Autometallographic tracing of mercury in frog liver

The distribution of mercury in the liver of the frog Rana ridibunda with the autometallographic method was investigated. The mercury specific autometallographic (HgS/SeAMG) technique is a sensitive histochemical approach for tracing mercury in tissues from mercury-exposed organisms. Mercury accumulates in vivo as mercury sulphur/mercury selenium nanocrystals that can be silver-enhanced. Thus, only a fraction of the Hg can be visualized. Six animals were exposed for one day and another group of six animals for 6 days in 1 ppm mercury (as HgCI2 ) dissolved in fresh water. A third group of six animals, served as controls, were sacrificed the day of arrival at the laboratory. First, mercury appears in the blood plasma and erythrocytes. Next, mercury moves to hepatocytes and in the apical part of the cells, that facing bile canaliculi. In a next step, mercury appears in the endothelial and Kupffer cells. It seems likely that, the mercury of hepatocytes moves through bile canaliculi to the gut, most probably bound to glutathione and/or other similar ligands. Most probably, the endothelial and Kupffer cells comprise the first line of defense against metal toxicity.     

Total arsenic and selenium analysis in Marcellus shale,high-salinity water,and hydrofracture flowback wastewater

Trace levels of arsenic and selenium can be toxic to living organisms yet their quantitation in high ionic strength or high salinity aqueous media is difficult due to the matrix interferences which can either suppress or enhance the analyte signal. A modified thiol cotton fiber (TCF) method employing lower flow rates and centrifugation has been used to remove the analyte from complex aqueous media and minimize the matrix interferences. This method has been tested using a USGS (SGR-1b) certified reference shale. It has been used to analyze Marcellus shale samples following microwave digestion as well as spiked samples of high salinity water (HSW) and flow back wastewater (WRF6) obtained from an actual gas well drilling operation. Quantitation of arsenic and selenium is carried out by graphite furnace atomic spectroscopy (GFAAS). Extraction of arsenic and selenium from Marcellus shale exposed to HSW and WRF6 for varying lengths of time is also reported.     

Total arsenic and selenium analysis in Marcellus shale, high-salinity water, and hydrofracture flowback wastewater

Trace levels of arsenic and selenium can be toxic to living organisms yet their quantitation in high ionic strength or high salinity aqueous media is difficult due to the matrix interferences which can either suppress or enhance the analyte signal. A modified thiol cotton fiber (TCF) method employing lower flow rates and centrifugation has been used to remove the analyte from complex aqueous media and minimize the matrix interferences. This method has been tested using a USGS (SGR-1b) certified reference shale. It has been used to analyze Marcellus shale samples following microwave digestion as well as spiked samples of high salinity water (HSW) and flow back wastewater (WRF6) obtained from an actual gas well drilling operation. Quantitation of arsenic and selenium is carried out by graphite furnace atomic spectroscopy (GFAAS). Extraction of arsenic and selenium from Marcellus shale exposed to HSW and WRF6 for varying lengths of time is also reported.     

The tail feathers of osprey nestlings (Pandion haliaetus L.) as indicators of change in mercury load in the environment of southern Sweden (1969-1998): a case study with a note on the simultaneous intake of selenium

The tail feathers of 104 osprey nestlings (Pandion haliaetus) from Lake Asnen, southern Sweden, were analyzed for total mercury and selenium content. Concentrations of mercury in feathers from the western part of the lake fell during the period 1969-1998, when pollution from industrial mercury had decreased and a paper mill upstream of the lake was closed down in 1979. Nestlings from the eastern part of the lake had initially lower levels of mercury, predominantly from atmospheric fallout. The levels did not decrease during the period. The reason for the differences seems to be the limited water flow between the western and the eastern part of the lake. The selenium concentrations were constant over time and approximately the same in both parts of the lake. The total-Hg/Se ratio in the western part of the lake was 2.94, which is somewhat higher than the 1:1 molar ratio constant (2.54). This indicates that the bioaccumulated quantity of selenium which is thought to be protective for the organisms against the toxic effects of mercury, is somewhat insufficient to bind all body mercury.     

Contaminant residues in seabird eggs from the Canadian Arctic. Part I. Temporal trends 1975-1998.

Concentrations of total mercury, selenium and a suite of organochlorine compounds were measured in eggs of thick-billed murres (Uria lomvia), northern fulmars (Fulmarus glacialis) and black-legged kittiwakes (Rissa tridactyla) collected on Prince Leopold Island in Lancaster Sound, Nunavut, Canada, between 1975 and 1998. Mercury levels in thick-billed murre and northern fulmar eggs increased significantly during this period while selenium concentrations decreased significantly in northern fulmar eggs. Mercury and selenium concentrations in black-legged kittiwake eggs exhibited no significant temporal trends. Concentrations of sigma PCB, sigma DDT and total chlorobenzenes decreased over time for all three species and there was a shift in the PCB congener pattern as the hexachlorobiphenyl fraction of sigma PCB increased and the lower chlorinated biphenyl fraction decreased. Total chlordane, dieldrin and mirex concentrations decreased in kittiwake eggs while no significant trends were observed for the other two species. Increases in sigma HCH levels were detected in thick-billed murre eggs but not in northern fulmar and black-legged kittiwake eggs. Levels of the beta-HCH isomer, however, increased significantly in murres and fulmars. Stable-nitrogen isotope analyses (delta 15N) indicate that the temporal trends observed for contaminant concentrations in eggs were not the result of shifts in trophic level. Changing deposition patterns of xenobiotic compounds over the summer and winter ranges of these birds provide a likely explanation for differing exposures through time.     

Forms and distribution of selenium at different depths and among particle size fractions of three Taiwan soils

The bioavailability of selenium in soils for plants depends more on its forms than on its total concentration. The purpose of the present study was to examine the solid-phase forms of selenium at different depths of three soil series representing major farming soil groups in Taiwan as well as the amounts of selenium in sand, silt and clay fractions of the soils. The study was conducted by means of sequential extraction to obtain the amounts of selenium and the distribution of various solid-phase forms of selenium at different depths of Pinchen (121 degrees 11(')E, 24 degrees 55(')N), Toulun-Sheto (120 degrees 55(')E, 24 degrees 50(')N), and Chunliao (120 degrees 25(')E, 23 degrees 57(')N) soil series. The amounts of metal oxide-bound form of selenium in the three soil series were the largest, with those of Pinchen and Toulun-Sheto soil series exceeding 50% of the total amounts of selenium and that of Chunliao soil series maintained at 30-40%. In the Pinchen and Toulun-Sheto soil series, the amounts of selenium in clay fractions were the largest, with a significant difference between the clays with and without metal oxides and organic matter removed. The amounts of selenium remained high in silt and/or sand fractions of the Chunliao soil series with metal oxides and organic matter removed. Metal oxide and organic matter contents of the three soil series mainly affect the amounts of various solid-phase forms of selenium and their distribution in different depths and particle size fractions of the soils. This observation of selenium associated with soil constituents was in good agreement with the results of the adsorption of selenite and selenate by the three soil series.     

Metallothione in-like protein in lobsters ( )

A metallothionein-like protein (MLP) was isolated from naturally cadmium-contaminated lobster hepatopancreas, gills, and green glands. Between 76–99% of the total cadmium was associated with this protein (molecular weight 9,500 daltons) while the remainder was associated with both high (68,000 daltons) and low (<6,000 daltons) molecular weight proteins. MLP was not present in uncontaminated lobster hepatopancreas and only 1% of the total cadmium was associated with the gel filtration fraction corresponding to the protein.     

Assessment of lead uptake in reptilian prey species

As part of an investigation determining the trophically available fraction of metals in a model terrestrial food web, i.e., invertebrate prey to Western fence lizards (Sceloporus occidentalis), we evaluated the ability of several invertebrate prey to bioaccumulate lead and to form metals-rich granules, which are hypothesized to be non-available to predators. Crickets (Acheta domestica), tenebroid beetle larvae (Tenebrio molitor), and isopods (Porcellio scaber) were selected as model prey organisms. Lack of standard exposure methodologies for these species has presented a barrier to trophic transfer evaluations, as each species has particular requirements that create challenges for designing exposure conditions. We were able to devise exposure conditions for all three species that allow long-term exposure studies. All prey organisms accumulated lead from contaminated food, and for all species the majority of the accumulated Pb was associated with the exoskeleton (>50%), with metals-rich granules accounting for most of the remaining accumulated lead.     

The evolution of December 2004 tsunami deposits: Temporal and spatial distribution of potentially toxic metalloids

The article presents the results of research into the content of metalloid fractions in the tsunami deposits from southern Thailand. The following fractions, which are potentially most easily released from deposits to the environment, have been distinguished: the water soluble fraction, the exchangeable fraction extracted with the phosphate buffer and the fraction eluted with the solution of hydrochloric acid. The analytical technique atomic absorption spectrometry with hydride generation was applied. Spatial variability of the metalloid fractions in deposits and changes occurring in deposits over a period of several years of observation were determined. Based on the statistical analysis of the results, an attempt was made to determine the post-depositional release of deposits components to the environment. Based on the conducted research, the 4 years forming process of the arsenic, antimony and selenium occurrence after the deposition of sediments on land were described, as well as the balance in the amount of deposit components released to the environment.     

The effect of consumption of pork enriched by organic selenium on selenium status and lipid profile in blood serum of consumers

Abstract

The aim of the research was to evaluate the effect of consumption of selenium-enriched pork on selected health indicators of probands. The intake of feed mixture with increased organic selenium at the dose of 0.3?mg.kg^?1 probably increases selenium concentration in MSM (musculus semimembranosus). In the pork enriched with organic selenium, the concentration was higher by 1.045?±?0.10?mg.kg^?1 compared with the control group 0.701?±?0.05?mg.kg^?1 at significance P?<?0.001. Sixteen participants in the experiment were represented by 8 men at the average age of 41.5?±?11.9?years and 8 women at the average age of 41.4?±?7.9?years. All the probands consumed meat enriched with selenium three times a week during one month. By consumption of the enriched pork, there was an increase of the selenium concentration in blood serum of probands traced with selenium increase from 73.19?±?15.68?μg.L^?1 to 73.73?±?15.13?μg.L^?1 (P?>?0.05). From the results we can see that consumption of enriched pork with selenium was significantly manifested in lowering of total cholesterol levels, which was associated with LDL cholesterol lowering (P?<?0.05). Differences among the HDL cholesterol and triglycerides samples were not significant.     

Accumulation of silver in the liver of three species of pinnipeds

Silver in the three species of pinnipeds [northern fur seal (Callorhinus ursinus), Steller sea lion (Eumetopias jubatus), and harbor seal (Phoca vitulina)] caught in the North Pacific Ocean were analyzed using inductively coupled plasma-mass spectrometry, in order to understand accumulation and distribution of silver in pinnipeds. In northern fur seals, relatively high concentrations of silver were observed in the liver and body hair. Some 70% of the silver burden was concentrated in the liver. Hepatic silver concentrations were significantly correlated to age in northern fur seals (r = 0.766, P < 0.001, n = 49) and Steller sea lions (r = 0.496, P < 0.01, n = 28). Levels of silver concentrations per wet weight (microgram g-1) in the three pinnipeds ranged from 0.04 to 0.55 for northern fur seals, from 0.1 to 1.04 for Steller sea lions and from 0.03 to 0.83 for harbor seals. Silver concentrations in liver for all pinnipeds were significantly correlated with mercury, and selenium (P < 0.001). Molar ratios between silver to selenium approximated 1:180 in northern fur seals, 1:120 in Steller sea lions, and 1:60 in harbor seals. The silver-mercury molar ratios were approximately 1:170 in northern fur seals, and 1:80 both in the other species. Increase in silver accumulation in the liver was caused by the retention in nuclei and mitochondria fraction together with mercury and selenium in the cells of northern fur seals.     

Study on transformation and enrichment behavior of selenium in particulate matter in combustion flame

An ethylene/air inverse diffusion flame (IDF) burner was employed to generate a stable flame, and selenium was introduced into the combustion flame in vapor phase under different air-fuel ratio (A/F) with SO2 additive. At different height above burner (HAB) along the flame edge, selenium of different speciation (gaseous selenium and particulate selenium) was sampled via the U.S. EPA method 29, and the samples were determined by hydride generation atomic fluorescence spectrometry (HG-AFS), in order to study the mechanism of transformation and enrichment behavior of selenium during the combustion process. The results showed that selenium presented in vapor phase, crossing the flame into air, which means gaseous phase is the main form of selenium during combustion process. Both gaseous selenium and particulate selenium increased with elevated temperature from 820K to 1650K, suggesting that higher temperature is beneficial to the release of selenium. Low concentration of sulfur dioxide would increase the concentration of particulate selenium and gaseous selenium, and accelerate the release of selenium.

Implications: The enrichment behavior of selenium and its transformation in combustion flame were studied. The results showed that gaseous selenium is found in higher quantity in compared to particulate selenium during combustion. Higher temperature and air–fuel ratio will cause an increase in the formation of selenium. While the presence of sulfur dioxide in a range of 0–200 ppm will promote the release of selenium, higher sulfur dioxide level in a range of 200–350 ppm will have a reverse effect.     

Using deuterated PAH amendments to validate chemical extraction methods to predict PAH bioavailability in soils

Validating chemical methods to predict bioavailable fractions of polycyclic aromatic hydrocarbons (PAHs) by comparison with accumulation bioassays is problematic. Concentrations accumulated in soil organisms not only depend on the bioavailable fraction but also on contaminant properties. A historically contaminated soil was freshly spiked with deuterated PAHs (dPAHs). dPAHs have a similar fate to their respective undeuterated analogues, so chemical methods that give good indications of bioavailability should extract the fresh more readily available dPAHs and historic more recalcitrant PAHs in similar proportions to those in which they are accumulated in the tissues of test organisms. Cyclodextrin and butanol extractions predicted the bioavailable fraction for earthworms (Eisenia fetida) and plants (Lolium multiflorum) better than the exhaustive extraction. The PAHs accumulated by earthworms had a larger dPAH:PAH ratio than that predicted by chemical methods. The isotope ratio method described here provides an effective way of evaluating other chemical methods to predict bioavailability.     

The effect of residual chemical oxygen demand on anoxic and aerobic phosphate uptake and release with various intracellular polymer levels.

This study investigated the anoxic and aerobic phosphate uptake and release reactions and the fraction of denitrifying phosphate-accumulating organisms (DPAOs) under various initial chemical oxygen demand (COD) and residual COD conditions. The results showed that DPAOs and non-DPAOs could release phosphate when high soluble COD was present. Consequently, the phosphate-uptake potential was dynamic and increased when the initial COD increased, the initial polyhydroxyalkanoates (PHA) increased, and the residual COD decreased. Furthermore, the electron acceptor (oxygen of nitrate) has more significant influence on the phosphate uptake/release characteristics, while the residual COD concentrations have little influence on that. The fraction of DPAOs to phosphate-accumulating organisms was 42% when the initial PHA storage was enough by both DPAOs and non-DPAOs. This was closely related to the relative phosphate uptake (47%) in the anoxic zone of the process.     

Potentially toxic element fractionation in technosoils using two sequential extraction schemes

This study reports the chemical fractionation of several potentially toxic elements (Zn, Pb, Cd, As, and Sb) in contaminated technosoils of two former smelting and mining areas using two sequential extraction schemes. The extraction schemes used in this study were the Tessier’s scheme and a modified BCR scheme. The fractions were rearranged into four equivalent fractions defined as acid soluble, reducible, oxidizable, and residual to compare the results obtained from two sequential extraction schemes. Surface soils were samples from a waste landfill contaminated with Zn, Pb, and Cd located at Mortagne-du-Nord (MDN; North France) and from a settling basin contaminated with PTE such as As, Pb, and Sb located at La Petite Faye (LPF; Limoges, France). The study of the Zn, Pb, Cd, As, and Sb partitioning in the acid soluble, reducible, oxidizable, and residual fractions of the technosoils revealed that Zn, Cd, and Pb were mainly associated with the acid soluble and reducible fractions for MDN site, while As, Sb, and Pb were associated with residual fraction for LPF site. Fractionation results indicate that the percentages of Zn, Pb, Cd, As, and Sb extracted in Fe–Mn oxide bound fraction of Tessier’s scheme were always higher than those extracted by modified BCR scheme. This may be attributed to the stronger Tessier’s scheme conditions used to extract this fraction. In contrast the percentages of Zn, Pb, Cd, As, and Sb extracted in the organic fraction of the modified BCR scheme were always higher than those of the Tessier’s scheme. The order of mobility of PTE was as follows: Cd?>?Zn?>?Pb in MDN site and As?>?Sb?>?Pb in LPF site. PTE were distributed in all soil fractions, with the most relevant enrichments in extractable and residual fractions. A significant amount of Cd, Pb, and Zn were rather mobile, which suggests that these elements can be readily available to plants and soil organisms.     

燃煤过程中微量元素砷和硒形态转化的热力学平衡模拟

砷和硒是煤中的易挥发有毒微量元素。由于砷和硒在燃煤烟气中的浓度极低以及实验条件的限制 ,目前化学热力学平衡分析已成为预报烟气中砷和硒等有毒元素形态分布的主要理论分析方法。本文综述了热力学平衡分析方法应用于砷和硒在燃煤过程中形态转化和平衡分布等方面的研究进展。首先用于热力学平衡分析的是只含有砷或硒一种微量元素和煤中主量元素及氯元素的简单体系 ,并假设烟气中只有理想气体组成的气相和纯凝聚相的理想模型。然而是否考虑砷和硒与其他微量、主量或次量元素的相互作用 ,砷和硒所有可能存在的反应 ,以及在熔融相砷和硒与熔融物的结合会严重地影响模型的预报结果 ,因此 ,目前热力学平衡体系已发展成为含有包括砷和硒在内的多个微量元素和煤中所有主量、次量元素 ,以及包括熔融相在内的非理想多相复杂体系     

Selenium,total mercury and methylmercury in sardine: Study of molar ratio and protective effect on the diet

The purpose of this work was to evaluate the risk-benefit associated with canned sardine consumption, considering the selenium, the mercury and the methylmercury contents and the Se:Hg molar ratio and the Se-health benefit value (HBV) index. In this study, 63 canned sardine samples were purchased worldwide and for the determination of selenium and mercury species, the inductively coupled plasma optical emission spectrometry and thermal decomposition and amalgamation atomic absorption spectrometry were employed. The mean results obtained for the Brazilian samples varied between 12.6 and 65.5?μg kg^?1 for Hg; <3.7 and 45.4?μg kg^?1 for methylmercury; 310 and 1370?μg kg^?1 for Se. The MeHg/Hg ratio showed that the most toxic forms of Hg (MeHg) is predominant in 52 and 39% of the Brazilian samples conserved in tomato sauce and in oil, respectively. Nevertheless, the Se-HBV index and the Hg:Se and Se:Hg molar ratios indicated that the selenium content in canned sardine samples is enough to provide a protective effect on the Hg species.     

A review of toxicity and mechanisms of individual and mixtures of heavy metals in the environment

The rational for the study was to review the literature on the toxicity and corresponding mechanisms associated with lead (Pb), mercury (Hg), cadmium (Cd), and arsenic (As), individually and as mixtures, in the environment. Heavy metals are ubiquitous and generally persist in the environment, enabling them to biomagnify in the food chain. Living systems most often interact with a cocktail of heavy metals in the environment. Heavy metal exposure to biological systems may lead to oxidation stress which may induce DNA damage, protein modification, lipid peroxidation, and others. In this review, the major mechanism associated with toxicities of individual metals was the generation of reactive oxygen species (ROS). Additionally, toxicities were expressed through depletion of glutathione and bonding to sulfhydryl groups of proteins. Interestingly, a metal like Pb becomes toxic to organisms through the depletion of antioxidants while Cd indirectly generates ROS by its ability to replace iron and copper. ROS generated through exposure to arsenic were associated with many modes of action, and heavy metal mixtures were found to have varied effects on organisms. Many models based on concentration addition (CA) and independent action (IA) have been introduced to help predict toxicities and mechanisms associated with metal mixtures. An integrated model which combines CA and IA was further proposed for evaluating toxicities of non-interactive mixtures. In cases where there are molecular interactions, the toxicogenomic approach was used to predict toxicities. The high-throughput toxicogenomics combines studies in genetics, genome-scale expression, cell and tissue expression, metabolite profiling, and bioinformatics.     

Long-term increased bioaccumulation of mercury in largemouth bass follows reduction of waterborne selenium

Average mercury concentrations in largemouth bass from Rogers Quarry in east Tennessee were found to increase steadily following the elimination of selenium-rich discharges of fly ash to the quarry in 1989. From 1990 to 1998, mean mercury concentrations (adjusted to compensate for the covariance between individual fish weight and mercury concentration) in bass rose from 0.02 to 0.61 mg/kg. There was no indication that the rate increase was slowing or that mercury concentrations in fish were approaching a plateau or steady state. Mean selenium concentrations in bass declined from 3 to 1 mg/kg over the first five years of the study, but remained at 1-1.5 mg/kg (about twice typical concentrations in bass from local reference sites) for the last three years of the study. Gross physical abnormalities were common in fish from the site in the first three years after elimination of fly ash discharges but disappeared after two more years. Although it remains possible that other chemical or physical changes related to fly ash disposal in the system were associated with increased mercury bioaccumulation, the most likely explanation is that selenium played a critical role. It appears as though aqueous selenium enrichment was capable of having a profound effect on mercury bioaccumulation in this system but at the cost of causing a high incidence of gross abnormalities in fish. However, it is possible that selenium concentrations between the national ambient water quality criterion for the protection of aquatic life, 5 microg/l, and that now found in Rogers Quarry (<2 microg/l) could reduce mercury bioaccumulation without causing adverse effects on aquatic biota and fish-eating wildlife.     

Reproduction of mallards following overwinter exposure to selenium

Forty pairs of mallards (Anas platyrhynchos) were fed 15 ppm selenium as selenomethionine for about 21 weeks during winter. Twenty pairs served as controls. At the end of 21 weeks, which coincided with the onset of the reproductive season, selenium treatment was ended. Four birds died while on selenium treatment. Treated females lost weight, and their egg-laying was delayed. Hatching success of some of the first eggs laid by selenium-treated females was lower than that of controls, and a few of these early eggs contained deformed embryos, but, after a period of about two weeks off the selenium-treated diet, reproductive success returned to a level comparable with that of controls. The return to normal reproductive success was the result of a corresponding decrease in selenium concentrations in eggs once selenium treatment ended.