Engineered nanomaterials in rivers--exposure scenarios for Switzerland at high spatial and temporal resolution

Probabilistic material flow analysis and graph theory were combined to calculate predicted environmental concentrations (PECs) of engineered nanomaterials (ENMs) in Swiss rivers: 543 river sections were used to assess the geographical variability of nano-TiO₂, nano-ZnO and nano-Ag, and flow measurements over a 20-year period at 21 locations served to evaluate temporal variation. A conservative scenario assuming no ENM removal and an optimistic scenario covering complete ENM transformation/deposition were considered. ENM concentrations varied by a factor 5 due to uncertain ENM emissions (15%-85% quantiles of ENM emissions) and up to a factor of 10 due to temporal river flow variations (15%-85% quantiles of flow). The results indicate highly variable local PECs and a location- and time-dependent risk evaluation. Nano-TiO₂ median PECs ranged from 11 to 1′623 ng L⁻¹ (conservative scenario) and from 2 to 1′618 ng L⁻¹ (optimistic scenario). The equivalent values for nano-ZnO and nano-Ag were by factors of 14 and 240 smaller.     

Comparing the sensitivity of soil invertebrates to pesticides with that of Eisenia fetida

The sole routine testing of the standard earthworm Eisenia fetida for the terrestrial risk assessment of pesticides has been under much debate since other soil invertebrates may be more sensitive than this standard test species. However, the very low availability of laboratory toxicity data for taxa other than E. fetida has greatly hampered sensitivity comparisons. In the present study, the relative tolerance (T_rel) approach was used to enable comparing toxicity thresholds obtained from the US-EPA ECOTOX database, for main terrestrial taxonomic groups and pesticidal types of action (insecticides, fungicides, herbicides, and other) separately. Analyses confirmed previously reported lower and higher sensitivity of collembolans to fungicides and insecticides, respectively. However, various other discrepancies in susceptibility relative to E. fetida were encountered as indicated by species sensitivity distributions and/or calculated 95% confidence intervals of T_rel values. Arachnids and isopods were found to be more sensitive to insecticides, and nematodes to fungicides, as compared to E. fetida. Implications of study findings for the terrestrial risk assessment of pesticides are discussed.     

大宝山矿区水体和沉积物中重金属的污染评价

分别于丰水期和枯水期对广东省大宝山矿区铁龙拦泥坝至凉桥河段水体中溶解态的重金属进行了调查,应用EPA推荐的健康风险评价模型发现,水体中非致癌物通过饮水途径所导致平均个人年风险排列顺序是Cu〉Pb〉Zn,最大值的平均个人年风险在丰水期和枯水期的平均值分别是2.14×10-7 a-1和4.13×10-7 a-1,小于国际防辐射委员会（ICRP）推荐的最大可接受平均个人年风险5.0×10-5a-1。致癌物Cd的平均个人年风险在丰水期和枯水期的平均值分别是3.52×10-4 a-1和4.53×10-4 a-1,大于ICRP推荐的最大可接受值,同时也大于非致癌物3～4个数量级。另外,通过对枯水期沉积物的重金属总量分析,发现凉桥槽对坑支流受水体pH的影响,导致其沉积物重金属的浓度最高。根据Long和Macdonald利用生物效应数据库法建立的沉积物质量基准,发现除冷水泾外,其他采样点的平均效应中值指数（mERMQ）值都大于1.5,可见沉积物中的重金属会对当地底栖生物产生毒害作用。     

Determination of the residue dynamics and dietary risk of thiamethoxam and its metabolite clothianidin in citrus and soil by LC-MS/MS

A modified quick, easy, cheap, effective, rugged and safe (QuEChERS) method was developed for the determination of thiamethoxam and its metabolite clothianidin in citrus (including the whole citrus, peel and pulp) and soil samples by liquid chromatography-tandem mass spectrometry. The sample was extracted with acetonitrile and purified with octadecylsilane. The detection limits of both compounds were 0.0001–0.0002?mg kg^–1, while the limit of quantification of thiamethoxam was 0.002?mg kg^–1 and the limit of quantitation of metabolites was 0.001?mg kg^–1. The recovery was 70.37%–109.76%, with inter-day relative standard deviations (RSD) (n?=?15) values ≤9.46% for the two compounds in the four matrices. The degradation curve of thiamethoxam in whole citrus and soil was plotted using the first-order kinetic model. The half-life of the whole citrus was 1.9–6.2?days, and the half-life of the soil was 3.9–4.2?days. The terminal residue of thiamethoxam (the sum of thiamethoxam and clothianidin, expressed as thiamethoxam) was found to be concentrated on the peel. The final residual amount of thiamethoxam in the edible portion (pulp) was less than 0.061?mg kg^–1. The risk quotient values were all below 1, indicating that thiamethoxam as a citrus insecticide does not pose a health risk to humans at the recommended dosage.     

Dissipation,residues, and risk assessment of imidacloprid in Zizania latifolia and purple sweet potato under field conditions using LC-MS/MS

A shortened version of Quick, Easy, Cheap, Effective, Rugged, and Safe method (QuEChERS) for determining the dissipation and residue of imidacloprid present in Zizania latifolia and purple sweet potato was established by using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The average recoveries of imidacloprid in the two crops ranged from 82.12 to 113.79%, with relative standard deviation (RSD) of <7.32%. The dissipation dynamics of imidacloprid in Z. latifolia plants and purple sweet potato plants followed first-order kinetics, with half-lives of 3.2–5.5?days in each of sampling locations. The terminal imidacloprid residues in Z. latifolia and purple sweet potato at each of location were <0.005–0.120?mg kg^?1. According to the risk assessment results, both the acute dietary risk quotient and chronic dietary risk quotient values were <1, indicating that imidacloprid is unlikely to pose health risks to humans with normal recommended use. The present study may serve as a valuable reference for the safe and reasonable use of imidacloprid in Z. latifolia and purple sweet potato fields.     

长三角经济能源约束下的大气污染问题及对区域协作的启示

长三角地区大气污染治理取得一定成效,然而空气质量改善逐渐进入瓶颈期和攻坚期,大气污染治理战略需要从宏观层面系统谋划。本文系统分析了近10年来长三角区域经济、能源、产业、交通的发展状况和趋势,结合区域大气污染物浓度水平的演变,分析了大气污染与经济社会发展的耦合关系。结合当前区域空气污染的空间分布差异以及经济能源交通结构的内在差别,识别了大气污染的区内差异特征及关键制约因素。在此基础上,从能源结构和产业结构调整、交通结构优化、分区施策、深化治理等角度,为深化区域大气污染联防联控,持续改善大气污染问题提出了政策建议。     

The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

Assessing the long-term supply risks for mineral raw materials—a combined evaluation of past and future trends

This paper develops a method for identifying and assessing long-term supply risks for mineral raw materials. The method is based on a combined evaluation of past and future supply and demand trends. By analysing raw material boom and bust cycles over the past 50 years, we have quantified indicators and defined benchmarks for identifying critical market situations. By applying the method, risks for supply shortage may be identified at an early stage. In addition, a numerical evaluation model has been developed for better comparison between various mineral raw materials. Compared to other assessment methods this method uses specific benchmarks for each raw material to better assess supply risks. The method is embedded within a systematic and comprehensive analytical approach.     

Balancing environmental and industry sustainability: A case study of the US gold mining industry

Mandatory insurance requirements and/or mitigation fees (royalties) for mining companies may help reduce environmental risk exposure for the federal government. Mining is examined since the Environmental Protection Agency (EPA) Toxic Release Inventory reveals that this sector produces more hazardous waste than any other industrial sector. Although uncommon, environmental expense can exceed hundreds of millions of dollars per development. Of particular concern is the potential for mines to become unfunded Superfund sites. Monte Carlo simulation of risk exposure is used to establish a plausible range of unfunded federal liabilities associated with cyanide-leach gold mining. A model is developed to assess these costs and their impact on both the federal budget and corporate profitability (i.e., industry sustainability), particularly if such costs are borne by offending firms.