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.     

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。     

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.     

晋北-宁北煤中痕量元素的地球化学特征

应用仪器中子活化 (INAA)、电感耦合等离子体原子发射光谱 (ICP- AES)和原子吸收光谱 (AAS)等方法测定了晋北-宁北一线 5对矿井、 2个露天矿、 5个电厂和 3个洗煤厂煤中环境敏感性痕量元素的含量;通过与中国土壤、其他地区煤以及世界范围煤中痕量元素含量进行对比,总结了研究区痕量元素的分布、富集特征,得知部分地区煤中 Hg、 Cd和 Se的含量较高,在燃烧利用过程中可能对环境造成影响.通过分析痕量元素与灰分、挥发分的相关性以及痕量元素间、痕量元素与 Al、 Fe和 Sp的相关、聚类特性,探讨了痕量元素间及其与矿物质间的亲合性及赋存特征.     

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…     

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。     

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。     

Element mobility during alteration of silicic ash to kaolinite—a study of tonstein

A laterally persistent kaolinitic mudstone parting (tonstein) occurring in a Wyoming coal bed of Eocene age was sampled to estimate the compositional contrast with a probable silicic ash precursor, and to determine the compositional influence of leached ash on immediately adjacent coal. With the exception of Al, and possibly Ti, the tonstein is highly to moderately leached of major elements, relative to a range of compositions estimated for silicic ash of the region. In agreement with the behaviour of geochemically similar major elements, alkali trace elements (Rb, Cs) are highly leached, transition-series metals moderately leached, and Ga is residual. Additional immobile trace elements are Zr and Hf but some other trace elements that are considered relatively immobile during low-temperature alteration (Th, Ta, Nb, REE, Y) were apparently leached by the low-Eh, low-pH, organic-rich pore fluids of the coal-forming swamp. The migrational range of many of the leached elements is highly limited by the intimate association of tonstein with enclosing organic matter. Mixtures of coal + minor tonstein that occur within 20 mm of contacts are consistently enriched in some elements relative to either tonstein or nearby coal (U, Cu), or relative to calculated mixtures of tonstein and coal in their measured proportions (Th, Y, REE, Pb, Ba, V, Ti). Direct observations by fission-track radiography and electron microprobe indicate a preference of U and Fe for the organic component of mixtures. Metal fixation is probably by adsorption on insoluble organic matter (humic acids), or by precipitation as minor sulphides in these low-sulphur coals.     

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。      

Geochemistry, mineralogy, and technological properties of the main Stephanian (Carboniferous) coal seams from the Puertollano Basin, Spain

This study is focused on the occurrence and distribution of mineral matter and major and trace elements in the high volatile bituminous coal from Puertollano (south-central Spain). The relationship between ash behaviour and inorganic composition, as well as the possible formation of fouling and slagging deposits in boilers during the conversion process, were investigated. The Puertollano coals do not exhibit plastic properties, despite their rank, probably because of their high ash and inertinite contents.The Puertollano coal has medium to low total S content (0.48% to 1.63% db, with a mean of 1.0% db) and is characterised by relatively high contents of Si, Pb, Sb, and Cs. Some elements such as As, Cd, Co, Cr, Cu, Ge, Li, Mn, Ni, W, and Zn are also present in relatively high contents. The enrichment in a number of heavy metals could be attributed to the common sulphide ores occurring near the Puertollano coal deposit.The following trace elements affinities are deduced: (a) sulphide affinity: As, Co, Cd, Cu, Ni, Sb, Tl, and Zn; (b) aluminum–silicate affinity: K, Ti, B, Co, Cr, Cs, Cu Ga, Hf, Li, Nb, Rb, Sn, Ta, Th, V, Zr, and LREE; (c) Carbonate affinity: Ca, Mg, Mn, and B; (d) organic affinity: B.The very high Si levels and the anomalous enrichment in Cs, Ge, Pb, Sb, and Zn shown by the Puertollano coals account for the high contents of these elements in the Puertollano fly ash when compared with the other Spanish coal fly ashes.The chemical composition of the high temperature ash (HTA) is consistent with the trend shown by the ash fusion temperatures (AFT) and also with the predictive indices related to slagging and fouling propensities. Thus, the ash fusion temperatures increase with high values of Al₂O₃ as well as with the decrease in Fe₂O₃, CaO, and MgO.     

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。     

Variability in the inorganic element content of U.S. coals including results of cluster analysis

Patterns of variability in trace element and major inorganic element content of 335 U.S. coal samples were investigated using the multivariate statistical techniques of principal component analysis and cluster analysis. Whole-coal basis values contain different information from ash basis values; therefore data expressed on each basis were treated separately. For each basis, major elements grouped together according to their occurrence in dominant inorganic groups in coal (aluminosilicates, sulfides, and elements organically bound or in carbonates), and relationships of trace elements to these groups were shown. Cluster analysis grouped samples based on their inorganic content. For data expressed on an ash basis, either three or four clusters were indicated. The three-cluster partition was similar to a partition into Eastern, Interior, and other (western) provinces. The partition into four clusters was more complex; is showed that samples from the Eastern and Interior provinces taken as a group can be divided into three clusters. One, characterized by low aluminosilicate and sulfur levels, contains both Interior and Eastern province samples. Thus not all Interior province samples are characterized by high levels of iron sulfide and associated elements; some are more similar to many Eastern province samples than to other Interior province samples.     

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.     

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.     

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.     

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.     

华能南京电厂不同粒径粉煤灰中微量元素分布及其富集规律

华能南京电厂不同粒径粉煤灰的化学成分和矿物相组成基本相同，煤粉所含矿物质在高温燃烧过程中的挥发－凝聚作用，导致微量元素趋向细粒径粒煤灰中富集，其富集的程度则与粉煤灰的平均粒径和元素的地球化学性质密切相关，粉煤灰排放的环境效应表明，尤以细粒径灰粒的影响最大。     

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.     

From in-situ coal to fly ash: a study of coal mines and power plants from Indiana

This paper presents data on the properties of coal and fly ash from two coal mines and two power plants that burn single-source coal from two mines in Indiana. One mine is in the low-sulfur (<1%) Danville Coal Member of the Dugger Formation (Pennsylvanian) and the other mines the high-sulfur (>5%) Springfield Coal Member of the Petersburg Formation (Pennsylvanian). Both seams have comparable ash contents (11%). Coals sampled at the mines (both raw and washed fractions) were analyzed for proximate/ultimate/sulfur forms/heating value, major oxides, trace elements and petrographic composition. The properties of fly ash from these coals reflect the properties of the feed coal, as well as local combustion and post-combustion conditions. Sulfur and spinel content, and As, Pb and Zn concentrations of the fly ash are the parameters that most closely reflect the properties of the source coal.