西湖景区土壤中邻苯二甲酸酯污染水平、来源分析和空间分布特征

为考察杭州西湖景区土壤环境中邻苯二甲酸酯(phthalate esters,PAEs)的污染情况,本研究采集了西湖景区4种不同土地利用类型土壤共42个土壤样品,利用气相色谱三重四级杆质谱联用仪(GC-MS/MS)对所有样品中6种PAEs的含量水平和组成情况进行了分析,并采用主成分分析法和普通克里金插值法对不同土地利用类型土壤中PAEs的来源与空间分布进行了详细探讨.结果表明,西湖景区6种邻苯二甲酸酯累计含量(ΣPAEs)范围为597. 6～7 360. 1μg·kg~(-1),邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二正丁酯(DBP)和邻苯二甲酸二(2-乙基)己酯(DEHP)是3种主要的PAEs污染物,三者总含量平均值贡献率高达98. 43%,而DEHP作为含量最高的PAEs单体贡献率为66. 28%;不同土地利用类型土壤中的PAEs组成由于其来源不同而具有差异性,交通运输与游客活动是西湖景区内PAEs的主要来源; 6种PAEs主要分布在西湖景区的东北区域,呈现出由北向南、自东向西递减趋势.     

臭氧降解水中邻苯二甲酸二甲酯的动力学及影响因素

利用臭氧(O3)降解含较高浓度邻苯二甲酸二甲酯(DMP)的模拟废水,采用竞争动力学法,以硝基苯为参比有机物,获得了DMP与O3及羟基自由基(·OH)的反应速率常数,研究了·OH抑制剂叔丁醇(TBA)、pH和多种离子对O3降解DMP效果的影响.结果表明,O3降解DMP符合拟一级动力学,DMP与O3的反应速率常数kO3-DMP为(0.064±0.014)L.(mol·s)-1,与·OH的反应速率常数k·OH-DMP为3.59×109L.(mol·s)-1;O3降解DMP过程中,生成的羧酸类中间产物使弱酸或弱碱性反应液的pH下降,但不足以影响强酸或强碱性反应液的pH;降解过程中产生大量中间产物使COD的去除率滞后于DMP的降解率,且部分中间产物不易被矿化;较低浓度的TBA不足以抑制·OH与DMP反应,当TBA的浓度增大到DMP的90.21倍时,DMP的降解率由98.7%降为8.8%,已经基本抑制了·OH与DMP的反应;用磷酸盐缓冲溶液调节反应液pH,DMP的降解效果优于用NaOH/H2SO4调节;水中常见低浓度阴阳离子对DMP的降解效果没有影响,高浓度SO24-、NO3-和HPO24-对DMP降解效果的影响相对较小,高浓度Cl-和HCO3-对DMP的降解有抑制作用,且HCO3-的影响大于Cl-,当Cl-和HCO3-的浓度分别为7 097 mg·L-1和6 093 mg·L-1时,反应40 min,DMP降解率分别为50.5%和26.2%.     

Hydrolysis of di-n-butyl phthalate, butylbenzyl phthalate and di(2-ethylhexyl) phthalate in human liver microsomes

Diester phthalates are industrial chemicals used primarily as plasticizers to import flexibility to polyvinylchloride plastics. In this study, we examined the hydrolysis of di-n-butyl phthalate (DBP), butylbenzyl phthalate (BBzP) and di(2-ethylhexyl) phthalate (DEHP) in human liver microsomes. These diester phthalates were hydrolyzed to monoester phthalates (mono-n-butyl phthalate (MBP) from DBP, mono-n-butyl phthalate (MBP) and monobenzyl phthalate (MBzP) from BBzP, and mono(2-ethylhexyl) phthalate (MEHP)) by human liver microsomes. DBP, BBzP and DEHP hydrolysis showed sigmoidal kinetics in V-[S] plots, and the Hill coefficient (n) ranged 1.37-1.96. The S₅₀, V_max and CL_max values for DBP hydrolysis to MBP were 99.7 μM, 17.2 nmol min⁻¹ mg⁻¹ protein and 85.6 μL min⁻¹ mg⁻¹ protein, respectively. In BBzP hydrolysis, the values of S₅₀ (71.7 μM), V_max (13.0 nmol min⁻¹ mg⁻¹ protein) and CL_max (91.3 μL min⁻¹ mg⁻¹ protein) for MBzP formation were comparable to those of DBP hydrolysis. Although the S₅₀ value for MBP formation was comparable to that of MBzP formation, the V_max and CL_max values were markedly lower (<3%) than those for MBzP formation. The S₅₀, V_max and CL_max values for DEHP hydrolysis were 8.40 μM, 0.43 nmol min⁻¹ mg⁻¹ protein and 27.5 μL min⁻¹ mg⁻¹ protein, respectively. The S₅₀ value was about 10% of DBP and BBzP hydrolysis, and the V_max value was also markedly lower (<3%) than those for DBP hydrolysis and MBzP formation for BBzP hydrolysis. The ranking order of CL_max values for monoester phthalate formation in DBP, BBzP and DEHP hydrolysis was BBzP to MBzP ? DBP to MBP > DEHP to MEHP > BBzP to MBP. These findings suggest that the hydrolysis activities of diester phthalates by human liver microsomes depend on the chemical structure, and that the metabolism profile may relate to diester phthalate toxicities, such as hormone disruption and reproductive effects.     

Study on the mechanism of action between dimethyl phthalate and herring sperm DNA at molecular level

Dimethyl phthalate (DMP), a typical phthalic acid ester, is widespread in the environment and causes extensive concern due to its adverse effects on human health. To understand the genotoxicity of DMP at molecular level, the toxic interaction of DMP with herring sperm (hs) deoxyribonucleic acid (DNA; hs-DNA) was investigated in vitro under simulated physiological conditions using multi-spectroscopic techniques and a molecular modeling method. The results of Ultraviolet-Visible absorption spectroscopy, fluorescence emission spectroscopy, and circular dichroism spectra indicated that DMP interacts with hs-DNA in a groove-binding mode that changes the double helical structure of DNA. The binding constant and the number of binding sites calculated from the fluorescence quenching data were 565.718 L mol^?1 and 0.7872, respectively. A molecular modeling study revealed that DMP tends to bind with DNA in the A-T-rich regions of minor groove and that hydrogen bonding and van der Waals forces play main roles in the interaction. This research can help to elucidate the mechanism of DMP toxicity in vivo.     

邻苯二甲酸二丁酯对拟南芥幼苗的氧化损伤（Oxidative Damage Induced by Dibutyl Phthalate to Stem and Leaves of Arabidopsis Seedlings）

为了探讨邻苯二甲酸二丁酯(DBP)对植物的氧化损伤作用,采用不同浓度的DBP溶液对拟南芥(Arabidopsis thaliana)进行染毒(终浓度为0、0.5、2.5、5、10mg·L-1),检测DBP对幼苗茎、叶超氧化物歧化酶(SOD)活性及丙二醛(MDA)含量的影响.结果表明:染毒1周后,随DBP浓度的升高,拟南芥幼苗茎叶MDA含量呈显著上升趋势,高浓度组(5、10mg·L-1)与对照组差异显著(p<0.01);SOD活性随DBP浓度的升高呈先升高后降低趋势,各染毒组与对照组均差异显著(p<0.01).以上结果表明DBP可对拟南芥幼苗产生明显的氧化损伤.     

邻苯二甲酸二异辛酯致赤子爱胜蚓体细胞氧化损伤的研究

以赤子爱胜蚓为实验材料,探讨了邻苯二甲酸二异辛酯(DEHP)对赤子爱胜蚓(Esisenia foelide)的毒性.DEHP染毒剂量:0、0.2、0.4、0.8、1.6mmol·L-1,染毒2h后采用KCl-SDS沉淀法检测细胞匀浆DNA-蛋白质交联(DPC)系数,硫代巴比妥酸法检测丙二醛(MDA)含量.结果表明:随着DEHP染毒浓度的增加,赤子爱胜蚓细胞匀浆的DPC系数显著升高(F=14.1,p<0.01),并具有剂量-效应关系(r=0.8877,p<0.05),而MDA含量变化不显著,各染毒组与对照组之间不存在显著性差异(F=0.27,p>0.05).以上结果表明,实验浓度的DEHP暴露可使赤子爱胜蚓体细胞发生显著的DNA蛋白质交联,具有遗传毒性.     

典型设施农业土壤酞酸酯污染特征及其健康风险

采用超声提取、气相色谱-质谱技术和CalTOX模型,分析了南京城郊典型设施菜地土壤中6种酞酸酯的污染特征、污染负荷及其健康风险.结果表明,所有的土壤样品中均检测出酞酸酯,6种酞酸酯的总量为0.15~9.68mg/kg,其平均含量为2.21mg/kg;邻苯二甲酸二丁酯(DnBP)、邻苯二甲酸(2-乙基己基)酯(DEHP)和邻苯二甲酸二辛酯(DnOP)为该地区设施农业土壤的主要酞酸酯种类,其检出率分别为88.2%、100%和79.8%,含量范围分别在n.d.~1.83、0.02~9.03、n.d.~1.74mg/kg之间;土壤pH值和有机碳含量与土壤酞酸酯含量之间无显著相关性,研究区域土壤酞酸酯总体污染负荷为4.31kg/hm2;健康风险评价结果表明DnBP和DEHP的潜在健康风险较高,设施农业从业者的主要暴露途径通过皮肤接触;设施菜地土壤酞酸酯含量、污染负荷以及健康风险均显著高于周边地区露天菜地土壤.     

Biodegradation of plasticizer di‐n‐butyl phthalate (DBP) by immobilized microbial cells

Microorganisms capable of degrading di‐n‐butyl phthalate (DBP) were isolated by acclimated and enrichment technique. The adaptation of microorganism to DBP was investigated. The microbial cells were immobilized on ceramic particles. The results showed that the biomass adsorbed on ceramic particles can reach 85 mg dry weight/g carrier. The immobilized microbial cells were used for the treatment of wastewater containing DBP. The results demonstrated that the DBP concentration of the outlet reached the stationary‐state level of less than 1.0 mg/1 within 2 days at inlet DBP concentration of 100mg/l and 12h of hydraulic retention time.     

臭氧-活性炭工艺对饮用水中邻苯二甲酸酯的去除

通过对臭氧-活性炭工艺和活性炭吸附等温线的研究,探讨了臭氧-活性炭工艺去除饮用水中微量邻苯二甲酸酯(Phthlate Esters,PAEs)的可行性.邻苯二甲酸二甲酯(Dimethyl Phthalate,DMP)、邻苯二甲酸二乙酯(Diethyl Phthlate,DEP)和邻苯二甲酸二丁酯(Dibutyl Phthlate,DBP)被选作目标物质.研究发现臭氧氧化能去除40%以上的DMP、DEP和DBP;活性炭对DMP、DEP和DBP有很好的去除效果,在空床停留时间(Empty Bed ContactTime,EBCT)4～12 min条件下能完全去除水中未被臭氧氧化的DMP、DEP和DBP;吸附等温线的数据可以用Freundlich公式拟合,并被用来估算活性炭的饱和时间.实验证明臭氧-活性炭工艺是去除饮用水中微量邻苯二甲酸酯的有效方法.     

响应面法建立不同经口介质中邻苯二甲酸酯生物有效性预测模型及相关因素

运用响应面法对不同消化基质下邻苯二甲酸酯(PAEs)生物有效性的相关因素进行筛选建立预测模型,并对主要因素设定值进行分析.研究表明,3种模型中因变量与自变量之间的相关性较好(土壤:R2=0.959;农作物及植物:R2=0.973;脂肪:R2=0.862),模型拟合度较高.通过多次试验模拟,初步认为在土壤消化基质中,设置人体摄入PAEs经口摄入浓度为10μg·g-1,基质质量为0.4g,pH值约为7时,生物吸收量最高.在植物源基质下,污染物浓度在10—11μg·g-1,消化时间在6—7h,基质质量为0.4g为生物吸收量最高.脂肪源中,基质质量在0.4g,污染物浓度在10μg·g-1,脂肪量在10%—11%时,PAEs生物吸收量最高.研究通过重复试验,充分体现了该模型的准确性,及设定条件的可靠性.但本研究仅考虑摄入介质相对单一,污染物化合形态等未在考虑范围内,在后期研究中将补充试验.