U and Th in some brown coals of Serbia and Montenegro and their environmental impact

GOAL, SCOPE AND BACKGROUND: The objective of this paper is to determine and compare the concentrations of U and Th in soft to hard brown (lignite to sub-bituminous) coals of Serbia and Montenegro. It also presents comparison of the obtained data on U and Th concentrations with the published data on coals located in some other countries of the world. Almost the whole coal production of Serbia and Montenegro is used as feed coals for combustion in thermal power plants. METHODS: Channel samples from open pit and underground mines and core samples were collected for hard and soft brown coals. For the analysis the samples were decomposed using microwave technique. Obtained solutions containing U and Th were analyzed by inductively coupled plasma mass spectroscopy (ICP-MS) using NIST standards. RESULTS: Concentration of U from the investigated basins and the corresponding mine fields ranges within 0.60-70.10 mg/kg, 0.65-3.20 mg/kg, 0.95-6.59 mg/kg, 1.20-6.05 mg/kg, 0.80-6.66 mg/kg, 0.18-89.90 mg/kg, 0.19-4.14 mg/kg, and 0.28-3.52 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. Concentration of Th ranges within 0.20-2.60 mg/kg, 0.84-6.57 mg/kg, 1.48-6.48 mg/kg, 0.12-2.71 mg/kg, 0.13-4.95 mg/kg, 0.14-3.48 mg/kg, 0.29-3.56 mg/kg, and 0.17-1.89 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. DISCUSSION: Brown coal from Senje-Resavica, Kolubara, Kostolac and Pljevlja is characterized by low U concentration. Coals form the Krepoljin, Soko Banja and Sjenica basins have slightly higher U concentrations than the mentioned group. The highest concentration of U is characteristic for the coal from the Bogovina East field. Concentration of Th in coals from Serbia and Montenegro has proved to be low. Out of all investigated coal basins, only the coal from the Krepoljin and Kolubara basins has high concentration of Th. The hydrothermally altered rocks of the Timok dacite-andesite complex, representing the basement of the Bogovina basin, could be a potential source of U, especially at the bottom part of the Lower seam of the Bogovina East field. CONCLUSIONS: This study shows that brown coals in Serbia and Montenegro (soft to hard brown coals or lignite to sub-bituminous) contain low levels of U (5.30 mg/kg, average value and 2.10 mg/kg geometric mean value) and Th (1.80 mg/kg, average value and 1.12 mg/kg geometric mean value). There are some obvious differences in concentration of U and Th in coals from different basins in Serbia and Montenegro. The approximate value for U and Th release mainly from power plants was 644.33 t and 983.46 t, respectively within the period 1965-2000 for the studied mines in Serbia, and 23.76 t and 15.05 t for the Potrlica mine (Montenegro) within the period 1965-1997. RECOMMENDATIONS: The coals in Serbia and Montenegro show no identifiable unfavourable impact on the surrounding environment, due to low natural radioactive concentration of U and Th, but further investigations concerning human health should be performed. PERSPECTIVES: Preliminary research revealed that in some Serbian coals (and, particularly, parts of the coal seam) U and Th content are rather high. Such coals should be carefully studied, as well as U and Th concentrations in ash, fly ash, waste disposals, nearby soil and ground water. Further studies should include determination of the radioactivity of all these products, and estimation of possible health impact.     

上海市大气气溶胶中铂元素污染状况调查

为调查上海市大气气溶胶中铂元素的污染状况,用PM10-2型可吸入颗粒物采样器采集了上海市大气气溶胶样品,采样时间分别为2003-12～2005-12.用微波消解密闭系统消解样品,电感耦合等离子体质谱法(ICP-MS)测定了大气气溶胶中Pt的含量.分析结果表明,同清洁对照点((0.65±0.16)pg·m-3)相比,上海市中心区大气中Pt((1.69±0.93)pg·m-3)的污染是明显的;装有三元催化转化器的汽车尾气中Pt的含量均在100ng·g-1以上,远远高于大气气溶胶样品(人民广场平均值21.7ng·g-1);不同交通密度区Pt含量分析结果表明,Pt含量与交通密度紧密相关,这说明装有三元催化器的汽车尾气是气溶胶中Pt污染的主要来源;此外,上海市大气气溶胶中Pt呈现季节性变化,并受气象条件影响.同世界其它城市相比,上海市气溶胶中铂元素污染程度还较低,但是这种潜在的重金属污染应该引起重视.     

Multivariate characterization of elements accumulated in Wolfiporia extensa mushroom from Yunnan province of China

ABSTRACT

Dried sclerotia of Wolfiporia extensa have been used as medicine in Asia from Eastern Han Dynasty, and also used as traditional snack called “fulingjiabing” in Beijing, China. In this paper, 18 macro and trace elements (Ag, As, Ba, Cd, Co, Cr, Cs, Cu, Fe, Li, Mn, Ni, Pb, Rb, Se, Sr, V, and Zn) in both flesh and peel of Wolfiporia extensa from seven sites of Yunnan province in China were determined by inductively coupled plasma mass spectrometer. The average recovery rates of certified reference materials for GBW10015 (spinach leaves) ranged from 90.5 to 113%, for GBW10028 (citrus leaves) from 92.8 to 106%, and for GBW07603 (bush branch and leaves) from 83.3 to 114.6%. Generally speaking, the concentration of all elements determined was at common level. The results of this survey indicate that mineral compositions in peel were higher than in flesh. In peel, the contents of investigated trace metals in mushroom samples were found to be in the range of 1,660–13,400 µg·g^?1 dry matter (dm) for Fe and 29.6–710 µg·g^?1 dm for Mn. The mean contents of Cr, Cu, Rb, V, and Zn in peel were between 10 and 20 µg·g^?1 dm, followed by As, Co, Li, Ni, Pb, Se, and Sr with mean contents between 1 and 10 µg·g^?1 dm, while Ag, Cd, and Cs had mean contents of <1 µg·g^?1 dm. In flesh, the concentration of Fe was in the range of 54–900 µg·g^?1 dm, and it was 1.5–49 µg·g^?1 dm for Mn, followed by Ba, Cu, Rb, and Zn in the range of 1 to 10 µg·g^?1 dm, while for Ag, As, Cd, Co, Cr, Cs, Li, Ni, Pb, Se, Sr, and V it was <1 µg·g^?1 dm. The concentration of toxic elements, such as As, Cd, and Pb, in both flesh and peel was below the permissible limits of World Health Organization. However, As and Pb contents in peel were higher than the limits permitted in the Chinese Pharmacopoeia. The results of principal component analysis showed that the flesh of Wolfiporia extensa from all the seven sites of the Yunnan province tend to cluster together, most probably because the origin of mineral elements in both flesh and peel is wood substrate (old and dead pine trees).     

珠江下游河段沉积物中重金属含量及污染评价

为了解珠江下游出海河道沉积物中重金属含量及各污染物的潜在生态危害程度,用电感耦合等离子质谱法和原子荧光法测定了21个样点沉积物中13种元素的总量,及对底泥中主要重金属污染状况和潜在生态风险进行了评价.结果表明,珠江下游河道总Fe、总Mn含量分别为41 658.73 mg.kg-1和1 104.73 mg.kg-1,微量元素Cr、Co、Ni、Cu、Zn、As、Se、Cd、Sb、Pb和Hg的平均值分别为86.62、18.18、54.10、80.20、543.60、119.55、4.28、10.60、20.26、104.58和0.520 mg.kg-1,地积累指数评价结果显示,表层沉积物重金属污染程度顺序为：Cd〉As≈Zn〉Hg〉Pb≈Cu≈Cr,潜在生态风险程度大小顺序：Cd〉Hg〉As〉Cu〉Pb〉Zn〉Cr,Cd是该水域污染和潜在生态风险最大的元素,单项潜在生态风险与区域综合潜在生态风险一致.珠江下游河道底泥Cd、Hg和Pb污染受输入影响北江大于西江和东江.聚类分析结果表明,研究站位潜在生态风险可分5类,基本反映了站位分布及沉积物环境污染变化特征.总体而言,重金属污染和生态风险程度较高的江段有陈村-沙湾段、陈村-顺德港段及外海-虎跳门段,北江及相关河道污染程度和潜在生态风险指数高于区域其他江段.     

衡山PM_（2.5）中痕量金属元素的分析

建立了微波消解-电感耦合等离子体质谱法同时测定PM2.5中12种痕量金属元素的方法。对不同消解体系进行了讨论,确定采用HNO3＋H2O2消解体系。方法检出限在0.01～6.4 ng/m3之间,精密度为0.5%～8.9%,加标回收率在69.2%～92.6%之间。应用该方法测定了衡山PM2.5中痕量金属元素的含量,讨论了痕量元素的浓度分布特征,对各元素进行了相关性分析,并应用富集因子法对来源进行了分析。     

广西一个典型矿业镇环境中重金属污染分析

广西河池市是我国重要的有色金属基地.以该市一个典型的矿业镇作为研究对象,采集了该镇周围23个旱地土壤样品,并在镇里布设两个大气采样点采集了可吸入颗粒物(PM10)样品,运用ICP-MS分析了样品中20种金属元素的含量,采用地积指数法判定旱地土壤和可吸入颗粒物中污染元素及来源.结果表明,这些与人们生活密切的环境介质(旱地土,可吸入颗粒物)均受到了多种重金属元素的复合污染,其共同的污染元素有Cd、As、Sb、Pb、Xn、Cu,而其中致癌元素Cd和As污染最为突出.大气可吸入颗粒物与旱地土壤中各污染元素的污染强度排序相同,均为Cd＞As＞Sb＞Pb＞Zn＞Cu.经过现场调查和识别,污染源主要来自当地开放性运矿产生的扬尘所致.因此加强该地区矿石运输管理是保护该地区耕地和人群健康的需要.     

微波消解－ICP－MS法测定土壤中稀土元素的研究

建立了电感耦合等离子体质谱（ ICP－MS）测定土壤中稀土元素的分析方法。采用HNO3＋HF酸体系用微波消解对土壤样品进行处理,以混合内标（ In、Bi）校正基体干扰和信号漂移,用ICP－MS对其中的16种稀土元素进行了测定。在优化的实验条件下,16种稀土元素标准曲线的相关系数r＞0．9999,检出限为0.012 ng／ml～0.069 ng／ml,加标回收率为84.0％～110％,相对标准偏差（n＝6）RSD均小于3.5％。该方法可用于四种不同类型土壤中稀土元素含量的测定。     

ICP-MS法测定不同类型水体可滤态与总量结果比对分析

本文运用电感耦合等离子体质谱(ICP-MS)法对不用类型水体(地下水、地表水、水库水和污水)中的10种重金属元素进行了测定和比对分析。结果显示地下水除钴元素可滤态与总量测定结果相当之外总量均大于可滤态、地表水总量均大于可滤态、水库水除锰元素和镍元素可滤态与总量测定值有较差别外其它8种元素总量与可滤态测定值均无明显差异、污水除钛元素外其余9种元素总量与可滤态测定值均无明显差异。其中,地表水与污水钛元素可滤态均未检出,总量测定值为检出限的1倍至3倍,结果可信。此结果证明对于本次用于检测的样品中的钛元素,全部来源于悬浮于水中的直径大于0.45μm的微粒上,其它元素无此特性。     

ASD-ICP-MS联合快速测定《土壤环境质量标准》中的金属元素简

采用HNO3-HCl-HF-HClO4体系在全自动消解仪消解土壤样品,以50.0μg/L的Rh作内标,用电感耦合等离子体-质谱仪同时测定《土壤环境质量标准》的7种元素Cd、 As、Cu、 Pb、 Cr、 Zn、 Ni。结果表明,土壤标样的测定值与标准值吻合,各元素对应的检出限和相对标准偏差分别为： Cd：0.002 mg/kg和3.6%, As：0.05 mg/kg和5.5%, Cu：0.10 mg/kg和2.9%, Pb：0.18 mg/kg和4.7%, Cr：0.25 mg/kg和2.2%, Zn：0.40 mg/kg和3.4%, Ni：0.20 mg/kg和3.8%。该方法简便快捷,灵敏度高,重现性好。     

Real time alteration of a nuclear waste glass and remobilization of lanthanide into an interphase

The development of predictive models for the long term evolution of nuclear waste glass requires the complete knowledge of the glass dissolution at the laboratory scale. A new approach was developed to determine the initial reaction during the first steps of experience, a new concept was developed, based on the combination of dynamic leaching test and the characterization of the altered materials. With this experimental set-up it is possible to follow in real time the glass alteration process at a fine temporal scale. The results put in evidence a singular behaviour of the lanthanide, shown by a concentration peak of La, Nd and Ce after 2 h and a quick decrease of their concentration measured on line in the solution during the leaching test. This fact is directly linked to the development of an interphase (altered layer which differs from the initial solid by its texture, structure and chemical composition) at the interface of the glass surface and the leaching solution. This work is an attempt to integrate the formation of the alteration products (here the interphase) during leaching into the dissolution mechanisms of a nuclear waste glass. A model is proposed and discussed.