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。     

全自动烷基汞分析系统分析水源水中烷基汞的实验研究

建立了全自动烷基汞分析系统测定水源水中烷基汞(甲基汞、乙基汞)的方法。实验采用直接法测定水源水中的烷基汞含量,在0.5~1 000 pg的范围内,甲基汞及乙基汞标准工作曲线线性均良好;取样体积为30 ml时,甲基汞及乙基汞的检出限分别为0.005 ng/L及0.003 ng/L,低于水源水中限量要求;实际水样甲基汞及乙基汞加标回收率为85.9%~89.4%及87.4%~91.3%;标准样品分析合格;测定甲基汞及乙基汞标准样品的相对误差为1.8%及2.4%;运用优化的仪器条件和适当的质控手段,可较好的满足水源水中痕量烷基汞的测定需求。     

水中汞监测存在的问题与解决办法

利用中日合作 (JICA)项目资金 ,对测定地表水中汞存在的主要问题 ,如水样的保存和处理 ,水样的消解 ,测汞的冷原子吸收法和原子荧光法等进行了研究。通过对 33个环境监测站的样品考核 ,发现测定结果与标准值相比 ,偏高的数据达 75 %以上。提出了用 1%H2 SO4 和 0 1%K2 Cr2 O7保存水样最好 ;高锰酸钾 -过硫酸钾消解法适用于消解含有机物、悬浮物和组成复杂的废水样 ,高锰酸钾 -硫酸消解法适用于消解被有机物轻度污染的废水 ,溴酸钾 -溴化钾消解法适用于消解地表水和含较少有机物的生活污水及工业废水。研究表明 :尤以硫酸 -高锰酸钾 -过硫酸钾消解体系消解地表水和废水效果良好。对冷原子吸收法和原子荧光法中影响汞测定的因素 ,如空白值高、干扰物的消除、载气种类和流量、反应瓶体积和气液比以及反应时间等提出了详尽的解决方法     

高效液相色谱-原子荧光联用测定天然水中烷基汞

应用在线紫外光照射-高效液相色谱分离-冷原子蒸发/氢化物发生-原子荧光光谱法(HPLC-UV-CV/HG-AFS)测定天然水中烷基汞,实验比较两种前处理方法-巯基棉富集和液液萃取,优化分析条件,建立一种简便、选择性好、高灵敏度分析天然水中烷基汞的方法.取1L水样时,甲基汞和乙基汞的检出限(3S/N)分别为0.3和0.6...     

全自动甲基汞分析仪测定水和废水中甲基汞

建立了全自动甲基汞分析仪测定水和废水中甲基汞的方法,对较清洁的地表水和一般废水样品可直接衍生化测定,对基体复杂水样则需蒸馏后再衍生化测定。该法在水样中甲基汞含量为0~1 000 pg范围内线性良好,相关系数r为0.999 7,检出限为0.002 ng/L,标准参考物质测定结果均在参考值范围内,相对标准偏差为1.1%,加标回收率为83.2%~96.6%。该法适用于水及废水中甲基汞的检测。     

高效液相色谱-电感耦合等离子体质谱联用测水中有机汞

建立了高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICP-MS)测定水样中甲基汞、乙基汞、苯基汞等3种有机汞的分析方法。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,Agilent Zorbax Plus C18柱分离,经前处理的水样在液相色谱中分离后,进入电感耦合等离子体质谱检测其甲基汞、乙基汞、苯基汞的浓度。3种有机汞化合物均在0.50~50.0μg/L范围内呈良好的线性关系,线性相关系数均大于0.999 5。仪器检出限为0.09~0.12μg/L,方法检出限为0.4×10-6~0.6×10-6mg/L,3种有机汞样品加标的RSD均小于11.3%,2个水平的加标回收率为74.4%~83.2%。     

测定水中铁、锰、汞时前处理问题探讨

基于大量实测数据统计,比较了测定水中铁、锰、汞3种重金属时,样品是否过滤、加酸保存等前处理方式对测定结果的影响,提出铁、锰水样需过滤检测,汞水样不能过滤检测,且3种金属的水样均需加酸保存,这样测定的结果才能根据现行水环境质量标准进行评价。     

HPLC-ICP/MS联用测定废水中甲基汞和无机汞

采用高效液相色谱(HPLC)-电感耦合等离子体质谱(ICP/MS)联用测定废水中可滤态的甲基汞和无机汞,优化了仪器工作条件,讨论了方法干扰及校正办法。甲基汞和无机汞在0.500μg/L~25.0μg/L范围内线性良好,检出限分别为0.03μg/L和0.07μg/L,废水样品平行测定的RSD分别为6.5%~7.6%和6.2%~6.8%,加标回收率分别为84.0%~87.0%和88.0%~92.4%。     

大气中不同形态汞的采集和分析方法

作为一种环境优先污染物,汞对人体和其它生物毒性很大。大气是全球汞生物地球化学循环的重要场所。不同形态的汞由于理化性质不同,迁移转化过程及其对生态环境的影响也不同,准确测定大气环境中各种形态的汞对于了解其在大气中的行为具有重要意义。1990年以来,大气汞的采集和分析方法技术已经取得了长足进步,一些自动测汞仪、低汞空白和高时间分辨率的采样及分析技术相继出现,使得准确测定大气中不同形态的痕量汞成为可能。文章就国内外近10多年来在这些方面所取得的研究进展进行了回顾和总结,主要介绍了气态总汞、颗粒态汞、活性气态汞、甲基汞等的采集和分析方法。     

液液萃取-HPLC-ICPMS联用技术测定水体中甲基汞

建立了二氯甲烷萃取,半胱氨酸-乙酸铵溶液反萃取,液相色谱-电感耦合等离子体质谱法测定水中甲基汞的方法。取样量为1 L时,方法检出限为0.1 ng/L,相对标准偏差为6.6%~13%,地表水、生活污水和工业废水3种实际水样的加标回收率分别为45.6%~70.5%、37.0%~65.6%、18.4%~61.8%。与5种甲基汞测定方法的前处理过程、分析仪器和检出限进行了比较,并讨论了无机汞的干扰情况及如何降低体系空白和消除无机汞干扰的质量控制手段。     

Application of cryofocusing hydride generation and atomic fluorescence detection for dissolved mercury species determination in natural water samples

The concentration levels of mercury (Hg) species in natural water samples are usually low. Consequently, accurate analysis with low detection limits is still a major problem. In this work, a method was applied for the simultaneous direct determination of dissolved mercury species in water samples by on-line hydride generation (HG), cryogenic trapping (CT), gas chromatography (GC) and detection by atomic fluorescence spectrometry (AFS). The suitability of the method for real samples with different organic matter and chloride contents was evaluated by recovery experiments in synthetic and natural spiked water samples. The HG method was compared with other current available methods for mercury analysis with respect to the different fraction of mercury analysed, i.e. 'reactive', 'reducible' or total. HG derivatization and SnCl2 reduction (with and without previous oxidation with BrCl) were applied to synthetic and natural (spiked and non-spiked) water samples. The influence of chloride and dissolved organic matter concentrations was studied. The results suggest that the HG procedure is suitable for the simultaneous determination of Hg2+ and MeHg+ in surface water samples. Inorganic mercury analysed by HG (i.e. reducible) is close to the total inorganic mercury.     

Contamination of Canadian and European bottled waters with antimony from PET containers

Using clean lab methods and protocols developed for measuring Sb in polar snow and ice, we report the abundance of Sb in fifteen brands of bottled water from Canada and forty-eight from Europe. Comparison with the natural abundance of Sb in pristine groundwaters, water bottled commercially in polypropylene, analyses of source waters prior to bottling, and addition of uncontaminated groundwater to PET bottles, provides unambiguous evidence of Sb leaching from the containers. In contrast to the pristine groundwater in Ontario, Canada containing 2.2 +/- 1.2 ng l(-1) Sb, 12 brands of bottled natural waters from Canada contained 156 +/- 86 ng l(-1) and 3 brands of deionized water contained 162 +/- 30 ng l(-1); all of these were bottled in PET containers. Natural water from Ontario bottled in polypropylene contained only 8.2 +/- 0.9 ng l(-1). Comparison of three German brands of water available in both glass bottles and PET containers showed that waters bottled in PET contained up to 30 times more Sb. To confirm that the elevated Sb concentrations are due to leaching from the PET containers, water was collected in acid-cleaned LDPE bottles from a commercial source in Germany, prior to bottling; this water was found to contain 3.8 +/- 0.9 ng l(-1) Sb (n = 5), compared with the same brand of water purchased locally in PET bottles containing 359 +/- 54 ng l(-1) (n = 6). This same brand of water in PET bottles, after an additional three months of storage at room temperature, yielded 626 +/- 15 ng l(-1) Sb (n = 3). Other German brands of water in PET bottles contained 253-546 ng l(-1) Sb (n = 5). The median concentration of Sb in thirty-five brands of water bottled in PET from eleven other European countries was 343 ng l(-1) (n = 35). As an independent check of the hypothesis that Sb is leaching from PET, the pristine groundwater from Canada (containing 2.2 +/- 1.2 ng l(-1) Sb) was collected from the source using PET bottles from Germany: this water contained 50 +/- 17 ng l(-1) Sb (n = 2) after only 37 days, even though it was stored in the refrigerator, and 566 ng l(-1) after six months storage at room temperature.     

测定游离氯和总氯样品保存方法研究

建立了游离氯和总氯样品保存方法。用氢氧化钠溶液作为固定剂,现场固定含有游离氯和总氯的水样,使水样pH>12。结果表明,样品经4℃低温避光保存,5 d内测定,测量结果没有显著变化,方法检出限(以Cl2计)为0.004mg/L,加标回收率为96.7%～104%。     

Risk assessment for methylmercury in fish from the Songhua River,China: 30 years after mercury-containing wastewater outfalls were eliminated

This study aims to investigate the methylmercury contamination of fish from the Songhua River, China. A total of 328 fish representing various trophic levels were captured from ten reaches of the river and determined for methylmercury by gas chromatography method. Total mercury in fish, water and sediments from three typical reaches were analyzed simultaneously. Methylmercury concentrations in fish from the Second Songhua River and the mainstream of the Songhua River were 0.024 ± 0.016 and 0.015 ± 0.007 mg/kg fresh weight, respectively. The proportion of methylmercury to total mercury ranged from 21.8% to 69.7%, with the mean value of 42.6%. The observed methylmercury concentrations were much lower than the historical values and were generally within the reported literature range, and health hazard assessment showed no health risk from exposure to methylmercury by consuming fish from this river, demonstrating that mercury contamination of the Songhua River has been effectively controlled by nearly 30 years of environmental governance and natural purification.     

Bacteriological quality of drinking water in Nyala, South Darfur, Sudan

The objective of this study was to determine the bacterial contaminations in drinking water in Nyala city, South Darfur, Sudan with special reference to the internally displaced people camps (IDPs). Two hundred and forty water samples from different sites and sources including bore holes, hand pumps, dug wells, water points, water reservoir and household storage containers were collected in 2009. The most probable number method was used to detect and count the total coliform, faecal coliform and faecal enterococci. Results revealed that the three indicators bacteria were abundant in all sources except water points. Percentages of the three indicators bacteria count above the permissible limits for drinking water in all samples were 46.4% total coliform, 45.2% faecal coliform and 25.4% faecal enterococci whereas the highest count of the indicators bacteria observed was 1,600 U/100 ml water. Enteric bacteria isolated were Escherichia coli (22.5%), Enterococcus faecalis (20.42%), Klebsiella (15.00%), Citrobacter (2.1%) and Enterobacter (3.33%). The highest contamination of water sources was observed in household storage containers (20%) followed by boreholes (11.25%), reservoirs (6.24%), hand pumps (5.42%) and dug wells (2.49%). Contamination varied from season to season with the highest level in autumn (18.33%) followed by winter (13.75%) and summer (13.32%), respectively. All sources of water in IDP camps except water points were contaminated. Data suggested the importance of greater attention for household contamination, environmental sanitation control and the raise of awareness about water contamination.     

Fractions and leaching characteristics of mercury in coal

A huge amount of coal is always stored in open spaces in coal-fired power plants before combustion. Mercury released from coal by rain or flowing water is an environmental risk and can cause contamination of the soil around the storage area. To better understand mercury pollution and to control mercury emission before combustion, it is necessary to determine the mobility and leaching characteristics of mercury from coal. In this study, we collected ten coal samples from one coal-fired power plant and proposed a sequential extraction procedure to get five fractions of mercury for evaluation. Elemental Hg was found as the most dominant fraction, and sulfate Hg was shown to be the second largest fraction. The mercury in the organic and the soluble fractions were not the major fractions, but they should still be considered because of their high mobility.     

Mercury contamination-what we have learned since Minamata

Atmospheric cycling of mercury and other pollutants has become a major concern as industrialized countries have eliminated point discharges, sometimes by relocating the industries to underdeveloped and developing countries where point sources have become problems. Such circumventions may be to no avail in the long run as pollution continues to elevate levels of methylmercury in fish in waterways that are remote from direct contamination as well as where the source can be readily identified. Much has been learned about the cycling of mercury in the environment since human disabilities and deaths at Minamata, Japan, initially drew attention to the problem of methylmercury poisoning from the consumption of contaminated seafood in the 1950s. In that instance, methylmercury produced industrially concentrated to toxic levels in fish. As this manufacturing process was not used outside Japan, concern did not become immediate in other developed nations until the 1960s when it was established that mercury was not only biomethylated by microorganisms but also biomagnified through the food chain. Point sources to the waterways may have been eliminated too late to return the levels in fish to background because of the geochemical cycling of mercury through the environment. Despite decreases in domestic, industrial and agricultural point source releases over the last two decades, large quantities from non-point sources such as fossil fuel combustion, smelters, and incinerators are still being released. Much of this mercury is transported from the atmosphere to aquatic ecosystems and stored in sediments until it is again released to the water and atmosphere.     

北京市大气气态汞变化特征

采用Tekran 2537X大气汞分析仪在线测量北京市城区大气中气态元素汞(GEM,简称大气汞) 浓度,研究大气汞浓度随不同气象条件的变化特征。通过分析2016年10月—2017年9月大气汞监测数据发现,该监测点全年大气汞浓度为0.48～16.25 ng/m³,均值为(3.41±1.79)ng/m³。春季、夏季、秋季和冬季大气汞浓度均值依次为2.93 、2.95、4.27、3.37 ng/m³,其中,秋季大气汞浓度明显高于其他季节 。秋季大气汞浓度显著偏高可能由不利的大气扩散条件导致。大气汞夜间浓度显著高于白天浓度。同时,将大气汞与SO₂、CO及PM_2.5进行相关性分析,发现大气汞浓度变化趋势与SO₂、CO和PM_2.5呈显著正相关。结合风向和风速进行污染来源分析,得到该点位大气汞在西南和东北方向上受人为排放源影响较大。污染源类型分析表明,冬季大气汞与CO同源性强,主要来自本地供暖用煤。     

Stability and storage problems in organotin speciation in environmental samples

The stability of both tributyltin (TBT) and triphenyltin (TPT) in water, sediment, oysters and cockles was studied over a period of 18 months using several storage conditions. Butyltins were stable in unacidified sea-water stored in polycarbonate bottles in the dark at 4 degrees C for 7 months, but half of the TBT concentration was lost after 540 d. A comparable preservation time was achieved for butyltins stored on C18 cartridges at room temperature. However, phenyltins extracted from sea-water were stable for only 60 d stored on cartridges and even more pronounced losses (about 90% after 540 d) occurred when they were stored in either polycarbonate or Pyrex glass bottles. Losses of organotins were observed in sediments after air drying and pasteurization treatments using a freeze-dried sediment as a comparator, whereas both butyltin and phenyltin species remained stable in sediments stored at -20 degrees C for the 18 months tested, irrespective of the treatment used for stabilization. Air drying followed by pasteurization was shown to be superior to other treatments for the stabilization of organotin compounds in sediments stored at higher temperatures, but 30% of TBT was lost after 540 d at 25 degrees C. Finally, butyltins were stable in both frozen cockles and oysters in the dark over a 7 month period and in freeze-dried samples stored at 4 degrees C for 5 months, but TBT losses of about 70% were observed after 540 d.     

Biomagnifications of mercury and methylmercury in tuna and mackerel

Seawater may be contaminated by harmful substances, including toxic elements released by human activities. The present study evaluates the total mercury and methylmercury concentrations and their correlations to fish body size in longtail tuna and short-bodied mackerel from Chendring, Kuantan, at east coast and Kuala Perlis at west costs of Peninsular Malaysia during May to November 2007. Total mercury and methylmercury in muscle tissue of 69 samples of longtail tuna and short-bodied mackerel, ranged from 0.180 to 1.460 μg/g and 0.0.169–0.973 μg/g and 0.251–1.470 μg/g and 0.202–1.352, whereas the methylmercury to total mercury ratio ranged from 70% to 83%, respectively. Samples of both species from the east coast showed higher levels of mercury compared to those from west coast. In all of the locations, significant positive correlations were found between fish body weight and mercury content (R²?> 0.470). The estimated weekly intake of total mercury and methylmercury from the consumption 66.33 g/week of short-bodied mackerel and 18.34 g/week of longtail tuna (based on local dietry survey) was found to be lower than the maximum limit of 5 and 1.5 μg/kg bodyweight established by FAO/WHO and codex, respectively.