电感耦合等离子体质谱法测定土壤样品中的痕量硒元素

随着电感耦合等离子体质谱技术的发展,准确测定环境样品中的痕量硒元素含量越来越受到关注。质量数76、78、80和82的硒元素受氩的多原子干扰非常严重,必须进行校正才能得到满意的结果。利用动态反应池模式对土壤样品的测定条件进行条件优化,将Cell Gas从0.3～0.7ml/min步幅0.1ml/min、RPQ从0.45～0.7步幅0.05进行同步优化,最终确定针对消解样品的Cell Gas为0.5ml/min,RPQ为0.45,78Se是最佳的测定同位素。通过石墨电热赶酸仪赶酸,适当稀释控制可溶性固体量,在线加入103Rh内标来克服基线漂移,提高了分析方法的准确性。2%甲醇的加入提高了硒在电感耦合等离子体中的离子化强度,在一定程度上增强了低浓度的响应值。根据国家标准参考物质的分析结果评价方法的准确性,证实所建立的方法简便、准确、快速。     

Influence of mercury and selenium chemistries on the progression of cardiomyopathy in pygmy sperm whales, Kogia breviceps

More than half of pygmy sperm whales (Kogia breviceps) that strand exhibit signs of cardiomyopathy (CMP). Many factors may contribute to the development of idiopathic CMP in K. breviceps, including genetics, infectious agents, contaminants, biotoxins, and dietary intake (e.g. selenium, mercury, and pro-oxidants). This study assessed trace elements in K. breviceps at various stages of CMP progression using fresh frozen liver and heart samples collected from individuals that stranded along US Atlantic and Gulf coasts between 1993 and 2007. Standard addition calibration and collision cell inductively coupled plasma mass spectrometry (ICP-MS) were employed for total Se analysis and pyrolysis atomic absorption (AA) was utilized for total Hg analysis to examine if the Se/Hg detoxification pathway inhibits the bioavailability of Se. Double spike speciated isotope dilution gas chromatography ICP-MS was utilized to measure methyl Hg and inorganic Hg. Immunoblot detection and colorimetric assays were used to assess protein oxidation status. Data collected on trace elements, selenoproteins, and oxidative status were evaluated in the context of animal life history and other complementary histological information to gain insight into the biochemical pathways contributing to the development of CMP in K. breviceps. Cardiomyopathy was only observed in adult pygmy sperm whales, predominantly in male animals. Both Hg:Se molar ratios and overall protein oxidation were greater in males than females and increased with progression of CMP.     

“The Kesterson effect”

Hypothesized to be derived from Cretaceous marine sedimentary rocks, selenium contamination of the Kesterson National Wildlife Refuge is traced through irrigation drainage to the source bedrock of the California Coast Ranges. This biogeochemical pathway of selenium is defined here as the “Kesterson effect.” At the refuge ponds, this effect culminated in 1983 in a 64% rate of deformity and death of embryos and hatchlings of wild aquatic birds. From the previous companion paper on irrigation drainage, the Kesterson effect has been implicated in nine of 11 reconnaissance areas studied in the western United States. Deformities have resulted in at least five of these sites. Climatic, geologic, hydrologic, and soil conditions in these reconnaissance areas are similar to those in the area surrounding Kesterson National Wildlife Refuge in the west-central San Joaquin Valley of California. In California, selenium, as selenate, was ultimately found weathered with sulfur from marine sources in soluble sodium and magnesium sulfate salts, which are concentrated by evaporation on farmland soils. The Se, mobilized by irrigation drainage, is bioaccumulated to toxic levels in refuge wetland ponds that are located mainly in hydrologically closed basins and thus act as concentrating disposal points. The depositional environment of the ponds may be similar to that of the nutrient-rich continental shelf edge and slope in which Cretaceous, Eocene, and Miocene sediments found to be seleniferous in the California Coast Ranges were deposited. Bioaccumulation may be therefore a primary mechanism of selenium enrichment in ancient sediments in addition to that of the formerly suggested Cretaceous volcanic pathway.     

Mercury and selenium in blue shark (Prionace glauca, L. 1758) and swordfish (Xiphias gladius, L. 1758) from two areas of the Atlantic Ocean

Muscle, liver and stomach contents of 64 blue sharks and 52 swordfishes, caught between September 2004 and February 2005 near the Azores (area A) and the Equator (area E), were analysed for mercury and selenium. Levels of mercury were relatively high (blue shark: 0.032-2.5microgg(-1); swordfish: 0.031-9.8microgg(-1)) and comparable to values reported in the literature. However, mercury and organic mercury concentrations in muscle and liver of specimens from E were significantly higher than those from A. A similar trend was registered in stomach contents, suggesting higher uptake of Hg in specimens from E. This difference was also observed in the relationship between concentration in muscle and size, indicating a higher accumulation rate in specimens from E. The accumulation of Se in the liver of both species showed a positive correlation with inorganic mercury concentrations, pointing to a detoxifying mechanism of organic mercury in these species through Se-Hg liasons.     

Evaluation of natural goethite on the removal of arsenate and selenite from water

Elevated arsenic and selenium concentrations in water cause health problems to both humans and wildlife. Natural and anthropogenic activities have caused contamination of these elements in waters worldwide, making the development of efficient cost-effective methods in their removal essential. In this work, removal of arsenate and selenite from water by adsorption onto a natural goethite(α-FeO OH) sample was studied at varying conditions. The data was then compared with other arsenate, selenite/goethite adsorption systems as much of literature shows discrepancies due to varying adsorption conditions. Characterization of the goethite was completed using inductively coupled plasma mass spectrometry, X-ray diffraction, Fouriertransform infrared spectroscopy, scanning electron microscopy, and Brunauer–Emmett–Teller surface area analysis. Pseudo-first order(PFO) and pseudo-second order(PSO) kinetic models were applied; including comparisons of different regression methods. Various adsorption isotherm models were applied to determine the best fitting model and to compare adsorption capacitates with other works. Desorption/leaching of arsenate and selenite was studied though the addition of phosphate and hydroxyl ions. Langmuir isotherm modeling resulted in maximum adsorption capacities of 6.204 and 7.740 mg/g for arsenate and selenite adsorption,respectively. The PSO model applied with a non-linear regression resulted in the best kinetic fits for both adsorption and desorption of arsenate and selenite. Adsorption decreased with increasing pH. Phosphate induced desorption resulted in the highest percentage of arsenate and selenite desorbed, while hydroxide induced resulted in the fastest desorption kinetics.     

Determination of dissolved selenium species in environmental samples

This article reports on the technique for the determination of selenium at ppt level and the procedure for the speciation of dissolved selenium in the environmental samples. By combining the high-performance liquid chromatography (HPLC) and a fluorescent detector (FLD), this technique permits the determination of selenium at 0.001 μg/L for Se(IV) and 0.005 μg/L for Se(VI) and the total concentration of selenium for a sample volume of 20 ml. In the speciation procedure, Se(IV) is firstly determined based on the selectivity of 2, 4 - diaminonaphthalene (DAN), the Se (VI) and the total element concentration are determined after reduced to Se(IV) by boiling in 4 mol/L HCl and by digesting in HNO3-HClO4 mixture, respectively. Discussions are given on the relationship between selenium speciation in waters and soil water extract and solution pH, EH and total organic carbon concentration (TOC).     

Modeling batch leaching behavior of arsenic and selenium from bituminous coal fly ashes

Correctly predicting the leaching potential of arsenic (As) and selenium (Se) is critical for assessing the environmental impact of coal fly ash. This study investigated the impacts of several key environmental factors, including pH, leaching time, and ash washing on the batch leaching behavior of As and Se from bituminous coal fly ashes. The experimental results demonstrated that As and Se leaching from fly ash increased beyond the minimal leaching pH ranges. Increasing leaching time increased As leaching but decreased Se leaching in the alkaline pH condition. A speciation-based adsorption model was used to quantify the batch leaching data, and determine the intrinsic leaching parameters including the total batch leachable mass and the adsorption constant of As or Se. The modeling approach was validated by correctly predicting the independent batch leaching data in a broad pH range and a different L/S condition. Experimental and modeling results also demonstrated that ash washing and ash aging (longer leaching time) did not change the adsorption constants of As and Se on the ash surface. However, ash washing could increase the availability of As and Se for leaching.     

氢化物-原子荧光光谱法测定土壤中硒

通过对比实验选择了最佳的仪器测定条件、主要试剂的浓度及土壤的前处理方式。实验结果表明：采用HN03-HClO4酸体系在沙浴中对土壤进行消解，硒的检出限为0．02mg/kg；线性范围为0ug/L～200ug/L；平均回收率可达100％～103％。方法经土壤国家标准物质中硒的测定验证，结果与标准值相符。     

不同硒水平对大豆不同部位累积镉的影响

通过大豆盆栽试验,土壤中Se含量分别为1.56、2.56、3.56、6.56、11.56 mg/kg,研究硒对大豆生物量的影响,大豆茎、叶、果、壳富集Se以及累积Cd的规律。结果表明,适量的Se对大豆累积Cd起缓解作用,其中,除2.56mg/kg体现出硒镉的协同作用外,其它随着土壤中硒的含量的增加,大豆的茎、果、壳、叶累积Cd的含量逐渐降低。同时,大豆的豆粒具有良好的富硒能力,富硒能力的顺序依次是果>叶>茎>壳。