土壤环境汞污染现状及其影响因素研究进展

土壤重金属污染导致土壤环境质量显著降低,影响食品安全、水源水质和空气质量等,严重威胁人类的生存和发展。汞（Hg）作为一种全球性的重金属污染物,广泛分布于多种环境介质中,其中土壤是全球汞最大的储存库。土壤中的汞可通过多种暴露途径进入人体,危害人类健康。伴随着全球气候变暖和人为活动加剧,全球土壤汞污染问题日益严重。然而,目前有关土壤汞污染的基础数据较为缺乏,大范围的土壤汞污染空间分布特征分析相对较少,对于土壤汞污染主控因子的分析方法缺乏系统的阐述。因此,本文基于文献调研的方法,分析了全球的土壤汞污染分布特征,发现全球土壤汞污染主要集中在矿区及工业聚集区,阐述了人为因素、气候条件和土壤环境因素等对土壤汞含量变化的影响,并总结了可应用于土壤汞污染主控因子分析的常用方法及其优缺点。同时,本文对未来土壤汞污染调查和研究进行了3方面的展望,以期为更加科学合理的解决土壤汞污染问题做出贡献。     

乌江流域梯级水库入出库河流中总汞和甲基汞的时空分布

2006年1~12月，每月采集乌江流域梯级水库入出库河流水样，用两次金汞齐-冷原子荧光光谱法和蒸馏-乙基化结合GC CVAFS法测定了水中总汞和甲基汞的浓度。结果表明：（1）入出库河流中总汞年均加权浓度分别为317和 2.34 ng/L，甲基汞为014和 0.18 ng/L。（2）不同水库入出库河流中总汞和甲基汞的时空分布特征不同，位于上游第一级的普定和洪家渡水库入库河流中总汞有明显的季节变化趋势，且显著低于出库河流；而甲基汞的季节变化在出库河流中较为明显，而且库龄大的普定、东风、乌江渡水库出库河流中甲基汞浓度显著高于入库河流。（3）相关分析发现水库入库河流中总汞、甲基汞浓度主要受悬浮颗粒物的影响，而与水量间的相关性因水库所处位置的不同而有差异，上游的普定和洪家渡水库中呈显著正相关，其它水库中呈负相关。     

Mercuric chloride effects on adult rat oval cells-induced apoptosis

In the present investigation, the toxicity of mercuric chloride (HgCl₂) was evaluated in adult oval cells isolated from rat utilizing the 2-acetylaminofluorene/partial hepatectomy technique. Isolated oval cells were incubated with 5 μM of HgCl₂ for 8 hr to elucidate in vitro cytotoxic responses. Recently, autophagic cell death was found in rat hepatocytes in vitro within 30 min of incubation with 5 μM of mercury (Hg) which triggered apoptosis and necroptosis in a time-dependent manner. Nuclear degradation occurred within 30 min of incubation and progressed with time until 8 hr. Apoptosis evidenced by activation of caspase-dependent pathway between 30 min to 8 hr of incubation was mediated via interchange of death domain signaling pathways. Receptor-interacting protein played a positive role to modulate the death domain receptors in the scenario of apoptotic death of oval cells until 6 hr. Autophagic marker proteins ATG12 and LC3B exerted a significant role in triggering apoptosis in 5 μM Hg-treated oval cells. No apparent expression of apoptosis-inducing-factor (AIF) and HMGB1 indicated absence of caspase-independent apoptosis and necrosis in the rat oval cells between 30 min and 8 hr. Thus a low concentration of Hg modulates programmed cell death in adult rat oval cells by altering expression of proteins involved in the molecular mechanisms of cellular functions.     

Combined effects of mercury and hexachlorobenzene in the rat

Abstract

The objective of the present study was to assess the potential interactive effects of two Great Lakes chemical contaminants, hexachlorobenzene (HCB) and mercury (HgCl₂). Groups of 10 female Sprague‐Dawley rats were administered by gavage single doses of HCB (400, 600 mg/kg b.w. in corn oil), HgCl₂ (10.0, 12.5 mg/kg b.w. aqueous) or combinations of both followed by observation for clinical signs of toxicity for 14 days. Five animals from treatment groups died before the termination of the study; one animal each in 600 mg HCB, 400 mg HCB + 10 mg HgCl₂, and 600 mg HCB + 10 mg HgCl₂, and two animals in 600 mg HCB + 12.5 mg HgCl₂. The surviving animals were necropsied at the termination of the study, and hematological, clinical chemistry, histopathological and tissue residue analyses were performed. Relative liver weights were increased in both low and high dose groups of HCB but not in animals treated with HgCl₂ alone. Co‐administration of HgCl₂ did not alter the HCB effects on the liver weight of the animals. Serum cholesterol levels were increased in all the groups receiving HCB but not HgCl₂. No interactive effects on other serum parameters were seen in animals administered with both chemicals. Mild to moderate morphological changes occurred in the liver, thyroid, thymus, ovary and bone marrow of rats exposed to HCB or HCB + HgCl₂, and in the kidney of HgCl₂ or HgCl₂ + HCB treated animals. More severe histological changes occurred in the groups receiving both chemicals. The histological effects appeared to be additive. It was concluded that co‐administration with HCB and HgCl₂ resulted in additive effects in some of the endpoints measured but no synergism or antagonism was observed.     

A GFP-based bacterial biosensor with chromosomally integrated sensing cassette for quantitative detection of Hg(II) in environment

A mercury biosensor was constructed by integrating biosensor genetic elements into E. coli JM109 chromosome in a single copy number, using the attP/attB recombination mechanism of λphage. The genetic elements used include a regulatory protein gene (merR) along with operator/promoter (O/P) derived from the mercury resistance operon from pDU1358 plasmid of Serratia marcescens. The expression of reporter gene gfp is also controlled by merR/O/P. Integration of the construct into the chromosome was done to increase the stability and precision of the biosensor. This biosensor could detect Hg(II) ions in the concentration range of 100-1700 nmol/L, and manifest the result as the expression of GFP. The GFP expression was significantly different (P ≤ 0.05) for each concentration of inducing Hg(II) ions in the detection range, which reduces the chances of misinterpretation of results. A model using regression method was also derived for the quantification of the concentration of Hg(II) in water samples.     

道南膜技术测定Ca(NO3)2溶液体系中汞的化学形态

虽然道南膜技术(DMT)已经成功用于土壤/溶液中多种重金属自由态离子浓度的测定,但DMT技术测定Hg的形态尚未解决.采用DMT测定Ca(NO3)2溶液体系中Hg化学形态.实验结果表明,Hg在阳离子交换膜内的吸附除静电吸附外还存在结合力更强的化学吸附,Hg在阳离子交换膜内扩散成为Hg跨膜传输受阻的主要因素,限制道南膜技术用于Hg形态测定.Hg2+和Hg(OH)2都表现出在阳离子交换膜上的强烈吸附,供端(Donor)Hg损失达50%以上.缩短试验时间至8h以内,可在一定程度上降低Hg吸附.计算结果表明,由于大量的Hg滞留在阳离子交换膜内,在计算受端(Acceptor)Hg浓度时引入滞留系数补偿供端Hg的损失,较好地预测了Ca(NO3)2溶液体系中Hg的化学形态.     

上海市大气总汞季节变化特征及与气象条件的关系

2008年到2010年对上海市西南部大气中总汞(TGM———Total Gaseous Mercury)的污染水平进行监测,结果表明TGM日均浓度为ND~57.23ng/m(3(7.79±3.29)ng/m)3。TGM呈现出一定的季节性变化特征,浓度最高的是秋季,然后依次是冬季、春季、夏季,平均浓度分别为(9.30±2.48)、(8.32±2.79)、(7.78±2.33)、(2.16±3.29)ng/m3。TGM浓度受东南风向影响最大,其次为西北和东北风向。在置信水平为95%的情况下,TGM浓度与日平均温度呈正相关性,而与日温差、相对湿度、日相对湿度差、风速无显著相关性。但TGM浓度分别与日均O3浓度和NO2浓度均呈显著正相关。利用HYSPLIT_4模型对TGM浓度高值与低值几天的空气气团来源轨迹进行反演,结果发现高低浓度日的气团来源略有差别,总体上看,冬季、春季和秋季受北方气团影响较大,夏季则受我国东部海域影响,具体的局部和长距离输送的贡献需要进一步研究。     

广州市“南肺”果园土壤H g和A s的形态分析

采用Tessier连续提取法、BCR连续提取法和Leleyter连续提取法,研究广州"南肺"果园土壤Hg和As的形态分布和生物可给性。结果表明,果园土壤Hg和As形态分布都以残渣态为主;3种方法的土壤生物可给性分析均表明,Hg和As生物可利用态的含量较少;生物不可利用态是主要形态,其次是潜在可利用态。     

青藏高原中汞的分布特征及影响因素——以典型海洋性冰川小流域为例

本研究以青藏高原典型海洋性冰川的雪冰-径流水为研究对象,分析讨论了雪冰-径流水中汞浓度变化趋势及控制因素.结果表明,贡嘎山冰川中雪、冰样品的THg浓度略高于全球背景值,而明永冰川以及米堆冰川的雪、冰、水样品均处于全球背景水平.3个冰川所有雪样、冰样、水样的THg浓度平均值分别为（4.78±5.99）ng/L、（1.72 ±1.15）ng/L、（1.31±0.91）ng/L.不同的环境介质中THg浓度变化总体表现为：雪 > 冰 > 水,其主要受颗粒汞沉淀作用及气态单质Hg挥发作用的控制.贡嘎山的径流水中THg浓度表现为六月最高（7.48±2.22）ng/L,十一月最低（1.39 ±0.27）ng/L.所有雪冰-径流水体系中HgP与THg存在极显著的正相关关系,雪中HgP/THg最高,其次为冰,最低为径流水.贡嘎山径流水中的HgP/THg及月均THg输出变化趋势受径流量和降雨量的影响.主成分分析表明了本研究区域雪冰中THg浓度主要受大气颗粒物沉降及季风传输的影响.此外,相比于其他2个冰川,贡嘎山冰川由于更加靠近人类活动密集区域,更易受到人类活动的影响.     

载铜氮化碳纳米片对单质汞的吸附脱除特性

用简易热剥离法合成了氮化碳纳米片（CNNS）,再通过等体积浸渍法将铜负载于CNNS表面合成了载铜CNNS吸附剂,用于低温下吸附脱除气态单质汞（Hg⁰）.利用氮气吸附-脱附、X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）等手段对吸附剂进行表征.结果表明：CNNS对Hg⁰具有良好的吸附性能,吸附温度为120℃时,脱汞效率约为54.2%;载铜修饰可极大提高CNNS的脱汞活性,脱汞效率在40~240℃温度范围内均大于82.3%,这归因于铜与氮化碳间的紧密接触.煅烧温度对载铜CNNS的脱汞活性影响较大,最佳煅烧温度为200℃.通过载铜修饰可有效活化CNNS,提高其对Hg⁰的氧化能力,这可能归因于铜离子与氮化碳之间的莫特-肖特基电子转移效应.SO₂和水蒸气对载铜CNNS的脱汞性能有抑制作用.