A statistical approach to the study of the distribution of trace elements and their organic/ inorganic affinity in lower Gondwana coals of India

Trace-element analyses of seventy six coal samples representing all the major Lower Gondwana coal basins of India were carried out. Eighteen trace elements, viz., B, Ba, Co, Cr, Cu, Ga, Ge, La, Mn, Mo, Nb, Ni, Pb, Sn, Sr, V, Y and Zr were determined quantitatively in coal ash. An attempt was made to correlate the coals of different coalfields on the basis of multivariate analysis. In addition, the organic/inorganic affinities between the trace elements were established by the coefficients of correlation between the trace elements and ash present. A synthesis of the data reveals that there is similarity in the concentration ranges of trace elements among the coal seams of different coalfields, but the possibility of environmental differences exists due to the statistically different multivariate means of the trace-element concentrations.It is inferred that Ge, Cr, Y and La occur in these coals as organo-metallic complexes and chelates. The elements Ni, Co, Ga, V and Cu show both organic and inorganic association, whereas Mn and Ba are exclusively incorporated in the inorganic fractions.     

Coal combustion by-product quality at two stoker boilers: Coal source vs. fly ash collection system design

Fly ashes from two stoker boilers burning Pennsylvanian Eastern Kentucky high volatile A bituminous coal blends were examined for their petrology and chemistry. The source coals have similar trace element contents. One of the ash collection systems was retrofitted with a baghouse (fabric filter) system, collecting a finer fly ash at a cooler flue gas temperature than the plant that has not been reconfigured. The baghouse ash has a markedly higher trace element content than the coarser fly ash from the other plant. The enhanced trace element content is most notable in the As concentration, reaching nearly 9000 ppm (ash basis) for one of the collection units. Differences in the ash chemistry are not due to any substantial differences in the coal source, even though the coal sources were from different counties and from different coal beds, but rather to the improved pollution control system in the steam plant with the higher trace element contents.     

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     

贵州普安-晴隆矿区晚二叠世煤及煤灰中伴生元素的富集特征

运用电感耦合等离子体质谱仪（ICP-MS）和电感耦合等离子体发射光谱仪（ICP-AES）分别对普安-晴隆矿区晚二叠世C17、C19、C22和C26号煤层中8个煤样和7个煤灰样进行微量元素含量的测试分析。结果表明,煤及煤灰中明显富集Li、Sc、V、Cr、Co、Ge、As、Nb、Mo、W、U等元素,且各元素在煤灰中更加富集,Nb、Zr、V、Ga和U等伴生金属元素的含量基本达到或超过了对应元素的边界品位或最低工业品位。煤中伴生元素的富集成因研究表明,V、Cr、Co、Nb和Zr等元素的富集主要受物源区峨眉山玄武岩风化碎屑物质供给的控制;U、S、Mo等元素的有限富集与海水作用有关;而受成煤期同沉积火山灰沉降的影响,煤中Li、Nb、Zr、Mo和U等微量元素表现出一致富集的特点;成煤期后的低温热液作用,使得各煤层,尤其是底部煤层（C19、C26）明显富集As、Mo、U和W等元素。综合分析认为,成煤期同沉积的火山灰沉降和成煤期后的低温热液作用是普安-晴隆矿区晚二叠世煤中伴生元素异常富集的主控地质因素。      

山西阳泉三矿煤层粘土岩夹矸地球化学特征

采用化学法和中子活化(INAA)法对采自山西阳泉三矿山西组3号煤层和太原组12号煤层的3件煤层夹矸粘土岩样品的8种常量元素(氧化物)和33种微量元素含量进行了测定。通过对具有示踪意义的元素及其比值的对比分析,3个样品总体上均不具有典型的沉积岩特征,应该是由酸性或酸性偏碱性火山物质(降落的或陆源搬运的)在地表覆水较浅的弱氧化条件下经原地淋滤、蚀变形成的。原岩蚀变程度较高,不稳定或较不稳定的元素大量流失,甚至一些较稳定的元素(如高岭岩中的铁、锰)也明显流失。强烈的化学蚀变以及岩石中矿物成分的变化是造成粘土岩间以及粘土岩与原岩间元素(尤其是REE)含量及REE配分模式差异的主要原因。      

Characteristics of Coal Ashes in Yanzhou Mining District and Distribution of Trace Elements in Them

In the process of combustion of coal organic and inorganic materials in it will undergo a complex variation.Part of thew will become volatiles and,together with coal smoke,enter into atmosphere,some will remain in micro-particulates such as ash and dust and find their way into atmosphere in the form of solid particles,and the rest will be retained in ash and slag.Coal ashes are the residues of organic and inorganic substances in coal left after coal combustion and the compostition of coal ashes in dependent on that of minerals and organic matter in coal.This paper deals with the chemical composition of coal ashes,the distribution of trace elements in them and their petrological characteristics,and also studies the relationship between the yield of coal ashes and the distribution of trace elements.In addition,a preliminary study in also undertaken on the factors that affect the chemical composition of coal ashes.As viewed from the analyses of coal ash samples collected from the Yanzhou mining district,it can be seen clearly that coal ashes from the region studied are composed chiefly of crystalline materials,glassy materials and uncombusted organic matter and the major chemical compositions are SiO2,Al2O3,Fe2O3,and CaO,as well as minor amounts of SO3,PWO5,Na2O,K2O and TiO2.During the combustion of coal,its trace elements will be redistributed and most of them are enriched in coal ashes.At the same time,the concentrations of the trace elements in flying ash are much higher than those of bottom ash,i.e.,with decreasing particle-size of coal ashes their concentrations will become higher and higher.So the contents of trace elements are negatively proportional to the particle-size of coal ashes.There has been found a positive correlation between the trace elements Th.V.Zn,Cu and Pb and the yield of coal ashes while a negative correlation between Cl and the yield of coal ashes.     

淮北煤中几种具有环境意义的微量元素分布

通过中子活化法,对淮北煤田主采煤层中和相对应的灰中几种具有环境意义的微量元素含量进行了测试,分析了它们在煤中和灰中的含量分布,并与中国和华北煤田煤中的平均值进行了对比,以便为煤和煤灰的综合利用提供基础资料。      

On the geochemistry of indium in coal-forming process

The content and distribution of In in 168 samples from 7 coal deposits in Bulgaria were studied, using a spectrochemical method with a detection limit of 0.002 ppm. Indium is present in all samples, its content varying from 0.002 to 0.167 ppm in the coal and from 0.005 to 0.57 ppm in the ash. The mean contents for individual deposits do not differ statistically, and for all the deposits the In concentration (ppm) can be expressed generally by the equation In = 0.00068 A (A is the coal ash content in %).Of the petrographic constituents of coal, vitrain, xylene and liptain are enriched in In. In is associated with both the organic and with the inorganic matter of the coal. Inorganic matter and clay minerals in particular, act only as carriers of Indium. In contrast, organic matter concentrates In only to a small degree relative to other trace elements.     

Geochemistry of Permian Coal and Its Combustion Residues in Huainan Coalfield, China

INTRODUCTIONMany environmental problems may arise during coal min-ing and utilization. Among these prob1ems, much attention hasbeen paid to S(), and NO. emission during coal combustion.But the environmental effects produced by hazardous elementsduring coal mining and utilization are also important and de-serve to be studied (Goodazi, 1995; Finkelman, 1993; Valk-ovic, l983). For example, when coal wastes are used for landreclamation, the harmful elements in them may pollute water,soil an…     

Condensing multi-element reconnaissance geochemical data from south Greenland using empirical discriminant analysis

Empirical discriminant analysis classified multivariate data from 2174 geochemical reconnaissance samples from South Greenland, so that they were related to known geological units or characterized as outliers. Training sets, comprising 514 samples from 14 geologic units were selected in order to reflect only the background conditions of each geological unit. A smoothing parameter of 0.5 maximized correct classification of the training sets and extracted a reasonable number of outliers (289, 13% of the samples) representing geographically grouped anomalies. Plots of the geochemical samples classified into the geological units corresponded well to the geological map.Q-mode cluster analysis classified the 289 outliers into 30 groups with different element associations. All types of mineral occurrence known in South Greenland could be recognized amongst the clusters. For example, there were seven clusters which were characterized by samples with high U values and different associated elements each one related to a different type of U mineralization. Another cluster containing samples with high Zr, Nb, and Y values reflects recently discovered pyrochlore mineralization. Other clusters were explained on the basis of geological units which were too small to be mapped or included amongst the training sets.Empirical discriminant analysis successfully reduced the multivariate data to one map, which made it easier to evaluate the varying element levels over the different geological units. Incorrectly classified samples require follow-up in order to appraise the accuracy of the geological mapping. Classification of the outliers by cluster analysis assists both in identifying samples influenced by mineral occurrences and in predicting the type of mineralization to be expected, thereby substantially aiding in the selection of areas for mineral exploration.     

煤中有害微量元素的赋存状态

基于前人资料的分析总结，系统探讨了煤中Ag等26种有害微量元素的赋存状态。研究结果表明：煤中有害元素或多或少都与无机质、有机质有联系，只是联系程度不同。有些在地壳中被认为彼此关系不大的元素，在煤中却密切相关。煤中B、Be、Br等主要以有机相赋存，其它有害元素主要与矿物质有关。     

Trace elements in high-S subbituminous coals from the teruel Mining District, northeast Spain

The elemental composition of high temperature ash (750°C) and forms of S were studied in 25 coal seams from the Escucha Formation (Middle Albian) in the Teruel Mining District, northeast Spain. The principal analytical method was ICP-MS, but ICP-ES was also used in the determination of some trace elements. The analytical data show wide ranges of trace element cotnents among the coal seams studied, even in the vertical profile of a single coal seam. These wide ranges of the trace element concentrations are attributed to both syngenetic and epigenetic processes.When a comparison was made between the average trace element contents of the Teruel Mining District coals, and those of the average content in worldwide coals, the Teruel coals show slightly higher concentrations of Be and U, and lower concentrations of Ba, Cd, Mn, Pb, Sr and Zr. Further, three main groups of trace elements were differentiated on the basis of the inorganic/organic association: (1) trace elements with inorganic affinity; Ba, Ce, Co, Cr, La, Mn, Ni, Rb and Zr. Between these, Ba, Ce, Cr and Rb show a well defined correlation with the clay mineral content, and Co and Ni with pyritic-S content; (2) trace elements with an intermediate (mixed) affinity; As, Cd, Cu, Dy, Er, Eu, Gd, Ge, Ho, Lu, Mo, Nd, Pb, Pr, Sb, Sm, Sr, Tb, Th, Tm, U, Yb and Zn. In this group, As, Cd, Cu, Ge, Mo, Th, U and Zn show a weak trend associated with the mineral matter and Sr with the organic matter; and (3) Be shows an organic affinity. The high mineral matter content (21.3% HTA) of the Teruel coals may account for the great number of elements with inorganic affinity. This classification represents a general trend, but the results show that the affinities of some trace elements (e.g. As, Sb and Zn) may vary from one coal seam to another in the Teruel Mining District.     

Geochemical characteristics of REY,Li, Ga trace elements in the No. 9 coal seam of the Daheng mine,Ningwu coalfield,Shanxi Province,China

To understand the geochemical characteristics of the No.9 coal in the Daheng Mine of the Ningwu coalfield, the trace element analysis was conducted through X-ray fluorescence spectroscopy (XRF) and inductively coupled plasma mass spectrometry (ICP-MS). The sedimentary environment was discussed according to the element geochemical parameters. The results show that Li, Ga, Hf, Zr, Nb, Th, and Ta are slightly enriched in the No. 9 coal of Daheng Mine. The average value of the rare earth elements and yttrium (∑REY) in coal here is 144.20 μg/g (excluding parting), which is higher than the average value of ∑REY in the world ’s coal and China ’s coal. The light rare earth elements (LREY) are enriched. The content of Eu was 0.12–2.10 μg/g with an average of 0.57 μg/g, and the Eu is obviously negatively abnormal. Most of the trace elements in the coal are positively correlated with the ash content, which shows that the occurrence of these trace elements is related to inorganic minerals. The results of sequential chemical extraction experiments show that rare earth elements mainly exist in coal in the form of aluminosilicate. The value of the Sr/Ba and the content of S reflect that the coal-forming environment was influenced by seawater. The values of V/Cr and Ni/Co reflect that the peat swamp is in an anaerobic environment and a strongly reducing environment during the coal-forming period.     

内蒙古胜利煤田0-1孔煤中微量元素地球化学特征

运用电感耦合等离子体质谱和煤质分析等技术方法,对内蒙古胜利煤田0-1号钻孔揭露的早白垩世1、2和4号煤层(共20个煤分层,1个夹矸)进行了研究。结果显示,1、2号煤层的挥发分产率大于44%,透光率小于50%,煤类为褐煤;4号煤层挥发分产率42%,透光率53%,煤类为次烟煤(长焰煤);1、2号煤层灰分和硫含量较高,4号煤层灰分和硫含量较低。与世界煤微量元素含量平均值相比,1、2和4号煤层中Sb富集,V、Zr、Nb、Hf、W等元素轻微富集,其它微量元素的含量接近或低于世界煤含量的平均值。1、2和4号煤层中稀土元素和钇(REY)含量较低,根据上地壳标准值(La/Lu)N比值,所有煤分层均显示重稀土富集类型特征,而煤中泥岩夹矸则显示轻稀土富集类型特征。     

The origin and distribution of HAPs elements in relation to maceral composition of the A1 lignite bed (Paleocene, Calvert Bluff Formation, Wilcox Group), Calvert mine area, east-central Texas

The origin and distribution of twelve potentially Hazardous Air Pollutants (HAPs; As, Be, Cd, Cr, Co, Hg, Mn, Ni, Pb, Sb, Se, and U) identified in the 1990 Clean Air Act Amendments were examined in relation to the maceral composition of the A1 bed (Paleocene, Calvert Bluff Formation, Wilcox Group) of the Calvert mine in east-central Texas. The 3.2 m-thick A1 bed was divided into nine incremental channel samples (7 lignite samples and 2 shaley coal samples) on the basis of megascopic characteristics. Results indicate that As, Cd, Cr, Ni, Pb, Sb, and U are strongly correlated with ash yield and are enriched in the shaley coal samples. We infer that these elements are associated with inorganic constituents in the coal bed and may be derived from a penecontemporaneous stream channel located several kilometers southeast of the mining block. Of the HAPs elements studied, Mn and Hg are the most poorly correlated to ash yield. We infer an organic association for Mn; Hg may be associated with pyrite. The rest of the trace elements (Be, Co, and Se) are weakly correlated with ash yield. Further analytical work is necessary to determine the mode of occurrence for these elements. Overall, concentrations of the HAPs elements are generally similar to or less than those reported in previous studies of lignites of the Wilcox Group, east-central region, Texas. Petrographic analysis indicates the following ranges in composition for the seven lignite samples: liptinites (5–8%), huminites (88–95%), and inertinites (trace amounts to 7%). Samples from the middle portion of the A1 bed contain abundant crypto-eugelinite compared to the rest of the samples; this relationship suggests that the degradation of plant material was an important process during the development of the peat mire. With the exception of Hg and Mn, relatively low levels of the HAPs elements studied are found in the samples containing abundant crypto-eugelinite. We infer that the peat-forming environment for this portion of the coal bed was very wet with minimal detrital input. Relatively high concentrations of crypto-humotelinite were found in samples from the top and base of the coal bed. The presence of abundant crypto-humotefinite in this part of the coal bed suggests the accumulation of wood-rich peat under conditions conducive to a high degree of tissue preservation in the peat mire. Although several of the trace elements (Be, Co, Ni, and Sb) exhibit enrichment in these samples, they are not necessarily chemically associated with humotelinite. We infer that these elements, with the exception of Be, are possibly associated with deposition of the roof and floor rock of the coal bed; however, further analytical work would be necessary to confirm this hypothesis. Beryllium may have an organic origin.     

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.     

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.     

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。     

兖州矿区山西组 3煤层中微量元素的特征分析

通过对兖州矿区山西组3煤层21个样品中全硫、硫化物硫、有机硫和具有环境意义的微量元素Cu、Pb、Zn、As、U、Th含量的测试，分析了微量元素在研究区煤层垂直方向上的变化特征及主要形成原因，并发现煤层中所选的微量元素、硫化物琉及全硫在煤层顶、底或煤层夹矸样品中含量相对较高。微量元素与硫化物硫、全硫的相关系数表明，所研究的微量元素与硫化物硫和全硫有明显的正相关关系，而且研究区3煤层中全硫的含量取决于硫化物硫的含量。同时还研究了原煤中微量元素的含量与灰产率的关系，并将研究区微量元素同世界和中国同类煤中的微量元素的含量进行了比较。     

淮南二叠纪煤及其燃烧产物地球化学特征

采用仪器中子活化分析法INAA（instrumental neutron activation analysis)测试了淮南煤田二叠纪主采煤层原煤煤样的地球化学组成，用X－射线荧光光谱XRFS（X－ray fluorescence spectrometry)测试了田家庵和洛河电厂的粉煤灰地球化学组成并与煤样作了对比分析，用电子探针测试了飞灰中主要类型颗粒的化学组成，淮南煤中多数微量元素属正常水平，与克拉克值相比，元素Se,S,As,Sb,Br,U和Cl等在煤中趋于富集，其他元素均趋于分散，有机亲和性弱的亲石元素趋于在粉煤灰中聚集，与铁关系密切的金属元素在粉煤灰中有明显的富集，有机亲合性强的元素在燃烧过程中趋于以气态形式向空气中逸散，粉煤灰中因矿物与粒度的分异明显，致使其化学组成在不同的粒度级和比重级中的分布也有较大的不同，飞灰中一些不定形颗粒主要由铁的氧化物和少量其他金属氧化物组成，硅酸盐类颗粒主要由硅，铝和铁的氧化物所组成，而玻璃珠主要由硅和铝的氧化物组成，残碳中测得的砷，硫和氯的含量最高，说明其对这些元素具有较强的吸附能力，研究粉煤灰的成分特点有助于粉煤灰的综合利用和评价其对环境的 影响。