马家塔矿煤层中有害痕量元素的质量分数特性

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）对神华集团马家塔露天矿2-2#煤层中Hg、As、Se、Pb、Be、Cr、Cd、Ni、Th、U、Mn、Mo、Co、Sb和Br共15种有害痕量元素的质量分数进行测定。结果表明，绝大部分痕量元素的质量分数都明显低于中国煤中元素质量分数的平均值，只有Hg和Mn的质量分数偏高，其中Hg的质量分数异常高；通过分析痕量元素在煤层垂向剖面上的质量分数变化特性，揭示出痕量元素在煤层中分布的非均一性,分析了影响痕量元素分布与富集的因素；通过痕量元素之间以及与黄铁矿硫、Fe、Al、Ca、P的聚类分析，研究了痕量元素之间以及与煤中不同矿物组分之间的亲和特性。     

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。     

石嘴山电厂煤中微量元素的迁移释放行为

应用电感耦合等离子体质谱（ICP-MS）和原子荧光光谱（AFS）对中国西北部石嘴山电厂的原煤、底灰和飞灰中Hg、As、Se、Pb、Cr、Cd、Mo、Ni、Co、U和Th 11种微量元素的含量进行了测定。根据底灰和飞灰的产率, 结合微量元素在底灰和飞灰中的含量计算了电厂燃煤过程中微量元素的挥发性。结果表明, Hg、Cd、Se、As四种元素在燃煤过程的挥发率均在50%以上, 最高可达70%。通过对底灰和飞灰在酸性介质下的柱淋滤实验研究了底灰和飞灰中微量元素在60h内的迁移释放行为。Mn、Ni、Co、As四种元素的最大淋出率均超过2.0%, 最高接近10.0%, 并且还未达到淋滤平衡。根据微量元素的挥发和淋滤释放特性建立了电厂煤中有害微量元素在燃烧和淋滤过程中的释放分配模型。结果显示, 燃煤过程中的挥发是微量元素释放的主要形式, 部分元素的淋滤释放也可对周围水环境造成污染。
     

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.     

Instrumental method for the determination of trace elements in water samples by neutron activation analysis

Thermal neutron activation analysis and a large-volume high-resolution Ge(Li) gammaray spectrometer, connected on-line to a DEC PDP 8/L computer, have been used to measure the concentrations of Na, Sc, Cr, Fe, Co, Ni, Zn, As, Se, Br, Rb, Ag, Sb, Cs, W and Hg in some Italian subsurface water samples. The instrumental method requires neither a chemical separation technique nor a pre- or post-concentration of the trace elements to be detected. As a consequence, this method eliminates many inherent errors associated with chemical determinations. The technique is sensitive, precise and particularly suitable for routine analysis of many trace elements at both natural and pollution levels in water samples. The interferences due to fast neutron (n, p) and (n, α) reactions are not appreciable, with the only exception of the⁵⁴Fe(n, p)⁵⁴Mn and⁵⁸Ni(n, p)⁵⁸Co reactions. Losses of volatile, elements, e. g. As, Br and Hg, during irradiation proved to be negligible.     

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。     

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。     

伊敏褐煤中微量元素的地球化学特征及其无机-有机亲和性分析

采用脱矿物质、提取腐殖酸等方法结合ICP-MS对伊敏15_上、16_下煤中的32种微量元素的含量及其赋存特征进行了分析。与地壳克拉克值及中国侏罗-白垩纪煤和世界褐煤中微量元素含量相比,伊敏褐煤中微量元素没有明显富集。脱矿物质处理后,Ni明显富集,As略比原煤高,其他微量元素都低于原煤。原煤提取腐殖酸和脱矿物煤提取腐殖酸中Ni、Mo、Cd、Sn、W明显富集,这表明Ni、Mo、Cd、Sn、W和腐殖酸形成了稳定的有机态化合物。原煤提取腐殖酸残煤和脱矿物煤提取腐殖酸残煤中V、Ni、As富集,表明V、Ni、As与煤的大分子结构形成了稳定的有机态化合物。根据微量元素和灰分的相关性系数,把微量元素分为以下几类:无机富集元素Cr、U;亲无机元素Cu、Cd、In、Sn、Ga、Y、Zr、Hf、Bi、Th;偏无机元素Be、Sc、Rb、Sr、Nb、Cs、Ta、Pb;偏有机元素V、As、Tl、Ba、Se;亲有机元素Li、Co、W;有机富集元素Ni、Zn、Mo、Sb。     

Determination of 18 trace elements in petroleum and its derivatives by neutron activation with a small nuclear reactor

Non-destructive neutron activation has been used to analyze 6 different samples of crude oil and heating oil, from Western Canada and Venezuela. These samples were irradiated with thermal neutrons for 2, 30 and 240 min in the SLOWPOKE reactor and the concentrations of 18 trace and minor elements (Al, As, Br, Cl, Co, Dy, Eu, Fe, I, La, Mn, Mo, Ni, Na, S, Se, Sm and V) ranging from 0.6 ppb to 2.24% have been measured. Eleven elements (As, Br, Co, Cl, Fe, Mo, Mn, Na, Ni, S and V) were determined in the fuel oil (SRM-1634) obtained from the National Bureau of Standards and were found to be in good agreement with the values certified by NBS     

Determination and geochemical significance of trace elements in Iraqi crude oils using instrumental neutron activation analysis

The trace-element composition of crude oil was studied using instrumental neutron activation techniques and a large-volume high-resolution Ge(Li) detector. A total of 29 elements were determined in oils representing the various producing formations of the Iraqi oil fields. These were: Al, Ar, As, Au, Br, Ca, Cl, Co, Cr, Cu, Eu, Fe, Ga, Hg, K, La, Mn, Mo, Na, Ni, Re, S, Sb, Sc, Se, Sm, V, W and Zn. The significance of these trace elements in the geochemical investigation of crude oil is discussed.     

Trace element determinations in shale oil products by neutron activation

Neutron activation offers some important advantages for the determination of selected trace elements in shale oil products. This paper gives techniques and results of a study of crude shale oil and naphtha, heavy distillate, and wax products of shale oil. The elements determined were Al, As, Au, Br, Ce, Cl, Co, Cr, Fe, Hg, I, K, Mn. Mo, Na, S, Sb, Se, V, and Zn. Some elements (Mn, Na, As) tend to accumulate in heavier fractions, whereas chlorine and iodine are concentrated in the more volatile fractions. The volatility of sulphur compounds in the shale oil products appears to be essentially uniform, with some tendency toward accumulation in distillation residues. The tendency for the trace elements to accumulate in the waxes that precipitated from cooled heavy distillates was very low.     

Single-step microwave digestion with HNO(3) alone for determination of trace elements in coal by ICP spectrometry

A microwave digestion method with HNO₃ alone was conducted at a temperature as high as 250 °C for determination of 19 trace elements (Li, Be, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Cd, Cs, Ba, Hg, and Pb) in coal jointly by inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and flow injection ICP-MS (FI-ICP-MS). The validity of determination was assessed by using three standard coals, SRM 1632c, BCR 180, and SARM 19. It was found that the high-temperature digestion led to an extensive decomposition of the organic matrix and clay in coal, and no dissolved and solid carbon remained in the final solution after evaporation. Good recoveries were observed for all trace elements in three coals, with the exception of V, Rb, and Cs in high-ash SARM 19. Additionally, FI-ICP-MS combined with the present digestion without evaporation pretreatment was proved to be a rapid and efficient approach for determination of ultra-trace elements such as Se, Cd, and Hg in coal.     

Trace elements in mussels (Mytilus Edulis) from coastal areas of the North Sea and the Baltic. Multielement analyses using instrumental neutron activation analysis

Samples of the mussel Mytilus edulis were collected from different sites of estuarine and coastal areas of the North Sea and the Baltic. The following elements were determined by INAA: Ca, Sc, Cr, Fe, Co, Ni, Zn, As, Se, Br, Rb, Sr, Zr, Ag, Cd, Sn, Cs, Ba, Ta, Eu, Tb, Yb, Hf, Au, Hg, Th. Multielement correlation analysis was used for the evaluation of the data. Differences in trace element patterns are found and described calculating trace element ratios. Regional differences in trace element concentrations are superimposed by typical seasonal variations, with highest concentration levels found in late winter and spring, and lowest in summer and autumn. With support of Deutsche Forschungsgemeinschaft     

Multielement neutron activation analysis of biological materials using chemical group separation and Ge(Li) gamma spectrometry

Neutron activation analysis (NAA) for the determination of some trace elements in biological materials is described. The method presented permits the simple and rapid determination of Se, Ag, Au, Sb, Pt (via¹⁹⁹Au), Hg, Co, Ni (via⁵⁸Co), Fe, Zn, Mo, Sn, Cr, Cd, Cu and As after radiochemical separation from Na, K, Cs, Rb and partially Br. For this purpose, postirradiation separation by extraction with mercury or zinc amalgam was used. Separation of gold by extraction with ethyl acetate or by precipitation with dimethylglyoxime was applied for the determination of gold and platinum in biological materials.     

Trace element content of some Polish hard and brown coals

Instrumental neutron activation analysis /INAA/ method was applied to measure major, minor and trace elements in 34 samples of hard and brown coal originating from eight Polish coal mines. The elemental concentrations of 38 elements /Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Mo, Ag, Cd, In, Sb, I, Cs, Ba, La, Ce, Sm, Eu, Lu, W, Au and Th/ are presented and compared with published data for coals from various origin. Enrichment factors, calculated relative to iron and the average crustal rock composition, indicated that several elements are highly enriched in Polish coals.     

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.     

The complementary use of radioanalytical methods and trace analysis methods for the characterisation of environmental IAEA reference materials

The IAEA laboratories have access to both nuclear analytical methods and conventional instrumental methods for trace analysis for the characterisation of its environmental and biological reference materials. A technical concept integrating the homogeneity data, the recommended test portion mass and the uncertainty on the trace element concentrations is explored using a combination of INAA, XRF, ICP-MS, ICP-AES, and AAS. The above approach is illustrated by selected examples of reference materials currently under evaluation for their trace element content. They include some or all of the following elements Al, As, Br, Ca, Cd, Co, Cr, Cs, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, Pb, Rb, Se, Sr, Th, U, Zn in environmental biomonitor organisms (lichen, algae) and air dust filters.     

藏药材白花龙胆花中微量元素的分析

对藏药材白花龙胆花中17种微量元素（Cu、Zn、Fe、Mn、Co、Ni、Se、Cr、Mg、Ca、K、Na、P、As、Hg、Pb、Cd）的含量作了测定。结果表明,白花龙胆花中含有较高的人体必需微量元素和常量元素,其中常量元素K、Ca、Na、Mg和微量元素Zn、Fe、Mn的含量均较高。     

Determination of trace elements by inductively coupled plasma mass spectrometry of biomass and fuel oil reference materials using milligram sample sizes

Most of the analytical techniques used to quantify elements associated with solid samples suffer from high detection limits and cannot be used for trace elements in biomass samples, particularly when only 20 mg are available for analysis. Inductively coupled plasma mass spectrometry (ICP-MS) can achieve detection limits of parts-per-trillion with liquid sample introduction by solution nebulisation. This technique was therefore tested with two standard biomass reference materials: oriental tobacco leaves and cabbage leaves. Two preparations successfully used on coal standards were used to digest the solid samples: a total digestion method (wet ashing digestion) and a partial leaching (microwave extraction). The concentrations of up to seventeen elements (As, Ba, Be, Cd, Co, Cr, Cu, Ga, Mn, Mo, Ni, Pb, Sb, Se, Sn, V and Zn) were measured after the two preparations. The accuracy and sensitivity of the measurements improved when the dilution factor decreased from 5000 to 1000 and to 500. Since the proportion of mineral matter in biomass samples is small (5%), the microwave digestion extracted elements that are generally not completely extracted from coal samples (e.g. Sb). However, some trace element concentrations were below the limit of quantification after microwave extraction, even with a reduced dilution factor (As, Se and Mo) and could not be quantified. A fuel oil was also digested. The trace element concentrations were very low (between 28 and 0.1 microgram g(-1)) but acceptable results were obtained by applying a dilution factor of 100. Only six elements in the fuel oil (As, Ba, Co, Ni, Se and V) had certified or indicated values. Factors affecting the accuracy and sensitivity of the analyses are discussed. The reproducibility of analysis of the tobacco leaf standard was checked over a period of nine months by both digestion methods. The wet ashing method gave acceptable reproducibility for Ba, Cd, Co, Cu, Ga, Mn, Mo, Ni, Pb, V and Zn but poor precision for Cr, Se and Sn and showed evidence of residual chloride interference for As. The microwave extraction gave good reproducibility for As, Ba, Cd, Co, Cr, Cu, Mo, Ni and Zn but poor precision for Se and low recoveries for Ga, Mn, Sn and V. In spite of the small quantities of material analysed, it proved possible to determine the trace elements at levels down to 0.1 microgram g(-1) in the reference materials.     

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.