Terminal double bonds in the alkenes and acetates of defensive secretion from the thrips Suocerathrips linguis Mound & Marullo, 1994 (Thysanoptera: Phlaeothripidae)

Defensive secretions of adult males and females of the subsocial thrips Suocerathrips linguis were examined using gas chromatography–mass spectrometry (GC–MS). The samples contained six long-chain acetates and five aliphatic alkanes and alkenes. Whole-body extracts yielded six methyl esters of fatty acids as well as hexadecyl acetate. Structures of the two main components, (11Z)-icosa-11,19-dienyl acetate and octadecyl acetate, were confirmed. The third most abundant substance was identified as octadec-17-enyl acetate, which is a new natural product. In addition, (9Z)-octadec-9-enyl acetate was identified along with other acetates. Pure icosadienyl acetate was found to remain liquid down to −15°C, and is the solvent for the solid components of the secretion cocktail. A tentative biosynthetic pathway for all of the 12 acetates, alkanes and alkenes is discussed, considering especially the components with terminal double bonds that are uncommon in Thysanoptera and other insects.     

邻苯二甲酸酯在长江重庆段水体的概率风险分析

以长江重庆段水体12个采样断面4种邻苯二甲酸酯（PAEs）的监测结果及水生生物的生态毒性参数无观察效应浓度（NOEC）为基础资料,采用安全阈值和概率曲线分布两种概率风险评价方法分析了邻苯二甲酸酯的相对生态风险。研究结果表明：邻苯二甲酸二甲酯（DMP）、邻苯二甲酸二乙酯（DEP）、邻苯二甲酸正丁酯（DBP）、邻苯二甲酸双（2 乙基己基）酯（DEHP）的安全阈值分别为4 31079、2171、147、199,对水生生物无风险。以5%水生生物物种受影响作为可接受的效应水平终点（HC5）,采用概率曲线分布进行分析,DBP、DEHP的浓度超过毒性值的风险概率分别为106×10-2、235×10-4,4种邻苯二甲酸酯风险大小依次为：DBP>DEHP>DEP>DMP,与安全阈值法结果一致。两种概率风险方法从不同的角度反映了污染物的生态风险。     

Mg/Al水滑石对水中痕量邻苯二甲酸酯的吸附动力学和热力学

研究了Mg／A1水滑石对水中痕量邻苯二甲酸二甲酯（DMP）、邻苯二甲酸二（2一乙基己基）酯（DEHP）和邻苯二甲酸二辛酯（DnOP）的吸附动力学和热力学特性。结果表明,在所研究的浓度范围内,3种邻苯二甲酸酯的吸附动力学曲线均符合准二级速率方程,DMP、DEHP和DnOP分别在600、200和200min基本达到吸附平衡;3种邻苯二甲酸酯的吸附等温线基本符合Langmuir和Freundlich吸附等温方程;在283～308K范围,pH=6．36,3种邻苯二甲酸酯初始浓度均为50μg／L时,吸附过程△H为负值且绝对值为5～12kJ／mol,表明吸附为放热过程,以表面物理吸附为主,邻苯二甲酸酯在Mg／Al水滑石上的吸附是色散力、诱导力、取向力和氢键力等多种作用力协同作用的结果。     

粘土矿物材料吸附去除水中痕量邻苯二甲酸酯

研究了天然沸石、2种有机改性沸石及Mg/Al水滑石对水中痕量邻苯二甲酸二甲酯、邻苯二甲酸二(2-乙基己基)酯和邻苯二甲酸二辛酯的等温吸附情况和吸附机理,并与活性炭的吸附性能进行了比较。结果表明,Freundlich和Langmuir吸附等温方程均可以很好地描述天然沸石和Mg/Al水滑石对邻苯二甲酸酯的吸附,2种有机改性沸石对邻苯二甲酸酯的吸附更符合Linear吸附等温方程。与活性炭相比,天然沸石对邻苯二甲酸酯的吸附效果较差;2种有机改性沸石和Mg/Al水滑石对分子尺寸较小的邻苯二甲酸酯物质邻苯二甲酸二甲酯的去除率较低,分别低31.8%、31.4%和19.8%,但对分子较大的邻苯二甲酸酯物质邻苯二甲酸二(2-乙基己基)酯和邻苯二甲酸二辛酯的去除效果相差不大。     

表面活性剂淋滤对土壤中邻苯二甲酸酯纵向迁移的影响

以无表面活性剂的去离子水为对照、设置1倍(1 CMC)和2倍临界胶束浓度(2 CMC)浓度,研究了单一和混合表面活性剂,包括十六烷基三甲基溴化铵(CTAB)、十二烷基苯磺酸钠(SDBS)和曲拉通X-100(TX-100)对人工污染土壤中邻苯二甲酸酯(PAEs)纵向迁移的影响,土柱中上层为PAEs污染土(3 cm),下层为清洁土(20 cm)。CTAB和SDBS在2 CMC时、TX-100为1 CMC时可增强污染土中PAEs的纵向迁移,其中DMP和DEP有无表面活性剂均可发生迁移,在相同表面活性剂条件下,延长老化时间对污染土中PAEs的迁移产生一定的影响。CTAB和SDBS在2 CMC时,清洁土中PAEs总含量较低,但TX-100在1 CMC时较低。清洁土中PAEs总含量均随土层深度的增加而降低。当老化时间较短时,土壤有机质对PAEs在清洁土柱的迁移影响较小,老化时间的延长对清洁土中的PAEs迁移影响较大。3种表面活性剂均可有效促进清洁土中DMP和DEP的迁移,CTAB和SDBS在2 CMC、TX-100在1 CMC时可促进DNBP和BBP的迁移,但3种表面活性剂对清洁土中DNOP迁移的影响较小。与单一表面活性剂相比,混合表面活性剂有助于污染土中PAEs的迁移,且随着浓度的升高,清洁土中PAEs的含量呈现降低的趋势。就整个土柱而言,单一表面活性剂CTAB和SDBS在较高浓度时、TX-100较低的浓度时对PAEs的淋滤效果更好;在较短老化时间下,土壤有机质含量的高低对淋滤率没有显著影响;老化时间延长有效降低了淋滤率;而混合表面活性剂的淋滤率有明显提高,更有助于PAEs的迁移。     

Sequestration of phorbolesters by the aposematically coloured bug Pachycoris klugii (Heteroptera: Scutelleridae) feeding on Jatropha curcas (Euphorbiaceae)

Summary. The phorbol ester DHPB has been detected in 5th instars and adults of Pachycoris klugii which feed on Jatropha curcas, a producer of phorbol esters with mollusc-, insect-, and vertebrate toxicity. DHPB from Pachycoris activates protein kinase C (PKC) which appears to be the main molecular target for phorbol esters. Phorbol esters of J. curcas exhibit a wide range of acute toxic effects in vertebrates and insects. It is therefore likely that the sequestration of DHPB, which would explain the aposematic colouration of the bugs, confers chemical protection to P. klugii against vertebrate predators. Received 26 April 2000; accepted 31 May 2000     

Cloud point extraction coupled with HPLC-UV for the determination of phthalate esters in environmental water samples

A method based on cloud point extraction was developed to determine phthalate esters including di-ethyl-phthalate （DEP）, di- （2-ethylhexyl）-phthalate （DEHP） and di-cyclohexyl-phthalate （DCP） in environmental water samples using high-performance liquid chromatography separation and ultraviolet detection （HPLC-UV）. The non-ionic surfactant Triton X-114 was chosen as extraction solvent. The parameters affecting extraction efficiency, such as concentrations of Triton X-114 and Na2SO4, equilibration temperature, equilibration time and centrifugation time were evaluated and optimized. Under the optimum conditions, the method can achieve preconcentration factors of 35, 88, 111 and detection of limits of 2.0, 3.8, 1.0 ng/ml for DEP, DEHP and DCP in 10-ml water sample, respectively. The proposed method was successfully applied to the determination of trace amount of phathalate esters in effluent water of the wastewater treatment plant and the lixivium of plastic fragments.     

Anoxic biodegradation of dimethyl phthalate （DMP） by activated sludge cultures under nitrate-reducing conditions

Worldwide extensive use of plasticized plastics has resulted in phthalates pollution in different environment. Nitrates from industry and agriculture are also widely disseminated in the soils, natural waters and wastewaters. Dimethyl phthalate (DMP) biodegradation by activated sludge cultures under nitrate-reducing conditions was investigated. Under one optimized condition, DMP was biodegraded from 102.20 mg/L to undetectable level in 56 h under anoxic conditions and its reaction fitted well with the first-order kinetics. Using the high-performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC-MS) analysis, mono-methyl phthalate (MMP) and phthalic acid (PA) were detected as the major intermediates of DMP biodegradation. When combined with the determination of chemical oxygen demand (CODCr) removal capacity and pH, DMP was found to be mineralized completely under anoxic conditions. The biodegradation pathway was proposed as DMP → MMP → PA → … → CO2 H2O.The molar ratio of DMP to nitrate consumed was found to be 9.0:1, which agrees well with the theoretical stoichiometric values of DMP biodegradation by nitrate-reducing bacteria. The results of the non-linear simulation showed that the optimum pH and temperature for the degradation were 7.56 and 31.4℃, respectively.     

城市污泥中邻苯二甲酸酯的好氧降解规律研究

为评价邻苯二甲酸酯类环境激素在环境中的滞留情况,妥善解决城市污泥的处理处置问题,对城市污泥中6种邻苯二甲酸酯的好氧生物降解规律进行了研究。结果表明,邻苯二甲酸酯的好氧生物降解性随烷基链含碳数的增加而降低;其好氧降解过程可用一级动力学模型描述;其好氧生物降解速率常数与烷基链含碳数、降解半衰期与烷基链含碳数、降解速率常数与正辛醇—水分配系数之间存在良好的相关性。     

太湖重点区域多介质水体中有机磷酸酯的分布特征及来源解析

有机磷酸酯（organophosphate esters,OPEs）具有细胞毒性、遗传毒性、发育毒性、神经毒性和内分泌干扰效应等,大量地使用导致其在多种环境介质中被检出,对生态系统造成潜在风险.本文分析了太湖重点区域（常州地区）典型行业企业废水、污水处理厂进出水和地表水中13种典型OPEs的浓度水平及分布特征,使用相关性分析和主成分分析方法解析地表水中OPEs来源,并评价了其生态风险.结果表明,7家企业废水中∑OPEs浓度为91.70~840.52 ng·L^-1,不同类型企业废水中OPEs组成各有差别,但多以磷酸三（1-氯-2-丙基）酯（TCPP）、磷酸三乙酯（TEP）和磷酸三（2-氯乙基）酯（TCEP）为主.污水处理厂进出水中∑OPEs浓度较高,为1859.59~2778.57 ng·L^-1,且传统污水处理工艺对其去除效果有限,2家污水厂对总∑OPEs去除率分别为14.97%和17.32%,其中对芳香基OPEs的去除率分别为97.91%和90.83%,而对氯代OPEs去除率仅为4.37%和5.40%.在京杭大运河和丹金溧漕河的14个地表水中∑OPEs浓度为219.47~689.85 ng·L^-1,明显低于污水厂进出水中OPEs浓度,主要以TEP、TCPP和TCEP为主.对OPEs来源进行解析,结果表明企业废水排放、废油废气的排放和建筑材料的释放可能是该地区地表水环境中OPEs的主要来源.风险商方法评价结果表明,水体中多数OPEs对水生生物具有较低的风险,但部分点位2-乙基己基二苯基磷酸酯（EHDPP）具有中等生态风险.