Seasonal distribution and speciation of mercury in a gold mining area,north-west province,South Africa

The seasonal speciation of mercury (Hg) was determined in water, soil, and sediments from watersheds located in the North-West province of South Africa. The study area is known to have a long history of mining activities which also include the recovery of gold from old tailings. Both inorganic (IHg) and methyl mercury (MHg) were detected at high concentrations (up to 8480 μg IHg kg^?1 and 13 μg MHg kg^?1) in surface sediments during dry season. A considerable remobilization of Hg from bottom sediments was observed in water from dry to wet season as well as the migration of Hg away from pollution sources due to seasonal influences. Hg in sediments mostly has been speciated as Hg⁰. Enhancement of Hg methylation occurred mainly in deeper sediments at regions corresponding to the lowest redox potential, higher pH, and enrichment of IHg. Hg values in borehole waters were very high (up to 3310 ng L^?1) suggesting a serious contamination of the site groundwater which needs to be addressed urgently in order to minimize further impact that affects the Vaal River and other water systems located nearby.     

环境中汞化学形态分析研究进展

作为一种剧毒元素,汞的毒性与其化学形态密切相关.环境介质中汞的化学形态监测分析主要涉及样品的采集、保存、前处理、分离和测定等步骤.本文综合国内外相关文献,系统介绍了开展环境介质中汞化学形态监测分析的相关测试技术和方法,并阐述了我国开展汞化学形态监测存在的问题及其意义.     

An Operationally Defined Method to Determine the Speciation of Mercury

This paper presents a modified method of an operationally determined speciation of mercury in soil. The analytical work was mainly concerned to suit properly with inductively coupled plasma-atomic emission spectrometry (ICP-AES). Soil samples analysed in this study were selected from open areas around a crematorium, a waste incinerator, and two power plants. Results show that both topsoil and subsoil samples were dominated by elemental mercury Hg(0) and mercuric sulphide (HgS). The significant correlation between sulphur concentration and HgS was found in topsoil samples.     

Principal Biogeochemical Factors Affecting the Speciation And Transport of Mercury through the terrestrial environment

It is increasingly becoming known that mercury transport and speciation in the terrestrial environment play major roles in methyl-mercury bioaccumulation potential in surface water. This review discusses the principal biogeochemical reactions affecting the transport and speciation of mercury in the terrestrial watershed. The issues presented are mercury-ligand formation, mercury adsorption/desorption, and elemental mercury reduction and volatilization. In terrestrial environments, OH^–, Cl^– and S^– ions have the largest influence on ligand formation. Under oxidized surface soil conditions Hg(OH)₂, HgCl₂, HgOH⁺, HgS, and Hg⁰ are the predominant inorganic mercury forms. In reduced environments, common mercury forms are HgSH⁺, HgOHSH, and HgClSH. Many of these mercury forms are further bound to organic and inorganic ligands. Mercury adsorption to mineral and organic surfaces is mainly dictated by two factors: pH and dissolved ions. An increase in Cl^– concentration and a decrease in pH can, together or separately, decrease mercury adsorption. Clay and organic soils have the highest capability of adsorbing mercury. Important parameters that increase abiotic inorganic mercury reduction are availability of electron donors, low redox potential, and sunlight intensity. Primary factors that increase volatilization are soil permeability and temperature. A decrease in mercury adsorption and an increase in soil moisture will also increase volatilization. The effect of climate on biogeochemical reactions in the terrestrial watershed indicates mercury speciation and transport to receiving water will vary on a regional basis.     

环境样品中汞形态分析技术的进展

汞的毒性、环境行为、生物有效性不仅跟其浓度有关,还决定于其化学形态,因此汞的形态分析在环境科学中具有重要意义。样品前处理几乎是汞形态分析研究中不可或缺的步骤,而色谱和光谱/质谱联用技术是目前普遍采用的分离检测方法。文章对近十年来这些方面的研究进展进行了综述,主要包括样品的前处理方法如酸/碱溶剂萃取、微波辅助萃取、固相萃取、固相微萃取、单滴微萃取、分散液液微萃取等,以及色谱（液相色谱、气相色谱）和毛细管电泳与光谱/质谱（紫外可见光谱、原子吸收光谱、原子荧光光谱、等离子体质谱等）的联用技术在汞化合物形态分析中的应用情况。最后提出今后应重点研究建立高效、简便的前处理方法,发展高分离度、高灵敏度、高速度的分离检测联用技术,以便更好地对汞的形态进行分析监测。     

环境样品中汞形态分析技术的进展

汞的毒性、环境行为、生物有效性不仅跟其浓度有关,还决定于其化学形态,因此汞的形态分析在环境科学中具有重要意义。样品前处理几乎是汞形态分析研究中不可或缺的步骤,而色谱和光谱/质谱联用技术是目前普遍采用的分离检测方法。文章对近十年来这些方面的研究进展进行了综述,主要包括样品的前处理方法如酸/碱溶剂萃取、微波辅助萃取、固相萃取、固相微萃取、单滴微萃取、分散液液微萃取等,以及色谱(液相色谱、气相色谱)和毛细管电泳与光谱/质谱(紫外可见光谱、原子吸收光谱、原子荧光光谱、等离子体质谱等)的联用技术在汞化合物形态分析中的应用情况。最后提出今后应重点研究建立高效、简便的前处理方法,发展高分离度、高灵敏度、高速度的分离检测联用技术,以便更好地对汞的形态进行分析监测。     

基于人工神经网络的燃煤汞排放预测模型

利用GA-BP的人工神经网络算法建立燃煤汞排放预测模型,确定煤中汞含量、煤的发热量、煤中硫含量、煤中氯含量、挥发份含量、排烟温度作为输入矢量,元素态汞、氧化态汞和颗粒态汞3个因素作为输出参数,通过对20个燃煤锅炉汞排放形态的测试数据进行模型训练,结合实际测试数据和预测数据对误差来源进行了分析. 通过对3个样本进行验证,分析人工神经网络的实际预测效果. 研究结果表明,训练与预测的精度都是符合汞排放预测实际要求的,预测精度达0.895,分析表明利用人工神经网络建立预测模型可对燃煤汞排放进行预测.     

北京市门头沟风化煤矸石中汞的赋存形态与溶出特征分析

为探究堆积煤矸石所产生的重金属的污染问题,本文以北京市门头沟5个典型矿区为研究对象,采集矸石山堆积表面风化煤矸石共45个样品,分析测试矸石样品中汞（Hg）的含量,对不同理化性质下各重金属的变化规律进行了初步探讨;利用改进BCR连续提取法,研究样品中Hg的赋存形态,分析其生物可利用性;采用富集因子法、地累积指数法、风险编码法和个体污染因子法对Hg进行有效性评价;再模拟酸雨条件下Hg的溶出特征及影响因素。结果表明,该研究区Hg的含量为0.085—0.519 mg·kg⁻¹,均值为0.169 mg·kg⁻¹,超过了北京市土壤背景值,超标倍数为4.225;Hg的平均富集系数与地累积指数分别为4.53和1.35,均表现为中度污染;风险编码法和次生相与原生相比值法结果显示为低风险和轻度污染,占比分别为86.67%和31.11%;Hg与Eh呈显著负相关,与含水率呈显著正相关;煤矸石中Hg的主要赋存形态为可氧化态Hg和残渣态Hg,其中可还原态Hg与可氧化态Hg存在显著负相关,TOC、pH与可还原态Hg呈显著正相关;静态淋溶试验表明,雨水酸度、粒径、固液比均会影响Hg的溶出量,在一定条件范围内,煤矸石浸泡液中Hg的溶出量随pH的增大而减小,随粒径的增大而增大,随固液比的增大而增大;在静态淋溶模拟试验中,Hg的最大溶出量严重超出国家标准,为Ⅳ类水质的6.4倍。该研究结果可为进一步了解Hg 在煤矸石中的活性、迁移规律、赋存形态及永定河Hg的污染治理提供科学依据。     

铜陵矿区土壤中镉存在形态及生物有效性

采取Tessier连续提取法，研究铜陵矿区不同功能区表层土壤中镉的化学形态分布和生物有效性。结果表明，各种土壤中的镉含量全部高于地区背景值，主要来源与矿业活动有关，部分样品还有矿体的风化富集叠加，土壤镉污染指数PCd为1．15～79。镉含量依次为矿体风化土壤→废矿堆下垫土→市郊菜地土→矿区铜草土、路边土和稻田土→其它土壤。其形态分布，酸性土壤中以Fe-Mn氧化态和可交换态为主，其余三态相对较低；碱性土壤中有机态和残渣态比例较高，碳酸盐态和可交换态所占的比例低。土壤中生物可利用态镉的含量较高，占土壤总镉的60．20%-98．3％，生物不可利用态仅占1．7％-39．2％。     

不同消解方法对土壤样品中汞含量测定的影响

利用欧洲标准样品，对比研究了3种不同消解方法测定表层土壤中总汞的差异。结果发现，利用(1)王水电热炉加热消解和(2)浓硝酸、浓硫酸及高锰酸钾水浴加热消解的方法测得的标准样的总汞最为接近实际值。而(3)硫酸(1：1)与高锰酸钾水浴加热消解法的测得值明显偏低，但方法3测得的土壤总汞值介于方法1和方法2之间；综合考虑各种因素，方法3测得的土壤总汞仍然有效。文章同时讨论可能影响总汞测定值的因素。     

板蓝根水煎液中13种金属元素形态分析

利用电感耦合等离子体-质谱仪（ICP-MS）测定板蓝根原药材和水煎液中13种元素的含量。形态研究采用高速离心和滤膜分离水煎液中的溶解态和颗粒态,元素的溶解态再用树脂XAD-4、树脂D001、树脂D301和树脂D751分别区分非极性吸附态、阳离子交换态、阴离子交换态和螯合吸附态。结果表明,板蓝根药材含有微量Cu、Pb和Cd等重金属,同时含有丰富的Mg、Ca、Fe、Al等大量元素,其中Ca含量最高,为2739 mg·kg-1;Zn、Mg、Ca、Mn、Al和Fe的浸出率较高,在42.9%到81.9%之间;Pb和Cu的浸出率最低,只有10%左右。Zn、Mg、Ca、Mn和Pb元素颗粒态比例在0%到9.3%之间,其他元素颗粒态比例在14.3%到85.7%之间。在溶解态当中,所有元素都具有阴离子交换态;Cu、Sn、Cr和Al没有或者很少有阳离子交换态,其余元素的阳离子交换态在32.4%到98.3之间;Al、Fe、Cu、Cr和Sn没有或者很少螯合吸附态,其余元素在54.9%到98.4%之间;Zn、Cu、Sn、Cd和Pb有非极性吸附态,其余元素没有。     

外加镍在土壤中的形态与再分配

镍处理土壤经室内培养12周后,采用连续提取技术对试验土壤中镍的形态与再分配方式进行了研究。研究结果表明,外加的水溶性镍进入土壤后的主要存在形态与添加的剂量有关:低剂量时,以铁锰氧化态为主,这一形态在100mg·kg-1处理土壤中占比例最大,达到31.6%;高剂量时,以交换态为主,这一形态在1600mg·kg-1处理土壤中占比例最大,达到48.4%。随着镍添加剂量由0(对照)增加到1600mg·kg-1,再分配系数逐渐由1.00增大到30.65;金属结合强度系数则由0.90减小至0.25,也反映出进入土壤中镍的剂量较大时,镍是以不稳定的形态占优。试验结果也证实了土壤具有减小镍的环境危害的作用,但这种缓冲能力是有限的。随着时间的推移,镍的形态会继续发生变化,但这一转化过程是缓慢的。因此,一旦土壤发生重金属污染,其对土壤环境的影响将是长期的。     

Assessment of air pollution by mercury in South African provinces using lichens Parmelia caperata as bioindicators

Environmental Geochemistry and Health - Large-scale assessment of atmospheric air pollution by mercury (Hg) using lichen Parmelia caperata as biological indicator was undertaken using samples from...     

Distribution of mercury in the atmosphere over Idrija, Slovenia

Idrija mine, the second largest mercury mine in the world, was in use since 1490. More than 107 000 tons of Hg were produced in its five centuries of history until 1990 when production was reduced to a few hundred kilos per year. The average recovery rate of mercury has been estimated to 73%; much of the remaining 27% was dissipated into the environment. In spite of present minimal levels of production, and only a few days of smelter operation per year, a real time survey with a mercury Zeeman analyser in a car showed relatively high mercury concentrations in the air. Amounts of 300--4000 ng Hg ^m-3 have been found around both the major sources of mercury vapour, the smelter and mine ventilation shaft -- while the amounts at the Old Place, at the City Museum, and near the Nikova-Idrijca confluence are of the order of 50 ng m^-3. Polluted air will be transported from those sources to a degree which depends on the weather conditions, mainly the direction and intensity of the wind. The high mercury contents in the air are not only due to anthropogenic sources (smelter and the ventilation shaft, dumps and smelter slag used in construction), but may also partly be natural as in the Pront area, where the outcropping bedrock contains native mercury.     

根际土壤中Cd、Pb形态转化及其植物效应

采用根袋盆栽试验和连续形态分析方法研究根际土壤中Cd、Pb形态转化及其植物效应。结果表明，(1)在低Cd质量分数(≤1mg／kg)污染条件下，根际土壤中cd主要以残渣态存在；在较高cd质量分数(≥5mg／kg)污染条件下，cd主要以交换态和碳酸盐结合态存在，即根际土壤中Cd由残渣态向交换态和碳酸盐结合态转化，Cd活性增强。(2)Pb在根际土壤中主要以有机结合态和铁锰氧化物结合态存在，交换态质量分数很低，并随Pb污染水平的提高，其主要存在形态未改变。(3)土壤中Cd、Pb总质量分数及各形态质量分数(残渣态除外)与小麦根、茎叶中Cd、Pb质量分数呈正相关性，而与鲜质量呈负相关性；当w(Cd)添加量≥5mg／kg时，小麦鲜质量明显下降；当w(Pb)≥500mg／kg时，小麦鲜质量下降。     

施肥及种植作物对汞污染土壤中微生物生态的修复

以中性紫色土为材料，通过向土壤添加氯化汞的模拟培养试验、施肥试验以及作物栽培试验，研究了汞对土壤中微生物区系和重要微生物生理群繁育的毒害效应。结果表明，向土壤中添加HgCl2，总体上抑制了细菌、真菌、放线菌及氨化细菌的繁育，硝化细菌、自生固氮菌、纤维素降解菌在一定质量分数范围内被汞刺激增长，在另一定质量分数段则被汞抑制。施肥和栽种作物削弱了汞对微生物的毒害，使土壤微生物生态得到一定程度的修复，说明利用农业措施修复汞污染的土壤是可行的。栽种作物时，汞对微生物的抑制效应受到掩蔽，作物产量和植株体内汞含量是汞污染程度的良好指标。以微生物和植物对汞污染的反应，基本一致的HgCl2危害质量分数指标是5mg．kg^-1。     

Exposure assessment for mercury from consumption of marine fish in Iran

Seven species of marine fish in the Persian Gulf and three species of marine fish in the Caspian Sea were collected from the local wholesale market in Mashhad, Iran. The mercury (Hg) concentration in muscle samples was determined by atomic absorption spectrophotometry. High total Hg concentration was found in Anchovy sprat (2.04 ± 1.23 µg g^?1) and Whitecheek shark (1.26 ± 1.85 µg g^?1) and the lowest content was detected in common carp (0.24 ± 0.24 µg g^?1) and Caspian salmon (0.25 ± 0.08 µg g^?1). The mean Hg content in all samples was 0.91 ± 1.07 µg g^?1. All samples of Persian Gulf and one sample of Caspian Sea had mean Hg concentration above 0.5 µg g^?1, the level established by joint FAO/WHO on Food Additives. Results showed that the estimated weekly intake of total Hg by a 60 kg adult is below the provisional tolerable weekly intakes recommended by joint FAO/WHO on Food Additives. For prevention of health risks, populations in Iran need to consume fish in moderate amounts.     

两种螯合剂对汞在土壤-植物系统中迁移的影响

盆栽试验表明,螯合剂种类、浓度、施用时间等对莴笋产量的影响程度分别为５７．７２%、１６、０６%、２６．２２%,对汞在莴笋中的积累影响程度分别为４９．１５%、２．４７%、４８．３８%。在莴笋移栽时,施用０．１０ ｍｏｌ/Ｌ的ＤＴＰＡ,既可削减蔬菜中汞含量,又可促进蔬菜产量的增加。模拟试验表明,不同螯合剂只是对淋洗速度产生影响,而对滤液汞、土壤残留汞的影响不明显     

小麦根际土壤汞的分布和形态变化

采用根际箱试验和连续化学萃取法,结合氢化物原子吸收光谱法,研究了非根际和根际土壤汞形态分布特征及小麦(Triticum aestivum)生长期土壤汞形态变化.结果表明.非根际汞形态分布顺序为:残渣态>强有机质结合态>碳酸盐铁锰氧化物结合态>腐殖酸络合态>水溶态>交换态,根际汞形态分布为:残渣态>碳酸盐铁锰氧化态>强有机质结合态>交换态>腐殖酸络合态>水溶态.当外源汞进入土壤后,在小麦生长60 d内,植物吸收使残渣态汞和水溶态汞含量明显降低,交换态汞和碳酸盐铁锰氧化态汞含量增加.土壤汞污染程度越大,在小麦中积累的汞就越多.其生物毒性增强,环境危害加大.     

桂林市菜地土壤-蔬菜汞污染研究和评价

对桂林市近郊8个不同片区蔬菜产地的118个土壤样品和71个蔬菜样品中汞的含量水平进行了调查和分析。运用单因子污染指数法评价了菜地土壤一蔬菜中汞的污染现状。研究表明，桂林市及近郊菜地土壤和蔬菜已受到不同程度的汞污染，全市各片区菜地土壤汞含量平均值为0．098-0．523mg／kg，以国家土壤环境质量标准二级标准评价，土壤平均污染指数在0．33-1．74范围内，属非污染或轻污染状态，除穿山南片和纸马铺外，其余采样点均有样本超过国家二级标准，其中七星公园东北片的土壤汞超标率较高，达71．4％，污染情况比较均一；虞山桥东南岸土壤汞超标率较低，为33．3％，但土壤汞含量变异较大，说明污染情况变化大。全市各片区老菜的汞含量平均值为0．0625-0．128mg／kg，为国家标准GB2762—1994规定蔬菜汞含量(0．01mg／kg)的6．25—12．8倍，超标率已达100％。实验还发现，蔬菜中的汞含量与土壤中的汞含量具有显著的相关性，且蔬菜汞的大部分分布于地上部可食部分。分析了菜地土壤汞污染的主要原因，可能与使用含汞农药和生活垃圾肥有关。