Methylmercury in mosquitoes related to atmospheric mercury deposition and contamination

A connection between loadings of inorganic Hg, especially from the atmosphere, and accumulation of methylmercury (MeHg) in aquatic biota has not been firmly established. Mosquitoes (Diptera: Culicidae) may be a useful indictor of Hg contamination or MeHg accumulation in aquatic ecosystems because they have aquatic life stages, and their ubiquitous distribution permits sampling across wide ranges of climate, biological productivity, and atmospheric Hg deposition. We examined MeHg in adult mosquitoes from subtropical (Florida), maritime (California), continental (Michigan), and arctic (Alaska) regions of North America that span a range in wet atmospheric Hg deposition (1.5-15 microg m(-2) y(-1)). More than 90% of the Hg in mosquitoes was MeHg, and concentrations varied among locations. Levels of MeHg differed among mosquito species at six sites in northwest Florida (Ochlerotatus atlanticus < Culex nigripalpus < Anopheles crucians); this may be related to differences in biogeochemical characteristics of the aquatic habitat that affect dietary accumulation of MeHg during the larval stage. Mosquito MeHg was related positively to wet atmospheric Hg deposition among locations where atmospheric deposition is the principal source of Hg, and it was greatly enhanced in Hg-polluted environs near the Sulphur Bank Mine in Lake County, California. These results suggest that MeHg in mosquitoes may be a useful and sensitive indicator of Hg loadings to aquatic systems, including that derived from atmospheric deposition.     

Methylmercury in freshwater fish linked to atmospheric mercury deposition

A connection between accumulation of methylmercury (MeHg) in wild fish populations and atmospheric mercury deposition has not been made. Large databases for both MeHg in fish and atmospheric mercury deposition have been assimilated from monitoring efforts spanning the contiguous United States. Here, we compare results of these data sets and show that state-wide average concentrations of MeHg in a cosmopolitan freshwater fish, the largemouth bass Micropterus salmoides, are related positively to wet atmospheric Hg fluxes among most of the 25 states that are analyzed, which span a 5-fold range in Hg deposition. Differences in largemouth bass MeHg concentrations among states are unrelated to average precipitation depth, wet atmospheric acid deposition, or interstate variations in the type of water body (river, lake, reservoir) from which the fish were sampled. There are modest correlations between MeHg in bass and surface water pH, temperature, and wet atmospheric deposition of sulfate. However, when fish and atmospheric mercury results are combined at the state level, wet atmospheric Hg deposition accounts for about two-thirds of the variation in bass MeHg among most states, and stepwise multiple regression analysis reveals thatthese variables do not improve the linear model significantly. This suggests the accumulation of MeHg in wild fish populations is linked to atmospheric Hg loadings, two-thirds of which are estimated to be from anthropogenic sources.     

Residues of total mercury and methyl mercury in eel products

Fifty-two samples of broiled eels and broiled eel liver were analyzed for total mercury (total Hg) and methyl mercury. The mean concentrations of total Hg in broiled eels and broiled eel liver were 0.21 ppm and 0.10 ppm, respectively. Meanwhile, the mean concentrations of methyl mercury in broiled eels and broiled eel liver were 0.085 ppm and 0.039 ppm, respectively. The rate of methyl mercury to total Hg mainly ranged from 60 to 80% in broiled eels and from 35 to 65% in broiled eel liver. The total Hg concentrations of 2 samples of broiled eels and one sample of broiled eel liver exceeded the provisional regulation limit (0.4 ppm) of total Hg in fish in Japan. In these samples, the rates of methyl mercury to total Hg were lower than 20%. The muscles and the skin of broiled eels were measured separately. The ratios of skin to muscle concentration of total Hg and methyl mercury were mainly in the range from 1/10 to 1/4. The mean intakes of total Hg from broiled eels and broiled eel liver per individual were 24.6 microg and 3.1 microg, respectively. The mean intakes of methyl mercury from broiled eels and broiled eel liver per individual were 10.4 microg and 1.2 microg, respectively.     

测汞仪测定稻谷及其制品中总汞含量研究

建立了采用测汞仪直接测定稻谷及其制品中总汞含量的方法,对20份稻谷及其制品中总汞含量进行了测定和分析。结果表明,方法在0~400 ng范围内呈良好线性关系,最低检出限为0.1μg/kg,定量下限为1μg/kg,相对标准偏差(RSD)均在2.0%以内。测定国家标准参考物质辽宁大米和湖南大米,测定值均在标示值范围内,与国标方法比较结果无显著差异。所测稻谷及其制成的糙米和大米的总汞含量均在国标限量值以下,稻谷中总汞主要分布在大米中,其次是糙米表皮部分,稻壳部分中含量相对较低。     

直接测汞仪测定食品中总汞

目的建立直接测汞仪测定食品中总汞的方法。方法采用直接测汞仪测定食品中的总汞,并对FAPAS 07322大豆粉样品采用直接测汞仪法、原子荧光光谱法、电感耦合等离子质谱法测定进行方法比对,结合FAPAS 07322能力验证报告对直接测汞仪法进行评价。结果直接测汞法在低浓度范围(0～20 ng)和高浓度范围(20～300ng)的相关系数均能达到0.999,方法检出限为0.07μg/kg,精密度小于8.0%,回收率范围为90.0%～103.5%。FAPAS 07322测定结果为323μg/kg, Z值为0.0,接近实验室比对中位值。结论直接测汞仪测定食品中的总汞,操作简便快捷,结果准确,适用于食品中总汞的分析。     

Mercury distribution across 14 U.S. forests. Part II: Patterns of methyl mercury concentrations and areal mass of total and methyl mercury

This study characterized distribution patterns of monomethyl mercury (MeHg) and areal mass of total mercury (THg) and MeHg across U.S. upland forests. MeHg concentrations increased from surface litter (average: 0.14 μg kg(-1)) to intermediate (0.47 μg kg(-1)) and deeper, decomposed litter (1.43 μg kg(-1)). MeHg concentrations were lower in soils (0.10 μg kg(-1) at 0-20 cm depth; 0.06 μg kg(-1) at >20 cm depth). Ratios of MeHg to THg were higher in litter compared to soils. In soils, MeHg concentrations positively correlated with THg across all sites, and MeHg concentrations also increased with C content and latitude. THg areal mass ranged from 41.6 g ha(-1) to 268.8 g ha(-1). Largest THg mass at all sites was sequestered in soils (average of 91%), followed by litter (8%) and aboveground biomass (<1%). MeHg mass (litter plus soils only) ranged from 75 to 443 mg ha(-1), of which 88% was found in soils. Both THg and MeHg mass correlated with latitude, with average mass increases of 10.6 g ha(-1) (THg) and 20 μg ha(-1) (MeHg) per degree latitude, indicating that highest THg and MeHg accumulation in upland forests are expected in northern sites.     

Modeling mercury in power plant plumes

Measurements of speciated mercury (Hg) downwind of coal-fired power plants suggest that the Hg(II)/(Hg0 + HgII) ratio (where HgII is divalent gaseous Hg and Hg0 is elemental Hg) decreases significantly between the point of emission and the downwind ground-level measurement site, but that the SO2/(Hg0 + HgII) ratio is conserved. We simulated nine power plant plume events with the Reactive & Optics Model of Emissions (ROME), a reactive plume model that includes a comprehensive treatment of plume dispersion, transformation, and deposition. The model simulations fail to reproduce such a depletion in HgII. A sensitivity study of the impact of the HgII dry deposition velocity shows that a difference in dry deposition alone cannot explain the disparity. Similarly, a sensitivity study of the impact of cloud chemistry on results shows that the effect of clouds on Hg chemistry has only minimal impact. Possible explanations include HgII reduction to Hg0 in the plume, rapid reduction of HgII to Hg0 on ground surfaces, and/or an overestimation of the HgII fraction in the power plant emissions. We propose that a chemical reaction not included in current models of atmospheric mercury reduces HgII to Hg0 in coal-fired power plant plumes. The incorporation of two possible reduction pathways for HgII (pseudo-first-order decay and reaction with SO2) shows better agreement between the model simulations and the ambient measurements. These potential HgII to Hg0 reactions need to be studied in the laboratory to investigate this hypothesis. Because the speciation of Hg has a significant effect on Hg deposition, models of the fate and transport of atmospheric Hg may need to be modified to account for the reduction of HgII in coal-fired power plant plumes if such a reaction is confirmed in further experimental investigations.     

测汞仪原子吸收光谱法测定野生食用菌中的总汞

目的建立应用测汞仪直接测定野生食用菌中总汞含量的测定方法。方法样品经均质器粉碎,称量后,直接进样。样品在催化管内加热分解,在氧气的作用下,汞在齐化管内与金粉反应被捕集下来,形成金汞齐,再经高温使金汞齐分解成汞原子蒸气经载气带入吸收池,在253.7 nm处进行吸收测定。结果测汞仪检测方法线性范围:0.0~1000 ng/L,检出限为0.005 ng/m L,相关系数(R2)优于0.999,相对标准偏差(RSD)小于1.5%,回收率大于99%。结论用此仪器检测的方法无需进行样品前处理、进样量少、方法灵敏度高、精密度好、结果准确可靠、操作简单快速、没有试剂污染、检测速度快和运行成本不高,适用于野生食用菌中总汞的测定。     

Determination of total mercury in foods of plant origin in Poland by cold vapour atomic absorption spectrometry.

Total mercury concentrations were determined in 573 samples of agricultural crops and foods of plant origin which included cereals, fruit and vegetables and their products commercially available on the Polish market. The method of cold vapour atomic absorption spectrometry (CVAAS) after a wet-acid digestion in a closed-vessels and microwave oven was used and the reliability of the procedure demonstrated. Mercury concentrations in the agricultural crops and plant foods were generally below the maximum permissible limits in Poland and rarely exceeded 5 microg x kg(-1). Values ranged from <0.1 to 14 microg x kg(-1), mean 2.4 +/- 2.3 microg x kg(-1) in wheat and rye grains; from <0.1 to 2.4 microg x kg(-1), mean 0.5 +/- 0.4 microg x kg(-1) in nine varieties of vegetables; from <0.1 to 5.1 microg x kg(-1), mean 1.1 +/- 0.9 microg x kg(-1) in seven varieties of fruit; from <0.1 to 5.6 microg x kg(-1) in cereal products and jams; and from <0.1 to 3.0 microg x l(-1) in fruit and vegetable juices, nectars and beverages. The contribution of the mercury in the analysed agricultural crops and foods of plant origin to the weekly dietary intake of total mercury was 8 microg/person, which represents only 3% of the provisional tolerable weekly intake (PTWI) for this metal.     

Correlation of fat content and dioxins, total mercury and methyl mercury levels in tuna

In this study, we analyzed the concentrations of mercury and dioxins in tuna with various fat contents (akami; the leaner meat, Chutoro; the belly area of the tuna along the side of the fish between the akami and the otoro. Otoro; the fattiest portion of the tuna) in wild and farmed bluefin tuna and farmed southern bluefin tuna. In the three kinds of tuna, average dioxins concentrations in Akami, chutoro and otoro were 1.7, 4.7 and 9.6 pg TEQ/g, respectively. The dioxins concentration in all three regions of tuna was in direct proportion to the fat content. In the farmed bluefin tuna, the dioxins concentration was almost the same as that of the wild tuna, but differed from that of the farmed southern bluefin tuna. Average total mercury concentration based on wet weight in akami was 0.42 μg/g, being higher than the values of 0.36 μg/g of chutoro and 0.31 μg/g of otoro, and in inverse proportion to the fat content. In all three regions, the total mercury concentration of the wild bluefin tuna was equal to that of the farmed tuna. The total mercury concentration in the latter was two to three times higher than that of the farmed southern bluefin tuna. If the Japanese intake is one fin of tuna (80 g) a day, the daily intake levels of dioxins and methyl mercury can be estimated as 0.48-37 pg TEQ/kg bw and 0.21-0.90 μg/kg bw, respectively.     

快速测定植物提取物中的汞

目的 建立快速测定植物提取物汞的分析方法。方法 采用直接测汞技术, 样品无需任何前处理直接测定。优化了仪器条件, 进行了检出限、精密度和准确性等方法学研究。结果 经过与国标GB/T 5009.17-2003的比对和国家标准物质的验证, 其线性范围为0?1000 ng, 最低检出限为0.430 μg/kg。相对标准偏差(RSD)小于3.5%, 回收率在93.5%?102.8%。结论 用茶叶、圆白菜和菠菜三种不同基质的有证标准物质进行验证, 测定值均在标准值范围内, 该方法适用于植物提取物汞的快速测定。     

湿法消解-原子荧光光谱法同时检测海产品中的总砷与总汞

目的建立湿法消解-原子荧光光谱法同时测定海产品中总砷、总汞含量的分析方法。方法采取硝酸、高氯酸和硫酸混合体系的冷消解及热消解结合的方法,并采用电炉高温短时间加热的优化条件进行消解样品,利用氢化物原子荧光光谱法同时进行总砷、总汞的测定。结果砷在0～40μg/L浓度范围内呈良好线性关系,汞在0～12μg/L浓度范围内呈良好线性关系,相关系数均大于0.999。砷的检出限为0.037μg/L,回收率为94.36%～96.62%,精密度为0.86%～1.36%,汞的检出限为0.048μg/L,回收率为93.33%～95.28%,精密度为0.88%～2.62%。通过对能力验证HMRL1601海鱼粉中总汞、总砷的检测,检测结果总汞为0.30 mg/kg,总砷为2.06 mg/kg,均为满意结果,黄鱼、紫菜质控样的检测值均在参考值允许范围内。结论该方法操作简便、准确灵敏,适用于每一个实验室开展海产品中总砷总汞的同时测定。     

茶叶中总汞含量测定的样品前处理研究

目的研究优化茶叶中总汞含量测定时的样品前处理。方法参照GB 5009.17-2014《食品安全国家标准食品中总汞及有机汞的测定》前处理过程,采用正交试验对影响微波消解的温度、时间和功率因素进行研究,获得较优的样品前处理参数,以此对盲审样品进行验证。结果测定茶叶中总汞含量时,可采用样品与硝酸直接加热方式进行预处理,微波消解过程对总汞回收率影响的因子由大到小为温度、功率和时间;最佳微波消解参数为温度80℃、时间8 min和功率1200 W,微波消解后的样品不需挥酸操作可直接定容测定;在最优前处理工艺参数条件下,盲审样品测定结果与其公布值基本一致。结论此样品前处理方式基本满足茶叶中中总汞含量测定的需求。     

Voltammetric determination of ultra-trace total mercury and toxic metals in meals

This paper reports the sequential voltammetric determination of Hg(II) and Cu(II) at the gold electrode (GE), and of Cu(II), Pb(II), Cd(II), Zn(II) at the hanging mercury drop electrode (HMDE) by square wave anodic stripping voltammetry (SWASV).     

测汞仪固体直接进样测定保健食品中总汞的方法研究及方法比较

目的 研究测汞仪固体直接进样方法测定保健食品中总汞,通过与国标方法比较验证结果的可靠性.方法 采用测汞仪固体直接进样和原子荧光光谱法两种方法对保健食品中的总汞进行测定.结果 几种不同浓度加标的保健食品测汞仪测定的总汞结果与原子荧光法测定结果相符,回收率在88％～116％之间,RSD＜ 10％.结论 测汞仪直接固体进样测定保健食品中总汞的方法具有准确、快捷、运行成本低、无环境污染等优点,和现有国标原子荧光法测定同一样品,测定结果具有可比性,方法具有可推广性.     

Importance of the forest canopy to fluxes of methyl mercury and total mercury to boreal ecosystems

The forest canopy was an important contributor to fluxes of methyl mercury (MeHg) and total mercury (THg) to the forest floor of boreal uplands and wetlands and potentially to downstream lakes, at the Experimental Lakes Area (ELA), northwestern Ontario. The estimated fluxes of MeHg and THg in throughfall plus litterfall below the forest canopy were 2 and 3 times greater than annual fluxes by direct wet deposition of MeHg (0.9 mg of MeHg ha(-1)) and THg (71 mg of THg ha(-1)). Almost all of the increased flux of MeHg and THg under the forest canopy occurred as litterfall (0.14-1.3 mg of MeHg ha(-1) yr(-1) and 110-220 mg of THg ha(-1) yr(-1)). Throughfall added no MeHg and approximately 9 mg of THg ha(-1) yr(-1) to wet deposition at ELA, unlike in other regions of the world where atmospheric deposition was more heavily contaminated. These data suggest that dry deposition of Hg on foliage as an aerosol or reactive gaseous Hg (RGM) species is low at ELA, a finding supported by preliminary measurements of RGM there. Annual total deposition from throughfall and litterfall under a fire-regenerated 19-yr-old jack pine/birch forest was 1.7 mg of MeHg ha(-1) and 200 mg of THg ha(-1). We found that average annual accumulation of MeHg and THg in the surficial litter/fungal layer of soils since the last forest fire varied between 0.6 and 1.6 mg of MeHg ha(-1) and between 130 and 590 mg of THg ha(-1) among sites differing in drainage and soil moisture. When soil Hg accumulation sites were matched with similar sites where litterfall and throughfall were collected, measured fluxes of THg to the forest floor (sources) were similar to our estimates of longterm soil accumulation rates (sinks), suggesting that the Hg in litterfall and throughfall is a new and not a recycled input of Hg to forested ecosystems. However, further research is required to determine the proportion of Hg in litterfall that is being biogeochemically recycled within forest and wetland ecosystems and, thus, does not represent new inputs to the forest ecosystem.     

Survey of total mercury in infant formulae and oral electrolytes sold in Canada

Total mercury (Hg) was measured in 150 infant formula products (as sold) and oral electrolyte solutions purchased in Canada in 2003. Results less than the limit of detection (LOD) were reported as the numeric value of the LOD. Electrolytes contained the lowest concentrations, averaging 0.026?ng/g. Average levels in milk-based ready-to-use, concentrated liquid and powdered concentrate were 0.028, 0.069 and 0.212?ng/g, respectively. In soy-based formulae, the respective mean concentrations were 0.049, 0.101 and 0.237?ng/g. These concentrations cannot be considered on an absolute basis because 76% of sample concentrations fell below the limit of detection. Despite the inability to measure many of the actual background concentrations, the method was sufficiently sensitive to identify clear cases of low-level Hg contamination (up to 1.5?ng/g) of individual lots of powdered formula. Also, all the different lots of one brand of concentrated liquid infant formulae had significantly higher concentrations of Hg than those of all other concentrated liquid products. After dilution with preparation water, the Hg concentrations in all products would be lower than the Canadian Drinking Water Guideline for Hg of 1?ng/mL and too low to impact on health.     

石墨消解-微波消解法测定乳粉中总砷、总汞、铅和镉

目的建立石墨消解-微波消解法测定乳粉中的总砷、总汞、铅和镉含量的分析方法。方法样品经石墨加热预消解,采用微波消解法前处理,并采用电感耦合等离子体质谱法(inductively coupled plasma mass spectrometry,ICP-MS)测定乳粉中的总砷、总汞、铅和镉含量。结果总砷、总汞、铅和镉的平均加标回收率为94.4%?108.3%,精密度的相对标准差(relative standard deviation,RSD)为1.1%?4.6%,方法检出限分别为4.4、4.8、4.9、0.6?g/kg。乳粉质控样和考核样中总砷、总汞、铅和镉的测定结果均在参考值范围内,结果均为满意。结论该方法操作简便,重现性良好,测定结果准确、可靠,适用于乳粉中总砷、总汞、铅和镉的含量测定。     

Levels of total mercury in predatory fish sold in Canada in 2005

Total mercury was analysed in 188 samples of predatory fish purchased at the retail level in Canada in 2005. The average concentrations (ng g(-1), range) were: sea bass 329 (38-1367), red snapper 148 (36-431), orange roughy 543 (279-974), fresh water trout 55 (20-430), grouper 360 (8-1060), black cod 284 (71-651), Arctic char 37 (28-54), king fish 440 (42-923), tilefish 601 (79-1164) and marlin 854 (125-2346). The Canadian standard for maximum total mercury allowed in the edible portions of fish sold at the retail level is 1000 ng g(-1) for shark, swordfish, marlin, orange roughy, escolar and both fresh and frozen tuna. The standard is 500 ng g(-1) for all other types of fish. In this study, despite the small number of samples of each species, the 1000 ng g(-1) maximum was exceeded in five samples of marlin (28%). The 500 ng g(-1) maximum was exceeded by six samples of sea bass (20%), four of tilefish (50%), five of grouper (24%), six of king fish (40%) and one of black cod (13%).