三门峡水库水体中不同形态汞的分布特征

为了解三门峡水库水体中不同形态汞的分布特征,在丰水期和枯水期对三门峡水库进行采样,分别采用冷原子荧光光谱法(CVAFS)和蒸馏-乙基化衍生-气相色谱-冷原子荧光法(GC-CVAFS)测定水样中总汞、总甲基汞、溶解态总汞和溶解态甲基汞的浓度.结果表明,三门峡水库水体中总汞、溶解态汞和颗粒态汞浓度范围分别为1.65~9.65、0.80~3.16和0.70~7.81 ng·L~(-1),符合国家地表水环境质量标准(GB 3838-2002)一类水汞浓度标准限值;总甲基汞、溶解态甲基汞和颗粒态甲基汞浓度分别为0.05~0.36、0.02~0.14和ND~0.26 ng·L~(-1).三门峡水库水体总汞和甲基汞在季节和空间分布上没有呈现出明显的变化规律.总汞和甲基汞与未受污染的天然水体差别不大,水库未受到明显的汞污染.丰、枯水期沉积物中总汞浓度分别为(92.96±10.65)ng·g~(-1)和(80.06±19.14)ng·g~(-1),甲基汞浓度分别为(0.33±0.14)ng·g~(-1)和(0.50±0.19)ng·g~(-1).较低的甲基汞浓度说明在三门峡水库汞的迁移转化过程中,甲基化作用可能并非主要的过程,这可能与水体底层溶解氧浓度较高以及沉积物中有机质浓度较低有关.     

微生物对汞矿区农田土壤汞甲基化的影响

为研究典型汞矿区农田土壤中汞的甲基化作用,实验以受汞污染的旱田土壤和稻田土壤为对象,分别进行灭菌,促进硫酸盐还原菌(SRB)活性处理,抑制SRB活性处理以及促进铁还原菌(FeRB)活性处理,分析非微生物作用和微生物作用对土壤甲基汞(MeHg)生成的影响.结果表明,促进SRB活性处理的土壤MeHg生成量最高,其中旱田土MeHg增量为0.15~0.38μg·kg~(-1),稻田土壤MeHg增量为1~2μg·kg~(-1);抑制SRB活性处理和促进FeRB活性处理的MeHg增量较小,最高值仅为0.025μg·kg~(-1).相比于旱田土壤,稻田土壤具有更高的汞甲基化能力,其MeHg生成量是旱田土壤的4~9倍.土壤SRB数量与MeHg生成量具有相同的变化趋势,二者具有显著的正相关性(R~2=0.57,P0.01).因此,该研究区土壤汞甲基化作用主要是微生物汞甲基化作用,且主要的汞甲基化细菌是SRB.此外,稻田是农田中MeHg生成的活跃地区,在评估和控制MeHg对人体健康危害时需要重点关注.     

三峡水库消落区土壤、植物汞释放及其在斑马鱼体的富集特征

利用室内模拟试验,探讨了三峡水库消落区淹没后土壤、植物汞释放特征及其在斑马鱼体的富集水平.结果表明,随淹水时间的延长,淹没土壤中总汞(THg)含量下降;水体THg浓度总体明显升高.淹没土壤及水体中甲基汞(MMHg)含量总体明显上升,其中稗草+土壤处理水体中增加尤为明显,淹水21 d后,其浓度是土壤处理的2.52倍.表明消落区土壤、植物是水库水体汞的一个重要来源.供试稗草淹水分解造成水体pH及溶解氧(DO)含量下降、溶解性有机碳(DOC)含量上升,对土壤MMHg含量无明显影响,对水体MMHg影响较大.供试斑马鱼头部、内脏及肌肉中THg含量总体明显上升,与水体中THg浓度具有显著相关性(P<0.01).鱼体头部、内脏及肌肉中均出现不同程度的MMHg富集现象,以头部与肌肉最为明显.淹水21 d后,添加土壤处理的鱼体头部、内脏及肌肉MMHg增加的含量分别是对照的1.75~6.25、3.53~8.38、2.22~3.36倍;稗草+土壤处理的分别是土壤处理的3.57、2.37、1.52倍.可见,淹没土壤是鱼体MMHg增加的重要来源,淹没植物改变原水环境条件影响其向水体释汞过程能提高鱼体中MMHg含量.     

万山汞矿区稻田土壤甲基汞的分布特征及其影响因素分析

运用等温气相色谱冷原子荧光技术(GC-CVAFS)对贵州万山汞矿区主要河流范围内稻田土壤甲基汞(MeHg)等含量进行了测定,并从区域层面对土壤甲基汞(MeHg)的分布特征及影响因素进行了研究。结果表明:万山汞矿区稻田土壤MeHg和总汞(THg)含量范围分别为0.72~6.70ng/g和0.49~188.00μg/g,甲基化率范围为0.002%~0.470%;在水平空间分布上,6个检测区域的土壤MeHg含量均随着远离汞矿核心区而降低,但是不同区域之间的降低变化程度不尽相同。通过对稻田土壤SiO2、Al2O3、Fe2O3、TS、TP、TN、有机质、pH等土壤性质与土壤MeHg以及甲基化率进行相关性分析发现,MeHg与THg、TS、TP、TN、有机质存在显著的正相关关系,与SiO2表现出显著性负相关,表明土壤甲基汞不但和总汞含量有关,还受到土壤其它理化因子,尤其是一些营养因子所控制。     

秋夏季黄河三角洲湿地土壤汞和甲基汞的变化

汞在湿地中的行为对湿地水生生物健康具有重要影响.于2011年和2012年分别采集干(夏初)湿(秋季)季节黄河三角洲湿地土壤样品,分析不同季节汞与甲基汞的含量差异和垂直变化.秋季总汞平均含量为0.064 mg·kg-1;夏季为0.027 mg·kg-1,总汞含量平均减少57%,湿地由积水到干旱过程中导致汞的释放.秋季各点位0~10 cm深甲基汞平均含量为0.28μg·kg-1,夏季甲基汞平均含量为0.066μg·kg-1,各点位含量平均减少76%.在秋季受湿地淹水影响,利于甲基汞的形成,水分减少和湿地干旱导致土壤中的甲基汞减少.在垂直方向上,夏季与秋季相比总汞在0~10 cm深度都有减少,土壤中的汞发生释放,因此,湿地在秋季表现为汇,而在春夏季为大气汞的源.硫酸盐还原细菌的含量秋季远高于夏季,在夏季硫酸盐还原菌与甲基汞和甲基化率均显著相关,硫酸盐还原菌、淹水环境、有机物质都会影响甲基汞产生和分布.     

贵州汞矿矿区不同位置土壤中总汞和甲基汞污染特征的研究

为了深入理解汞矿矿区土壤中总汞和甲基汞的污染特征,应用AAS、GC-CVAFS方法,分别对贵州万山、务川和滥木厂汞矿矿区不同位置土壤以及对照区土壤中的总汞(THg)和甲基汞(MeHg)进行了测定.结果表明,万山汞矿区土壤THg和MeHg含量范围分别为1.1～790 mg·kg^-1和0.19～15μg·kg^-1,务川汞矿区土壤THg和MeHg含量范围分别为0.33～317mg·kg^-1和0.41～20μg·kg^-1,滥木厂汞矿区土壤THg和MeHg含量范围分别为0.41～610 mg·kg^-1和0.70～8.8μg·kg^-1.对照区土壤汞含量明显低于矿区土壤,其THg和MeHg含量范围分别为0.14～1.2 mg·kg^-1和0.09～0.23μg·kg^-1;对照区土壤THg含量接近或稍高于全球背景土壤THg含量0.01～0.5 mg·kg^-1.研究表明,汞矿区稻田土壤具有较强的汞甲基化能力,其MeHg含量明显高于菜地和旱田土壤;万山汞矿区土壤汞污染程度明显高于滥木厂和务川汞矿区土壤汞污染.     

Effect of methylmercury on LPO levels, SH groups and activities of GSH-Px, SOD, XOD in liver of rats

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贵州东风水库沉积物间隙水中溶解态汞及甲基汞的分布特征及界面交换

为弄清水库沉积物间隙水中汞及甲基汞的分布及扩散特征,于2009年春、夏两季对东风水库进行了采样,分别采用两次金汞齐-CVAFS法和蒸馏-乙基化结合GC-CVAFS法测定沉积物间隙水中溶解态(DHg)和甲基汞(DMeHg)浓度。结果表明夏季沉积物间隙水DHg浓度远高于春季,而DMeHg浓度却略低于春季;沉积物间隙水中DHg和DMeHg均有向上覆水体扩散的趋势,其夏季扩散通量高于春季;间隙水中DMeHg对上覆水体的贡献率大于DHg,最高可达30%,再次证明了沉积物间隙水中的DMeHg是其上覆水体的重要来源。     

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.     

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.