固相微萃取-气相色谱/质谱联用法测定饮用水中苯类化合物

用固相微苹取(ＳＰＭＥ)－气相色谱/质谱联用法测定饮用水中苯类化合物,以１００μｍ ＰＤＭＳ(聚二甲基硅氧烷)萃取针提取、浓缩、分离与测定九种目标化合物．萃取时间经优化选定为８ｍｉｎ,而热解析时间设定为２ｍｉｎ． 本方法的相对标准偏差小于５%,线性范围宽(２０ｎｇ·ｍｌ－１－１００００ｎｇ·ｍｌ－１),多数化合物的检测限低于５μｇ·ｌ－１．饮用水样品检测显示,样品加标回收率范围在８４%至１１０%内．     

Assessment of trace element contamination in sediment cores from the Pearl River and estuary,South China: geochemical and multivariate analysis approaches

Twenty-four major and trace elements and the mineralogical composition of four sediment cores along the Pearl River and estuary were analyzed using ICP-AES, ICP-MS, and X-ray diffraction (XRD) to evaluate contamination levels. The dominant minerals were quartz, kaolinite, and illite, followed by montmorillonite and feldspars, while small amounts of halite and calcite were also observed in a few samples. Cluster analysis (CA) and principal component analysis (PCA) were performed to identify the element sources. The highest metal concentrations were found at Huangpu, primarily due to wastewater treatment plant discharge and/or the surreptitious dumping of sludge, and these data differed from those of other sources. Excluding the data from Huangpu, the PCA showed that most elements could be considered as lithogenic; few elements are the combination of lithogenic and anthropogenic sources. An antagonistic relationship between the anthropogenic source metals (K, Ba, Zn, Pb, Cd, Ag, Tl, and U) and marine source metals (Na, Mg, Ti, V, and Ca) was observed. The resulting normalized Al enrichment factor (EF) indicated very high or significant pollution of Cd, Ag, Cu, Zn, Mo, and Pb at Huangpu, which may cause serious environmental effects. Conflicting results between the PCA and EF can be attributed to the background values used, indicating that background values must be selected carefully.     

Effects of adsorption onto silica sand particles on the hydrolysis of tetracycline antibiotics

Due to high usage of tetracycline antibiotics, concerns have been raised about their environmental fate. In this study, potential changes in the pseudo-first-order hydrolysis rate constants for three tetracyclines, tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC), were evaluated by measuring the rate constants in batch and column leaching experiments. The first-order hydrolysis rate constants were measured at pH 5, 7, and 9 using batch tests. The values were highest at pH 7 for all three tetracyclines (0.0030 ± 0.0004, 0.0042 ± 0.0001, and 0.0323 ± 0.0003 h(-1) for TC, OTC, and CTC, respectively), indicating relatively short environmental half-lives of tetracyclines. Interestingly, it was found that the rates of degradation of the parent tetracyclines were much faster when silica sand was present in a batch solution or when the solution was passed through a silica column. For example, the ratios of the first-order degradation rate constants obtained in the column experiments to those in batch experiments were 13.2, 2.1, and 2.0 for TC, OTC, and CTC at a volumetric flow rate of 0.08 mL h(-1), with an observed tendency for this ratio to increase with an increased flow rate. This indicates that the silica surface may serve as a catalyst for hydrolysis and that the actual environmental half-lives of tetracycline antibiotics could be shorter than those estimated from laboratory hydrolysis rate constants using the standard batch protocol. Furthermore, the toxicity of the column effluent containing hydrolysis metabolites was assessed using bioluminescence inhibition in Vibrio fischeri. It was estimated that the toxicity of the metabolites of CTC was lower than that of their parent compound, whereas the toxicity of metabolites of TC and OTC was as high as or higher than that of their parent compounds.     

水样发光细菌急性毒性测试的方式与表征

选取不同类型的环境和污染源水样开展了发光细菌毒性测试,针对不同环境管理目标,探讨了急性毒性定量表征方式。发光细菌急性毒性测试在环境应急监测、水源早期生物预警中,采用绘制毒性预警基线图的方式比较可行。在污染源监督监测中,对于发光抑制率低于60%、无法求出EC50的样品,采用等效毒性参照物的质量浓度表征废水的毒性;对于发光抑制率高于60%,采用稀释因子表示样品的毒性更直观可靠。     

Investigation of organic pollutants in wastewater-irrigated soil and its DNA damage and oxidative damage on mice

This work aimed to determine the DNA and oxidative damage on mice by mixtures of organic contaminants in wastewater-irrigated soil, in order to assess their usefulness as markers for this kind of pollution. Wastewater-irrigated soil samples in the vicinity of an industrial area in Tangshan, China were collected, and soil irrigated by underground water satisfying drinking water standards was used as control group. Organic pollutants were extracted from the soil using ultrasonic oscillation, and analyzed by gas chromatography–mass spectrometry (GC-MS). Meanwhile, DNA damage on mice was determined by the Comet assay after oral gavage with the extracts, and changes in total superoxide dismutase (T-SOD) activity, glutathione peroxidase glutathione, GSH peroxidase (GSH-P_X) activity and malondialdehyde content in serum of mice were investigated. The number of categories and concentrations of organic compounds in the wastewater-irrigated soil is more than those in groundwater-irrigated soil, as identified by the GC-MS. The toxicity test of mice showed that compared with reagent control group, the activities of T-SOD and GSH-P_X decreased; the tailing rate of peripheral blood lymphocyte of mice increased and was more than that of the control group. This shows that mammalian toxicity end points can be used to determine the joint toxicity of organic pollutants in soil. When there is no means to identify each and every pollutant in soil, it is feasible to evaluate the combined effects of various pollutants to determine the extent to which the soil is polluted.     

Biodegradation of Poly(Aspartic Acid-Itaconic Acid) Copolymers by Miscellaneous Microbes from Natural Water

Poly(aspartic acid-itaconic acid) copolymers (PAI) is a new scale inhibitor for water treatment. Thus, it is necessary to investigate its biodegradability. The biodegradability of PAI was investigated through CO₂ evolution tests under different conditions based on determination of carbon dioxide production. The investigation results showed that the degradation rate of PAI on day 10 and day 28 were respectively 38.7 and 79.5%, indicating that PAI was one kind of easily biodegradable scale inhibitors. With the increase in the content of itaconic acid in copolymerization process, the biodegradability of PAI was significantly reduced. In addition, the high biodegradability might be attributed to the existence of C–N bone-structure and more –COO–. Finally, Cu²⁺ could decrease the degradation percentage and the enzyme inhibition effect of Cu²⁺ was not the linear effect, but the “low-dosage effect”.     

钙钛矿型催化剂催化湿式氧化处理煤气化废水纳滤浓缩液

采用溶胶-凝胶法制备了Mn掺杂钙钛矿型催化剂LaFexMn1-xO3,并以其为催化剂催化湿式双氧水氧化处理煤气化废水纳滤浓缩液。采用XRD,SEM,FTIR技术对催化剂进行了表征。表征结果显示：制备的催化剂均具有标准的钙钛矿型结构,其中,LaFe0.9Mn0.1O3的结构稳定,比表面积大。实验结果表明：制备的催化剂中LaFe0.9Mn0.1O3的催化活性最高,且稳定性好,连续使用5次后催化活性未见明显减弱;在H2O2投加量3.0 g/L、n（H2O2）∶n（LaFe0.9Mn0.1O3）=12∶1、反应温度160 ℃、反应压力1 MPa、浓缩液pH 3、反应时间60 min的最优条件下,COD、UV254和TOC的去除率分别达到80.9%、95.2%和68.0%,BOD5/COD由0.02提升至0.40,可生化性大幅提高。     

Absorption characteristics of potassium carbonate-based solutions with rate promoters and corrosion inhibitors

In this research, absorbents for CO₂ capture were prepared by blending 30 wt% potassium carbonate, 3 wt% of a rate promoter, and 1 wt% of a corrosion inhibitor. Pipecolic acid, sarcosine, and diethanolamine were chosen as rate promoter candidates. Based on a rate promoter screening test for CO₂ loading capacity and absorption rate, pipecolic acid and sarcosine were selected to be used as rate promoters. 1,2,3-benzotriazole and ammonium thiocyanate were chosen as corrosion inhibitors, and they were mixed with a 30 wt% potassium carbonate-based absorbent mixture containing one of the rate promoters. The absorption rates for four absorbent solutions (30 wt% potassium carbonate?+?3 wt% pipecolic acid?+?1 wt% 1,2,3-benzotriazole, 30 wt% potassium carbonate?+?3 wt% pipecolic acid?+?1 wt% ammonium thiocyanate, 30 wt% potassium carbonate?+?3 wt% sarcosine?+?1 wt% 1,2,3-benzotriazole, and 30 wt% potassium carbonate?+?3 wt% sarcosine?+?1 wt% ammonium thiocyanate) were measured, tabulated, and graphically displayed. These types of absorbents can be used for capturing CO₂ under high temperature and pressure conditions, such as those found in coal-fired power plants.     

计算毒理学在内分泌干扰物筛选上的应用和展望

内分泌干扰物通过干扰内分泌系统导致多种疾病,如生殖疾病、肥胖症甚至癌症。然而,面对环境中大量潜在的内分泌干扰物,传统的体外、体内评估方法由于成本高、耗时长等问题,难以实现内分泌干扰物的高通量筛查。计算毒理学逐渐发展成为被美国环保局(Environmental Protection Agency,EPA)、经济合作与发展组织(Organization for Economic Co-operation and Development,OECD)等机构所推荐的内分泌干扰物筛选与预测方法。本文综述了计算毒理学在内分泌干扰物筛选上的进展,主要包括分子对接和分子动力学模拟的应用,并对有害结局路径(adverse outcome pathway,AOP)的方法进行介绍和展望。     

Investigation of titanium liquid/gas diffusion layers in proton exchange membrane electrolyzer cells

In a proton exchange membrane electrolyzer cell (PEMEC), liquid/gas diffusion layer (LGDL) is expected to transport electrons, heat, and reactants/products to and from the catalyst layer with minimum voltage, current, thermal, interfacial, and fluidic losses. In addition, carbon materials, which are typically used in PEM fuel cells (PEMFCs), are unsuitable in PEMECs due to the high ohmic potential and highly oxidative environment of the oxygen electrode. In this study, a set of titanium gas diffusion layers with different thicknesses and porosities are designed and examined coupled with the development of a robust titanium bipolar plate. It has been found that the performance of electrolyzer improves along with a decrease in thickness or porosity of the anode LGDL of titanium woven meshes. The ohmic resistance of anode LGDL and contact resistance between anode LGDL and the anode catalyst play dominant roles in electrolyzer performance, and better performance can be obtained by reducing ohmic resistance. Thin titanium LGDLs with straight-through pores and optimal pore morphologies are recommended for the future developments of low-cost LGDLs with minimum ohmic/transport losses.