华北农村水环境污染评价及源解析

近年来,国家相继发布多项重要文件要求整治农村人居环境、建设美丽乡村,但当前针对农村水环境问题研究相对较少,制约了农村环境治理工作开展。选取华北某镇农村河道坑塘,评价农村水环境污染水平、生态风险并进行污染溯源。结果表明,57处调查点位中有1处水体黑臭,但有多处调查点位水体溶解氧在2~3 mg∙L⁻¹、透明度在25~35 cm、氨氮在8~15 mg∙L⁻¹,接近黑臭阈值。仅有约9%的水体全部水质指标均能满足地表水V类要求 (检测指标为18项) ,超标指标主要为pH、COD_Mn、BOD、氨氮、总磷、总氮、粪大肠菌群等8项。底泥总磷、总氮标准指数分别处于中度、重度污染状态,营养盐综合指数属于重度污染状态。底泥存在不同程度的重金属富集,铜、锌、汞、镉、铬、铅、砷、镍等8项重金属的平均浓度是天津土壤背景值的0.45~2.73倍。汞的地累积指数平均值为0.64,为轻度污染;铜、锌、镉、铬、铅、砷、镍等其他7项重金属为清洁状态。汞的潜在生态风险指数约110,为较高生态危害;其他7项重金属生态风险指数均小于80,为轻微生态危害。综合Pearson相关性、主成分及PMF分析,研究区重金属最主要的污染来源是交通源和大气沉降,其次是工业源,最后是农业源。总体来看,研究区水体水质较差,沉积物有重金属轻度富集,其中汞是沉积物生态风险的主要贡献元素。     

电极材料对电解法处理循环式准好氧垃圾填埋场渗滤液效果的影响研究

分别用3种不同材料电极（不锈钢、Ti／Pt和Ti／RuO2-IrO2）作阳极、石墨电极作阴极在同一条件下分别对循环式准好氧填埋垃圾场渗滤液进行电解处理对比研究。研究结果表明，随着电解时间的变化，渗滤液中的COD、BOD5、BOD5／COD、重金属离子浓度、色度和pH值均会发生改变。当电解时间为10—20min时，用上述3种电极作阳极电解均会出现渗滤液COD、BOD5、BOD5／COD增大的现象；当电解时间为30—40min时，用Ti／RuO2-IrO2或Ti／Pt电极作阳极电解均可使渗滤液的色度降为0；当电解时间为120min时，分别用3种电极作阳极电解都可使渗滤液中的COD、BOD5和重金属得到有效的去除，其中用Ti／RuO2-IrO2电极作阳极电解对COD、BOD5的去除效果最好：用Ti／Pt电极作阳极电解对Pb^2＋的去除效果最好。     

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.     

Insights into aqueous carbofuran removal by modified and non-modified rice husk biochars

Biochar has been considered as a potential sorbent for removal of frequently detected pesticides in water. In the present study, modified and non-modified rice husk biochars were used for aqueous carbofuran removal. Rice husk biochars were produced at 300, 500, and 700 °C in slow pyrolysis and further exposed to steam activation. Biochars were physicochemically characterized using proximate, ultimate, FTIR methods and used to examine equilibrium and dynamic adsorption of carbofuran. Increasing pyrolysis temperature led to a decrease of biochar yield and increase of porosity, surface area, and adsorption capacities which were further enhanced by steam activation. Carbofuran adsorption was pH-dependant, and the maximum (161 mg g^?1) occurred in the vicinity of pH 5, on steam-activated biochar produced at 700 °C. Freundlich model best fitted the sorption equilibrium data. Both chemisorption and physisorption interactions on heterogeneous adsorbent surface may involve in carbofuran adsorption. Langmuir kinetics could be applied to describe carbofuran adsorption in a fixed bed. A higher carbofuran volume was treated in a column bed by a steam-activated biochar versus non-activated biochars. Overall, steam-activated rice husk biochar can be highlighted as a promising low-cost sustainable material for aqueous carbofuran removal.     

Bringing together raptor collections in Europe for contaminant research and monitoring in relation to chemicals regulations

Raptors are good sentinels of environmental contamination and there is good capability for raptor biomonitoring in Europe. Raptor biomonitoring can benefit from natural history museums (NHMs), environmental specimen banks (ESBs) and other collections (e.g. specialist raptor specimen collections). Europe’s NHMs, ESBs and other collections hold large numbers of raptor specimens and samples, covering long periods of time. These collections are potentially a valuable resource for contaminant studies over time and space. There are strong needs to monitor contaminants in the environment to support EU and national chemical management. However, data on raptor specimens in NHMs, ESBs and other collections are dispersed, few are digitised, and they are thus not easy to access. Specimen coverage is patchy in terms of species, space and time. Contaminant research with raptors would be facilitated by creating a framework to link relevant collections, digitising all collections, developing a searchable meta-database covering all existing collections, making them more visible and accessible for contaminant research. This would also help identify gaps in coverage and stimulate specimen collection to fill gaps in support of prioritised contaminant monitoring. Collections can further support raptor biomonitoring by making samples available for analysis on request.     

The effects and the toxicity increases caused by bicarbonate,chloride, and other water components during the UV/TiO<Subscript>2</Subscript> degradation of oxazaphosphorine drugs

The influences of HCO₃ ^?, Cl^?, and other components on the UV/TiO₂ degradation of the antineoplastic agents ifosfamide (IFO) and cyclophosphamide (CP) were studied in this work. The results indicated that the presence of HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2? in water bodies resulted in lower degradation efficiencies. The half-lives of IFO and CP were 1.2 and 1.1 min and increased 2.3–7.3 and 3.2–6.3 times, respectively, in the presence of the four anions (initial compound concentration = 100 μg/L, TiO₂ loading =100 mg/L, anion concentration = 1000 mg/L, and pH = 8). Although the presence of HCO₃ ^? in the UV/TiO₂/HCO₃ ^? system resulted in a lower degradation rate and less byproduct formation for IFO and CP, two newly identified byproducts, P11 (M.W. = 197) and P12 (M.W. = 101), were formed and detected, suggesting that additional pathways occurred during the reaction of ?CO₃ ^? in the system. The results also showed that ?CO₃ ^? likely induces a preferred ketonization pathway. Besides the inorganic anions HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2?, the existence of dissolved organic matter in the water has a significant effect and inhibits CP degradation. Toxicity tests showed that higher toxicity occurred in the presence of HCO₃ ^? or Cl^? during UV/TiO₂ treatment and within 6 h of reaction time, implying that the effects of these two anions should not be ignored when photocatalytic treatment is applied to treat real wastewater.     

Investigation of low-level <Superscript>242</Superscript>Pu contamination on nutrition disturbance and oxidative stress in <Emphasis Type="Italic">Solanum tuberosum</Emphasis> L.

Plutonium associated with higher molecular weight molecules is presumed to be poorly mobile and hardly plant available. In our present study, we investigate the uptake and effects of Pu treatments on Solanum tuberosum plants in amended Hoagland medium at concentrations of [²⁴²Pu] = 100 and 500 nm, respectively. We found a direct proof of oxidative stress in the plants caused by these rather low concentrations. For the confirmation of oxidative stress, we explored the production of nitric oxide (NO) and hydrogen peroxide (H₂O₂) by epifluorescence microscopy. Oxidative stress markers like lipid peroxidation and superoxide radicals (O₂ ^??) are monitored through histochemical analysis. The biochemical parameters i.e. chlorophyll and carotenoids are measured as an indicator of cellular damage in the tested plants including the enzymatic parameters such as catalase and glutathione reductase. From our work, we conclude that Pu in low concentration has no significant effects on the uptake of many trace and macroelements. In contrast, the content of O₂ ^?? , malondialdehyde (MDA), and H₂O₂ increases with increasing Pu concentration in the solution, while the opposite effects was found for NO, catalase, and glutathione reductase. These findings prove that even low concentration of Pu regulates ROS production and generate oxidative stress in S. tuberosum L.     

Application of chemical oxidation to remediate HCH-contaminated soil under batch and flow through conditions

This is the first study describing the chemical oxidation of hexachlorocyclohexanes (HCHs) in contaminated soil under water saturated and unsaturated flow through conditions. Soil contaminated with β-HCH (45 mg kg^?1) and γ-HCH (lindane, 25 mg kg^?1) was sampled from former lindane waste storage site. Efficiency of following treatments was tested at circumneutral pH: H₂O₂ alone, H₂O₂/Fe^II, Na₂S₂O₈ alone, Na₂S₂O₈/Fe^II, and KMnO₄. Experimental conditions (oxidant dose, liquid/solid ratio, and soil granulometry) were first optimized in batch experiments. Obtained results revealed that increasing dose of H₂O₂ improved the oxidation efficiency while in Na₂S₂O₈ system, maximum HCHs were removed at 300 mM. However, oxidation efficiency was slightly improved by Fe^II-activation. Increasing the solid/liquid ratio decreased HCH removal in soil samples crushed to 500 μm while an opposite trend was observed for 2-mm samples. Dynamic column experiments showed that oxidation efficiency followed the order KMnO₄ > Na₂S₂O₈/Fe^II > Na₂S₂O₈ whatever the flow condition, whereas the removal extent declined at higher flow rate (e.g., ~50% by KMnO₄ at 0.5 mL/min as compared to ~30% at 2 mL/min). Both HCH removal and oxidant decomposition extents were found higher in saturated columns than the unsaturated ones. While no significant change in relative abundance of soil mineral constituents was observed before and after chemical oxidation, more than 60% of extractable organic matter was lost after chemical oxidation, thereby underscoring the non-selective behavior of chemical oxidation in soil. Due to the complexity of soil system, chemical oxidation has rarely been reported under flow through conditions, and therefore our findings will have promising implications in developing remediation techniques under dynamic conditions closer to field applications.     

Assessing demineralization treatments for PVC effluent reuse in the resin polymerization step

To reduce fresh water consumption in a polyvinyl chloride (PVC) plant, the effluent from a biological treatment must be demineralized to be re-used in the resin polymerization process. Demineralization is a critical process, since the quality and the stability of the PVC resins are highly influenced by the water quality used in the process. The main target values for water parameters are the following: conductivity <10 μScm^?1, TOC < 10 mg L^?1, and Al < 0.1 mg L^?1. To achieve this quality, several reverse osmosis membranes from different materials and suppliers were tested and compared in the demineralization treatment. Polyamide membranes showed higher salt rejection compared to cellulose acetate membranes yielding both types similar flux and permeability. Two-pass reverse osmosis treatment was necessary to reach conductivities lower than 10 μS cm^?1. On the other hand, a good quality effluent for reuse was obtained by combining RO and ionic exchange resins. Results showed that good quality PVC resins in terms of color, granulometry, porosity, and bulk density were obtained when demineralized water from two-pass reverse osmosis was used as fresh water, proving the feasibility of the effluent reuse in the PVC industry.     

Fenton试剂-生物法联合处理有机废水研究进展

本文对Fenton试剂和生物法联合处理有机废水的工艺流程、适用废水种类、废水处理机理和衡量指标进行了综述,并对Fenton试剂和生物法相结合处理有机废水研究进行了展望。