Mixed acid solubilization procedure for determination of total mercury in food samples

A mixed acid solubilization procedure has been developed for the determination of total mercury in food samples. This procedure has eliminated the problem of mercury loss from samples that are high in lipid or carbohydrate content. The solubilization is rapid and quantitative and can be used for a wide range of food items.     

The methylmercury to total mercury ratio in selected marine,freshwater, and terrestrial organisms

Total and methylmercury concentrations were determined in muscle and organ tissue from a wide variety of marine and terrestrial organisms spanning several trophic levels. Sediment and water samples from many of the tissue sampling sites were also analyzed to assess the degree of mercury contamination to which the animals were exposed. The methylmercury to total mercury ratios were examined to determine whether this ratio is indicative of elevated exposure to organic or inorganic mercury and how it varies relative to tissue type and position in the food chain. As an ancillary study, a subset of these tissues was analyzed as 1) wet tissue, and 2) freeze-dried, ball-milled tissue to determine whether the form of sample preparation can adversely affect mercury analysis. Results indicate that the methylmercury to total mercury ratios generally approach unity only in muscle tissue of higher food chain carnivorous fish residing in waters that are relatively uncontaminated with respect to inorganic mercury species. Herbivorous terrestrial mammals and low food chain marine organisms tend to have very low methylmercury to total mercury ratios. Marine animals placed higher on the food chain, such as crabs and lobsters, exhibit somewhat higher methylmercury to total mercury ratios and can exhibit a large variation in this ratio between, organ tissue and muscle tissue of the same animal. The samples analyzed as both wet and freeze-dried, ball-milled tissue indicate that freezedrying and ball-milling in no way result in mercury loss or contamination and, in fact, result in better replicate analyses and create a sample sufficiently stable to be archived for several years without refrigeration.     

Bioenergetic calculation of mercury accumulation in fish

A numerical model was developed for the bioaccumulation of mercury (Hg) in fish. The model is based on the bioenergetic calculation of fish growth, food consumption, respiration, specific dynamic action and waste losses (egestion/excretion) using the program of Hewett and Johnson (1992). Based on the predation and food results obtained, the accumulation of Hg in fish is calculated taking into account the concentrations of methyl mercury (MeHg) in food and water, its intake and accumulation from food and from water, and the removal of Hg from the body. Some species at various levels of food web are considered in the multistep model applications. The model is used to compute the changes of Hg contents in perch (as prey) and pike (as predator) caused by the release of Hg from the bottom sediments when the Kokemäki River in Western Finland was dredged. The model results were not far from the observed results even though the forcing conditions had been described only roughly.     

Speciation analysis of mercury in cereals by liquid chromatography chemical vapor generation inductively coupled plasma-mass spectrometry

A simple and rapid procedure for the separation and determination of inorganic, methyl, and ethyl mercury compounds was described using liquid chromatography (LC) followed by vapor generation inductively coupled plasma-mass spectrometry (VG-ICP-MS). Well resolved chromatograms were obtained within 5 min by reversed-phase liquid chromatography with a C8 column as the stationary phase and a pH 4.7 solution containing 0.5% v/v 2-mercaptoethanol and 5% v/v methanol as the mobile phase. The separated mercury compounds were converted to mercury vapors by an in situ nebulizer/vapor generation system for their introduction into ICP. The concentrations of NaBH4 and HNO3 required for vapor generation were also optimized. The method was applied for the speciation of mercury in reference materials NIST SRM 1568a Rice Flour and NIST SRM 1567a Wheat Flour and also rice flour and wheat flour samples purchased locally. The accuracy of the procedure was verified by analyzing the certified reference material NRCC DOLT-3 Dogfish Liver for methyl mercury. Precision between sample replicates was better than 13% for all the determinations. The detection limits of the mercury compounds studied were in the range 0.003-0.006 ng Hg mL(-1) in the injected solutions, which correspond to 0.02-0.06 ng g(-1) in original flour samples. A microwave-assisted extraction procedure was adopted for the extraction of mercury compounds from rice flour, wheat flour, and fish samples using a mobile phase solution.     

Simple combustion-vapor trapping technique for determination of mercury in fish

A simple combustion train was constructed for analyzing mercury in fish samples. A nitric acid trap was used to capture the mercury vapors which were released later by adding a tin salt. The method is rapid, accurate, and reproducible and permits one person to analyze 40 samples daily. Sample matrix had no apparent effect on the recovery of mercury. Mean recoveries from fish samples spiked with 0.3 and 1.0 microgram mercuric chloride/g ranged from 97 to 105% with an average recovery of 101.5% and a standard deviation of 2.74%.     

Measurement of Atmospheric Mercury Species with Manual Sampling and Analysis Methods in a Case Study in Indiana

Ground-level concentrations of three atmospheric mercury species were measured using manual sampling and analysis to provide data for estimates of mercury dry deposition. Three monitoring stations were operated simultaneously during winter, spring, and summer 2004, adjacent to three mercury wet-deposition monitoring stations in northern, central, and southern Indiana. The monitoring locations differed in land-use setting and annual mercury-emissions level from nearby sources. A timer-controlled air-sampling system that contained a three-part sampling train was used to isolate reactive gaseous mercury, particulate-bound mercury, and elemental mercury. The sampling trains were exchanged every 6 days, and the mercury species were quantified in a laboratory. A quality-assurance study indicated the sampling trains could be held at least 120 h without a significant change in reactive gaseous or particulate-bound mercury concentrations. The manual sampling method was able to provide valid mercury concentrations in 90 to 95% of samples. Statistical differences in mercury concentrations were observed during the project. Concentrations of reactive gaseous and elemental mercury were higher in the daytime samples than in the nighttime samples. Concentrations of reactive gaseous mercury were higher in winter than in summer and were highest at the urban monitoring location. The results of this case study indicated manual sampling and analysis could be a reliable method for measurement of atmospheric mercury species and has the capability for supplying representative concentrations in an effective manner from a long-term deposition-monitoring network.     

Comparison of fractal dimensions of soils estimated from adsorption isotherms,mercury intrusion,and particle size distribution

The values of the surface fractal dimensions were determined for several samples of Cambisols and Luvisols from analysis of nitrogen and water vapor adsorption isotherms and from mercury intrusion data. Moreover, the values of fractal dimension characterizing the particle size distributions of soil samples were calculated by using a number‐based method. For almost all investigated soils the values of the surface fractal dimension, obtained from water vapor isotherms were lower than those obtained from nitrogen isotherms. Largest were the surface fractal dimensions evaluated form mercury intrusion data. No significant correlations between different kinds of surface fractal dimensions were found, and the reasons of this finding are discussed. However, the values of the surface fractal dimensions calculated from mercury intrusion data correlate with those characterizing the texture of soils. The paper also reports on correlations between of the values of surface area, fractal dimensions and some selected physico‐chemical characteristics of soils.     

Rapid determination of mercury in food colorants using electrothermal atomic absorption spectrometry with slurry sample introduction

The determination of mercury in different types of color food additives using electrothermal atomic absorption spectrometry is proposed. The procedure involves direct introduction of the additive samples as suspensions, and fast-program methodology is used to avoid mercury volatilization losses. Suspensions are prepared in a medium containing 0.1% w/v Triton X-100, 1% v/v concentrated nitric acid, 2% w/v potassium permanganate, and 3% w/v silver nitrate before being directly introduced into the furnace. Calibration uses aqueous standards, and compensation of the background is carried out using the Zeeman device. The characteristic mass is 61 pg and the detection limit is 59 pg. The reliability of the procedure is checked by comparing the results obtained with other results based on microwave-oven sample digestion, and by analyzing a certified reference material.     

Seabirds as monitors of mercury in the marine environment

The oceans play a major role in global cycling of mercury and widespread contamination of marine ecosystems has been demonstrated in recent years. Monitoring mercury in the marine environment is a priority and biomonitoring has featured prominently in this respect. Seabirds, as top predators, present high mercury levels due to food chain amplification and thus will reflect slight variations in environmental mercury and its hazards to humans better than do most invertebrates and cold blood vertebrates. There is experimental evidence that levels of mercury in seabirds show a dose-response relationship, so that increased contamination of the environment causes a corresponding increase in the level in birds. This coupled with current knowledge on the dynamics of mercury in birds gives a good basis for the use of seabird as monitors of mercury. Internal tissues, blood, eggs, feathers and chicks have been used as monitoring units. Feathers are the most attractive amongst them. They are both chemically and physically stable, accumulate higher mercury levels than other tissues and their sampling is non-destructive. However, it is essential to sample a consistent feather area from all birds to minimise the effects of moult and body feathers are the most adequate. Feathers from birds in museum collections offer a great potential for the study of synoptic geographical and historical of changes in mercury levels on a global scale with large sample sizes. For example, studies with time series of feather samples from seabirds provide evidence of a 3-fold increase of mercury contamination in the marine ecosystem of North-eastern Atlantic over the last 100 years and little increase in mercury contamination in the Southern hemisphere during the same period.     

桂林市土壤汞存在形态的研究

采用连续浸取-形态分析(Speciation)方法,对桂林市及市郊土壤样品中以7种形态(species)存在的汞进行了测试分析,结果表明,以残渣态或晶格态形式存在的汞含量最高,达165. 2ng·g-1,占总汞含量的41. 60%;其次为腐殖酸结合或络合态汞、难氧化降解有机质或某些硫化物结合态汞,分别为86. 2ng·g-1、52. 4ng·g-1,占21. 5%、13. 2%。其它4种形态汞含量较低,相应比例均小于10% 。研究表明,桂林土壤汞虽然多以惰性形态存在,但不容忽视它们对生物体内富集汞的长期影响。     

Liquid chromatographic-atomic absorption spectrophotometric method for determination of methyl mercury in seafood: collaborative study

A previously developed method that uses a simplified sample preparation procedure and atomic absorption detection of liquid chromatographic eluates for the determination of methyl mercury in seafood has been collaboratively studied. The unique feature of the method involves the use of a specially designed interface for the generation of mercury vapor. Methyl mercury is isolated from the blended sample by chloroform elution from a diatomaceous earth-hydrochloric acid column. The organomercury compound is then extracted into a small volume of 0.01M sodium thiosulfate solution. An aliquot of this solution is injected onto a Zorbax ODS column and eluted with methanol-ammonium acetate solution (3 + 2), pH 5.7, containing 0.01% mercaptoethanol. Mercury is detected by flameless atomic absorption spectrophotometry using the interface. The samples analyzed in the study were unspiked swordfish, unspiked and spiked lobster, and unspiked and spiked tuna. The spiked samples contained methyl mercury both above and below the U.S. Food and Drug Administration guideline level of 1 microgram Hg/g. Reproducibility relative standard deviations ranged from 10.5% at 1 microgram Hg/g to 18.2% at about 0.1 microgram Hg/g. Accuracy, measured by comparison to reference values obtained by the Associate Referee, ranged from 94.4 to 99.6%. The method has been adopted official first action.     

Simple automated wet digestion of animal tissues for determination of seven elements by atomic absorption spectroscopy

A simple, automated wet digestion procedure was developed for the quantitative determination by atomic absorption spectroscopy (AAS) of arsenic, cadmium, copper, mercury, lead, selenium, and zinc in animal tissue. A commercial digestion block system with automated temperature programming was used. Recoveries of all elements from spiked bovine liver and kidney samples exceed 95%. The analytical results obtained for samples of NBS Bovine Liver (No. 1577a) agree well with certified values. The procedure is safe and requires minimum analyst time.     

Mercury content of soils in Western Britain with special reference to contamination from base metal mining

Mercury was determined in 51 soil samples from historic base metal mining areas of England and Wales, together with cadmium, copper, lead, zinc, pH and organic content. Background mercury was calculated as 0.093 ppm whence 51% of the samples were judged to be contaminated. A very strong statistical correlation between mercury and lead and weaker but significant correlations between mercury and copper and zinc were found. Highest levels of mercury (maximum, 1.78 ppm Hg) and other metals occurred in soils derived from the floodplain of a river which was at one time badly polluted by mine waste. In a profile pit near a lead mine in the west of England both mercury and lead were enriched in surface horizons. It is concluded that land contaminated by heavy metals, especially lead, in the historic metal mining areas of England and Wales is also likely to be contaminated by mercury.     

黑龙江省肇源县土壤汞的空间分异研究

研究土壤汞的空间分异,可以探明影响汞分布的因素,从而有助于解决汞污染等重大生态环境问题。以肇源县的表层和深层土壤为研究对象,利用统计指标、GS⁺软件中的半方差函数模型和ArcGIS软件支持下的克里格插值法,对258个深层土壤样品和1 030个表层土壤样品进行分析,探讨了研究区重金属汞的积累特征。结果表明:样本点之间具有一定的空间相关性。表层土壤汞分布较深层更为不均匀,表层差异更大主要是受人为因素影响,与灌溉、施肥、工农业活动密切相关。深层土壤汞分布状况主要受自然因素影响。     

Mercury and Methylmercury in Freshwater Fish and Sediments in South Korea Using Newly Adopted Purge and Trap GC-MS Detection Method

The use of purge and trap gas chromatography–mass spectrometry (GC-MS) technique for the determination of methylmercury in biological and sediment samples was described. The GC-MS detection system was combined with the dithizone extraction method for biological samples and the distillation method for sediment samples to alleviate matrix interference problems. The method was validated by analysis of CRMs such as SRM 966 (human blood), BCR 463 (tuna fish), IAEA 407 (fish), ERM CC580 (estuarine sediment), and IAEA 405 (sediment). The performance of the purge and trap GC-MS method was also tested on field samples of freshwater fish and sediment. The results were compared with those of the GC-ECD and the GC-CVAFS, which were used widely for methylmercury analysis. Additionally, total mercury and methylmercury levels in freshwater fish and sediments from various reservoirs and streams in Korea were measured to understand mercury contamination status in Korean peninsula. Methylmercury concentrations in freshwater fish were found to correlate with body weight, diet habit, and food availability. In sediment, total mercury concentrations correlated with methylmercury concentrations and organic matter such as %C and %S. However, no significant relationships between methylmercury and sediment organic matter have been found.     

葫芦岛锌厂周围蜘蛛体内的汞含量及分布

以葫芦岛锌厂周围草地中的蜘蛛为研究对象,研究了汞在蜘蛛体内的含量及分布规律。结果表明,蜘蛛体内汞含量范围为6.72～185.01ng·g^-1,平均60.19ng·g^-1,远高于对照地区蜘蛛。不同采样点蜘蛛体内汞含量之间存在较大差异,距离锌厂远近对蜘蛛汞含量影响明显。蜘蛛体内总汞含量、头胸部及腹部汞含量分别同蜘蛛体重、对应器官重量之间呈显著负相关关系。蜘蛛不同器官中汞含量差异显著,表现出头胸部〉足〉腹部的规律。但是同其他昆虫相比,蜘蛛对汞的富集程度并不明显。     

Heavy metal, total arsenic, and inorganic arsenic contents of algae food products

The total arsenic, inorganic arsenic, lead, cadmium, and mercury contents of 18 algae food products currently on sale in Spain were determined. The suitability of the analytical methodologies for this type of matrix was confirmed by evaluating their analytical characteristics. The concentration ranges found for each contaminant, expressed in milligrams per kilogram of dry weight, were as follows: total arsenic, 2.3-141; inorganic arsenic, 0.15-88; lead, < 0.05-1.33; cadmium, 0.03-1.9; and mercury, 0.004-0.04. There is currently no legislation in Spain regarding contaminants in algae food products, but some of the samples analyzed revealed Cd and inorganic As levels higher than those permitted by legislation in other countries. Given the high concentrations of inorganic As found in Hizikia fusiforme, a daily consumption of 1.7 g of the product would reach the Provisional Tolerable Weekly Intake recommended by the WHO for an average body weight of 68 kg. A more comprehensive study of the contents and toxicological implications of the inorganic As present in the algae food products currently sold in Spain may be necessary, which might then be the basis for the introduction of specific sales restrictions.     

STABILITY OF SOIL PORES DURING MERCURY INTRUSION POROSIMETRY

Mercury intrusion porosimetry is one of the techniques used to measure pore size distributions of dry soil samples. It is known that incorrect pore size distributions can be obtained for some porous materials due to sample damage occurring during mercury intrusion, but little evidence relating to soil samples has been published. The pore size distributions of aggregates from three soils, differing in texture, strength and porosity, were measured after heating to 300 °C by mercury intrusion porosimetry. After the first intrusion, all of the intruded mercury was removed from each sample by heating under vacuum. Samples were then re-intruded. The pore size distribution curves for both intrusions were very similar, indicating an absence of sample damage during the first intrusion run.     

农业土壤中汞的生物地球化学行为及其生态效应

综述了国内外近年来农业土壤中汞的生物地球化学行为,包括了土壤环境中汞的来源,汞的形态和生物有效性,汞在农业生态系统中的迁移和转化途径,影响汞对植物有效性的主要因子。同时讨论了汞对植物、动物生长发育的影响,特别强调了土壤中汞污染对食物中汞积累和分配的影响及通过食物链途径给人类健康带来的危害。最后提出了汞污染土壤的各种修复措施,展望了今后研究的方向。     

基于Menger海绵模型的煤矸石粉改良膨胀土微结构特征

为解决膨胀土对工程结构以及农业生态环境的危害，进行煤矸石粉改良膨胀土的试验研究。对煤矸石粉掺量为0、3%、6%、9%的膨胀土土样进行压汞试验，测得微观孔隙特征值；选取Menger海绵模型建立孔隙分分形模型，计算土体孔隙分形维数，探究土体孔隙分形维数与孔隙特征参数以及煤矸石粉掺量变化的关系。结果表明：随着煤矸石粉掺量增加，土中大孔隙所占的含量较素膨胀减少61.5%，孔隙类型从团粒间孔隙转化为颗粒间孔隙；煤矸石粉的掺入改变了土体的孔隙结构特征，煤矸石粉与膨胀土发生胶结反应，孔隙连通性降低，使得总孔隙体积、孔隙率、孔隙平均孔径、孔隙临界孔径等孔隙特征参数呈减小趋势；基于分形理论分析孔隙分形维数，分形维数随煤矸石粉掺量的增加而增加，且与孔隙特征参数呈显著相关性。孔隙分形维数反应了孔隙特征参数以及孔隙发育程度，为土的孔隙表征提供方法借鉴。