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。     

几种沼渣中Cu和Zn的含量及其形态分布

通过CaCl2、EDTA、HOAc一步提取法和改进的BCR三步法对6种沼渣中的重金属Cu和Zn的形态进行了研究.结果表明,沼渣中重金属的形态组成与重金属的种类和沼渣的类型有关;单一提取剂对沼渣中Cu、Zn的提取效率顺序为：EDTA〉HOAc〉CaCl2,其中EDTA的提取效率可达70%以上,HOAc提取效率在11%和62%之间,中性盐CaCl2的提取效果最差,其提取效果最高不到0.6%;沼渣中Zn的可移动性大于Cu的可移动性,若原沼渣中含有高浓度的Zn,施入土壤中可能使得植物吸收过多的Zn,从而产生农用风险.     

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.     

重金属在环境中的化学形态分析研究进展

重金属在环境中的形态与迁移转化决定了其污染风险和生物有效性.本文从影响重金属形态的主要环境条件和结合物特性出发,分析了重金属在环境中与有机物、无机矿物质等的交互作用机理,对目前重金属形态分析的主要研究方法(化学提取、电化学、分子尺度仪器检测技术、模型计算等)展开综述与讨论.     

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。     

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.     

攀枝花尾矿库溪流中钒的分布及化学形态

采用ICP-AES方法测定攀枝花尾矿库溪流水、悬浮物、沉积物中钒的含量,以及沉积物中钒的化学形态,结果表明:不同介质中钒的含量均高于全球钒的平均值;钒主要存在于沉积物及悬浮物中;水相中钒的含量主要与沉积物中钒的含量及存在形态有关;沉积物中的钒以残留态为主,各形态钒的比例主要受上覆水体理化性质的影响.     

Factors affecting methyl and inorganic mercury dynamics in mussels and shrimp

Radiotracer experiments were designed to study the effect of certain factors on the accumulation and loss of methyl and inorganic mercury in mussels (Mytilus galloprovincialis) and benthic shrimp (Lysmata seticaudata). Methyl mercury was accumulated from both food and water to a greater degree than inorganic mercury by both species. There was a tendency for small mussels to concentrate more mercury than larger individuals, but the reason for this difference remains unclear. A trend towards greater mercury accumulation at higher temperatures was noted for mussels, but the temperature effect was relatively small over a 10 C^o range between 8° and 19°C. Methyl mercury residues were eliminated by both species more slowly than those of the inorganic form. Loss from mussels was somewhat more rapid at higher temperatures; however, as in the case of accumulation, the effect of temperature was relatively small. Loss rates for small mussels were not significantly different from those for large individuals. Enhanced methyl mercury elimination was noted for the group of mussels maintained in their natural environment. The more rapid metal turnover in these individuals compared with mussels held in the laboratory was attributed to differences in the availability of natural particulate food matter and, hence, subsequent growth of the animals in the two experimental systems. The observed differences underscore the need for caution in predicting in situ flux of metals such as mercury in certain species based solely on data derived from laboratory experiments.     

汞在海洋浮游植物中的生物累积和毒性效应

浮游植物是海洋生态系统的主要初级生产者,同时作为食物也是许多水生生物摄取汞的主要途径。本文综述了近年来汞在海洋浮游植物中的最新研究进展,包括汞在浮游植物中的吸收、累积规律及其影响因素,汞对浮游植物的毒性效应(生长抑制、光合作用影响)以及生物的适应机制(汞的还原、螯合解毒、矿化固定等),最后对浮游植物中汞累积和毒性的未来研究方向进行了展望。     

Extraction of arsenic species in soils using microwave-assisted extraction detected by ion chromatography coupled to inductively coupled plasma mass spectrometry

We have developed a novel microwave-assisted extraction method for determining the arsenic (As) speciation in soils that is based on extraction with phosphate solutions, including orthophosphoric acid, ammonium dihydrogen orthophosphate, and ammonium hydrogen orthophosphate. The highest extracting efficiency was obtained with 1 M ortho-phosphoric acid solution as the extractant, and this efficiency is associated with the pH of the extractant. Total As content and As species in the soil extracts were determined by inductively coupled plasma mass spectrometry (ICP-MS) alone and by the combined ion chromatography (IC) with ICP-MS, respectively. The proposed extraction procedure was applied to National Institute of Standards and Technology (NIST) standard reference material (SRM) 2711 (Montana soil) as well as to environmental soil samples collected from the agricultural lands of Bangladesh. As(V) was detected in all the soil samples, and As(III) was detected in nine soils of the 20. These results of extractable As testing indicate that the extraction of As species mainly depends on the composition of the soils. The As speciation results also indicate that As adsorption is highly dependent on the iron, aluminum, and manganese concentrations in the soil. The stability of As species in the extracts was also studied.     

Substitution of toxicologically critical solvents in the residue analysis of acetamiprid: Towards green chemistry

The article presents the reduced use of toxicologically critical solvents for the extraction and clean-up of a neo-nicotinoid pesticide, acetamiprid from vegetables. Acetamiprid was extracted from spiked vegetable samples of cabbage by the use of different techniques like microwave-assisted extraction (MWAE), sonication and by the conventional method of homogenization. The study revealed that though higher percent recoveries of 78–92 were obtained in the blending method, solvent use was high as compared to MWAE. In MWAE, the percent recoveries recorded were in the range of 46–89 depending upon the solvent used and power employed. A mixture of methanol–water and methanol–acetone at 400 W power levels gave percent recoveries of 72 and 82, respectively, as compared to solvent mixtures, namely, acetone–hexane and acetone–hexane–water, which recorded recoveries of 49 and 67%. The study indicates that the choice of solvent and power employed plays a significant role in MWAE for enhanced recoveries.     

物种敏感度分布的非参数核密度估计模型

针对目前物种敏感度分布参数方法建模所存在的缺点,首次提出基于非参数核密度估计方法的物种敏感度分布模型,并提出相应的最优窗宽和检验方法。选用无机汞作为案例研究对象,利用非参数核密度估计方法和3种传统参数模型分别推导了保护我国水生生物的无机汞的急性水质基准值。结果表明,非参数核密度估计方法在推导无机汞水质基准中的稳健性和精确度都大大优于传统参数模型,能够更好地构建物种敏感度分布曲线。该方法的提出丰富了水质基准的理论方法学,为更好地保护水生生物提供了有力的支撑。     

太湖表层沉积物中重金属的形态分析

采用BCR三步分级提取法和ICP-AES测定了太湖沉积物中8种重金属不同形态的含量，初步评估了太湖沉积物中重金属的生物有效性，探讨了沉积物总有机碳（TOC）与重金属不同形态之间的关系。     

Relative extraction ratio (RER) for arsenic and heavy metals in soils and tailings from various metal mines, Korea

This study focused on the evaluation of leaching behaviours for arsenic and heavy metals (Cd, Cu, Ni, Pb and Zn) in soils and tailings contaminated by mining activities. Ten representative mine soils were taken at four representative metal mines in Korea. To evaluate the leaching characteristics of the samples, eight extraction methods were adapted namely 0.1?M HCl, 0.5?M HCl, 1.0?M HCl, 3.0?M HCl, Korean Standard Leaching Procedure for waste materials (KSLP), Synthetic Precipitation Leaching Procedure (SPLP), Toxicity Characteristic Leaching Procedure (TCLP) and aqua regia extraction (AR) methods. In order to compare element concentrations as extraction methods, relative extraction ratios (RERs, %), defined as element concentration extracted by the individual leaching method divided by that extracted by aqua regia based on USEPA method 3050B, were calculated. Although the RER values can vary upon sample types and elements, they increase with increasing ionic strength of each extracting solution. Thus, the RER for arsenic and heavy metals in the samples increased in the order of KSLP?相似文献   

Analysis of psychoactive substances and metabolites in sludges,soils, sediments and biota: a review

The use of psychoactive substances, including illegal drugs, drugs of abuse and psychiatric pharmaceuticals, is a major health and environmental issue. In particular, drugs are found in urban sewage and water ecosystems. The analysis of drugs in wastewater is challenging because drugs occur at trace levels in complex organo-mineral media, calling for advanced analytical methods. Here we review recent methods developped to analyze drugs in sludge, sediments, soils and biota. Extraction methods include solid–liquid extraction, sonication, microwave, and quick, easy, cheap, effective, rugged and safe extraction (QuEChERS). We compare and discuss advantages and disadvantages of each analytical step for various sample types.

     

滇池沉积物有机磷形态分级特征

考察沉积物磷对湖泊富营养化贡献时,大量研究涉足无机磷,对有机磷的研究十分薄弱.针对滇池的33个沉积物样品,采用有机磷分级提取方法,将沉积物有机磷分为活性磷、中等活性磷、非活性磷等三种具有不同稳定性的有机磷.结果表明:排除滇池西北部外源污染严重的样品后,沉积物有机磷与总磷有自北向南逐渐降低的变化趋势,有机质与总磷、活性有机磷、中等活性有机磷以及非活性有机磷都表现出了显著相关关系.沉积物活性有机磷和中等活性有机磷与NaHCO3提取无机磷均显著相关,说明二者具有潜在的生物有效性.     

沉积物中汞的生物可利用性研究进展

沉积物是汞在水体中的主要分布相,同时也被认为是许多水生生物摄取汞的主要途径,本文综述了近年来在沉积物中汞的生物可利用性领域所取得的最新研究进展,包括体外消化液萃取法估测沉积物中汞的生物可利用性、可能影响汞生物可利用性的生物地球化学因素(汞在沉积物中的浓度、沉积物的组成、汞与沉积物的接触时间、汞与沉积物的结合形式,以及沉...     

选择性萃取方法在生物膜上铁、锰氧化物分离中的应用

1　IntroductionSurfacecoatings (biofilmsandassociatedminerals)existonallkindsofsolidphasesinnaturalaquaticenvironments.FeandMnoxideswerefoundedtobethemostimportantcomponentsofsur facecoatingsfortheirhighadsorptioncapacity[1—3].Tostudytherelativeroleofdif…     

Microprofiles of oxygen in epiphyte communities on submerged macrophytes

Mussels (Mytilus edulis) transferred in net bags from clean to chronically mercury polluted water readily accumulated mercury during an exposure period of three months. Growth of the transplanted mussels had a diluting effect on the mercury concentration, but the absolute weight of mercury uptake increased throughout the entire period, though there was a tendency for decreased efficiency of the removal of mercury per liter of water filtered by the mussels. Mussels were also translocated from polluted to clean (laboratory) water to depurate mercury. The biological half-lives of mercury was 293 d for M. edulis from the chronically polluted area in contrast to only 53 d for mussels from a temporary massive mercury polluted area near a chemical deposit. In both cases about 75% of the total mercury in the mussels was inorganic, and it is suggested that both inorganic and organic mercury species were immobilized in mussels from the long-term mercury polluted area, whereas the immobilization capacity was exceeded in the short-term mercury exposed mussels near the chemical deposit. Very slow elimination of mercury was observed in the deposit-feeding bivalve Macoma balthica from the chronically polluted area, and about 6% of the total mercury was methyl-+phenyl-mercury. This is more than three times lower than found in M. edulis from the same collecting site. A pronounced difference in the mercury speciation (i.e., total mercury, total organic mercury, methyl-mercury and phenyl-mercury) in M. edulis from the two mercury polluted areas is thought to reflect the different character of the mercury pollution in the two areas.