高效液相色谱-电感耦合等离子体质谱联用测定生物样品中的有机汞

建立了酸提取-高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICP-MS)测定生物样品中甲基汞、乙基汞、苯基汞等3种有机汞的分析方法。鱼肉和贝类样品经盐酸消解,苯萃取,硫代硫酸钠溶液反萃取后,采用醋酸铵/L-半胱氨酸缓冲盐及甲醇体系组成的流动相按一定比例进行梯度洗脱,经前处理的生物样品在液相色谱中经C18柱分离后,进入电感耦合等离子体质谱检测其甲基汞、乙基汞和苯基汞的浓度。3种有机汞化合物均在0.50~50.0μg/L范围内呈现良好的线性关系,线性相关系数(r)均大于0.9998。方法检出限为0.010~0.038mg/kg;3种有机汞样品加标的RSD均小于12.2%;两个水平的加标回收率在50.8~129%。     

三峡库区消落带甲基汞变化特征的模拟

为探寻三峡水库消落带在干湿交替条件下甲基汞的变化规律,以库区典型消落带土壤为研究对象,采用模拟试验,研究了干湿交替条件下消落带土壤和水体甲基汞含量和动态变化趋势及其影响因素.结果表明:淹水过程会促进土壤无机汞向有机汞转化,土壤甲基汞含量在淹水和落干过程均呈现先增加后减少的趋势;随着干湿交替周期的增加,土壤甲基汞含量增加,第二次淹水后土壤甲基汞平均含量比第一次淹水增加了22.13%,第二次落干后土壤甲基汞平均含量比第一次落干增加了58.17%.第二次淹水过程土壤甲基汞占总汞的比例明显高于第一次淹水,土壤中汞的甲基化主要与干湿交替循环有关.土壤淹水后会迅速向水体释放甲基汞,水体中甲基汞含量明显增加,两次淹水过程增幅分别为119.42%和334.72%,水体甲基汞和土壤甲基汞之间无显著相关.干湿交替环境土壤甲基汞含量主要受pH值、有机质含量、Eh和土壤含水量等因素的影响;水体中甲基汞含量的影响因素则主要有水体pH值、DO、DOM、水温等.     

水华束丝藻和铜绿微囊藻对水中甲基汞的吸附特征及动力学研究

本文探究了活、死水华束丝藻和铜绿微囊藻对水中甲基汞（MeHg）的吸附动力学特征和等温吸附模型。结果表明,当MeHg浓度为100 ng/L时,活、死水华束丝藻能吸附水中99.2%和90.9%的MeHg,平衡吸附量分别为9.9×10^-2 ng/（10⁸cells）和9.1×10^-2 ng/（10⁸cells）,活、死铜绿微囊藻能吸附水中98.5%和94.0%的MeHg,平衡吸附量分别为9.9×10^-2 ng/（10⁸cells）和9.4×10^-2 ng/（10⁸cells）;两种藻对MeHg的吸附过程符合准一级、准二级动力学模型;活水华束丝藻和活、死铜绿微囊藻对MeHg的等温吸附过程符合Freundlich等温吸附模型,死水华束丝藻对MeHg的等温吸附过程符合Langmiur等温吸附模型;对藻细胞结构进行表征,发现活藻和死藻对MeHg的吸附在细胞表面均呈现为生物快速吸附过程,活藻还呈现为生物慢速富集过程,故活藻对MeHg的吸附率高于死藻。     

Environmental mercury contamination of an artisanal zinc smelting area in Weining County, Guizhou, China

To investigate the extent of Hg contamination due to artisanal Zn smelting activities in Weining County, northwestern Guizhou, China, total Hg and methyl mercury (MeHg) concentrations in soil and surface water were determined. Samples of corn plants growing in the study area were also collected for total Hg analysis. A high geometric mean Hg emission factor of 75gHgt(-1)Zn was estimated and significantly elevated total gaseous mercury (TGM) concentrations were found in the atmosphere adjacent to the Zn smelting sites, ranging from 30 to 3814ngm(-3). Total Hg and MeHg concentrations in topsoil samples ranged from 62 to 355microgkg(-1) and from 0.20 to 1.1microgkg(-1), respectively. Total Hg Concentrations in corn plant tissues increased in the order of grains相似文献   

水稻甲基汞富集对大气气态单质汞浓度升高的响应研究

水稻具有很强的甲基汞(MeHg)富集能力,从而增加了汞污染地区居民甲基汞暴露的风险.本研究利用开顶气室熏蒸实验和土壤加汞培育实验探究水稻各组织中MeHg富集对大气中的气态单质汞(GEM)浓度升高的响应.结果表明:水稻根中甲基汞含量与土壤中甲基汞含量显著正相关(r=0.9462~0.9870,p0.05),与大气汞含量无线性关系(p0.05),表明水稻根中的MeHg主要来自土壤.水稻茎中甲基汞含量随土壤甲基汞含量的增加而线性增加(上部茎:r=0.8560,p0.05;下部茎:r=0.9178~0.9484,p0.05),与大气汞含量没有相关性(p0.05),但在气室熏蒸实验中上部茎中的甲基汞含量高于下部茎;而在土壤加汞培育实验中下部茎中的甲基汞含量高于上部茎,表明水稻茎主要受土壤汞的影响,且大气汞可能对水稻上部茎甲基汞的富集有一定的影响.水稻叶中甲基汞含量与土壤甲基汞含量显著正相关(r=0.9708,p0.01),与大气汞含量无线性关系,但在气室熏蒸实验中实验组叶中甲基汞的含量高于对照组,表明水稻叶中的甲基汞可能受土壤甲基汞和大气汞的共同影响.水稻籽粒中甲基汞的含量与土壤甲基汞含量呈显著正相关(r=0.9046~0.9865,p0.05),与大气汞含量无明显的线性关系(p0.05),表明水稻籽粒中的甲基汞主要来自土壤,但在水稻上部茎和叶中甲基汞含量受一定程度大气汞含量影响的情况下势必会对水稻籽粒甲基汞的富集产生影响,但究竟有多大程度影响或量化其贡献还需进一步实验研究.     

第二松花江水中甲基汞的时空变化规律

为研究第二松花江水中甲基汞的时空变化规律,分别在平水期和丰水期沿二松流域进行了采样分析,得出其空间变化规律：红石、十号线和泔水缸3个断面甲基汞含量较高,在这3个断面两侧甲基汞含量均下降.季节性变化规律：除涝州和四方台断面外,其他各采样断面丰水期甲基汞含量均低于平水期.通过对比分析1981年、 1983年和本研究结果,得出了年际性变化规律：1981年甲基汞含量随与排污口距离的增加而降低;1983年污染源已切断1 a,水中甲基汞含量骤降,达到天然背景值水平,但肇源至四方台江段甲基汞含量均在0.35 ng·L^-1以上;2006年各相应断面甲基汞含量高于1983年,低于1981年.此外,本研究给出了二松水中甲基汞的污染程度.     

中国环境与生物标准参考物质中甲基汞的测定

应用了多种分离技术分离有机汞，以气相色谱电子捕获检测器测定甲基汞和乙基汞，测定了一些已经定值总汞的中国环境与生物标准参考物质及一些别国制备的标准测参考物质。采用不同分离技术，所得结果基本一致，也存在些差异。实验室之间的测定结果也很接近。建议上述物质可作为测定甲基汞和乙基汞的标准参考物质。     

Study on the simultaneous reduction of methylmercury by SnCl2 when analyzing inorganic Hg in aqueous samples

Mercury (Hg) is among the most concerned contaminants in the world. It has three major chemical forms in the environment, including Hg⁰, Hg^2 +, and methylmercury (MeHg). Due to their differences in toxicity, mobility, and bioavailability, speciation analysis is critical for understanding Hg cycling and fate in the environment. SnCl₂ reduction-atomic fluorescence spectrometry detection is the most commonly used method for analyzing inorganic Hg. However, it should be noted that MeHg may also be reduced by SnCl₂, which would result in the overestimation of inorganic Hg. In this study, the reduction of MeHg by SnCl₂ in both de-ionized (DI) water and four natural waters was investigated. The results showed that MeHg could be reduced by SnCl₂ in DI water whereas this reaction was hard to occur in tested natural waters. By investigating the effects of water chemical characteristics (dissolved organic matter, pH and common anions and cations) on this reaction, SO₄^2 ? was identified to be the dominant factor prohibiting SnCl₂ induced MeHg reduction in natural waters. SO₄^2 ? in natural waters was evidenced to be reduced to S^2 ? by SnCl₂ and the generated S^2 ? can complex with MeHg to form MeHgS^? which is hard to be reduced by SnCl₂. Findings of this study indicate that the effect of MeHg reduction by SnCl₂ on inorganic Hg analysis is negligible in natural waters; however, at simulated experimental systems without SO₄^2 ?, SO₄^2 ? should be added as protecting agents to prevent MeHg reduction when analyzing inorganic Hg if it would not cause any other unwanted effects.     

壳聚糖改性生物炭对水稻土甲基汞生成及其稻米积累的影响

研究发现稻米易富集甲基汞（MeHg）,汞污染区稻米的食用也是人体MeHg暴露的一个重要途径.因此,如何抑制MeHg在稻田中的生成及其在稻米中的富集,是亟需解决的重要问题.为此,本文采用盆栽试验,通过对间隙水、土壤及水稻植株各组织汞含量的分析,探讨了添加壳聚糖改性生物炭对水稻生长期土壤MeHg生成及籽粒MeHg富集的影响.结果表明,添加壳聚糖改性生物炭后能明显降低土壤及间歇水中的总汞（THg）及MeHg含量,与对照相比,土壤中汞的甲基化率降低了51.1%~79.1%;水稻成熟时,添加壳聚糖改性生物炭处理（CMBC）水稻根部MeHg含量比未添加生物炭处理（CK1）低73.1%,比添加未改性生物炭处理（CK2）低62.0%;稻米MeHg含量比CK1低75.8%,比CK2低72.9%;添加生物炭能促进水稻生长,CMBC和CK2处理的植株生物量分别是CK1的1.6倍和1.7倍.盆栽模拟试验结果表明,壳聚糖改性生物炭在促进水稻生长的同时,可以抑制MeHg在稻米中的富集,有一定的推广应用价值.     

Distribution of mercury and methylmercury in river water and sediment of typical manganese mining area

Manganese (Mn) ores contain substantial concentrations of mercury (Hg), and mining and smelting of Mn ores can bring Hg into the surrounding aquatic environment through atmospheric deposition, leaching of electrolytic Mn residue and Mn gangue dump. However, limited is known that how these processes influence the environmental behaviors of Hg in waterbody. Therefore, the seasonal distribution and existing form of Hg in water and sediment in one Mn ore area in Xiushan County, Chongqing were investigated. Our results showed that the mean Hg and methylmercury (MeHg) concentrations in water (n=35) were 5.8 ± 4.6 ng/L and 0.22 ± 0.14 ng/L, respectively. The mean Hg concentrations in retained riverbed and fluvial bank sediment (n=35) were 0.74 ± 0.26 mg/kg and 0.63 ± 0.27 mg/kg, respectively (the mean MeHg concentrations were 0.64 ± 0.40 µg/kg and 0.51 ± 0.30 µg/kg, respectively). It indicated that the mining and smelting of Mn ores were the main sources of anthropogenic Hg, and Mn may inhibit Hg methylation in rivers in Mn ore areas. Mercury in the bound to iron/ Mn (Fe/Mn) oxides of low crystallinity fraction (Hg-OX) accounted for 4.01% and 5.25% of the total Hg concentrations in the retained riverbed and fluvial bank sediment, respectively. The amount of Hg bound to Fe/Mn oxides in sediment increased significantly due to the manganese mining activities in the investigated area. Therefore, it could be hypothesized that high Hg concentrations in river sediment in Mn mining areas are closely related to high Mn concentration in sediment.