Recycling of high purity selenium from CIGS solar cell waste materials

Copper indium gallium diselenide (CIGS) is a promising material in thin film solar cell production. To make CIGS solar cells more competitive, both economically and environmentally, in comparison to other energy sources, methods for recycling are needed. In addition to the generally high price of the material, significant amounts of the metals are lost in the manufacturing process. The feasibility of recycling selenium from CIGS through oxidation at elevated temperatures was therefore examined. During oxidation gaseous selenium dioxide was formed and could be separated from the other elements, which remained in solid state. Upon cooling, the selenium dioxide sublimes and can be collected as crystals. After oxidation for 1 h at 800 °C all of the selenium was separated from the CIGS material. Two different reduction methods for reduction of the selenium dioxide to selenium were tested. In the first reduction method an organic molecule was used as the reducing agent in a Riley reaction. In the second reduction method sulphur dioxide gas was used. Both methods resulted in high purity selenium. This proves that the studied selenium separation method could be the first step in a recycling process aimed at the complete separation and recovery of high purity elements from CIGS.     

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.     

Plant/soil concentration ratios for paired field and garden crops, with emphasis on iodine and the role of soil adhesion

In the effort to predict the risks associated with contaminated soils, considerable reliance is placed on plant/soil concentration ratio (CR) values measured at sites other than the contaminated site. This inevitably results in the need to extrapolate among the many soil and plant types. There are few studies that compare CR among plant types that encompass both field and garden crops. Here, CRs for 40 elements were measured for 25 crops from farm and garden sites chosen so the grain crops were in close proximity to the gardens. Special emphasis was placed on iodine (I) because data for this element are sparse. For many elements, there were consistent trends among CRs for the various crop types, with leafy crops > root crops ≥ fruit crops ≈ seed crops. Exceptions included CR values for As, K, Se and Zn which were highest in the seed crops. The correlation of CRs from one plant type to another was evident only when there was a wide range in soil concentrations. In comparing CRs between crop types, it became apparent that the relationships differed for the rare earth elements (REE), which also had very low CR values. The CRs for root and leafy crops of REE converged to a minimum value. This was attributed to soil adhesion, despite the samples being washed, and the average soil adhesion for root crops was 500 mg soil kg⁻¹ dry plant and for leafy crops was 5 g kg⁻¹. Across elements, the log CR was negatively correlated with log Kd (the soil solid/liquid partition coefficient), as expected. Although, this correlation is expected, measures of correlation coefficients suitable for stochastic risk assessment are not frequently reported. The results suggest that r ≈ −0.7 would be appropriate for risk assessment.     

New best estimates for radionuclide solid–liquid distribution coefficients in soils. Part 3: miscellany of radionuclides (Cd,Co, Ni,Zn, I,Se, Sb,Pu, Am,and others)

New best estimates for the solid–liquid distribution coefficient (K_d) for a set of radionuclides are proposed, based on a selective data search and subsequent calculation of geometric means. The K_d best estimates are calculated for soils grouped according to the texture and organic matter content. For a limited number of radionuclides this is extended to consider soil cofactors affecting soil–radionuclide interaction, such as pH, organic matter content, and radionuclide chemical speciation. Correlations between main soil properties and radionuclide K_d are examined to complete the information derived from the best estimates with a rough prediction of K_d based on soil parameters. Although there are still gaps for many radionuclides, new data from recent studies improve the calculation of K_d best estimates for a number of radionuclides, such as selenium, antimony, and iodine.     

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.     

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。     

碎米荠对硒、镉超富集特性研究

超富集植物在营养元素生物强化及重金属污染植物修复技术领域有重大应用前景。通过野外调查和栽培实验,研究了碎米荠植物对硒镉的吸收富集特征。研究表明:野生碎米荠中Se含量达数百mg/kg,叶片中Se最高含量为1 365 mg/kg。地上部Se的生物富集系数在2.8~43.8的范围内,大部分超过10;生物转移系数在0.46~1.88之间,大部分大于1。地上部Cd含量都超过了100 mg/kg,叶中的Cd含量大部分在400~800 mg/kg之间。富集系数都大于1,且农田及小溪流域植株地上部Cd的生物富集系数高达几十甚至上百,Cd的生物转移系数大部分超过1。露天栽培条件下,碎米荠中的硒镉含量随盆栽土壤中硒镉浓度的上升呈现出先增加后降低的特征,当Se含量为50 mg/kg时植物中的Se含量最高,此时地上部Se含量为995 mg/kg,地下部Se含量1 100 mg/kg。当Cd浓度为80 mg/kg时,植株当中Cd含量最高,地上部和地下部中的Cd含量分别高达550 mg/kg、337 mg/kg。研究认为湖北渔塘坝发育的碎米荠植物是硒镉多元素超富集植物,在硒镉生态环境污染修复方面具有重大应用前景。     

Trace element levels in foetus-mother pairs of short-beaked common dolphins (Delphinus delphis) stranded along the French coasts

Tissues of foetus-mother pairs of common dolphins (Delphinus delphis) stranded along the French coasts (Bay of Biscay and English Channel) were analysed for their Cd, Cu, Hg, Se and Zn contents. In the kidneys, foetal Cd levels were extremely low, and strong relationships between Cu and Zn suggested the involvement of metallothioneins since early foetal life. The results also indicated a limited maternal transfer of Hg during pregnancy since levels in the tissues of foetuses were below 1 microg g(-1) w.wt. However, hepatic Hg levels in foetuses increased with body length, and were also proportionate to maternal hepatic, renal and muscular Hg levels. Lastly, affinities between Hg and Se in tissues would participate in Hg neutralisation in both mothers--through tiemannite granules--and fetuses--through reduced glutathione--counteracting the toxic effects linked to the particularly high quantities of methyl-Hg to which marine mammals are naturally exposed.     

Removal of Se(IV) from aqueous solution using sulphuric acid-treated peanut shell

A carbonaceous sorbent was prepared from peanut shell via sulphuric acid treatment. Se(IV) removal from aqueous solution on the sorbent was studied varying time, pH, Se(IV) concentration, temperature and sorbent status (wet and dry). Se(IV) removal was faster using the wet sorbent than the dry sorbent following a pseudo-first-order model. Se(IV) removal increases at low pH values, and decreases as pH increases until pH 7. Sorption was found to fit the Langmuir equation and sorption capacity for the wet sorbent was higher than that for the dry one. Both sorbents showed an increased selenium sorption by rising the temperature. Redox processes between Se(IV) and the carbon sorbent are involved. Analysis by scanning electron microscope and X-ray powder diffraction for the sorbent after the reaction with acidified Se(IV) confirmed the availability of elemental selenium as particles on the sorbent surface as a result of Se(IV) reduction. Physicochemical tests showed an increase in sorbent acidity, cation exchange capacity (CEC) and surface functionality after the reaction with acidified Se(IV), indicating the oxidation processes occurring on the sorbent surface. Due to its reduction properties, the sorbent seems efficient for Se(IV) removal from aqueous solution.