水产品中汞的形态分析研究进展

汞是具有很强毒性的重金属元素,其毒性大小与汞的形态密切相关。水产品是人体摄入汞化合物的主要来源,大量摄入含汞的水产品将对人体健康造成严重的威胁。本文从水产品中汞的主要来源及形态、国内外水产品中汞的卫生标准、样品前处理方法、汞的形态分离与检测技术,以及分析方法验证等方面对近年来汞形态分析研究进行了综述,旨在为水产品质量安全研究提供技术参考。      

Atmospheric mercury emissions and speciation at the sulphur bank mercury mine superfund site, Northern California

One pathway for release of mercury (Hg) from naturally enriched sites is emission to the atmosphere. Elemental Hg, when emitted, will enter the global atmospheric pool. In contrast, if reactive gaseous Hg or Hg2+ (as HgCl2, HgBr2, or HgOH2) is formed, it will most likely be deposited locally. This study focused on the measurement of elemental Hg flux and reactive gaseous Hg concentrations at the Sulphur Bank Superfund Site, an area of natural Hg enrichment with anthropogenic disturbance and ongoing geothermal activity. Mean Hg emissions ranged from 14 to 11000 ng m(-2) h(-1), with the highest emissions from anthropogenically disturbed materials. Reactive gaseous Hg concentrations were the highest ever reported for a natural setting (0.3-76 ng m(-3)). Measured Hg fluxes were used within a Geographic Information System to estimate mercury releases to the atmosphere from the site. Results indicated approximately 17 kg of Hg y(-1) of is emitted to the atmosphere from the 3.8 km2 area, with half from mine waste, ore, and tailing piles and half from relatively undisturbed naturally enriched substrate.     

Atmospheric mercury speciation: laboratory and field evaluation of a mist chamber method for measuring reactive gaseous mercury

Knowledge of atmospheric mercury speciation is critical to modeling its fate. Thus there is a crucial need for reliable methods to measure the fraction of gaseous atmospheric Hg which is in the oxidized Hg(II) form (termed reactive gaseous mercury, RGM). We have developed a novel method for measurement of RGM using a refluxing mist chamber, and we recently reported the results of sampling campaigns for RGM in Tennessee and Indiana. In general, measured RGM levels were about 3% of total gaseous mercury (TGM), and our results support prevailing hypotheses about the nature and behavior of RGM in ambient air. Because its use for RGM is growing, we now report in more detail the development and testing of the mist chamber method. Several styles of mist chambers have been investigated. The most versatile design employs a single nebulizer nozzle and can operate at flows of 15-20 L/min. The water-soluble Hg is collected in ca. 20 mL of absorbing solution, which is then analyzed for Hg(II) by SnCl2 reduction and CVAFS. One-hour samples (ca. 1 m3 of air) generally contain 50-200 pg of RGM. The method detection limit for 1-h samples is approximately 6-10 pg/m3. Thus short sample times can reveal temporal variations in RGM that would not otherwise be observable. The efficiency of collecting RGM in mist chambers is highly dependent on Cl- concentration in the absorbing solution, in keeping with equilibrium calculations. Artifact formation of Hg(II) by oxidation of Hg0 under ozone ambient conditions appears to be sufficiently slow so as to be negligible for the short (ca. 1 h) runs that are typically employed. We observed no significant error from cosampled particles or aerosols in rural nonimpacted air samples. We have developed a simple approach to analyzing mist chamber samples in the field using an automated Hg sampler.     

Influence of mercury and chlorine content of coal on mercury emissions from coal-fired power plants in China

China is the largest mercury emitter in the world and coal combustion is the most important mercury source in China. This paper updates the coal quality database of China and evaluates the mercury removal efficiency of air pollution control devices (APCDs) based on 112 on-site measurements. A submodel was developed to address the relationship of mercury emission factor to the chlorine content of coal. The mercury emissions from coal-fired power plants (CFPPs) in China were estimated using deterministic mercury emission factor model, nonchlorine-based and chlorine-based probabilistic emission factor models, respectively. The national mercury emission from CFPPs in 2008 was calculated to be 113.3 t using the deterministic model. The nonchlorine-based probabilistic emission factor model, which addresses the log-normal distribution of the mercury content of coal, estimates that the mercury emission from CFPPs is 96.5 t (P50), with a confidence interval of 57.3 t (P10) to 183.0 t (P90). The best estimate by the chlorine-based probabilistic emission factor model is 102.5 t, with a confidence interval of 71.7 to 162.1 t. The chlorine-based model addresses the influence of chlorine and reduces the uncertainties of mercury emission estimates.     

L-半胱氨酸快速绿色提取稻米中汞形态的前处理方法研究

本研究选择L-半胱氨酸作为提取剂,超声破碎作为提取方式,通过优化L-半胱氨酸浓度和超声破碎参数,建立了 L-半胱氨酸超声破碎快速绿色提取稻米中无机汞和甲基汞的前处理方法.结果表明,在确保前处理过程中不同汞形态间不发生相互转化的前提下,超声破碎功率150W,1％L-半胱氨酸15 min即可完成稻米中2种汞形态的提取.本方...     

Selenium and arsenic speciation in fly ash from full-scale coal-burning utility plants

X-ray absorption fine structure spectroscopy has been used to determine directly the oxidation states and speciation of selenium and arsenic in 10 fly ash samples collected from full-scale utility plants. Such information is needed to assess the health risk posed by these elements in fly ash and to understand their behavior during combustion and in fly ash disposal options, such as sequestration in tailings ponds. Selenium is found predominantly as Se(IV) in selenite (SeO3(2-)) species, whereas arsenic is found predominantly as As(V) in arsenate (AsO4(3-)) species. Two distinct types of selenite and arsenate spectra were observed depending upon whether the fly ash was derived from eastern U.S. bituminous (Fe-rich) coals or from western subbituminous or lignite (Ca-rich) coals. Similar spectral details were observed for both arsenic and selenium in the two different types of fly ash, suggesting that the postcombustion behavior and capture of both of these elements are likely controlled by the same dominant element or phase in each type of fly ash.     

Solution speciation controls mercury isotope fractionation of Hg(II) sorption to goethite

The application of Hg isotope signatures as tracers for environmental Hg cycling requires the determination of isotope fractionation factors and mechanisms for individual processes. Here, we investigated Hg isotope fractionation of Hg(II) sorption to goethite in batch systems under different experimental conditions. We observed a mass-dependent enrichment of light Hg isotopes on the goethite surface relative to dissolved Hg (ε(202)Hg of -0.30‰ to -0.44‰) which was independent of the pH, chloride and sulfate concentration, type of surface complex, and equilibration time. Based on previous theoretical equilibrium fractionation factors, we propose that Hg isotope fractionation of Hg(II) sorption to goethite is controlled by an equilibrium isotope effect between Hg(II) solution species, expressed on the mineral surface by the adsorption of the cationic solution species. In contrast, the formation of outer-sphere complexes and subsequent conformation changes to different inner-sphere complexes appeared to have insignificant effects on the observed isotope fractionation. Our findings emphasize the importance of solution speciation in metal isotope sorption studies and suggest that the dissolved Hg(II) pool in soils and sediments, which is the most mobile and bioavailable, should be isotopically heavy, as light Hg isotopes are preferentially sequestered during binding to both mineral phases and natural organic matter.     

外源硒处理的花生芽蛋白中五种硒形态分析

为了探究花生发芽后的富硒规律,本研究用不同浓度Na2SeO3浸泡花生子粒发芽5d后,分析外源硒对花生发芽情况的影响,并分别通过电感耦合等离子体质谱法（Inductively Coupled Plasma-Mass Spectrometry,ICP-MS）和高效液相色谱-电感耦合等离子体质谱联用（High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry,HPLC-ICP-MS）分析花生芽不同部位（子叶、胚轴、胚根）的总硒含量和花生芽蛋白中5种硒形态（硒代胱氨酸SeCys2、硒代半胱氨酸MeSeCys、亚硒酸根SeIV、硒代蛋氨酸SeMet、硒酸根SeVI）的组成特征及变化规律。结果表明,随着Na2SeO3浸泡浓度的升高,花生芽长、芽粗和发芽率均呈降低的趋势;高浓度的外源硒抑制了花生发芽过程中硒元素由子叶向胚轴和胚根的转移;未经硒浸泡的花生发芽后,三个部位均检测到三种硒形态,其中SeCys2占比最高,随着硒浓度升高,各部位硒形态种类增加,无机硒（SeIV和SeVI）占比逐渐升高,SeCys2和MeSeCys占比逐渐降低,SeMet占比没有规律性变化,各部位有机硒总量占比降低,无机硒向有机硒转化率收到抑制。     

Effect of chemical speciation on toxicity of mercury to Escherichia coli biofilms and planktonic cells

While it is known that microbial uptake of mercury (Hg) by planktonic cultures is influenced by the extracellular speciation of mercury in aquatic systems, Hg uptake in biofilm cultures is understudied. We compared the importance of Hg(II) speciation in toxicity to both planktonic and biofilm cultures of the Gram-negative bacterium Escherichia coli 055. Variable chloride chemistry experiments were carried out to modify mercury speciation. Biofilms were observed to be more resistant to Hg than planktonic cells. In both planktonic and biofilm cultures, the toxicity of Hg increased and then decreased along the chloride gradient. The percent reduction in cell viability was linearly related to the concentration of HgCl2(0) when Hg-chloro complexes dominated the speciation, consistent with a passive diffusion model. However, toxicity to both planktonic cells and biofilms at low salinities could not be explained by passive diffusion alone, which suggests that microbial uptake of Hg in both planktonic cells and biofilms may occur by both passive diffusion of neutral species and facilitated uptake. The relationship between toxicity and chloride concentration was similar in the presence and absence of a biofilm, indicating that the presence of the biofilm does not drastically change the relative availability of the dominant mercury species.     

Residual mercury content of seed potatoes treated with organo-mercury disinfectant solutions

Before export from Scotland, certain seed potatoes are mechanically washed and then dipped in organo-mercury fungicide solutions to control tuber-borne diseases. During transit and after receipt, these potatoes may be accidentally eaten by humans or animals, and the work reported here was done to find out whether the mercury residues reach a level likely to constitute a toxic hazard. Analyses were carried out on both cooked and uncooked whole potatoes, and on the peel and the flesh. The potatoes were stored and analysed at intervals over a period of time comparable with the time taken during export. The effect of haulm destruction on the subsequent uptake of the disinfectant was investigated. Also included are analyses of tubers which were dipped in organo-mercury solutions after being washed over different types of rollers in a commercial machine. The results indicated that the levels of mercury present would make treated potatoes unacceptable for consumption. However, potatoes grown from treated seed were found to contain very small amounts of mercury, which were no greater than untreated control material, and which were of no toxicological significance.     

Understanding mercury transformations in coal-fired power plants: evaluation of homogeneous Hg oxidation mechanisms

Homogeneous mercury oxidation mechanisms described by Niksa and Qiu, and three theoretical mercury oxidation reaction rate constants developed by Wilcox were evaluated for their predictions of the extent of mercury oxidation under coal combustion conditions. Predictions were compared to results from bench-scale experiments to determine whether such models were suitable for predicting measured levels of homogeneous mercury oxidation. Experiments considered different flue gas compositions (O2, Cl, NO, and SO2) and quench rates to provide a broad range of conditions for analysis. Regardless of the mechanism chosen, most mercury oxidation was predicted to occur at temperatures below 900 K. The Niksa mechanism predicted Hg oxidation to occur only in systems that were close to isothermal at temperatures above 900 K followed by a rapid gas quench. This mechanism provided the best agreement with the experimental data of Sliger. The Qiu mechanism predicted Hg oxidation in several experimental systems and conditions fairly accurately although it did not provide the best agreement in all cases. Qiu mechanism predictions for the experimental system at the University of Connecticut operating at an equivalence ratio of 0.9 in the presence of HCl/Cl2 and also SO2 were within the bounds of experimental uncertainty. Additionally, for an experimental dataset obtained from the University of Utah for quench rates of 210 and 440 K/s in the presence of HCI, the Qiu model predicted the experimental observations with a high degree of accuracy. The effects of flue gas composition and quench on Hg oxidation are qualitatively represented by the Qiu mechanism suggesting a relative robustness of the model, although there is still need to refine rate constants to achieve greater accuracy. The Wilcox rate constants when substituted in the Qiu mechanism predicted near-complete oxidation of Hg irrespective of HCl concentrations in systems that involve flue gas quench below temperatures of 450 K.     

Hg speciation and stable isotope signatures in human hair as a tracer for dietary and occupational exposure to mercury

Exposure of humans and wildlife to various inorganic and organometallic forms of mercury (Hg) may induce adverse health effects. While human populations in developed countries are mainly exposed to marine fish monomethylmercury (MMHg), this is not necessarily the case for developing countries and diverse indigenous people. Identification of Hg exposure sources from biomonitor media such as urine or hair would be useful in combating exposure. Here we report on the Hg stable isotope signatures and Hg speciation in human hair across different gold miner, indigenous and urban populations in Bolivia and France. We found evidence for both mass-dependent isotope fractionation (MDF) and mass-independent isotope fractionation (MIF) in all hair samples. Three limiting cases of dominant exposure to inorganic Hg (IHg), freshwater fish MMHg, and marine fish MMHg sources are used to define approximate Hg isotope source signatures. Knowing the source signatures, we then estimated Hg exposure sources for the Bolivian gold miner populations. Modeled IHg levels in hair correspond well to measured IHg concentrations (R = 0.9), demonstrating that IHg exposure sources to gold miners can be monitored in hair samples following either its chemical speciation or isotopic composition. Different MMHg and inorganic exposure levels among gold miners appear to correspond to living and working conditions, including proximity to small towns, and artisanal vs large scale mining activity.     

Survival of pathogenic bacteria in pesticide solutions and on treated tomato plants

The ability of Salmonella, Escherichia coli O157:H7, Listeria monocytogenes, and Shigella to survive or grow in pesticide solutions (Ambush 240EC, Benlate T-N-G, Bravo 500, Botran 75WP, Captan 80WDG, Parasol, and Vendex 50W) used by the horticultural industry was examined. In the laboratory, individual cultures were inoculated at 4 log CFU/ml in pesticides diluted with sterile saline to the lowest recommended spray concentrations. During 21 degrees C incubation for < or =96 h, bacterial survivors in the samples and a control consisting of saline were enumerated either by agar surface plating or hydrophobic grid membrane filtration. Most formulations tested were somewhat inhibitory to the pathogenic bacteria. All inoculated bacteria survived or grew in Bravo 500. Among bacteria tested, Salmonella spp. were best able to survive and Listeria spp. were least able to survive in pesticide solutions. When the incubation temperature or pesticide concentration was increased, survival of Salmonella varied depending on the type of formulation. In the field, when a bacterial cocktail containing E. coli O157:H7 and Salmonella Enteritidis was added to Bravo 500 at 6 log CFU/ml, both organisms were recovered from leaves and fruit skins of sprayed tomato plants after the recommended 1 day-to-harvest interval. E. coli and Salmonella survived longer on tomato leaves when sprayed in saline (at least 26 and 56 days, respectively) than when sprayed in Bravo 500 (>45 h and <15 days, respectively). While Salmonella serovars Typhimurium and Heidelberg grew in the fungicide Bravo, and Enteritidis grew in the insecticide Vendex within 96 h at 21 degrees C in the laboratory, pathogen growth in other pesticide formulations did not occur. Higher temperature (< or =30 degrees C) or doubling pesticide concentrations had either no or a negative effect on Salmonella Heidelberg survival. Use of unexpired pesticide formulations may have contributed to the reduced bacterial survival and growth found in the laboratory and during the field trials with Bravo.     

Using bromine gas to enhance mercury removal from flue gas of coal-fired power plants

Bromine gas was evaluated for converting elemental mercury (Hg0) to oxidized mercury, a form that can readily be captured by the existing air pollution control device. The gas-phase oxidation rates of Hg0 by Br2 decreased with increasing temperatures. SO2, CO, HCl, and H2O had insignificant effect, while NO exhibited a reverse course of effect on the Hg0 oxidation: promotion at low NO concentrations and inhibition at high NO concentrations. A reaction mechanism involving the formation of van der Waals clusters is proposed to accountfor NO's reverse effect. The apparent gas-phase oxidation rate constant, obtained under conditions simulating a flue gas without flyash, was 3.61 x 10(-17) cm3 x molecule(-1) x s(-1) at 410 K corresponding to a 50% Hg0 oxidation using 52 ppm Br2 in a reaction time of 15 s. Flyash in flue gas significantly promoted the oxidation of Hg0 by Br2, and the unburned carbon component played a major role in the promotion primarily through the rapid adsorption of Br2 which effectively removed Hg0 from the gas phase. At a typical flue gas temperature, SO2 slightly inhibited the flyash-induced Hg0 removal. Conversely, NO slightly promoted the flyash induced Hg0 removal by Br2. Norit Darco-Hg-LH and Darco-Hg powder activated carbons, which have been demonstrated in field tests, were inferred for estimating the flyash induced Hg0 oxidation by Br2. Approximately 60% of Hg0 is estimated to be oxidized with the addition of 0.4 ppm of gaseous Br2 into full scale power plant flue gas.     

Arsenic sequestration in iron plaque, its accumulation and speciation in mature rice plants (Oryza sativa L.)

A compartmented soil-glass bead culture system was used to investigate characteristics of iron plaque and arsenic accumulation and speciation in mature rice plants with different capacities of forming iron plaque on their roots. X-ray absorption near-edge structure spectra and extended X-ray absorption fine structure were utilized to identify the mineralogical characteristics of iron plaque and arsenic sequestration in plaque on the rice roots. Iron plaque was dominated by (oxyhydr)oxides, which were composed of ferrihydrite (81-100%), with a minor amount of goethite (19%) fitted in one of the samples. Sequential extraction and XANES data showed that arsenic in iron plaque was sequestered mainly with amorphous and crystalline iron (oxyhydr)oxides, and that arsenate was the predominant species. There was significant variation in iron plaque formation between genotypes, and the distribution of arsenic in different components of mature rice plants followed the following order: iron plaque > root > straw > husk > grain for all genotypes. Arsenic accumulation in grain differed significantly among genotypes. Inorganic arsenic and dimethylarsinic acid (DMA) were the main arsenic species in rice grain for six genotypes, and there were large genotypic differences in levels of DMA and inorganic arsenic in grain.     

Tin and mercury and their speciation (organotin compounds and methylmercury) in worldwide red wine samples determined by ICP-MS and GC-ICP-MS

ABSTRACT

One hundred and twenty-two red wines were analysed for their total tin, total mercury and speciation concentrations. Total Sn and Hg concentrations were in average 4.4 ± 7.2 µg/L and 0.22 ± 0.12 µg/L, respectively. Two GC-ICP-MS methods were developed and validated for speciation purposes: one to measure organotin compounds (OTCs) with internal standard correction; the other, to evaluate methylmercury (MeHg⁺) by isotopic dilution. Methyltins (mainly dimethyltin, but also monomethyltin) were the most abundant OTCs recovered. Methylation seems to occur biotically during the wine making process and not during the bottling time. Therefore, it also seems to be roughly dependent on the geographical origin of the wine. For higher OTCs, monobutyltin was the most regularly found, but dibutyltin and monooctyltin were also detected sometimes. MeHg⁺ was not recovered in any of the samples investigated, probably due to the low level of Hg. These results suggest that, in terms of these parameters, normal consumption of wine is not a hazard for human health.     

超声辅助提取—HPLC—ICP—MS同时测定水产及其制品中3种形态汞的含量

建立了采用超声辅助提取,高效液相色谱-电感耦合等离子体质谱联用技术测定水产及其制品中汞形态分析的方法。在盐酸+L-半胱氨酸体系下,对样品进行超声辅助萃取,以10mmol/L乙酸铵+0.10%L-半胱氨酸缓冲盐与甲醇(体积比982)组成流动相,用高效液相色谱-电感耦合等离子体质谱仪同时检测无机汞、甲基汞和乙基汞的含量。无机汞、甲基汞和乙基汞的检出限(3S/N)分别为0.18,0.09,0.15ng/mL,标准曲线回归方程相关系数(R)均0.999。以实际样品对无机汞、甲基汞、乙基汞进行加标回收试验,回收率在78.5%~96.8%,相对标准偏差(RSD)≤3.0%。经对标准物质进行检测,测得值与标准值吻合。该方法准确可靠、简单快速、精密度及准确度结果理想,可用于实际水产及其制品中汞形态的分析。     

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.