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。     

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.     

煤中微量元素研究进展

煤炭是我国的主要能源，在煤炭开采、运输、洗选、淋溶（滤）、燃烧等其它加工利用过程中，煤中的微量元素要发生迁移、析出，并入侵到大气、水、土壤和生态环境中，最终影响人类生存和生活环境。煤中微量元素十分重要，是因为它们与环境问题、动、植物及人类健康密切相关。在研究微量元素时必须考虑微量元素的性质及毒性，它们主要依靠其含量、种类、存在形式、pH值、氧化-还原条件及其它因素。在全面综合国内外研究文献的基础上，分析了煤中微量元素的发现、分布规律、赋存状态、成因机理及微量元素的应用等方面研究的历史、现状，并对今后研究的重点内容和发展方向进行了较为详细的论述和分析，并指出在进一步深入研究煤中微量元素地球化学的基础上，加强微量元素环境学方面的研究是今后煤中微量元素环境地球化学研究的重要内容。     

The occurrence of potentially hazardous trace elements in five Highveld coals, South Africa

Permian coals of the southern hemisphere are generally considered to contain lower concentrations of sulfides, halogens, and trace elements when compared to northern hemisphere Carboniferous coals. Few studies have considered the trace element content in South African coals, and little or no work has been published for Highveld coals. Of the nineteen coal fields in South Africa, the Highveld coal field is one of the nine currently producing, and is second largest in terms of production. Five run of mine samples and a high ash middlings product from the Number 4 Lower seam were analyzed, totaling six sample sets. Fourteen trace elements (As, Cd, Co, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se, V, and Zn) were selected for this study based on the global perception that these elements may be hazardous to human health and/or the environment when they are released during coal utilization. Several sample preparation techniques were tested using certified reference materials (SARMs 18, 19 and 20) to determine the most repeatable technique for these coals. The samples were analyzed by ICP-AES and CVAA (Hg only). Microwave digestion proved to be generally unreliable despite the utilization of several different methods. A slurry direct injection method into the ICP-AES provided good correlations with the reference material, but requires further development to enhance the confidence level in this relatively unexplored technique. Samples prepared based on three ASTM standards for the determination of trace elements in coal provided repeatable results in most instances, and were the preparation methods utilized for the Highveld coals.The trace element values determined for the Highveld coals are generally in good agreement with values available in literature for South African coals, with the exception of Hg, Mn and Cr. Hg values reported here are lower, Cr and Mn higher. Results generally agree well with analyses on the same samples conducted by the United States Geological Survey. When considering the global ranges for trace elements, the Highveld range values are within Swaine's range boundaries with the exception of Cr. Compared to the cited global average values for the fourteen trace elements determined, the values obtained for the Highveld coals generally fall below or well below these average values, with the exception of Cr and Mn. Concentrations of Cd and Cu are lower compared to global average values, and As, Mo, Pb, Se, Sb, and Zn can be considered low to very low. Arsenic is ten times lower compared to typical USA values. Concentrations of Co and Ni are similar to global averages, with V and Hg being very slightly higher. The middlings samples reported higher concentrations of most elements, related to the higher ash content of these samples. Of interest, the chalcophile elements determined are all depleted in the Highveld coals compared to global averages, and the siderophile elements are enriched or comparable to global averages.Risk-based health studies in the USA on coals with similar or higher Hg and significantly higher As contents have not reported negative health effects, and therefore it could be assumed that the mobilization of these trace elements from the five Highveld coals are unlikely to cause human health problems. Work is ongoing to determine the modes of occurrence of these HAPs and to address the partitioning behaviors and speciation states of these elements during coal utilization.     

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…     

Environmental geochemistry and health of fluorine in Chinese coals

Fluorine is one of the potential hazardous trace elements in coal. Fluorine may be released into atmosphere mostly during coal combustion process. When the coal is burning indoors without any controlling methods (chimney), the fluorine will pollute the room and is absorbed by food fired (dried) over stoves. Now many people have suffered from fluorosis due to coal burning indoors in Southwest China. In this paper, the concentration, distribution, mode of occurrences and impact factors of fluorine in Chinese coals are analyzed. The environmental impacts and typical features of fluorosis are studied. It is concluded that the value of fluorine in Chinese coals ranges from 20 to 300 mg/kg, and with average value of 122 mg/kg from 5,603 coal samples. It is higher than the average value of the world coals (80 mg/kg). In provincial coalfields of the SW China, the content of F is highest and many people have been affected due to coal combustion indoors.     

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.     

煤中微量元素分布特征初步研究

 采自我国不同聚煤区的不同时代的89件煤样品,用中子活化分析法(INAA)分别测定了29种微量元素。据统计分析结果表明:(1)绝大多数微量元素的平均值高于世界的平均值,含量范围也较美国宽。我国各聚煤区不同时代间相比较,煤中大多数元素的平均含量和富集因数,从华南二叠纪至华北石炭—二叠纪到全国中-新生代逐渐降低。(2)中-新生代的煤中,元素间的相关性较好,华南二叠纪次之,而华北石炭—二叠纪的煤最差。(3)REE分布模式类型以中-新生代的煤最复杂;而华北石炭—二叠纪的煤较简单。     

辽宁北票地区煤中微量元素研究

对辽宁北票地区煤中微量元素进行了研究 ,将研究区煤中微量元素的平均质量分数与世界范围煤的微量元素的平均质量分数进行比较 ,发现北票煤中的Cr、Co、Ni、As、Sr、Y、Zr、Ba、Ta、Sc具有较高的富集 ,而Sn、U具有较低的富集 ,这种差异可能主要与聚煤区域的地球化学背景有关。计算了微量元素之间的相关系数 ,得出北票地区煤中稀土元素总量较世界范围稀土元素总量的平均值偏高 ,且煤中稀土元素分布模式十分相似 ,表明在成煤期间陆源物质供应相对稳定。煤中矿物主要为高岭石、石英及方解石及少量的伊利石 ,并对其中的地质成因进行了初步解释。     

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     

Composition and quality of coals in the Huaibei Coalfield, Anhui, China

The Huaibei Coalfield, Anhui Province, China, is one of the largest coalfields in China. The coals of Permian age are used mainly for power generation. Coal compositions and 47 trace elements of the No. 10 Coal of the Shanxi Formation, the No. 7, 5, and 4 Coals of the Lower Shihezi Formation, and the No. 3 Coal of the Upper Shihezi Formation from the Huaibei Coalfield were studied. The results indicate that the Huaibei coals have low ash, moisture, and sulfur contents, but high volatile matter and calorific value. The ash yield increases stratigraphically upwards, but the volatile matter and total sulfur contents show a slight decrease from the lower to upper seams. Magmatic intrusion into the No. 5 Coal resulted in high ash, volatile matter, and calorific value, but low moisture value in the coal. Among the studied 47 trace elements, Ba, Co, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Th, U, V, and Zn are of environmental concerns. Four elements Hg, Mo, Zn, and Sb are clearly enriched in the coals as compared with the upper continental crust.     

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.     

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.     

淮北花沟西井田煤中微量元素及其环境意义分析

通过对30件煤样微量元素含量的测定,分煤层、分类型(稀土元素、环境意义微量元素)讨论了煤中微量元素的分布特征。研究发现各样品的稀土元素主要赋存于矿物质中,稀土元素含量均呈正常质量分数水平分布,各煤层的稀土元素分布表现为轻稀土富集、重稀土亏损。受陆源影响的煤,ΣREE含量高,稀土元素主要由陆源物质继承而来。受海水影响的煤,ΣREE含量低,分布模式具有海水性质。形成后受河流冲刷的煤,灰分增加,煤中稀土元素含量增加。该研究成果为煤炭资源的合理开发和利用提供基础资料。     

煤中氟的研究进展

在全面综合国内外研究文献的基础上,分析了煤中氟的含量、分布规律、赋存状态以及燃烧释放规律等方面的研究进展和存在的问题。我国煤中氟的研究总体上说滞后于煤中其它某些微量元素（如砷、硒、汞等）的研究。进一步深入研究煤中氟+K313的分布规律、赋存状态、来源及迁移转化规律,是今后煤中氟研究的重点。     

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。     

山西平朔安太堡露天矿9号煤层中的微量元素

使用ＩＣＰ－ＡＥＳ方法对安太堡露天矿９号煤层中的微量元素进行了系统测定,检测出５３种微量元素,将研究煤样的平均微量元素质量分数与世界范围微量元素平均质量分数相比较,煤样中Ｌｉ,Ｇａ,Ｓｒ,Ｚｒ,Ｎｂ,Ｓｎ和Ｔａ具有较高的富集,而Ｃｒ,Ｃｏ,Ｎｉ,Ｇｅ,Ｒｂ,Ｙ,Ｃｓ和Ｂａ具有较低的富集,研究资料表明不同微量元素在垂向剖面上其质量分数具有不同的分布特征。经相关分析表明：（１）与镜质组含量相关的元素有     

Characterization of Turkish coals: a nationwide perspective

The U.S. Geological Survey (USGS) and the Turkish General Directorate of Mineral Research and Exploration (Maden Tetkik ve Arama Genel Müdürlügü, MTA) are working together to provide a better understanding of the chemical properties of Turkish coals from major Turkish lignite producing areas.The coals in Turkey are generally low rank (lignite or subbituminous) formed in several different depositional environments at different geologic times and have differing chemical properties. Eocene coals are limited to northern Turkey; Oligocene coals, found in the Thrace Basins of northwestern Turkey, are intercalated with marine sediments; Miocene coals are generally located in Western Turkey. The coal deposits, which have limnic characteristics, have relatively abundant reserves. Pliocene–Pleistocene coals are found in the eastern part of Turkey. Most of these coals have low calorific values, high moisture, and high ash contents.Analysis of 143 coal channel samples (most are lignite and subbituminous in rank, but a few are bituminous and one is anthracitic in rank) has been completed for up to 54 elements and other coal properties using a variety of analytical techniques, including inductively coupled plasma emission and mass spectrometry, instrumental neutron activation analysis, and various single element techniques and ASTM standard procedures. Many of these coals have elemental concentrations similar to U.S. lignites found in the Gulf Coast and Fort Union regions. However, maximum or mean concentrations of B, Cr, Cs, Ni, As, Br, Sb, Cs, and U in Turkey are higher than the corresponding maximum or mean values found in either the Fort Union or Gulf Coast regions.     

Trace elements in the Goze Delchev coal deposit, Bulgaria

The geochemistry of trace elements in the underground and open-pit mine of the Goze Delchev subbituminous coal deposit have been studied. The coals in both mines are highly enriched in W, Ge and Be, and at less extent in As, Mn and Y as compared with the world-wide Clarkes for subbituminous coals. Ni and Ti are also enhanced in the underground coals, and Zr, Cr and Mo in the open-pit mine coals.Characteristic for the trace element contents in the deposit is a regular variation with depth. The following patterns were distinguished for profile I: a — the element content decreases from the bottom to the top of the bed paralleling ash distribution (Fe, Co, As, Sb, V, Y, Mo, Cs, REE, Hf, Ta, Th, P and Au); b — Ge and W are enriched in the near-bottom and near-top coals; c — in the middle part of the bed the content of K and Rb is maximal, while that of U is slightly enriched; d — Ba content decreases from the top to the bottom of the bed. In profile II, W and Be contents decrease from the bottom to the top. The near-bottom, and especially the near-roof samples of profile IV are highly enriched in Ge, while for W the highest is the content of the near-bottom sample.Ge, Be, As, Mn, Cl and Br are mainly organically associated. The organic affiliation is still strong for Co, B, Sr, Ba, Sb, U, Th, Mo, La, Ce, Sm, Tb and Yb in the underground coals, and Fe, Co, Na, W, Sr, Y and Ag in the coals from the open-pit mine. K, Rb, Ti, Zr, Hf and Ta are of dominant inorganic affinity. The chalcophile and siderophile elements correlate positively with Fe and each other and may be bound partly with pyrite or other sulphides and iron containing minerals.Compared statistically by the t-criteria, the elements Na, Li, Cu, Zn, Pb, Cr, Ni, Co, Mo, Fe and Be are of higher content in the open-pit mine. Tungsten is the only element of higher concentration in the underground mine. The contents of Ge, As, Sr, V, Mn, Y, Zr and P are not statistically different in both mines.It was supposed that there were multiple sources of the trace elements in the deposit. The source of the highly enriched elements (W, Ge, Be, and As) most probably were the thermal waters in the source area. The contemporary mineral springs are of high content of these elements. Another source were the hosting Mesta volcanic rocks, which are enriched in Sb, Mo, Hf, U, Th, As, Li and Rb. Some of the volcanics were hydrothermally altered and enriched or depleted of many elements. Thus, the hydrothermal solutions were also suppliers of elements for the coals. It is obvious that the contents, distribution and paragenesis, of the trace elements in both Goze Delchev coals reflect the geochemical specialization of the source area, including rocks, paleo- and contemporary thermal waters.     

A review of chlorine and bromine in some United Kingdom coals

In the UK there is a longstanding interest in the Cl content of coals because of the adverse effects associated with high-Cl coals during combustion. An average Cl content of a representative suite of coal samples is 0.44 wt.%, but the range is from near zero to over 1%. Several lines of evidence show that in the high-Cl coals the Cl is associated with the coal moisture and that other sources, such as the silicate minerals, are negligible. Although the Cl is moisture associated there is anion exchange with the organic matter, which means that Cl is less than 100% water- soluble unless the Cl is exchanged with other anion species. This occurs if carbonates are present and calcite in particular. The Cl and Br are closely related and the location within the coal is thought to be common to both. These two elements differ from nearly all other trace elements in UK coals in that they are not present in significant concentrations in the mineral matter or bound within the organic matter. Whereas there is a good understanding of the geochemical behaviour of these other elements this is not the case for Cl and Br in the coal moisture. Chlorine and Br are thought to be conservative elements in the diagenetic evolution of the porewaters, in which an original marine depositional imprint could have been preserved. In some areas the porewaters may have fully evolved pre-Permian, whereas in other areas the diagenetic evolution could be much longer.