贵州普安矿区晚二叠世煤中微量元素的质量分数和赋存状态

运用电感耦合等离子体质谱（ICP-MS）、X射线荧光光谱（XRF）、冷原子吸收光谱（CV-AAS）、原子荧光光谱（AFS）、离子选择性电极法（ISF）、带能谱仪的扫描电镜（SEM EDX）和逐级化学提取技术（SCET）对贵州普安矿区晚二叠世煤中微量元素的质量分数、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黏土矿物；与贵州煤、中国大部分煤和美国煤相比，该煤中As (36.9×10－6)、Cd (10.2×10－6)、 Cr (167.3×10－6)、Cu (365.4×10－6)、Hg (2.82×10－6)、Mo (92.6×10－6)、Ni (82.6×10－6)、Pb (184.6×10－6)、Se(6.23×10－6)、Zn (242.3×10－6)和U (54.6×10－6)显著富集。而另外4个主采煤层（1号、8号、11号和17号煤层）中微量元素的质量分数与贵州煤、中国大部分煤和美国煤中的相当。普安矿区2号煤层中的As、Cd、Hg、Mo、Ni、Pb和Zn等元素主要赋存在黄铁矿中，而Cr、Cu和U主要存在于高岭石中，表明低温热液流体和陆源碎屑对煤中微量元素的富集起了决定作用。     

青山烟煤中痕量元素的分布特性

青山烟煤中痕量元素的分布特性晏蓉，欧阳中华，曾汉才，吴育松，王秋华，陆晓华，徐涛（华中理工大学煤燃烧国家重点实验室，武汉４３００７４）（华中理工大学化学系，武汉４３００７４）关键词烟煤，痕量元素，分布特征煤中矿物质的存在对煤的使用有很大影响，最大影响...     

豫东地区煤中有害痕量元素的分布研究

以豫东地区主要煤层为研究对象,初步研究和分析了豫东地区4个矿区煤样中As、Cr、Pb、Cu、Mn、Se等14个痕量元素含量,并结合现有资料和文献给出了其在煤中的赋存状态。结果表明,Pb、Hg、Cr、Mo、Mn和Cu含量的平均值是美国煤的1.5~5倍,除Hg外,其它的元素含量均低于全国土壤中含量的平均值;Se高于全国平均值而仍低于美国平均值,且远高于全国土壤的平均值;Co的含量比全国和美国的平均值都高,但仍低于全国土壤的平均值;Th的平均值接近于美国平均值,几乎分别占全国平均值和土壤平均值的二分之一和四分之一;所有痕量元素都比世界范围的值低;豫东地区原煤中As和P的含量低,基本属于一级含As煤和特低P煤层;在原煤的利用中应关注这些痕量元素所导致的污染。为豫东地区的综合开发和洁净煤炭利用提供参考资料。     

煤燃烧过程中有害痕量元素形态分布的化学热力学平衡分析

采用化学热力学平衡分析方法，应用真实煤质数据预测了煤燃烧过程中国内六种具有代表性的煤种有害易挥发性痕量元素As和Se的化学形态分布。计算中考虑了痕量元素和卤素（如氯元素）的相互作用，也考虑了痕量元素与主量矿物元素之间的相互作用。研究结果表明，不同煤级、不同产地的煤中痕量元素As的化学形态分布有较大差异。As的热力学平衡计算中，数据库中是否忽略AsO形态对结果影响非常显著，忽略AsO形态的限制性模拟结果似乎更能反映真实煤燃烧过程中As的化学形态分布。煤级和煤的产地对Se的化学形态分布没有显著影响。     

因子分析法在煤中痕量元素分布特征研究中的应用

因子分析法在煤中痕量元素分布特征研究中的应用陆晓华，徐涛，刘汉珍，曾汉才（华中理工大学化学系４３００７４）（华中理工大学煤燃烧国家重点实验室）关键词煤，痕量元素，因子分析在化学或环境化学等学科研究中，经常涉及到对多变量大样本集的复杂数据的分析，以获得...     

煤灰及各种矿物质对SO2排放特性的影响

利用TG-DTG采用低加热速率实验研究了煤阶、脱灰及煤中主要矿物质成分对煤燃烧过程中SO2排放特性的影响，并对矿物质成分的影响机理进行了讨论。结果表明，煤中硫质量分数的高低对烟气中SO2的排放有明显影响，排放水平与硫质量分数不成比例；煤中硫向SO2转化率与煤阶之间没有明显的关联；脱灰能较小程度地促进SO2的生成，抚顺煤主要矿物质成分中Na、K、Mg以及Ca等碱金属与碱土金属明显抑制SO2的排放，同时纳米级的TiO2也减少烟气中SO2体积分数，这些成分对SO2抑制作用的顺序为MgNa≈K>Ca>Mg>Ti的次序加速焦炭的氧化；Si和Al属于惰性成分，对煤中硫的迁徙以及煤的燃烧特性没有显著影响。     

催化剂对东都风化煤硝酸氧解及其产物特性的影响

对东都风化煤进行硝酸氧解，利用元素分析与红外光谱分析研究产物硝基腐植酸（NHA）的结构和性质，讨论硝酸氧解中催化剂对硝基腐植酸的产率、元素组成和官能团的影响。结果表明，浓硫酸、过氧化氢、碳纳米管负载过渡金属和固体酸催化剂都能显著提高煤氧解NHA的产率，产物C、H的质量分数和H/C原子比降低，氮的质量分数增加，E4/E6增加。固体酸与浓硫酸对提高产物氮的质量分数更明显，镀镍碳纳米管（CNTs）负载三氧化二铁、碳纳米管负载镍和浓硫酸作为催化剂得到腐植酸分子更小。催化剂存在下产物活性官能团增加更多，不同催化剂对产物有不同的影响。     

贵州省普安矿区17号煤层中Au的富集成因研究

运用中子活化分析（INAA）、带能谱的扫描电镜（SEM-EDX）和电子探针（EMPA）研究了贵州省普安矿区17号煤层刻槽样中Au元素的含量、分布特征、赋存状态及富集机理。结果表明,17号煤层中Au的质量分数为2.61×10^-9～9.73×10^-9,平均6.29×10^-9,大于世界煤和中国煤中Au的平均含量;煤中Au主要以矿物吸附态存在,载体矿物为黄铁矿和黏土矿物;17号煤层Au的物质来源为低温热液流体;在低温热液流体沿断裂带进入煤层的过程中,受到疏松多孔的煤层吸附而使Au元素发生沉淀,加之17号煤层沉积环境为较为封闭的浅海环境的综合作用而富集在煤中。Au的富集类型为深大断裂-热液作用富集型。     

煤中痕量元素在循环流化床锅炉中的迁移行为与富集特性

对天津市某电厂循环流化床(CFB)锅炉燃用的原煤及燃烧产物底灰、飞灰、细飞灰(≤50 μm)进行痕量元素含量的测定,分析了Be、Zn、Hg、V、Cr、Mn、Co、Ni、Cu、As、Se、Cd、Pb 13种痕量元素在燃烧过程中的迁移行为,揭示了痕量元素在CFB锅炉中的分配、富集特性。结果表明,CFB锅炉中,较低的炉温对于痕量元素的迁移富集产生了较大的影响。由相对富集系数得知,Be、V、Co、Se在底灰中耗散,在飞灰中富集,Zn、Mn倾向于在底灰中富集,元素Cd、Pb、Ni、Cu挥发性较强,在底灰和飞灰中均是耗散。As受钙氧化物影响,挥发性表现并不明显。Hg在底灰和飞灰中相对富集系数均很低,表明Hg在整个燃烧过程中以气态形式排放;Hg、As、Se、V、Cr、Mn、Co、Ni、Cu、Zn、Pb均有向小颗粒物中富集的趋势。根据相对富集系数以及研究的13种元素在低温CFB锅炉中的迁移行为,将这些元素分为三类:A类(E_R<0.1),主要是以气态形式排放元素Hg;B类(0.1R≤0.85),较易挥发元素As、Be、Ni、Cu、Se、Cd、Pb、Co、V;C类(E_R>0.85),主要残留在固体产物中元素Zn、Mn、Cr。     

低熟煤中常量、微量元素与煤生烃潜力参数的相关性研究

应用电离耦合等离子体原子反射光谱（ICP AES）和X射线荧光光谱（XRF），对新疆准噶尔六道湾侏罗纪低熟煤中36种微量元素的质量分数进行了测定，同时作岩石热解分析，有机碳测定，并对获取的各种数据进行回归分析，以考察它们之间的相关性。实验结果表明，除个别具有一定化学催化能力的元素外，多数常量元素及其所形成的矿物质，由于其对成煤有机物质的负增量作用，会明显降低煤的生烃潜力；微量元素对煤的生烃性能影响则较为复杂,既与其对煤的各种化学组成的有机亲和性之差异有关，亦与其在煤的大分子热裂解成烃中的某种化学催化作用有关。此外，由于某些微量元素所特有的古气候、古成煤沼泽类型的“指相”作用，亦能间接地指示煤的生烃潜力。其中Cu既是一个有着与煤的大分子物质较强亲和力的元素，又是一个可以显示古气候古成煤沼泽类型的“指相”元素，因而在指示煤的生烃潜力方面可能具有普适性。     

煤中有害元素的洗选洁净潜势

基于8个洗煤厂实采煤样的测试分析以及2个煤样的模拟洗选实验，对煤炭洗选过程中灰分、硫分及20种有害微量元素的脱除率进行了研究，并系统地探讨了这些有害元素的洁净潜势。结果表明：物理洗选不但能降低煤中的灰分与硫分，还能不同程度地脱除煤中有害微量元素；预测在物理洗选过程中，多数煤中灰分以及有害微量元素As、Co、Cu、Cr、Hg与Mn的脱除率大于50％，硫分的脱除率大于30％，其它有害微量元素Ba、Be、Cd、Cl、Mo、Ni、P、Pb、Sb、Se、Th、U、V与Zn的脱除率相对较低或表现出一个宽的变化范围。     

Neutron activation as a routine method for the determination of trace elements in water

By freeze-drying the following elements can be determined in natural water except sea water: Au, Ba, Br, Ca, Ce, Co, Cr, Eu, Fe, K, La, Mo, Na, Sb, Sc, Se, U, Zn. Some problems may arise with respect to As and Hg. Cu, Cd and Ni can only be determined if present in high concentrations. Separation by adsorption on charcoal in presence of complexing agents gives yields between 75 and 100% for the following elements in sea water: Ag, Au, Cd, Ce, Co, Cr, Eu, Fe, Hg, La, Mo, Sc, Se, U, Zn (As 67%, Sb 56%). Activation or use of labelled ions and study of exchange give information about mobility of trace elements in suspended matter.     

Interlaboratory study of trace and other elements in the iaea powdered human hair reference material,HH-1

A powdered intercomparison material for trace element studies was prepared from human scalp hair and distributed to more than 100 laboratories of which 66 reported results for altogether more than 40 elements. By statistical evaluation of these data certified concentration values were derived for 20 elements, namely As, Au, Br, Ca, Cd, Cl, Co, Cr, Cu, Fe, Hg, Mg, Mn, Na, Pb, S, Sb, Se, Sr and Zn. The data also made it possible to compare different methods of analysis and to judge the value of different levels of experience on the part of the analyst concerned; these comparisons are presented here with special reference to the elements As, Cd, Hg, Pb and Sb.     

Major elements as possible factors of trace element urban pedochemical anomalies

The relationship between real total contents of the major elements Na, Mg, Al, Si, P, S, K, Ca, Ti, Fe and the trace elements Ag, As, B, Ba, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, Se, Sn, V, U, Zn in topsoil from the central part of Vilnius is analysed. The amounts of most elements were determined by energy-dispersive X-ray fluorescence, while amounts of Ag, B, Co were measured by optical atomic emission spectrophotometry. Two factors were distinguished according to major elements: anthropogenic (A) including Ca, Mg, Fe, P, S and clayey (C) including K, Al, Ti. Boron, Mn, Cr and U are significantly correlated with members of both factors, Sb with none of them and other trace elements either with all (Cu, Zn, Pb, Se, Ba, Ni, Co) or with separate (V, Ag, Sn, Mo, As) members of the A-factor. Only B, Mn, Cr, U (partly their additive index Z1) are influenced by the C-factor, while twelve other trace elements (also their additive index Z2) are influenced by the A-factor. The additive index Z of all 17 elements is also affected by the A-factor. Four groups of sites have been distinguished according to normal or higher contents of both factors. The majority of trace element anomalies are related to the sites affected by the A-factor.     

Dietary intake of 25 elements by man estimated by neutron activation analysis

The trace element content of the total daily diet (food and beverages) of each of 4 adult males was determined over a period of one week. A method of radiochemical neutron activation analysis is briefly described which enables the determination of up to 31 elements in biological samples. Of the 25 elements determined in the diet 12 are essential elements (Ca, Cl, Co, Cr, Cu, Fe, K, Mn, Mo, Na, Se, Zn) while 6 (As, Ba, Br, Cd, Hg, Sb) are classified as toxic. The average concentrations of the toxic trace elements As, Cd and Hg of the diet are below the provisional tolerable dietary intakes recommended by WHO/FAO. The contents of Cl, Cu, Fe, K, Mn, Na and Zn are adequate to the proposed nutritional requirements.     

Determination of trace element levels in polyethylene by instrumental neutron activation analysis

Elements Al, As, Au, Br, Cl, Co, Cr, Cu, Fe, Hg, K, La, Mn, Mo, Na, Sb, Sc, Sm, V, and Zn were determined by INAA in several brands and batches of high pressure polyethylene (PE) Bralen (Slovnaft Bratislava, Czechoslovakia). A large scatter of trace element contents was found in both granules and foils, indicating an inhomogeneous distribution for the majority of the above mentioned elements present as impurities in PE. Larger amounts of the elements Al, Mn, and Sb were found in foils than in granules. Blank values resulting from using of PE Bralen as a canning material for INAA were compared to trace element concentration in human hair samples, too.     

不同产地高良姜无机元素含量的比较

用等离子体发射光谱法测定了三个不同产地高良姜的元素含量，在２７种被测元素中，除Ａｓ、Ｂｅ、Ｃｒ、Ｍｏ、Ｐｂ、Ｓｂ、Ｔｌ７种元素未被检出外，三个产地的高良姜均含有Ａｇ、Ａｌ、Ｂ、Ｂａ、Ｃａ、Ｃｄ、Ｃｏ、Ｃｕ、Ｆｅ、Ｍｇ、Ｍｎ、Ｎａ、Ｎｉ、Ｓｅ、Ｓｉ、Ｖ、Ｚｎ、Ｋ、Ｐ、Ｓ２０种元素，湛江产的高良姜大多数元素的含量要高于其它两地。Ｚｎ和Ｍｎ两种人体必需微量元素的含量较丰富。     

Identification of organically associated trace elements in wood and coal by inductively coupled plasma mass spectrometry

1-Methyl-2-pyrrolidinone (NMP) was used to extract samples of wood (forest residue) and coal; the extracts were analysed by inductively coupled plasma mass spectrometry (ICP-MS) using two different sample preparation methods, in order to identify trace elements associated with the organic part of the samples. A sample of fly ash was similarly extracted and analysed in order to assess the behaviour of the mineral matter contained within the wood and coal samples. 32% of the biomass was extracted at the higher temperature and 12% at room temperature while only 12% of the coal was extracted at the higher temperature and 3% at room temperature. Less than 2% of the ash dissolved at the higher temperature. Size exclusion chromatograms of the extracts indicated the presence of significant amounts of large molecular mass materials (>1000 mu) in the biomass and coal extracts but not in the ash extract. Trace element analyses were carried out using ICP-MS on the acid digests prepared by 'wet ashing' and microwave extraction. Sixteen elements (As, Ba, Be, Cd, Co, Cr, Cu, Ga, Mn, Mo, Ni, Pb, Sb, Se, V and Zn) were quantified, in the samples before extraction, in the extracts and in the residues. Concentrations of trace elements in the original biomass sample were lower than in the coal sample while the concentrations in the ash sample were the highest. The major trace elements in the NMP extracts were Ba, Cu, Mn and Zn from the forest residue; Ba, Cu, Mn, Pb and Zn from the coal; Cu and Zn from the ash. These elements are believed to be associated with the organic extracts from the forest residue and coal, and also from the ash. Be and Sb were not quantified in the extracts because they were present at too low concentrations; up to 40% of Mn was extracted from the biomass sample at 202 degrees C, while Se was totally extracted from the ash sample. For the forest residue, approximately 7% (at room temperature) and 45% (at 202 degrees C) of the total trace elements studied were in the extract; for the coal, approximately 8% (at room temperature) and 23% (at 202 degrees C) were in the extract. For the ash, only 1.4% of the trace elements were extracted at 202 degrees C, comprising 25% of Cd but less than 1% of Pb.