沉积物中汞的甲基化研究进展

汞是环境中存在的一种重要污染物质,其毒性与之化学形态密切相关。环境中的汞主要以无机汞形态存在,然而无机汞可以通过甲基化作用转化为毒性更强的甲基汞,从而给受到暴露的生物及人类带来更高的健康风险。沉积物是汞在水生环境系统中的主要分布相,也是无机汞甲基化过程发生的主要场所。沉积物中汞的甲基化过程受到生物种类、汞的生物可利用性等生物因素及温度、含硫化合物、有机质、氧化还原条件等环境理化性质的影响。本文对汞在沉积物中甲基化过程的作用机制及其影响因素的研究现状及最新进展进行了总结,并对未来更深入的研究进行了展望。     

外源稀土La在沉积物中的形态及其生物可利用性

将沉积物中的外源稀土La分为可溶解态、酸可提取态、有机质及硫化物结合态,研究了小球藻(Chlorella Vulgaris Beijerinck)对这三种形态La的生物可利用性.研究结果表明:这三种形态的La在沉积物中的含量与其在藻中的含量有很好的相关关系.其中可溶解态La的生物可利用性最大,这说明,沉积物中La的释放对其生物可利用性至关重要.     

外源稀土La在沉积物中的形态及其生态可利用性

可沉积物中的外源稀土Ｌａ分为可溶解态，酸可提取态、有机质及硫化物结合态，研究了小球藻对这三种形态Ｌａ的生物可利用性，研究结果表明：这三咱开矿的Ｌａ在沉积物中的含量与在藻中的含量有很好的相关关系，其中可溶解态Ｌａ的生物可利用了大，这说明，沉积物中Ｌａ的释放对其生物可利用性至关重要。     

通讯

沉积物中有机污染物的生物可利用性的化学测量方法 准确测定疏水性有机污染物（HOCs）的生物可利用性对于评估沉积物生态毒性风险,实施沉积物污染修复极其重要．在研究生物可利用性的理论机制的同时,不少工作也从实践上探索测定生物可利用性的快速有效方法．传统的沉积物生态风险评估,常常运用沉积物中HOCs的有机碳标准化浓度来表征该...     

生物扰动对沉积物中污染物环境行为与生物可利用性的影响

疏水性有机污染物进入环境水体后易于与沉积物结合,对沉积物中的底栖动物造成危害。底栖动物引起的生物扰动作用可以通过改变沉积物的地球化学性质,对其中污染物的赋存形态、迁移转化和生物可利用性产生重要影响。在综述了国内外生物扰动影响沉积物中污染物环境行为和生物可利用性的最新研究进展基础上,重点讨论了沉积物颗粒交换、水体环境条件改变、疏水有机污染物解吸释放过程以及对生物扰动影响的定量化表征。最后对该研究方向进行了展望,指出应重点研究多种污染物及不同生物共存条件下的生态效应,以及造成沉积物扰动的影响因素的定量化表征等。     

黑碳对土壤和沉积物中菲的吸附解吸行为及生物可利用性的影响

利用淡水单孔蚓Monopylephorus limosus的生物富集实验,研究了黑碳对土壤和沉积物中多环芳烃类有机化合物菲生物可利用性的影响,同时研究了黑碳对菲吸附和解吸行为的影响,并用"双元平衡解吸(DED)模型"对解吸行为进行了预测.结果表明,土壤和沉积物中黑碳的存在直接导致了菲在颤蚓体内的生物累积因子(BSAF)的降低,其原因在于菲在黑碳沉积物样品中的不可逆吸附程度的显著增强.研究发现,土壤和沉积物中菲的生物可利用性与土壤和沉积物中菲的吸附相浓度无关而与孔隙水浓度密切相关.     

沉积物中有机污染物的生物可利用性的化学测量方法

准确测定疏水性有机污染物(HOCs)的生物可利用性对于评估沉积物生态毒性风险,实施沉积物污染修复极其重要.在研究生物可利用性的理论机制的同时,不少工作也从实践上探索测定生物可利用性的快速有效方法.传统的沉积物生态风险评估,常常运用沉积物中HOCs的有机碳标准化浓度来表征该污染物在生物体内的蓄积量及其对生物体     

深圳湾红树林沉积物-植物体系汞的分布规律和形态分配特征

为了解重金属汞在非根际沉积物-根际沉积物-红树植物连续体系中的分布特征和迁移规律,以及沉积物中汞的化学形态特征,于深圳湾福田红树林实地采集红树植物幼苗样品及其林下沉积物样品,采用连续提取法对沉积物中汞的各种化学形态进行提取,通过冷原子荧光光谱仪进行定量分析。研究对象包括福田红树林3种常见红树植物,包括白骨壤(Avicennia marina)、桐花树(Aegiceras corniculatum)2个本土种和海桑(Sonneratia caseolaris)1个引进种,并以无植被覆盖的光滩作为空白对照。结果表明,在沉积物-红树植物体系中,根际和非根际沉积物中的总汞含量均高于红树植物幼苗。进入植物体后,汞在茎中的含量均小于根和叶。本土种植株表现出较强的汞积累能力。白骨壤幼苗汞积累量最高,质量分数达到45.32 ng·g-1,其次为桐花树幼苗,汞质量分数为23.49 ng·g-1。3种红树植物对汞的生物积累因子在0.02~0.35范围内,迁移因子处于0.4~0.99范围内,均低于1,表明它们从土壤吸收、并向地上部分运输汞的能力较弱,倾向于采取金属排斥策略,以实现植物体的自我保护。非根际沉积物中汞的各个化学形态质量百分比表现为有机结合态可挥发态残渣态可交换态碳酸盐结合态铁锰氧化物结合态,根际沉积物中汞表现为可挥发态机结合态残渣态铁锰氧化物结合态可交换态碳酸盐结合态,总体表现为生物可利用态和潜在可利用态质量分数较高,不可利用态较少。与本土种相比,引进种海桑能够将更多汞以稳定性相对较高的生物不可利用态和潜在可利用态形式固定于土壤中,表现出较好的治理汞污染能力。     

两种海源可溶性有机物对汞在沉积物中吸附特性的影响

选取两种常见的近海滩涂养殖海产品菲律宾蛤仔和海带,分别制备了两种海源性生物的可溶性有机物(DOMc和DOMk),研究了海源性DOM影响下汞在胶州湾两种沉积物样品中的吸附解吸特征.结果表明,Elovich方程能够很好拟合不同DOM处理下汞在沉积物中的动力学过程,其次为双常数方程.添加两种海源性DOM均显著提高了汞在沉积物样品中的吸附速率,其中DOMc促进作用最为显著.Langmuir和Freundlich方程均能很好描述汞的等温吸附过程;与对照处理相比,DOMc使两个沉积物样品对汞的最大吸附量分别增加了70.1%和80.9%,DOMk则分别提高了12.4%和10.2%;海源性DOM抑制了沉积物中汞的释放,其中DOMc的抑制作用最强.添加DOM没有改变汞的吸附量随p H的变化趋势,但在相同p H条件下,DOM仍然明显促进了汞在沉积物中的吸附.研究结果显示,近海水产养殖产生的DOM可通过增加沉积物对汞的吸附而降低其生物有效性,而这却在一定程度上抑制了海湾水体中汞的对外交换,从而增加水体汞污染的风险.     

城市滨海湿地表层沉积物磷形态与相关关系分析

以九龙江口滨海湿地为例,采用连续提取法对沉积物中的磷进行连续提取和测定,探究城市滨海湿地表层沉积物中磷的生物可利用性,同时分析沉积物磷形态以及与环境参数的相关关系。结果表明：总磷（TP）含量为（456.34±13.13）mg·kg-1,生物可利用性磷（Bio-P）占TP59.46%;NaOH-P、HCl-P是TP的主要组成形态;NaOH-P是Bio-P的主要组成形态。相关性研究表明,沉积物中TP含量的增加主要来自NaOH-P,其次是HCl-P。NH4Cl-P、BD-P、NaOH-P、HCl-P之间未呈显著相关,其来源具有差异性。NaOH-P与pH显著负相关,与Fe、Al未呈显著相关;OP与有机质含量亦无显著相关。研究成果将为海域生态环境保护和城市滨海湿地环境恢复提供基础数据。     

Mercury fractionation in the sediments of Vembanad wetland, west coast of India

Transformations among different mercury species associated with sediments can have a major effect on the metal's mobility and potential for methylation and hence bioaccumulation. In the present study, various fractions of mercury in the sediments of Vembanad wetland system analysed. Total mercury (THg) concentration in the surface sediment varied from 16.3 to 4,230?ng/g. The results of sequential extraction showed that the major portion of mercury in these sediments existed as elemental form followed by organo-chelated form. The least portion observed was the residual fraction (mercury of natural origin). Even though the percentage of mercury observed in the easily available fractions is relatively small, absolute values of these mobile Hg fractions are quite high due to the very high total mercury values. The fractionation of mercury in the sediment was controlled by the organic matter, sulphur complexes and concentration of THg. The results showed that the bioavailability of mercury is high as the amount of mercury found in the initial three fractions is high, which can also enhance the methylation potential of the Vembanad wetland sediments. The fractionation pattern of mercury also revealed the presence of anthropogenic mercury content in the Vembanad wetland sediments.     

Mercury in a northeastern Brazilian mangrove area, a case study: potential of the mangrove oyster Crassostrea rhizophorae as bioindicator for mercury

The Channel of Santa Cruz is a mangrove area in northeastern Brasil 40 km north of Recife. Until 1991 a chlor-alkali factory discharged large amounts of mercury into the main tributary of the channel, the Rio Botafogo. The objective of this study was to assess the potential of the mangrove oyster Crassostrea rhizophorae as a bioindicator for mercury in this area and to examine the influence of condition on mercury concentrations in the oysters. The investigation was carried out in the late rainy season (July to September) 1993, in the rainy season (April to June) 1994 and in the dry season (November/December) 1994. At 11 stations in the channel, mangrove oysters, surface sediments and suspended matter were sampled, representing different compartments of the system. The distribution of mercury in the Channel of Santa Cruz exhibited for all compartments the same distinct spatial pattern with maxima in the Rio Botafogo. Seasonal variations were small and revealed no clear tendencies. In addition, mangrove oysters were transplanted from more contaminated stations to less contaminated stations and vice versa. These experiments were designed to study the oysters' capability to adjust their mercury concentrations to a changing bioavailability of mercury. The transplantation experiments suggest that the oysters are capable to adjust to changing ambient mercury availability within a few months. The transplantation experiments also revealed the importance of condition changes on the mercury concentration of the oysters. This factor should not be ignored during pollution studies. However, condition had apparently no strong influence on the spatial or seasonal mercury variations of the oysters. The mangrove oyster is a suitable bioindicator for long-term changes in mercury availability. Received: 20 August 1997 / Accepted: 15 January 1998     

Metal distribution in marine sediments of the Mar Piccolo in Taranto (Ionic Sea,southern Italy)

The spatial distribution of selected metals (Fe, Ni, Mn, Zn, Cu, Pb, Hg and Cd) and their partition in the different chemical forms (speciation) were determined in benthic sediments from Mar Piccolo, Taranto (Ionic Sea, southern Italy). The aim of this study was to assess the degree of sediment contamination and bioavailability of metals, very important for Italian mussel culture, in a semi-enclosed marine ecosystem. In sediments, grain size distribution, total organic carbon (TOC), and humic (HA) and fulvic (FA) acids contents were also determined. The compounds TOC, HA and FA, in fact, have a great influence on metal complexation. High concentrations of copper, lead, zinc and mercury were found, especially in sediments of the first inlet of Mar Piccolo. Statistical analysis of results shows significant correlation among Cu, Pb and Zn concentrations and the influence of organic matter on the sediment distribution of Cu, Pb and Zn. Metal speciation analysis, carried out with sequential extraction method, shows that Fe and Ni are present in sediments mainly as sulphides. Mn and Pb are present principally in an ion-exchangeable form or bound to carbonate and Cu is associated to organic matter. Metal pollution index (MPI), calculated as a weighed mean of the metal contamination factors in each station, shows that with regard to Cu, Ni, Pb and Zn, some stations investigated are unpolluted (MPI <1), whereas in other areas, pollution level is not very high. On the contrary, for mercury, the pollution level in the first inlet of the basin is very high.     

广东柘林湾养殖海域沉积物中汞的分布、累积及其生态风险

柘林湾是广东省养殖规模最大的海湾之一,为了解养殖海域沉积物中汞的分布、累积及其可能产生的生态风险,于2008年1月在柘林湾海域采集了5个站位的柱状沉积物和3个站位的表层沉积物,对其中的总汞含量进行了测定,并对其含量分布、累积特征进行了分析.结果表明,柘林湾海域表层沉积物中总汞平均含量为0.0645μg·g-1,径流输入是其空间分布特征的主要影响因素;柱状沉积物表层部分总汞含量相对较低,但不同采样区域柱样中总汞含量的垂直分布却有着显著的差异,网箱养殖区主要是由于汞近40年来来源变小导致沉积物表层部分中的总汞含量较底层低,而贝类养殖区则由于沉积后的再迁移作用使汞在氧化还原边界层富集累积;利用潜在生态危害指数法和沉积物质量基准法对此次调查的沉积物中汞的潜在生态风险进行的评价表明,汞虽对底栖生物基本无负面效应,但其潜在生态风险程度达到了中等水平,尤其是养殖区2号站位28～36cm、4号站位20～32cm和48～56cm以及6号站位36～56cm柱样中的汞甚至达到了高的潜在生态风险程度.因此,养殖区次表层沉积物中较高含量的汞应当引起足够重视.     

Mercury distribution,speciation and potential ecological risk assessment in sediments from Lake Taihu,China

Abstract

Twenty-one surface sediments collected from seven surroundings areas of Lake Taihu in two different years were analyzed for total mercury (THg) concentrations, physicochemical characteristics and speciation using a sequential extraction method to assess spatial distribution, sources, and potential ecological risk. Surface sediments from Lake Taihu contained elevated levels of Hg in two sampling years with THg levels ranging from 77 to 346?ng/g (mean 145?ng/g) in October 2010 and ranging from 122 to 573?ng/g (mean 266?ng/g) in November 2012, respectively. The mean THg concentrations in all studied surface sediments exhibited an increasing trend over time. The oxidizable fraction (F3) and residual fraction (F4) were the predominant Hg species in sediments, while more mobile Hg phases of acid-soluble fraction (F1) and reducible fraction (F2) made up less than 0.5% THg. Significant relationships were found between total organic carbon (TOC) and THg and geochemical speciation indicating an important role for organic matter in affecting distribution, mobility, and bioavailability of Hg in sediments. As evidenced by Hakanson’s potential risk index the total ecological risk of Hg was low in the entire Lake Taihu in 2010 but considered moderate in Zhushan Bay, West Coast, and Meiliang Bay in 2012. These findings provide conservation managers with information needed to more effectively regulate the environment of Lake Taihu.     

Metal levels in some benthic organisms of Haifa Bay,mediterranean (Israel)

Benthic organisms revealed enhanced uptake of mercury from polluted surface sediments (in the vicinity of a chlor‐alkali plant) which were enriched in mercury by up to 148 times relative to sediments from an unpolluted area. There is a strong correlation between the concentrations of mercury in the benthic organisms and sediments. No correlation was found between cadmium, lead, copper and zinc levels in the benthic fauna populations and the concentrations of these metals in the sediments. Ranges of concentrations (μg/g wet wt.) in the whole soft tissues varied: Hg, <0.005–3.31; Cd <0.018–1.99; Pb, <0.025–1.56; Cu, 0.242–28.8; and Zn, 9.75–310.2. The three gastropod molluscs show higher metal concentrations than do the bivalves.     

Environmental geochemistry studies in the area of Idrija mercury mine, Slovenia

Five centuries of mining and processing of mercury ore in the Idrija area have resulted in widespread contamination of different environmental compartments. Environmental impacts on a regional and local scale, caused by atmospheric emissions from the Idrija ore roasting plant, were established in the investigations of mercury spatial distribution in soil and attic dust in 160 km(2) area. Very high values were determined in the Idrijca River valley, and they decrease exponentially with the distance from Idrija. Mercury concentrations in attic dust are higher than in surrounding soils and the attic dust/soil ratio changes with distance. Measurements of mercury in the air confirmed widespread dispersion of mercury and showed highly elevated mercury concentrations around roasting plant and mine ventilation shaft. Beside, systematic monitoring of mercury contents in the stream sediments has demonstrated that huge amounts of mercury are stored in areas where ancient overbank sediments were deposited, and there was no decrease in mercury concentration in active sediments during the last 15 years. Recently, interesting and extremely polluted locations of historical small-scale roasting sites in the Idrija surroundings were discovered. Ongoing geochemical study aims to determine the extreme pollution and significance of these sites for wider contamination of soils and aquatic systems. Presented studies have shown that Hg mining in Idrija caused intense pollution of local and regional environment including the aquatic systems in the Gulf of Trieste, which is seen as the final sink of a major part of the Hg stored in soils and river sediments in the Idrija area.     

Urban sediment contamination in a former Hg mining district,Idrija, Slovenia

Road sediments from gully pots of the drainage system and stream sediments from local streams were investigated for the first time in the urban area of Idrija town, the central part of the second largest and strongly contaminated Hg mining district in the world. Hg concentrations in road sediments were lower than in stream sediments. They ranged from 16 to 110 mg/kg (Md = 29 mg/kg) for <0.125 mm particles and from 7 to 125 mg/kg (Md = 35 mg/kg) for <0.04 mm particles, while Hg concentrations in stream sediments ranged from 10 to 610 mg/kg (Md = 95 mg/kg) for <0.125 particles and from 10 to 440 mg/kg (Md = 105 mg/kg) for <0.04 mm particles. High Hg loadings in stream sediments were successfully linked with identified mercury sources (rocks containing mercury ore, areas of former ore roasting sites, ore residue dumps), because they are located in the drainage areas of streams, from which the sediments were collected. Links between Hg loadings in road sediments and identified mercury sources were not recognized. Solid phases of Hg were determined by thermo-desorption technique and are similar for both types of sediments. Results show the occurrence of three different forms: elemental mercury, mercury bound to matrix components and cinnabar. Approximately 50 % of Hg in samples consist of non-cinnabar fractions. This is important, since they are potentially bioavailable. An interesting new discovery according to previous research of environmental media from Idrija area by solid-phase Hg thermo-desorption technique is that elemental mercury was determined in almost all investigated sediments in minor amounts (Md = 3 %).     

Distribution of mercury in the sediments of some freshwater bodies in Ethiopia

Sediment samples were collected from Tinishu Akaki River (TAR), Lake Awassa, and Lake Ziway, Ethiopia for determination of mercury. The air-dried samples were analyzed for mercury with a differential atomic absorption spectrometer after thermal evaporation of bound mercury converting it to its atomic form. Certified reference materials (CRMs) of sediments and soils were used to validate the method. The recovery of mercury from CRMs and sediments was in the range of 95–100%. The limit of detection for the determination of mercury was 50?ng?kg^?1. The concentration of total mercury in the sediments varied from 3.9 to 110?µg?kg^?1 for TAR, 14 to 67?µg?kg^?1 for Lake Awassa, and 17 to 110?µg?kg^?1 for Lake Ziway. It was found that the total mercury concentrations in all samples were below the United States Environmental Protection Agency guideline of 200?µg?kg^?1.