长寿湖水体甲基汞光化学降解特征

为明确长寿湖水体甲基汞(MMHg)光化学降解特征,采用硼硅玻璃瓶对水样进行原位培养,探讨了长寿湖水体MMHg光化学降解的季节差异性及垂直变化特征,分析了不同波段光波对MMHg光化学降解反应的贡献,并估算了MMHg光化学降解的通量.结果发现,在光的作用下,长寿湖水体表层MMHg会发生明显的降解反应,未发现明显的净甲基化结果.在水体表层,夏季MMHg光化学降解速率最快((6.10±0.38)×10-3E~(-1)·m~2),其次为春季((4.90±0.24)×10-3E~(-1)·m2),秋冬季节的降解速率较低,分别为(3.10±0.19)×10-3E~(-1)·m~2和(2.60±0.12)×10-3E~(-1)·m~2;UV-A、UV-B和可见光(PAR)对表层水体MMHg光化学降解反应的贡献分别为49%~52%、21%~31%和21%~34%.MMHg光化学降解速率随水深增加而逐步衰减,其中,UV-B引发的光化学降解反应速率衰减最快,其次为UV-A.对整个水体而言,PAR对MMHg光化学降解的贡献最大(67%~77%),其次为UV-A(25%~31%),UV-B的贡献最小(4.3%~8.1%).夏、秋、冬和春4个季节的MMHg日降解通量分别为7.2、0.73、1.1和5.9 ng·m-2·d~(-1),年降解通量估算为1.5μg·m-2·a~(-1).可见,长寿湖水体MMHg光化学降解反应具有明显的季节和水深剖面变化特征,不同波段光波对降解反应的贡献有较大的差异.     

Methylmercury and total mercury in estuarine organisms from Rio de Janeiro, Brazil

Guanabara Bay (GB), located in the Rio de Janeiro State, is still a productive estuary on the south-eastern Brazilian coast. It is an ecosystem heavily impacted by organic matter, oil and a number of other toxic compounds, including Hg. The present study aimed to comparatively evaluate the aquatic total mercury (THg) and MeHg contamination, and the ratios of MeHg to THg (% MeHg), in 3 species of marine organisms, Micropogonias furnieri-carnivorous fish (N = 81), Mugil spp.--detritivorous fish (N = 20) and Perna perna--filter-feeding bivalves (N = 190), which are widely consumed by the population. A total of 291 specimens were collected at the bay in different periods between 1988 and 1998. THg concentrations were determined by cold vapour AAS with stannous chloride as a reducing agent. MeHg was extracted by dithizone-benzene and measured by GC-ECD. Analytical quality was checked through certified standards. All organisms presented both low THg and MeHg concentrations and they were below the maximum limit of 1,000 micrograms Hg.kg-1 wet wt. as established for human intake of predatory fish by the new Brazilian legislation. Carnivorous fish showed higher THg and MeHg concentrations, and also % MeHg in muscle tissues, than organisms with other feeding habits and lower trophic levels. The average of THg concentrations in carnivorous fish was 108.9 +/- 58.6 micrograms.kg-1 wet wt. (N = 61) in 1990 and 199.5 +/- 116.2 micrograms.kg-1 wet wt. (N = 20) in 1998, but they presented different total length and body weights. The average THg content in detritivorous fish was 15.4 +/- 5.8 micrograms.kg-1 wet wt., whereas THg concentrations ranged from 4.1 to 53.5 micrograms.kg-1 wet wt. for the molluscs. The THg and MeHg contents of mussel varied according to the sampling point and water quality. MeHg concentration in detritivorous fish was similar to MeHg concentration in molluscs, but there was a significant difference in the MeHg/THg ratio: the carnivorous fish presented higher MeHg percentages (98%) than the detritivorous fish (54%) and the molluscs (33%). Weight-normalised average concentration of THg in carnivorous fish collected in 1990 (0.18 +/- 0.08 microgram.g-1/0.7 kg wet wt.) and in 1998 (0.16 +/- 0.09 microgram.g-1/0.7 kg wet wt.) presented no significant difference (t = 1.34; P < 0.5). In conclusion, the low THg and MeHg concentrations in the organisms from the GB ecosystem, are related to its eutrophic conditions and elevated amounts of suspended matter. In this situation, Hg could be strongly complexed or adsorbed by the particulate, which would dilute the Hg inputs and reduce its residence time in the water column, with a consequent decrease in its availability to organisms.     

Methylmercury, total mercury and total selenium in four common freshwater fish species from Ya-Er Lake, China

Snakehead fish (Ophiocephalus argus cantor), silver carp (Hypophthalmichthys molitrtix), crucian carp (Carassius carassius), and common carp (Cyprinus carpio) are four common freshwater fish species in China. In this study, the level of methylmercury (MeHg), total mercury (T-Hg), and total selenium (T-Se) in muscle samples of these four fish species from Ya-Er Lake, China, were analyzed using atomic fluorescence spectrometry coupled with high-performance liquid chromatography, and inductively coupled plasma mass spectrometry. The concentrations of MeHg in all the fish species were significantly correlated with those of T-Hg. Higher T-Hg and MeHg concentrations had accumulated in the snakehead fish, which is a strongly predatory fish, than in the other three species. The concentration ratios of MeHg and T-Hg in the muscles of these four fish species were almost equal. Conversely, there was negative correlation between the concentrations of T-Hg and T-Se, which implies that there is a competition between these two elements with respect to bioaccumulation. It is noteworthy that of all the muscle samples tested, the level of T-Hg exceeded the maximum allowable limit in fish [0.4 mg kg⁻¹ (w/w) recommended by the World Health Organization] in 38.46% of those of the silver carp, 18.18% of those of the crucian carp, and 100% of those of snakehead fish. These results show that the consumption of contaminated fish is a potential threat to human health and that necessary preventive measures to safeguard public health should be emphasized.     

盐渍化环境下秸秆还田对稻米汞及甲基汞累积的影响

通过盆栽试验探讨了盐渍化环境下秸秆还田对土壤中总汞（THg）、甲基汞（MeHg）含量和转化以及对水稻吸收汞的影响.试验用土采集自天津典型污灌地区,人为添加不同梯度的盐分（0、0.2%、0.5% NaCl）及外源汞（0、5mg/kg~Hg（NO₃）₂）,秸秆还田按照0.1%进行处理.结果显示：1.秸秆还田促进稻田系统中无机汞的甲基化.与未添加秸秆的处理相比,秸秆还田后土壤MeHg含量提高了56.8%~76.8%,水稻MeHg含量增加了127%~171.6%.2.在轻度盐渍化稻田开展秸秆还田,会进一步提高稻田土壤中汞的甲基化水平,进而增加水稻籽粒中甲基汞含量.与不添加盐分处理相比,轻度盐渍化环境中（0.2% NaCl）,秸秆还田处理导致土壤MeHg含量提高了92.2%~101.2%,水稻籽粒MeHg含量增长了52.8%~132.1%.更高的盐渍化水平会抑制土壤汞甲基化趋势,水稻籽粒中甲基汞含量降低.在中度盐渍化环境中（0.5% NaCl）,秸秆还田导致土壤MeHg含量降低了57.9%~88.6%,水稻籽粒MeHg含量降低了72.9%~86.8%.以上研究结果表明,在盐渍化且汞污染稻田开展秸秆还田可能大幅度增加该地区汞食物链暴露风险,因此在中轻度盐渍化的污灌区,对秸秆还田等农艺措施需要格外慎重.     

The use of the embryo‐culture techniques in the research on the Teratogenic and Mutagenic properties of metals†

Actually, embryos can be cultured from the one‐cell stage up to the blastocyst stage, and their development can be easily monitored at any time: severe effects caused by toxic compounds are traduced by rapid embryonic death, less pronounced effects can be expressed by a lowered cleavage activity or by an arrest of the development from a particular stage. The system can be improved by transferring the embryos at the blastocyst stage in another more complete medium where they can “implant”; and form an inner cell mass with differentiated ectoderm and endoderm. Since last years, it has also become possible to culture postimplantation rodent embryos for short periods involving a number of particularly critical stages of organogenesis, such as the formation and closure of the anterior neuropore. Embryo‐culture also represents a useful system to study cytogenetic effects of chemicals which are often linked to lethal or teratogenic effects. These different possibilities are illustrated by examples of studies already performed with metals, and dealing with their teratogenic and/or cytogenetic effects on pre‐ and postimplantation rodents.     

碱提取-丙基化衍生法同时测定土壤中的甲基汞和乙基汞

建立了碱提取-丙基化衍生方式同时测定土壤中甲基汞和乙基汞的方法。优化了仪器分析条件，研究了碱提取温度、提取时间、缓冲溶液加入量和衍生化试剂加入量对测定结果的影响。应用本方法对5种实际土壤样品进行测定，甲基汞和乙基汞的方法检出限分别为0.5 μg/kg和0.3 μg/kg，相对标准偏差分别为1.3%~17%和0.94%~16%，平均回收率分别为88.2%~110%和66.1%~110%。该法适用于批量土壤样品中甲基汞和乙基汞的分析测定。     

施用污泥堆肥品对土壤和植物总汞及甲基汞的影响

采用田间试验,分别施加两种不同的污泥堆肥品(含生物质炭和不含生物质炭),研究污泥堆肥土地利用过程土壤及植物总汞和甲基汞变化情况、迁移转化特征和植物富集能力.结果表明,施加污泥堆肥品会引起土壤总汞和甲基汞含量升高,但总汞含量低于国家土壤环境质量二级标准.生物质炭堆肥品可能促进土壤汞的甲基化,但不同处理土壤甲基汞/总汞(Me Hg/THg)比值较低.植物成熟后不同处理植物总汞含量明显低于幼苗期,而甲基汞含量均高于幼苗期.施加两种堆肥品对植物富集总汞没有明显差异,但对甲基汞富集影响显著.施加生物质炭堆肥品的土壤甲基汞含量明显高于施加无生物质炭堆肥品的土壤,而植物甲基汞含量则相反.生物质炭的加入可能有利于土壤甲基汞形成,但不利于甲基汞的迁移,抑制植物对土壤甲基汞的富集.植物对甲基汞的富集能力较强(富集系数为1.24~14.63),需关注长期施肥带来的土壤环境汞生态风险.     

稻壳生物炭吸附无机汞和甲基汞的特征研究

为了探究稻壳生物炭吸附溶液无机汞(Hg²⁺)和甲基汞(MeHg⁺)的特征,研究了不同稻壳生物炭用量和溶液pH对汞吸附的影响,及其吸附动力学和热力学特征。结果表明:当溶液中无机汞浓度为50 mg/L且pH为7.0时,施用50 mg生物炭后,生物炭对无机汞的吸附在18 h后达到平衡且最大吸附量为23.52 mg/g;当溶液中甲基汞浓度为30 ng/L且pH为4.0时,施用20 mg生物炭后,生物炭对甲基汞的吸附量在3 h后达到吸附平衡且最大吸附量为58.54 ng/g。生物炭对无机汞和甲基汞的吸附研究过程均符合准一级、准二级模型,其中准二级模型的拟合效果更好,说明该吸附作用过程更倾向于化学吸附。Freundlich和Langmuir等温吸附模型都能很好的拟合稻壳生物炭对无机汞的等温吸附,而稻壳生物炭对甲基汞的吸附符合Langmuir等温吸附模型。稻壳生物炭对总汞和甲基汞的吸附机制主要为离子交换、静电吸附、沉淀以及络合作用。研究结果可为稻壳生物炭修复汞污染环境提供理论依据。     

三峡库区消落带土壤中硫酸盐还原菌对汞甲基化作用的影响

为探究三峡水库这一特殊的周期性干湿交替环境中,硫酸盐还原菌(sulfate-reducing bacteria,SRB)是否在汞的生物甲基化过程中起主导作用,本文以库区消落带原土为研究对象,以灭菌土+接种硫酸盐还原菌Desulfovibrio africanus(D.africanus,DSM-2603)为对照(试验A),在每公斤土壤分别添加0、1、5 mg汞浓度条件下,模拟研究原土(试验B)中总汞(THg)和甲基汞(MeHg)含量的动态变化、总硫酸盐还原菌(SRB)数量变化,以及影响土壤中甲基汞含量的环境因子分析.结果表明,淹水状况有利于THg从土壤中释放,且Hg含量越高,释放越快;菌株D.africanus对汞具生态适应性,其菌数与MeHg含量显著正相关:在5 mg·kg~(-1)Hg条件下,D.africanus菌数可达3.65×10~4cfu·g~(-1),MeHg含量也高达7.60×10~4ng·kg~(-1).值得注意的是,试验B处理中,一方面消落区原土中SRB菌数较少,平均仅193 cfu·g~(-1);另一方面,土壤MeHg含量较低:在5mg·kg~(-1)Hg条件下,MeHg含量仅为5.54×10~3ng·kg~(-1),且总SRB菌数与MeHg含量无显著相关性.由此可以推测,在三峡水库消落区这种非严格厌氧土壤环境中,SRB并非优势菌群,其中还存在着其它对生物汞甲基化起主导作用的好氧或兼性厌氧微生物种群.     

Tissue distribution of inorganic mercury, methylmercury and cadmium in the Asiatic clam (Corbicula fluminea) in relation to the contamination levels of the water column and sediment

The comparative experimental study of inorganic mercury (HgII), methylmercury (MeHg) and cadmium (Cd) bioaccumulation in the Asiatic clam Corbicula fluminea was based on a 14 days' exposure to the water column or sediment compartments, as initial contamination sources. For each contaminant and exposure source, a five-point concentration range was set up in order to quantify the relationships between the contamination pressure and bioaccumulation capacity, at the whole soft body level and in five organs: gills, mantle, visceral mass, kidney and foot. Hg and Cd bioaccumulation at the whole organism level was proportional to the metal concentrations in the water column or sediment. For similar exposure conditions, the average ratios between the metal concentrations in the bivalves - [MeHg]/[HgII] and [MeHg]/[Cd] - were close to 10 and 5 for the sediment source and 8 and 15 for the water column source. Metal distribution in the five organs revealed strong specificities, according to the different contamination modalities studied: kidney and gills were clearly associated with Cd exposure, mantle and foot with MeHg exposure and the visceral mass with inorganic Hg exposure.