矿物类,包括Ba。本文研究结果对于指导进口煤炭开发、利用过程中的环境评价和洁净化处理具有一定的参考价值。