长江南京段水源水中有机磷酸酯的污染特征与风险评估

为探究长江南京段水源水中有机磷酸酯(organophosphate esters,OPEs)的污染特征、时空分布、生态风险和健康风险,利用固相萃取-高效液相色谱-串联质谱法测定了13种OPEs.结果表明,除磷酸三(2,3-二溴丙基)酯外,其余12种OPEs均有不同程度的检出,总浓度范围为85. 21～1 557. 96 ng·L~(-1),氯代烷基磷酸酯是主要化合物,其中检出浓度最高的是磷酸三(2-氯乙基)酯[tri(2-chloroethyl) phosphate,TCEP],高达447. 08 ng·L~(-1).长江南京段水源水中OPEs呈现明显的季节变化特征,夏季总检出浓度为220～1557. 96 ng·L~(-1),平均浓度是493. 78 ng·L~(-1),是春秋季的1. 7～2. 6倍.生态风险评估显示磷酸三甲苯酯和2-乙基己基二苯基磷酸酯对有机体(藻类,甲壳类动物和鱼类)具有中或高等风险.高暴露浓度下,OPEs的总非致癌风险为4. 41×10~(-3)～2. 91×10~(-2),均小于1,0～3个月的婴儿最高,总致癌风险值为5. 88×10~(-7)～3. 89×10~(-6),其中TCEP和磷酸三(1,3-二氯-2-丙基)酯对儿童有潜在的致癌风险.长江南京段水源水中OPEs对儿童的长期暴露风险需引起高度重视.     

塑胶跑道中有机磷酸酯的含量及健康风险

采用超声萃取-层析净化-气相色谱/质谱联用仪定量分析塑胶跑道中7种有机磷酸酯(OPEs),方法回收率为71.41%~110.58%,标准曲线相关系数r0.99,质控良好.采集并分析了成都市12个学校内的塑胶跑道样品中OPEs的含量及分布.结果表明2/3学校内的塑胶跑道样品中检出了OPEs,其中磷酸三正丁酯[tri-n-butyl phosphate,TnBP]、磷酸三异辛酯[tris(2-ethylhexyl)phosphate,TEHP]的检出率较高,而磷酸三(2-氯乙基)酯[tri(2-chloroethyl)phosphate,TCEP]、磷酸三(1,3-二氯异丙基)酯[tridichloropropyl phosphate,TDCPP]、磷酸三苯酯[triphenyl Phosphate,TPh P]在所有样品中均未检测到.Σ7OPEs含量范围为ND~534.89 ng·g~(-1),其中单体含量最高的是TnBP(ND~462.18 ng·g~(-1)).一个样品中检出了毒性较大的氯代磷酸酯-TCPP[trichloropropyl phosphate],含量为205.94 ng·g~(-1).成人和儿童通过皮肤接触摄入的Σ7OPEs日均暴露剂量(以bw计)最高,分别为0.14 ng·(kg·d)~(-1)和0.64 ng·(kg·d)~(-1),儿童的日均暴露剂量明显高于成人.成人及儿童的风险熵值(RQ)为10~(-7)~10~(-5).建议政府对塑胶跑道中OPEs使用量及添加种类进行管控,以更好地保护人群健康.     

生物质炭对沉积物中有机污染物的吸附固定作用机理

不同来源生物质炭表面和理化性质差别很大,对沉积物中有机污染物的吸附固定不同.以3种不同来源生物质炭（椰壳粉末、草木灰和聊城电厂灰）为研究对象,应用被动采样技术监测治理过程中污染物浓度的变化,揭示生物质炭理化性质及其与吸附固定效果之间的关系.结果表明:①3种生物质炭粒径相差不大,但椰克粉末的BET比表面积比草木灰和聊城电厂灰高2个数量级,孔隙结构发达.②吸附固定沉积物中有机污染物的静态模拟试验结果显示,椰克粉末对3类有机物（多环芳烃、苯系物和酞酸酯）的吸附固定作用均很强,投加10个月,沉积物孔隙水中3类有机物的质量浓度降低92.7%以上,与其属于非极性吸附剂、BET比表面积大、孔隙结构发达有关;草木灰和聊城电厂灰对酞酸酯的吸附固定作用较弱,分别为62.5%和59.6%,与其表面积小、孔隙结构不发达有关.③生物质炭吸附固定沉积物中有机污染物的动力学研究结果显示,草木灰和聊城电厂灰对酞酸酯的吸附固定作用能很快达到平衡,也与其BET比表面积小、孔隙结构不发达相关.研究显示,生物质炭的理化性质（如BET比表面积、孔隙结构等）是影响有机物污染沉积物治理效果的主要因素.      

酸化蛭石的表面有机修饰及其对疏水性微污染物的吸附

插层法制备有机黏土存在比表面积低、负载不均等问题,限制了此类材料吸附性能的进一步提高.基于此,通过选择性酸浸的方法预处理天然蛭石,以三甲基氯硅烷(CTMS)和三乙基氯硅烷(CTES)对其进行表面有机修饰,利用FTIR、BET、SEM和热重等方法对材料进行表征.结果表明,改性酸化蛭石的比表面积可达361.0 m2.g-1,而有机插层蛭石的比表面积仅为6.0m2.g-1,有机基团更稳定地以共价键形式负载于酸化蛭石表面.以疏水性有机微污染物邻苯二甲酸二乙酯(DEP)为测试目标,考察材料的吸附性能.在本实验条件下,测得CTES改性酸化蛭石、CTMS改性酸化蛭石和有机插层蛭石对DEP的吸附量分别为63.7、51.2和15.7 mg.g-1,证明有机修饰后的酸化蛭石具有更强的疏水性吸附能力,有机负载的均匀性是决定吸附能力的关键因子.动力学研究表明吸附行为遵循拟二级动力学方程;吸附等温线表现出线性特征,可由Henry和Freundlich模型进行描述,表明分配作用是吸附过程的主要机制.     

Efficient microwave-assisted photocatalytic degradation of endocrine disruptor dimethyl phthalate over composite catalyst ZrOx/ZnO

A highly active ZrOx/ZnO catalyst for microwave-assisted photocatalytic (MW/PC) degradation of endocrine disruptor dimethyl phthalate (DMP) has been prepared via cetyltrimethylammonium assisted hydrothermal method. The ZrOx/ZnO was characterized by XPS, XRD, UV-Vis, BET and SEM techniques. The XPS result showed that Zr oxides with different valences (+2, +3, +4) co-existed in ZrOx/ZnO. By using the ZrOx/ZnO (0.1 g), the TOC removal efficiency of DMP (100 mL of 50 mg/L) was 88% after 30 min reaction, which was about 15% higher than P25 TiO2. It was found that the removal process of DMP by MW/PC followed pseudo first-order kinetics in all cases, and ZrOx/ZnO significantly accelerated the degradation of DMP. The degradation half-life time of DMP was shortened 45% compared with P25 TiO2. A possible catalytic mechanism was proposed based on microwave response and interfacial charge transfer. ZrOx/ZnO could be reused for six times without obvious decrease in catalytic activity. The study offers new insights into designing highly efficient catalysts for MW/PC process and is applicable for MW/PC environmental remediation.     

Activated sludge-mediated biodegradation of dimethyl phthalate under fermentative conditions

The biodegradation of dimethyl phthalate(DMP)was investigated under fermentative conditions in this study.The nature of the intermediate compounds and the extent of mineralization were probed using high-pressure liquid chromatography(HPLC)and liquid chromatography-mass spectrometry(LC-MS)methods.The fermentative bacteria were able to biodegrade the DMP under anaerobic conditions,with the biodegradation rate of 0.36 mg DMP/(L·h).The results demonstrated that the DMP degradation under fermentative conditio...     

室内环境中的邻苯二甲酸酯类化合物的研究进展

综述了室内环境中的邻苯二甲酸酯类化合物的存在状况,及其对人的危害。介绍了主要的几种环境中邻苯二甲酸酯类化合物的前处理方法及其分析测定技术。     

环境中的PAES对蟾蜍蝌蚪红细胞微核的影响研究

通过对邻苯二甲酸酯对蟾蜍蝌蚪红细胞微核的影响进行了研究。目的探讨邻苯二甲酸酯对蟾蜍蝌蚪的致突变作用。方法以邻苯二甲酸二甲酯为污染物对蟾蜍蝌蚪染毒24小时,并观察其细胞核变化。所用蟾蜍蝌蚪处于变态期,对污染物较为敏感。结果邻苯二甲酸酯使蟾蜍蝌蚪红细胞微核率以及核异常细胞率上升,微核率随着浓度的增大而上升,在浓度为78 ug/ml,对照组相比有极显著差异P〈0.01,浓度在18.5 ug/ml时试验组突变的细胞核的形态发生显著改变,核异常细胞率与对照组核异常细胞率有显著差异P〈0.05。此时显微镜下观察可见微核、双核、核内凹、核碎裂、无丝分裂时核分裂不均等核的形态变化。结论邻苯二甲酸酯对蟾蜍蝌蚪具有明显的致突变作用。     

常见有机物对催化臭氧化降解水中硝基苯的影响

考察了有机物甲醛、甲醇、甲酸和邻苯二甲酸二丁酯对单独臭氧氧化和蜂窝陶瓷催化臭氧化工艺去除水中硝基苯降解效果的影响规律.单独臭氧氧化和蜂窝陶瓷催化臭氧化对硝基苯的去除率随着甲醛浓度的升高(0～12 mg·L-1)分别降低了11.6%和9.6%;2种工艺对硝基苯的去除率都随着甲醇浓度的增加(0～16mg·L-1,)先增高再降低,单独臭氧氧化和蜂窝陶瓷催化臭氧化分别在浓度为2 mg·L-1和4 mg·L-1时去除率达到最大值;随着甲酸浓度的增加(0～8 mg·L-1)去除率也都先增高再降低,单独臭氧氧化和蜂窝陶瓷催化臭氧化分别在浓度为0.5 mg·L-1和2 mg·L-1时去除率达到最大值;低浓度的甲醇和甲酸促进了硝基苯的降解,高浓度的甲醇和甲酸抑制了硝基苯的降解.单独臭氧氧化和蜂窝陶瓷催化臭氧化在邻苯二甲酸二丁酯浓度增加(0～10 mg·L-1)的情况下对硝基苯的去除率分别降低了19.7%和18.6%.     

Electrochemical incineration of dimethyl phthalate by anodic oxidation with boron-doped diamond electrode

The anodic oxidation of aqueous solutions containing dimethyl phthalate (DMP) up to 125 mg/L with sodium sulfate (Na2SO4) as supporting electrolyte within the pH range 2.0–10.0 was studied using a one-compartment batch reactor employing a boron-doped diamond (BDD) as anode. Electrolyses were carried out at constant current density (1.5–4.5 mA/cm2). Complete mineralization was always achieved owing to the great concentration of hydroxyl radical (.OH) generated at the BDD surface. The e ects of pH, apparent current density and initial DMP concentration on the degradation rate of DMP, the specific charge required for its total mineralization and mineralization current e ciency were investigated systematically. The mineralization rate of DMP was found to be pH-independent and to increase with increasing applied current density. Results indicated that this electrochemical process was subjected, at least partially, to the mass transfer of organics onto the BDD surface. Kinetic analysis of the temporal change of DMP concentration during electrolysis determined by High Performance Liquid Chromatography (HPLC) revealed that DMP decay under all tested conditions followed a pseudo first-order reaction. Aromatic intermediates and generated carboxylic acids were identified by Gas Chromatography- Mass Spectrometry (GC-MS) and a general pathway for the electrochemical incineration of DMP on BDD was proposed.