酞酸酯DMP、DEP和DBP对明亮发光杆菌的毒性研究

酞酸酯（PAEs, phthalate acid esters）是目前最普遍的有机污染物之一,一定剂量的酞酸酯会产生生殖和发育毒性等健康危害。以明亮发光杆菌（Photobacterium phosphoreum T3）为受试生物,评价了甲醇和3种PAEs [dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP)]对其剂量—效应关系,以期为酞酸酯暴露风险评价提供一定理论依据。结果表明,采用Logit和Weibull非线性函数（全浓度区间）分别对甲醇和3种PAEs的浓度—效应曲线进行拟合,效果均优于线性函数（局部浓度区间）拟合。其中,甲醇的线性与Logit函数拟合r2分别为0.9592和0.9863,两者EC50分别为1.185和1.044 mol·L-1,结果相近。数据结果表明,采用明亮发光杆菌测试PAEs急性毒性时,以甲醇为助溶剂（浓度<0.247 mol·L-1,毒性效应可忽略）是可行的。在一定浓度范围内,首次以甲醇为助溶剂,以DMP?DEP和DBP 3种PAEs对明亮发光杆菌进行毒性测试。线性拟合DMP?DEP和DBP对明亮发光杆菌的浓度-效应曲线,拟合r2分别为0.9262、0.9214、0.9339,其EC50分别为2.64E-04、2.79E-04和1.14E-05 mol·L-1。与此同时,3组PAEs毒性数据均能以Weibull函数进行非线性拟合, r2分别为0.9749?0.9742和0.9648,效果良好,其EC50分别为1.49E-04、2.72E-04和9.00E-06 mol·L-1。两种拟合结果表明, Weibull 函数非线性拟合效果更优,半致死浓度 EC50结果相近。由上述结果可知,以甲醇为助溶剂时,DMP?DEP 和 DBP分别在6.14E-9~6.14E-3、5.04E-5~2.52E-3和3.76E-9~3.76E-5 mol·L-1浓度范围内,3种PAEs对明亮发光杆菌的急性毒性强弱为DBP>DMP>DEP。在上述浓度范围内,DMP、DEP和DBP对明亮发光杆菌的抑制率分别为96.87%、95.24%和88.35%。     

邻苯二甲酸二异壬酯致小鼠肾组织氧化损伤的研究

邻苯二甲酸二异壬酯是一种新型替代增塑剂,对其毒性研究已受到广泛关注。为探究邻苯二甲酸二异壬酯对肾组织的氧化损伤作用,将昆明小鼠随机分为5组,包括1个阴性对照组、4个邻苯二甲酸二异壬酯染毒组,按0.5、5、50和500 mg·kg-1四个剂量水平灌胃染毒14天。制备小鼠肾组织切片进行病理学观察,以肾组织匀浆测定活性氧(reactive oxygen species,ROS)、还原型谷胱甘肽(glutathione,GSH)、丙二醛(malondialdehyde,MDA)和8-羟基脱氧鸟苷(8-hydroxy-2-deoxyguanosine,8-OHd G)的含量,以肾组织细胞悬液测定DNA-蛋白质交联(DNA-protein Crosslink,DPC)系数。随着邻苯二甲酸二异壬酯染毒剂量的升高,小鼠肾组织的损伤程度加重,ROS、MDA、8-OHd G含量和DPC系数逐渐上升,GSH含量逐渐降低,各指标均呈一定剂量-效应关系。染毒剂量为5 mg·kg-1时,ROS、DPC系数差异有统计学意义(P0.05,P0.01);染毒剂量为50 mg·kg-1和500 mg·kg-1时,ROS、GSH、8-OHd G、MDA含量和DPC系数差异均有统计学意义(P0.05,P0.01)。结果表明较高剂量(≥50 mg·kg-1)邻苯二甲酸二异壬酯可造成小鼠肾组织氧化损伤。     

黑土微生物量和酶活性对邻苯二甲酸二丁酯污染的响应

邻苯二甲酸二丁酯(di-n-butyl phthalate,DBP)是一种在环境中广泛存在的有毒有机化合物,已被我国列为优先控制污染物之一。本研究探讨了不同浓度的DBP污染对黑土呼吸、微生物量以及黑土酶活性的影响。结果表明,DBP污染处理的黑土呼吸速率和微生物量碳较对照均显著增加;微生物氮在DBP污染过程中呈"降低-升高-降低"波动性变化;微生物磷与DBP污染浓度呈显著负相关;DBP对黑土多酚氧化酶表现为先促进后抑制,对转化酶和蛋白酶活性表现为低浓度促进而高浓度抑制;在DBP污染过程中脲酶呈现被激活状态;黑土过氧化氢酶和酸性磷酸酶均受到DBP污染的显著抑制。通过相关性分析发现,土壤微生物量、土壤酶活性与DBP污染浓度之间存在着高度的相关性。由此可推断,DBP污染改变了黑土呼吸、微生物量和酶学活性的代谢特征,进而有可能影响了黑土的生态系统功能,威胁到黑土的可持续利用。     

Investigation on removal pathways of Di 2-ethyl hexyl phthalate from synthetic municipal wastewater using a submerged membrane bioreactor

Highly hydrophobic Di 2-ethyl hexyl phthalate (DEHP) is one of the most prevalent plasticizers in wastewaters. Since its half-life in biological treatment is around 25 days, it can be used as an efficiency indicator of wastewater treatment plant for the removal of hydrophobic emerging contaminants. In this study, the performance of submerged membrane bioreactor was monitored to understand the effect of DEHP on the growth of aerobic microorganisms. The data showed that the chemical oxygen demand (COD) and ammonia concentration were detected below 10 and 1.0 mg/L, respectively for operating conditions of hydraulic retention time (HRT) = 4 and 6 hr, sludge retention time (SRT) = 140 day and sludge concentration between 11.5 and 15.8 g volatile solid (VS)/L. The removal efficiency of DEHP under these conditions was higher and ranged between 91% and 98%. Results also showed that the removal efficiency of DEHP in biological treatment depended on the concentration of sludge, as adsorption is the main mechanism of its removal. For the submerged membrane bioreactor, the pore size is the pivotal factor for DEHP removal, since it determines the amount of soluble microbial products coming out of the process. Highly assimilated microorganisms increase the biodegradation rate, as 74% of inlet DEHP was biodegraded; however, the concentration of DEHP inside sludge was beyond the discharge limit. Understanding the fate of DEHP in membrane bioreactor, which is one of the most promising and futuristic treatment process could provide replacement for conventional processes to satisfy the future stricter regulations on emerging contaminants.     

气相色谱/串联质谱法分析水中痕量酞酸酯

采用C18固相萃取结合气相色谱/三重串联四极杆质谱联用仪建立了地表水中痕量酞酸酯(PAEs)类化合物的分析方法。使用串联质谱特有的多反应监测模式可以很好的去除基质的背景干扰,对列入美国环保局优先控制污染物名单的六种PAEs均实现基线分离,在50～1 000 ng/mL范围内线性良好,6种PAEs的相关系数均大于0.99,加标回收率在89.8%～103.4%之间,方法的精密度较好(RSD<10%)。应用于实际地表水样品中PAEs的分析表明,某市地表水中含有邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯和邻苯二甲酸(2-乙基己基)酯,其中邻苯二甲酸二丁酯含量最高(均值为1.25μg/L),邻苯二甲酸丁基苄基酯和邻苯二甲酸二辛酯均未检出。     

DEHP暴露对小鼠神经行为学及脑脂质过氧化物的影响

为研究增塑剂邻苯二甲酸二乙基己酯(Di-2-ethylhexyl phthalate,DEHP)对脑组织造成氧化损伤以及对小鼠神经行为(主要包括学习、记忆能力与情绪)的影响.将24只雄性昆明小鼠随机分成4组,每组6只,分别为对照组(生理盐水),低浓度染毒组(5mg·kg-1DEHP,L组),中浓度染毒组(50mg·kg-1DEHP,M组),高浓度染毒组(500mg·kg-1DEHP,H组).利用Y型电迷宫检验小鼠的学习记忆能力变化,利用悬尾实验和强迫游泳实验检测小鼠抑郁行为的变化.然后取出脑组织,检验活性氧簇(ROS)及丙二醛(MDA)含量.数据显示,染毒组小鼠的学习记忆及行为学控制能力明显低于对照组(p<0.05),并且随DEHP浓度的增大小鼠的学习记忆及行为学控制能力降低.DEHP低、中、高剂量染毒组与对照组氧化应激反应均具有显著性(p<0.05),且呈剂量效应关系.因此,DEHP可导致小鼠学习记忆能力下降、抑郁情绪增加,其分子机制可能涉及DEHP对脑组织造成的氧化损伤.     

水体系中3种常见邻苯二甲酸酯的光化学降解研究

采用固相微萃取-气相色谱-质谱联用(GC-MS)技术,研究了不同介质、光源、起始浓度、H2O2浓度等对3种常见邻苯二甲酸酯(PAEs)光化学降解过程的影响,并对邻苯二甲酸二(2-乙基己基)酯(DEHP)光降解的中间产物进行了检测,提出了可能发生的降解路径.结果表明:在不同介质中,邻苯二甲酸二甲酯(DMP)和邻苯二甲酸二乙酯(DEP)在Millipore-Q水中降解速度最快,而DEHP在天然海水中降解速度最快;3种PAEs在紫外灯照射下比模拟日光下降解速度快;相同紫外光照条件下,不同初始浓度的DMP、DEP和DEHP在研究浓度范围内(0.5~10μg·L-1)的光降解率随着浓度的增加呈现减小趋势;此外,体系中H2O2的存在会明显加快PAEs的降解速率;通过GC-MS分析,检测出了DEHP在UV/H2O2条件下降解产生的中间产物,并且发现DEHP是从侧链开始降解的.     

Sorption and desorption kinetics of phthalates and phenol on water/sediment interface

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银川城区地表灰尘中邻苯二甲酸酯污染特征及人群健康风险评价

采集银川市城区不同功能区的40个地表灰尘样品,采用气相色谱质谱联用的检测方法,测定了美国环保局（EPA）优先控制的6种PAEs化合物的含量,并对其污染特征、污染分布和人体暴露的健康风险进行了评价.结果表明,6种邻苯二甲酸酯化合物在地表灰尘样品中均被检测出,Σ₆PAEs的含量为0.096~24.952 mg·kg^-1,平均值和中位数分别为3.452 mg·kg^-1和1.905 mg·kg^-1.各功能区地表灰尘中Σ₆PAEs平均含量由高到低依次为住宅区、文教区、公园、工业区、商业区和交通区.各功能区地表灰尘中的主要PAEs单体为邻苯二甲酸（2-乙基）己酯（DEHP）和邻苯二甲酸二丁酯（DnBP）,二者占到Σ₆PAEs的97.07%.对人体健康风险评价表明,研究区6种优先控制化合物对人体产生的非致癌风险均小于1,未超过EPA推荐的非致癌水平,邻苯二甲酸丁基苄基酯（BBP）的致癌风险在可接受的标准范围内,有2个样点的DEHP致癌风险超过EPA推荐的致癌水平,应引起一定的重视.     

Degradation mechanism of 2,4,6-trinitrotoluene in supercritical water oxidation

The 2,4,6-trinitrotoluene(TNT)is a potential carcinogens and TNT contaminated wastewater,which could not be effectively disposed with conventional treatments.The supercritical water oxidation(SCWO)to treat TNT contaminated wastewater was studied in this article.The TNT concentration in wastewater was measured by high-performance liquid chromatograph(HPLC)and the degraded intermediates were analyzed using GC-MS.The results showed that SCWO could degrade TNT efficiently in the presence of oxygen.The reaction temperature,pressure,residence time and oxygen excess were the main contributing factors in the process.The decomposition of TNT was accelerated as the temperature or residence time increased.At 550℃,24 MPa,120 s and oxygen excess 300%,TNT removal rate could exceed 99.9%.Partial oxidation occured in SCWO without oxygen.It was concluded that supercritical water was a good solvent and had excellent oxidation capability in the existence of oxygen.The main intermediates of TNT during SCWO included toluene,1,3,5-trinitrobenzene,nitrophenol,naphthalene,fluorenone,dibutyl phthalate,alkanes and several dimers based on the intermediate analysis.Some side reactions,such as coupled reaction,hydrolysis reaction and isomerization reaction may take place simultaneously when TNT was oxidized by SCWO.