长三角典型地区土壤环境中Se的空间变异特征及其与人类健康的关系

农业土壤环境中硒（Se）的缺乏或过量都会通过食物链最终影响人类健康。在203个土壤采样点的基础上,利用GIS和地统计学相结合的方法,对江苏省如皋市农田土壤环境中Se的空间变异特征及其影响因素进行分析,同时,对土壤中Se的空间分布与长寿人口的空间分布进行空间叠加分析。研究结果表明,如皋市土壤环境中总Se及水溶态Se的平均含量分别为0.13 mg/kg和2.16 μg/kg,研究区处在相对低Se的土壤环境中。总Se的空间变异性不大,其空间分布比较均一;但水溶态Se的空间变异性较大,主要受成土条件及土壤母质、土壤类型及地形地貌等结构性因子的影响。水溶态Se对土壤的理化性质也比较敏感,特别是速效磷、有机质及全钾含量与水溶态硒的相关性较显著,因此在有机质及土壤养分含量较高、土壤颗粒组成较细的东部及北部地区水溶态硒的含量也较高。土壤水溶态Se的空间分异与长寿人口比率的空间分异呈极显著的正相关关系(〖WTBX〗P〖WTBZ〗<001),相关系数达〖WTBX〗r〖WTBZ〗=0325,表明人类的健康长寿现象与环境中水溶态硒的含量有很大关系,但人类长寿的本质和真正机理仍需进一步研究验证。     

Efficacy of supplementation of selected medicinal mushrooms with inorganic selenium salts

The aim of the study was to evaluate the possibility of supplementation with inorganic forms of selenium (Na₂SeO₄ and Na₂SeO₃) in concentrations of 0, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0 and 1.5 mM of three medicinal mushroom species: Agrocybe aegerita, Hericium erinaceus and Ganoderma lucidum. Tested mushroom species grew in Se additions of 0–0.6 mM (A. aegerita and H. erinaceus), while growth of G. lucidum bodies was observed for 0–0.8 mM. For the latter mushroom species, the total Se content was the highest. Content of Se_org was diverse; for control bodies it was the highest for G. lucidum (only organic forms were present), lower for A. aegerita (84% organic forms) and the lowest for H. erinaceus (56% organic forms). Accumulation of Se(IV) was generally significantly higher than Se(VI) for all tested mushroom species. There was no significant decrease of A. aegerita or G. lucidum biomass with the exception of G. lucidum bodies growing under 0.8 mM of Se species addition (15.51 ± 6.53 g). Biomass of H. erinaceus bodies was the highest under 0.2 (197.04 ± 8.73 g), control (191.80 ± 6.06 g) and 0.1 mM (185.04 ± 8.73 g) of both inorganic salts. The addition to the medium of Se salts brought about macroscopic changes in the fruiting bodies of the examined mushrooms. Concentrations exceeding 0.4 mM caused diminution of carpophores or even their total absence. In addition, colour changes of fruiting bodies were also recorded. At Se concentrations of 0.4 and 0.6 mM, A. aegerita fruiting bodies were distinctly lighter and those of H. erinaceus changed colour from purely white to white-pink.     

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.     

X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by Fe-bearing minerals

The long-lived radionuclide ⁷⁹Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (Se^VIO₄²⁻) and selenite (Se^IVO₃²⁻). Previous investigations have demonstrated, however, that Se^IV and Se^VI are reduced by surface-associated Fe^II, thereby forming insoluble Se⁰ and Fe selenides. Here we show that the mixed Fe^II/^III (hydr)oxides green rust and magnetite, and the Fe^II sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the Fe^II carbonate siderite produces elemental Se. In the case of mackinawite, both S^−II and Fe^II surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these Fe^II systems is controlled by the concentration of HSe⁻; Se⁰ forms only at lower HSe⁻ concentrations related to slower HSeO₃⁻ reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe²⁺-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 × 10^− 8 M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since Fe^II phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product ⁷⁹Se may be much lower than previously assumed.     

混合酸消解变化对土壤和沉积物中痕量硒分析影响

基于各3种采集环境样本、国家标准物质的土壤和沉积物,以当前环境监测行业常用的3种消解方法,探讨20种混合酸系统条件在消解条件变化中对复杂样本硒元素测定的影响。确定了最佳土壤和沉积物消解的组合为王水系统(盐酸∶硝酸∶氢氟酸∶过氧化氢∶高氯酸=3∶1∶1∶1∶1),各消解法的处理结果部分(n=5)∶水浴法消解时间仅需0.5h,总处理时间2h,准确度回收率达101%~104%,精密度RSD为1.95%~2.20%;电热板法总处理时间较长(7.5h),回收率106%,RSD偏高为8.46%,不推荐使用;微波法处理的总时间亦长达7.0h,回收率93.8%,但精密度亦偏高为8.24%,因此采用水浴法应用于环境样本的测定。该优化消解方法已直接应用于环境中农业、建筑用土和管道淤泥沉积物的3种样品类型前处理,利用同一优化条件即可快速对应土壤和沉积物性质样品,单次可批量处理72~84个样本,解决高通量样品痕量硒测定需求,提供环境污染监测和检测行业一参考依据。     

Biological effects of selenium and relationships with carcinogenesis†

Selenium is an element that is both essential, at low levels of dietary intake, and toxic, at high levels, to man and a wide range of animals. The purpose of the communication is to review the evidence for the involvement of hyper‐ and hypo‐selenosis in the aetiology of cancer. High levels of selenium intake have been blamed for an increase in cancer, dental caries and an array of other conditions. Critical evaluation of the evidence, however, leads to the conclusion that such claims have little substance. On the other hand, low levels of selenium intake may be associated with an increased incidence of certain forms of cancer and there appears to be an inverse relationship between blood selenium levels and cancer death rate in the United States. Keshan Disease, in the People's Republic of China has only been shown to occur in populations severely depleted of selenium. In well nourished populations there is no evidence to indicate that selenium supplements have any prophylactic or therapeutic benefit against human diseases such as cancer, cardiovascular disease or cystic fibrosis.     

The biogeochemistry of selenium in Sunan grassland,Gansu, Northwest China,casts doubt on the belief that Marco Polo reported selenosis for the first time in history

In order to clarify the historic academic problem of whether or not livestock poisoning in ancient Suzhou of Northwest China, recorded by Marco Polo in 1295, was selenosis, this study deals with the biogeochemistry of selenium in Sunan County in the Hexi Corridor, which is part of ancient Suzhou in China. It was found that quite a number of farm animals had suffered from intoxication and died as a result of grazing poisonous grasses, mostly Oxytropis DC, Stellera chamaejasme, and Achnatheru inebrians. Toxic symptoms of livestock grazing on Oxytropis DC are similar to those of selenium toxicity, for instance, hair loss and hoof lesions as described by Marco Polo. Therefore, we thought that toxic grass, probably Oxytropis DC, led to the intoxication of livestock recorded by Marco Polo. Average Se concentrations in two members of this species were 0.112 +/- 0.038 mg/kg for the root of Oxytropis glabra, 0.102 +/- 0.027 mg/kg for the stem and leaf of Oxytropis glabra, and 0.066 +/- 0.009 mg/kg for Oxytropis ochrocephala. The average soil selenium concentration was 0.205 +/- 0.127 mg/kg on grassland producing Oxytropis glabra and 0.152 +/- 0.024 mg/kg on grassland producing Oxytropis ochrocephala. The average Se concentration in other plants was 0.076 mg/kg in the root of Ephedra monosperma Mey, 0.029 mg/kg in the root of Rheum palmatum, 0.031 mg/kg in the root of Stellera chamaejasme, 0.037 mg/kg in Achnatherum inebrians, and 0.067 mg/kg in forage grass (Achnatherum splendens ohwi). Selenium concentrations in soils and plants in Sunan County are far less than the thresholds causing selenium toxicity in livestock. As a result, this study concludes that the livestock poisoning recorded by Marco Polo in 1295 might not have been selenosis.     

溴酸钾—酸性铬红—CTMAB动力学光度法测定硒的研究

根据痕量硒（Ⅳ）对溴酸钾氧化酸性铬红的褪色催化作用,建立了一种测定硒的新方法。检出限为4μg／L,硒的含量在20～240μg／L内符合比耳定律。方法用于食品中硒的测定,结果满意。     

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.