Concentrations and distribution of elements in milled-coal, power plant ashes and stack-emitted materials in a Western Canadian coal-fired power plant

The focus of this study is to determine the concentrations and the distributions of elements of prime environmental concern （As, Cd, Cr, Cu Hg, Mo, Ni, Pb, Se and V） and other elements of environmental interest （B, Ba, Be, Co, Mn, U） in milled coals, power plant ashes, and stack-emitted materials from a Western Canadian power plant using bituminous coal. The concentrations of elements were determined using neutron activation analysis （NAA）, Inductively Coupled Plasma Emission Spectroscopy （ICPES）, and Inductively Coupled Plasma-Mass spectroscopy （ICP-MS） for most elements, Graphite Furnace Atomic Absorption （GFAA） for Pb, and Cold Vapor Atomic Absorption （CVAA） for Hg. The result of the study shows that the total rate of input is 423.5 kg/d for elements of prime environmental concern and 280 kg/d for elements of environmental interest. The concentrations of most elements in milled coal are low as compared to world coals and other Canadian milled coals. The total output of these two groups of elements is 2.9 kg/d and 110.4 kg/d, respectively. This indicates that only a small amount of the total input elements from the milled coal is emitted. Most of it is captured by the bottom and ESP ashes with the exception of the highly volatile As Hg, F, Br, and Cl. The element with highest rate of emission for elements of prime environmental concern is Se （0.73 kg/d） and B （95 kg/d） for the elements of some environmental interest.     

Environmental assessment of elements and polyaromatic hydrocarbons emitted from a Canadian coal-fired power plant

A detailed assessment of elements was carried out at a power plant rated at approximately 760 MW of electricity using western Canadian subbituminous coal. The concentrations of elements of environmental concern (As, Cd, Cr, Hg, Ni, and Pb) in milled coals, ashes, stack-emitted materials. Speciation of As, Cr, and Ni were determined. The polyaromatic hydrocarbons (PAHs) emitted from the stack were also measured. The rates of input of elemental input for As, Cd, Cr, Hg, Ni, and Pb were 28, 0.94, 230, 0.44, 44, and 88 kg/day, respectively; of which only 0.16, 0.01, 0.40, 0.27, 0.15, and 0.04 kg/day, respectively, were stack emitted. The total stack emission of toxic elements is 1.02 kg/day, with Cr being the highest contributor to this group with 0.4 kg/day. However, Hg at 0.27 kg/day has the highest percentage rate of emission at about 60%, while Cd has the lowest at about 1%. The electrostatic precipitator (ESP) removes a significant portion of the elements indicated by their relative enrichment (RE) ratios greater than 0.7. The results show that most of the elements in milled coal are low compared to world coals and other Canadian milled coals.Mercury is mostly ( 81%) emitted as gaseous elemental mercury (GEM), with 19% as reactive gaseous mercury (RGM). Particulate mercury is very low and averages about 0.1% of the total mercury at this station. Most of the arsenic in the milled coal is primarily associated with pyrite or as arsenate in its less toxic form of As⁺⁵ (> 95%). In both bottom and fly ashes, more than 95% of the total arsenic is present as As⁺⁵. Chromium in the milled coal and bottom ash is mostly non-toxic (Cr⁺³). The more toxic Cr⁺⁶ comprise less than 5% of the total Cr in the ESP fly ash and the stack-emitted ash. Nickel in milled coal and ashes is in the form of non-toxic Ni⁺², predominantly in coordination with oxygen.The emitted PAHs include acenapthene, fluorene, 2-methyl-fluorene, phenathrene, anthracene, fluoanthene, and pyrene; which are emitted from stack at the combined rate of 3.6 g/day. The concentrations of elements of environmental concern (As, Cd, Hg, Ni, and Pb) emitted to the atmosphere by the power plant in the zone of maximum impact at ground level are lower than those listed in the Health Guidelines of the USEPA and Canadian National Air Pollution Surveillance. This is based on stable meteorological conditions, down wind from the power plant for a maximum distance of 3 km.     

Mineralogy and geochemistry of feed coals and their combustion residues from the Cayirhan power plant,Ankara, Turkey

A total of 48 samples, feed (run-of-mine) coals and their combustion residues (fly ash and bottom ash) were systematically collected twice a week over a 4 week period (June 1998) from two boiler units (I and II) of the Cayirhan power plant (630 MW) that burns zeolite-bearing coals of late Miocene age. The feed coals are high in moisture (22.8% as-received) content and ash (44.9%) yield and total S content (5.1%), and low in calorific value (2995 kcal/kg). The mineralogy of the feed coals contains unusually high contents of the zeolites (clinoptilolite/heulandite and analcime), which are distributed within the organic matter of coal. Other minerals determined are gypsum, quartz, feldspar, pyrite, dolomite, calcite, cristobalite and clays. Common minerals in the crystalline phase of the combustion residues are anhydrite, feldspar, quartz, hematite, lime and Ca–Mg silicate. Minor and trace amounts of magnetite, cristobalite, maghemite, gehlenite, calcite and clinoptilolite/heulandite are also present in the combustion residues. Trace element contents of the feed coals, except for W, fall within the estimated range of values for most world coals; however, the mean values of Mn, Ta, Th, U and Zr are near maximum values of most world coals. Elements such as As, Bi, Ge, Mo, Pb, Tl, W and Zn are enriched more in the fly ash compared to the bottom ash.     

Crocoite: an unusual mode of occurrence for lead in coal

What is believed to be a very unusual mode of occurrence for lead in coal has been identified as crocoite (PbCrO₄). As part of a larger study on trace elements and mineralogy in the Cretaceous Main Seam in New Zealand, crocoite was found in raw coal samples within the lower part of the coal seam. X-ray diffraction (XRD) and bulk chemical data from a SEM equipped with an energy dispersive X-ray analyser (EDXA) have confirmed the identity of this mineral. This is apparently the first time that crocoite has been reported in coal. Crocoite usually occurs only in the oxidised zone of lead mineral deposits. The occurrence of this mineral in the Main Seam coal implies that the deposit was exposed to an oxidising environment at some stage, most likely after coalification.     

土壤和沉积物中元素的化学形态及其顺序提取法

介绍了形态分析的概念和化学形态分析方法,探讨了广泛应用于土壤、沉积物重金属形态分析中的Tessier和BCR顺序提取方案及其异同,综述了顺序提取方法在地球化学、环境科学、农业科学等方面的应用及中国相关标准物质的研制现状。     

Assessment of elemental content of milled coal,combustion residues,and stack emitted materials: Possible environmental effects for a Canadian pulverized coal-fired power plant

Two monitoring studies were carried out at four-year intervals on a power plant that uses western Canadian subbituminous coal and generates approximately 800 Mw/h of electricity. The distributions of elements of environment concern (As, Hg, Ni, Pb, and Cd) and elements of environmental interest (B, Ba, Be, Cl, Co, Cr, Cu, Mn, Mo, Th, Se, V, U, and Zn) in milled coals, power plant ashes, and emitted materials from the stack were determined using neutron activation analysis (NAA), Inductively Coupled Plasma Emission Spectroscopy (ICPES), and Inductively Coupled Plasma-Mass spectroscopy (ICP-MS) for most elements, Graphite Furnace Atomic Absorption (GFAA) for Pb, and Cold Vapor Atomic Absorption (CVAA) for Hg.The concentrations of most of elements in milled coal are low as compared to world coals and other Canadian milled coals. For example, in both studies mercury is within the lower range of world coal. Bottom ashes from both studies have low concentrations of As, Cd, Hg, Pb, and Zn, as well as low relative enrichment factors (RE) for the same elements, indicating that they were not enriched in the bottom ash. The ESP's remove most of the elements of environmental interest as indicated by their high RE ratios of greater than > 0.7.The rates of input of elements of environmental concern (As, Cd, Hg, Pb and Ni) for this station were 23.65, 1.24, 0.54, 98.2 and 95.2 kg/day, respectively, of which only 0.20, 0.02, 0.31, 0.48 and 0.36 kg/day were emitted from the stack. Thus only a small amount of these elements found in the milled coal was emitted while most were captured in the bottom and the ESP ashes. Nickel has the highest rate of emission (0.48 kg/day) within the elements of environmental concern group. However, the Ni emitted from this station does not belong to the toxic species. The element with the lowest rate of emission is Cd (0.02 kg/day). The total emission of elements of environmental concern is 1.37 kg/day, which is low as compared their ambient concentrations in either rural or urban air. The total rate of emission of B, Ba, Be, Co, Cr, Cu, Mn, Mo, Se, Th, U, V, and Zn is 56.51 kg/day and is mostly comprised of the total emission of Ba (21.73 kg/day) and Zn (19.14 kg/day).     

黔西晚二叠世煤地球化学性质变异及特殊组构的火山灰成因

运用仪器中子活化分析(INAA)、电感耦合等离子体原子发射光谱(ICP—AES)、X射线衍射(XRD)、带能谱仪的扫描电镜(SEM—EDX)及光学显微镜等手段，对黔西晚二叠世煤地球化学性质变异及其特殊组构的火山灰成因进行了研究。结果表明，贵州西部织金矿区9煤层中异常高含量的Fe(4．24％)、Cu(369．90μg／g)、U(49．6μg／g)、Mo(63．10μg／g)、Zn(33．97μg／g)等是来源于同沉积基性火山灰降落到泥炭沼泽中所致；高含量的Fe、Cu并非以通常意义的煤中硫化物状态存在；除煤中有机质和陆源碎屑外，发现了由火山灰、有机质和陆源碎屑所形成的煤层中的特殊组构，暂定名为沉碳质火山胶凝物，它是一种有机—无机高度混合物质，根据沉碳质火山胶凝物的形态特征和物质组成，厘定出6种组构类型，分别是：网状组构、细屑组构、基质组构、孔腔组构、均质组构和碎屑组构。     

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.     

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。     

The fate of trace elements in a large coal-fired power plant

 A quick approach is proposed to evaluate the environmental fate of trace elements in coal-fired power plants. It is based on the analysis of feed coal and solid combustion by-products, together with the leachates of the latter. The application of this method in a 1050 MW power plant from NE Spain shows that: (1) Ba, Ce, Co, Cs, Cu, Dy, Ga, Ge, La, Lu, Mn, Ni, Rb, Sr, Tb, Th, Y, Yb, Zn and Zr were retained in the solid wastes; (2) As, B, Be, Cd, Cr, Li, Mo, Pb, Sb, Sn, Ta, Tl, U, V and W were only partially retained in the solid wastes; and (3) Hg and Se were primarily emitted to the atmosphere. Received: 2 February 2000 · Accepted: 18 May 2000     

渭北煤田下峪口矿二叠纪煤中稀土元素地球化学研究

运用电感耦合等离子体质谱（ICP MS）对渭北煤田韩城下峪口矿二叠纪主采煤层及其顶底板中的稀土元素进行了测定。在此基础上,全面分析了稀土元素的含量特征和分布模式,探讨渭北煤田二叠纪煤中稀土元素的主要来源及赋存状态。结果表明：与华北和中国煤均值相比,本区煤层中稀土元素相对不富集,∑REY平均含量为87.70 μg/g;剖面上,2号煤中稀土含量稍高于3号煤,3号煤层中自上而下,稀土元素含量呈降低的趋势,在顶底板中出现富集。研究区煤层中轻稀土元素相对于重稀土元素明显富集,Ce呈微弱正异常,成煤沼泽受海水的影响程度较小。Eu明显负异常,且∑REY含量与CaO含量呈负相关关系,说明当时的成煤环境为酸性还原环境。煤层与其顶底板样品中稀土元素分布模式相似,成煤期间物质来源基本一致,陆源物质供应相对稳定。煤中稀土元素含量与灰分呈不太显著的正相关关系（R=0.216）,表明煤中稀土元素可能以无机态和有机吸附态共存。     

Trace elements in world steam coal and their behaviour in Dutch coal-fired power stations: A review

Trace elements associated with the combustion of coal have received more attention recently, as can be seen from the increasing demands laid down in legislation and permits.Knowledge of the trace element content of coal is essential. Coal used in the Netherlands is imported from all over the world. As a consequence, Dutch power stations are designed to burn a wide range of bituminous coals. The largest share nowadays originates from South Africa, Colombia, and Indonesia, with these three countries accounting for more than 85% of the coal fired in the Netherlands in recent years. The coals, as imported in the Netherlands, have been monitored for their (trace) element content. At present the database contains results of own analyses of about 170 coals, originating from 14 different countries. An important uncertainty was the question of how homogeneous the imported lots are. It appears that the lots as imported from overseas are fairly homogeneous.The behaviour and fate of trace elements in coal-fired power stations has been studied in more than 40 mass balance studies since 1977. More than 50 test series have been completed during co-combustion of biomass and waste materials (up to 40% on mass base) since 1993. It has therefore been possible to establish a relationship between (trace) elements in the fuel and the ash, as well as with emissions into the atmosphere.     

煤中常量元素的赋存特征与研究意义

煤中常量元素 (包括Na、Mg、Al、Si、K、Ca、Ti、P和Fe)是煤的重要无机组成,也是影响煤物理化学性质及加工利用的主要影响因素。本文结合华北鄂尔多斯盆地、开滦矿区和峰峰矿区晚古生代煤、贵州西部晚二叠世煤的具体实例,对煤中常量元素的赋存状态、地质成因和指相意义进行了总结,并对煤中常量元素在煤加工利用过程中的影响做了简要陈述。     

滇东上二叠统煤层煤岩特征及其对瓦斯涌出量的控制

基于滇东上二叠统赋煤区煤层的煤岩学特征、瓦斯含量、瓦斯涌出量及煤矿瓦斯事故统计分析,对研究区煤层的煤岩组成、煤体结构、煤炭筛分试验成果、煤层瓦斯含量和煤矿瓦斯涌出量进行了比对研究。研究表明：煤变质程度、显微煤岩组分、筛分粒级煤及煤的孔隙率等煤岩学特征控制了瓦斯的分布特征,并造成煤矿瓦斯涌出呈现区域性的差异;滇东上二叠统赋煤区瓦斯涌出类型可分为低煤阶均匀涌出型、中煤阶均匀涌出型、中煤阶非均匀突出型、高煤阶均匀涌出型和高煤阶非均匀突出型,且以中煤阶均匀涌出型为主。     

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。     

Depositional Environment and Lithofacies Analyses of Eocene Lacustrine Shale in the Bohai Bay Basin: Insights from Mineralogy and Elemental Geochemistry

The effect of various depositional parameters including paleoclimate, paleosalinity and provenance, on the depositional mechanism of lacustrine shale is very important in reconstructing the depositional environment. The classification of shale lithofacies and the interpretation of shale depositional environment are key features used in shale oil and gas exploration and development activity. The lower 3^rd member of the Eocene Shahejie Formation(Es₃^x shale) was sel...     

民用蜂窝煤燃烧排放颗粒物的化学组成和稳定碳同位素特征

本文选用了镜质组反射率在0.77%-1.88%之间5 种不同成熟度的煤, 将其制成民用蜂窝煤球, 研究民用蜂窝煤燃烧排放颗粒物（PM）的化学组成, 包括元素（C、N、O、S）、有机碳（OC）、元素碳（EC）和水溶性无机离子（WSII）, 稳定碳同位素组成特征和质量吸收效率值（MAE）, 并讨论了它们与煤成熟度之间的关系.结果表明, 5 种原煤C、N、O、S 元素组成差别不大, 但是燃烧后排放的PM 化学组成差别比较大.无烟煤燃烧排放的PM 粒径分布呈双峰结构, 峰值分别在0.09 μm 和0.25 μm; 而烟煤PM 的峰值为0.58 μm.无烟煤排放PM 的颗粒数远小于烟煤.PM、OC 和EC 的排放受煤成熟度的影响非常大, 无烟煤排放的量最小, 分别为2.21 g/kg、0.22 g/kg 和0.004 g/kg; 成熟度最低的烟煤排放量最大, 分别为70.3 g/kg 、46.1 g/kg 和2.42 g/kg.PM、OC 和EC 的排放因子与煤的成熟度成幂指数关系.EC 的MAE 在0.17-21.9 m^2/g 之间, 与煤成熟度呈指数相关关系.燃煤WSII 的平均排放因子为801 mg/kg, WSII 当中含量最高的是NH4^＋ 和24SO4^2- , 平均分别占WSII总量的23.5%和44.4%.燃煤排放PM 的δ^13C 变化范围为–24.5‰-–22.8‰, 平均值为–23.6‰.以上研究有助于人们从原煤性质的角度去考察民用燃煤对人类健康和气候变化的影响, 并为大气污染源解析提供一些科学依据.     

安徽巢湖凤凰山石炭系黄龙组红色灰岩矿物地球化学特征

安徽巢湖凤凰山晚石炭世黄龙组的地层主体为肉红色生物屑微晶灰岩,顶部为夹灰岩条带的泥岩。矿物学分析显 示,肉红色生物屑微晶灰岩的矿物主要为方解石,含少量针铁矿和赤铁矿。漫反射光谱分析表明,常用的古气候指标“红 度”与灰岩中铁氧化物、氢氧化物的光谱强度具显著的正相关性,而与岩石的全铁含量相关性较低,据此推测铁的氧化物 和氢氧化物是灰岩呈肉红色的重要原因。元素地球化学分析结果显示,黄龙组灰岩相对富Fe,Mn,而贫Co,Ni,在 Al-Fe-Mn,Fe-Mn-(Cu+Co+Ni)以及Cu-Pb-Zn三角判别图上,均靠近或落入热液成因区。综合地球化学特征与前人研究成 果,该文认为巢湖凤凰山黄龙组肉红色灰岩的形成很可能受到海底热液活动的影响。     

老厂矿区煤体结构测井判识与分布规律

煤体结构是制约煤储层可改造性的最重要地质因素之一。基于视电阻率、人工伽玛和自然伽玛射线测井响应,通过钻孔及煤层对比分析,建立了滇东老厂矿区晚二叠世龙潭组煤体结构的判识方法,并对9、13、19号三套主煤层的煤体结构及其分布特征进行了研究。结果表明,在利用测井响应曲线判识煤体结构时,采用对比的方法可以减少相应误差,从而更准确判识出结果。煤体结构变化与构造发育程度相关。平面上,一勘区构造较为简单,原生结构煤(Ⅰ类)较发育;白龙山井田受次级褶曲及断层发育的影响,构造煤(Ⅲ类)最发育;雨旺井田构造相对简单,主要发育过渡型(2类)煤。垂向上,随着煤层埋深增加,Ⅰ+Ⅱ类煤的厚度比例有增高趋势,且皆超过60%,揭示出深部煤层受构造破坏的影响程度较浅部低。     

古泥炭沉积环境及其对微量元素的控制:以宁武煤田东露天煤矿11#煤层为例*

古泥炭形成时期沉积环境对煤中微量元素的富集具有重要的影响,而煤相和相关地球化学参数是指示古泥炭沉积环境的重要标志。以宁武煤田平朔矿区东露天煤矿11#煤层为例,利用煤相参数、地球化学参数和矿物学特征对东露天11#煤层的古泥炭沉积环境进行了重建,并探讨了沉积环境对微量元素富集的影响。结果表明: (1)东露天煤矿11#煤层煤相类型包括障壁岛潟湖低位沼泽相、下三角洲平原低位沼泽相和上三角洲平原低位沼泽相3种类型,受海侵影响,沼泽水体pH、古盐度、氧化还原状态和水动力条件呈现动荡变化; (2)11#煤层中元素Li(平均133.50 μg/g)、Zr(平均198.12 μg/g)和Pb(平均60.76 μg/g)含量远高于世界硬煤; (3)微量元素在11#煤层剖面中表现为2种不同的组合,即Li-Zr-Nb-Ta-Hf组合和Pb-Cu-Ga-Ge-Tl-REY组合,前者主要在DLT-11-2、DLT-11-6和DLT-11-10这3个层位富集,这些层位具有相似的沉积环境,为海水(咸水)、酸性、缺氧—还原、水动力较强、硫含量相对较低的障壁岛—潟湖低位沼泽相,而后者主要在DLT-11-0、DLT-11-4和DLT-11-8这3个层位富集,沉积环境也相似,为海水(咸水)、碱性、氧化或缺氧、水动力较弱、硫含量相对较高的下三角洲平原低位沼泽相。该成果将为含煤盆地关键金属矿产资源的勘探开发和煤炭资源的清洁利用提供理论依据。