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.     

Relations between mercury, methyl-mercury and selenium in tissues of Octopus vulgaris from the Portuguese Coast

Mercury, methyl-mercury (MeHg) and selenium were determined in digestive gland and mantle of Octopus vulgaris, from three areas of the Portuguese coast. To our knowledge these are the first data on MeHg in cephalopods. Concentrations were higher in the digestive gland and percentage of MeHg in mantle. Enhanced Hg and MeHg levels were obtained in digestive gland of specimens from Olhão (3.1-7.4 and 2.0-5.0 μg g⁻¹, respectively). Differences between areas may be partially related to Hg availability. Relationships between concentrations in mantle and digestive gland pointed to proportional increases of Hg and MeHg in tissues of specimens from Matosinhos and Cascais, but relatively constant values in mantle of individuals from Olhão (higher contamination). Se:Hg molar ratio in digestive gland was 32 and 30 in octopus from Matosinhos and Cascais, respectively, and 5.4 from Olhão. The proximity to the unit suggests demethylation as response to elevated MeHg levels in digestive gland.     

Year-to-year correlations in blood metal levels among individuals of two species of North American sea ducks

Sea duck populations have declined in North America. Contaminants, especially metals, have been listed as possible contributing factors. Sea ducks are long-lived. Thus, individuals chronically exposed to elevated metal levels may be at greatest risk. Information about long-term exposure (> or =1year) of individuals to metals is absent. To address this information gap, we examined year-to-year correlations among individual White-Winged Scoters and King Eiders in levels of blood cadmium, lead, mercury and selenium. Positive correlations (r> or =0.43), were found in six, five, five and two of seven correlations for cadmium, selenium, lead and mercury. Thus, certain individuals of these species may be exposed over two or more years to higher levels of cadmium, selenium and lead (but apparently not mercury) than other individuals. Single blood samples are appropriate metrics of exposure for studies that examine long-term effects of certain metals on these birds.     

Modeling effects of toxin exposure in fish on long-term population size, with an application to selenium toxicity in bluegill (Lepomis macrochirus)

A primary goal in ecotoxicology is the prediction of population-level effects of contaminant exposure based on individual-level response. Assessment of toxicity at the population level has predominately focused on the population growth rate (PGR), but the PGR may not be a relevant toxicological endpoint for populations at equilibrium. Equilibrium population size may be a more meaningful endpoint than the PGR because a population with smaller equilibrium size is more susceptible to the negative effects of environmental variability. We address the individual-to-population extrapolation problem with modeling utilizing classical mathematical theory. We developed and analyzed a general model applicable to many freshwater fish species, that includes density-dependent juvenile survival and additional juvenile mortality due to toxicity exposure, and we quantified effect on equilibrium population size as a means of assessing toxicity. Individual-level effects are typically greater than population-level effects until the individual effect is large, due to compensatory density-dependent relationships. These effects are sensitive to the recruitment potential of a population, in particular the low-density first-year survival rate S_b. Assuming high S_b could result in underestimating effects of population-level toxicity. The equilibrium size depends directly on S_b, the reproductive potential, the toxin concentration at which mean mortality is 50% (LC₅₀), and the rate at which individual mortality increases with increasing toxin concentration. More experimental data are needed to decrease the uncertainty in estimating these parameters. We then used existing data for selenium toxicity in bluegill sunfish to parameterize a simulation version of the model as an example to assess the effects of environmental stochasticity on toxicity response. Effects of environmental variability resulted in simulated extinctions at much lower toxin concentrations than predicted deterministically.     

Mutual detoxification of mercury and selenium in unicellular Tetrahymena

Selenium(Se) is commonly recognized as a protective element with an antagonistic effect against mercury(Hg) toxicity. However, the mechanisms of this Hg–Se antagonism are complex and remain controversial. To gain insight into the Hg–Se antagonism, a type of unicellular eukaryotic protozoa(Tetrahymena malaccensis, T. malaccensis) was selected and individually or jointly exposed to two Hg and three Se species. We found that Se species showed different toxic effects on the proliferation of T. malaccensis with the toxicity following the order:selenite(Se(IV)) selenomethionine(SeMeth) selenate(Se(VI)). The Hg–Se antagonism in Tetrahymena was observed because the joint toxicity significantly decreased under co-exposure to highly toxic dosages of Hg and Se versus individual toxicity. Unlike Se(IV) and Se(VI), non-toxic dosage of SeM eth significantly decreased the Hg toxicity, revealing the influence of the Se species and dosages on the Hg–Se antagonism. Unexpectedly, inorganic divalent Hg(Hg~(2+)) and monomethylmercury(MeHg) also displayed detoxification towards extremely highly toxic dosages of Se, although their detoxifying efficiency was discrepant. These results suggested mutual Hg–Se detoxification in T. malaccensis, which was highly dependent on the dosages and species of both elements. As compared to other species, SeM eth and MeHg promoted the Hg–Se joint effects to a higher degree. Additionally, the Hg contents decreased for all the Hg–Se co-exposed groups, revealing a sequestering effect of Se towards Hg in T. malaccensis.     

A study on "selenium-health" database in China

A database for "Se and health" has been established using DATA-TRIEVE data management system on a VAX-11/780 computer. Over 5000 pieces of information including 300 kinds of samples from 28 provinces in China were stored. The information relates to endemk diseases such as Keshan disease, Kaschin-Beck disease, Se-poison disease, cancers, heart disease and so on. The database can be accessed through keywords: samples, province, county, analytical method and the Se-content values can be obtained in tabulated form. The output includes primary statistics of the retrieved data sets. A multi-variable statistic program package featuring in pattern recognition is attached to the system.     

硒,砷联合致畸作用的体外全胚胎培养实验研究

用体外全胚胎培养模型探讨在硒和砷共存环境下，对旋转培养４８ｈ的大鼠胚胎（９．５ｄ）的生长发育和器官形态分化所产生的联合作用。结果表明，硒，砷联合毒性的主效应呈相互相拮抗的（Ｐ＝０．０００１）。除细胞干重指标外，其它反映胚胎生长发育和器官形态分化的各项指标均有明显好转，与正常对照组比较没有显著性差异（Ｐ〈０．０５），砷在高剂量在（３．０μｇ／ｍＬ０，硒（０．５￣２．０μｇ／ｍＬ）对砷的毒性无明显缓解     

青海省海东市平安区土壤Se的地球化学特征

通过对平安区表层土壤样品的系统采集,测定了Se及其它元素的含量,研究了区内土壤Se的地球化学特征,探讨土壤Se富集机理。结果表明,表层土壤Se处于0.04～5.79 mg/kg之间,均值为0.29 mg/kg,富Se(Se≥0.4 mg/kg)和足Se(0.175≤Se0.4 mg/kg)土壤面积分别为121.4 km~2和464.1 km~2,总共占平安区总面积的75.1%,主要分布在古-新近纪棕红色泥岩风化物和第四纪冲洪积物为母质的土壤区。富Se土壤存在两个区带,分布位于平安盆地和拉脊山。平安区Se富集机理主要有两种:平安盆地Se与Sr、Mo活动相近,在咸水、干旱、氧化的沉积环境与盐类物质同时发生富集;拉脊山Se与Cu、S、Mo活动相近,与铜硫化物伴生并受表层高有机质吸附所致。     

Chemical endemic diseases and their impact on population in china

This paper deals with some endemic diseases related to selenium, iodine and fluoride in eco-environment. Keshan disease and Kaschin-Beck disease are associated with low selenium, they mainly occur in a belt zone across China ranging from North-East to South-West. Selenium contents in food grains and human hair from the disease affected areas are usually below 0.020ppm and 0.20ppm respectively. The endemic goitre caused by iodine deficiency distributes extensively in China, mainly in mountainous and hilly districts, swamp and peat areas, some sand soil and limestone areas. Also there is another kind of endemic goitre which caused by iodine excess in interior and coast areas. Endemic cretinism usually occurs in the endemic goitre seriously affected areas. Endemic fluorosis is also widely distributed in China, but mainly occurs in dry or semi-dry areas of north China. The fluoride sources for causing endemic fluorisis are drinking water and food grains polluted by coal smoke in the backing process of maize     

Effect of selenium on the growth of Lemna minor

The effect of selenium on the vegetative reproduction of cultured Lemna minor was investigated. Cultures were grown for 28 days at a temperature of 23 ± 3°C and under a constant (24 h) light cycle. Growth was monitored every seven days. The growth of L. minor was inhibited at high concentrations (>5mg/L [Se]), but stimulated at low concentrations (0.2—2mg/L [Se]). This stimulation of growth at low selenium concentrations has significant implications for the use of selenium enriched superphosphate fertilisers on selenium deficient pastures.