南京某城市污水二级处理系统中酞酸酯类的分布及去除特征简

以南京某城市污水厂污水和污泥中的酞酸酯类（PAEs）为研究对象，分别采用固相萃取-气相色谱-质谱联用（SPE-GC-MS）和超声提取-气相色谱-质谱联用（USE-GC-MS）检测其中的优先控制污染物邻苯二甲酸二甲酯（DMP）、邻苯二甲酸二乙酯（DEP）、邻苯二甲酸二丁酯（DBP）和邻苯二甲酸单（2-乙基己基）酯（MEHP），研究其在厌氧/好氧（A/O）污泥处理过程中的分布特征及降解规律。研究结果表明，各类PAEs在该污水厂的污水和污泥中均有检出，二级处理出水中4种酞酸酯类物质的浓度在0.151~2.419 μg/L。污水中4种酞酸酯的分布规律为MEHP>DBP>DMP>DEP，污泥中4种酞酸酯的分布规律为MEHP>DBP>DEP>DMP。该污水厂二级处理工艺对4种PAEs的去除效果较明显，去除效率DBP>DEP>DMP>MEHP。     

臭氧-生物活性炭工艺对饮用水中邻苯二甲酸酯类的去除中试研究

以嘉陵江源水的自来水厂滤后水为研究对象,在中试规模上研究了臭氧-生物活性炭工艺对饮用水中微量邻苯二甲酸酯（又称为酞酸酯,phthalate esters,PAEs）的去除效果。选择邻苯二甲酸二甲酯（DMP）、邻苯二甲酸二丁酯（DBP）、邻苯二甲酸二（2-乙基己基）酯（DEHP）、邻苯二甲酸二辛酯（DOP）为目标物质。研...     

天津市大气PM_(10)与降尘中邻苯二甲酸酯的污染特征及相关性分析

采集天津市4个采样点的大气 PM_(10)与降尘样品,利用CH_2Cl_2和超声对样品中的邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸(2-乙基己基)酯(DEHP)和邻苯二甲酸二辛酯(DOP)等6种邻苯二甲酸酯(PAEs)进行提取分离,采用气相色谱/质谱联用仪(GC/MS)定量分析。结果表明,4个采样点大气 PM_(10)样品中6种PAEs总质量浓度为2.371~24.201ng/m3,降尘样品中6种PAEs总质量浓度为222.310~1 184.503ng/g。对于6种PAEs,夏季浓度均高于冬季浓度,且DBP与DEHP是大气 PM_(10)与降尘样品中的主要污染物。6种PAEs总浓度、DBP浓度、DEHP浓度在大气 PM_(10)与降尘样品中存在相关关系,斯皮尔曼相关系数分别为0.929、0.881、0.905(双尾检验,在显著性水平0.01下)。回归分析表明,大气 PM_(10)与降尘样品中6种PAEs总浓度、DBP浓度、DEHP浓度具有一定的共变趋势。     

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。     

TiO2／Ni PECO体系降解DMP的动力学和光电协同作用研究

以采用微波辅助法制备的TiO2／Ni光电极为阳极，纤维状石墨毡材料（graphite felt，GF）为阴极，饱和甘汞电极（saturated calomel electrode，SCE）为参比电极建立TiO2／Ni光电催化氧化（PECO）体系。以邻苯二甲酸二甲酯（dimethy phthalate，DMP）为目标物，研究其光电催化降解反应动力学和光电协同作用。结果显示：DMP的降解符合拟一级动力学规律；当DMP初始浓度一定时，影响DMP光电催化降解速率的因素由强到弱依次为：催化剂有效面积，紫外光强度，曝氧速率，外加偏转电压等。实验证明本体系中光电之间具有协同作用。     

污泥活性炭的表征及其对Cr（Ⅵ）的吸附特性

以城市污水处理厂污泥为原料，采用磷酸活化一微波热解法制备得到污泥活性炭，并将其用于吸附水溶液中的Cr（Ⅵ）。分别采用元素分析仪（VarioELcube）、比表面积孔径分布测定仪（ASAP2020）、扫描电镜（SEM）和傅里叶红外光谱（FT—IR）等仪器对原污泥及污泥活性炭的表面组成和结构进行表征，探讨污泥活性炭的孔隙结构参数和表面化学性能。通过静态吸附实验，考察了溶液初始pH，接触时间，初始Cr（Ⅵ）浓度对污泥活性炭吸附Cr（Ⅵ）效果的影响，并探讨了污泥活性炭去除Cr（Ⅵ）的机理。实验结果表明，pH越低吸附效果越好，吸附平衡时间为100h。不同温度下吸附过程均符合Langmuir等温吸附模型，30℃时最大吸附容量为27．55mg／g；吸附动力学过程符合准二级速率方程（R2〉0．99）；污泥活性炭对Cr（Ⅵ）的去除是一个吸附-还原耦合的过程。     

厌氧膨胀床处理低浓度污水的污泥颗粒和生物活性变化

污泥的聚集形态和活性，是影响厌氧反应器处理效率的关键因素。通过对厌氧膨胀床反应器（anaerobicex—pandedblanketreactor，AEBR）处理低浓度城镇污水在启动和稳定运行期的污泥活性研究，AEBR在启动运行期内，接种颗粒污泥为适应低浓度基质条件，污泥粒径经历从大变小，再重新颗粒化粒径变大的过程。在运行期第103天，粒径小于1000μm污泥的体积比达到44．7％，平均粒径为952μm，到运行期第173天，粒径小于1000μm污泥的体积比降为28％，平均粒径达1179μm，污泥重新颗粒化完成。颗粒污泥适应新的环境后，单位重量污泥的最大比产甲烷活性（specificmetha．nogensisactivity，SMA）值和胞外聚合物含量增加，分别达到112mLCH4／（gVSS·d）和215mg／gVSS。在处理实际城镇污水的AEBR反应器内，辅酶F420含量可以有效指示污泥样品的产甲烷活性，AEBR反应器不同高度位置的污泥活性不一样，反应器底部污泥活性低于中上部区域污泥的活性。     

天氧膨胀床处理低浓度污水的污泥颗粒和生物活性变化

污泥的聚集形态和活性，是影响厌氧反应器处理效率的关键因素。通过对厌氧膨胀床反应器（anaerobicex—pandedblanketreactor，AEBR）处理低浓度城镇污水在启动和稳定运行期的污泥活性研究，AEBR在启动运行期内，接种颗粒污泥为适应低浓度基质条件，污泥粒径经历从大变小，再重新颗粒化粒径变大的过程。在运行期第103天，粒径小于1000μm污泥的体积比达到44．7％，平均粒径为952μm，到运行期第173天，粒径小于1000μm污泥的体积比降为28％，平均粒径达1179μm，污泥重新颗粒化完成。颗粒污泥适应新的环境后，单位重量污泥的最大比产甲烷活性（specificmetha．nogensisactivity，SMA）值和胞外聚合物含量增加，分别达到112mLCH4／（gVSS·d）和215mg／gVSS。在处理实际城镇污水的AEBR反应器内，辅酶F420含量可以有效指示污泥样品的产甲烷活性，AEBR反应器不同高度位置的污泥活性不一样，反应器底部污泥活性低于中上部区域污泥的活性。     

硝化颗粒污泥的快速培养及其硝化特性分析

以好氧颗粒污泥接种小试柱形SBR，采用自配无机氨氮废水为进水，在中温（28～30℃）条件下通过逐步提升进水NH4^＋-N浓度（100～650mg／L）和缩短水力停留时间（8～4h）快速培养硝化颗粒污泥。实验结果证实，以好氧颗粒污泥接种可以促使硝化颗粒污泥快速形成，36d时粒径〉0．21mm的颗粒污泥占总数的93％，颗粒污泥NH4-N比去除速率为50．53mgNH4^＋-N／（gSS·h）。硝化颗粒污泥具有良好的短程硝化性能，亚硝酸盐产生速率和累积率分别保持在3．3kgNO2-N／（m^3·d）和85％以上。反应初期高FA和反应末期高FNA的共同抑制是该研究中实现和维持稳定短程硝化的关键因素。     

城市污水再生处理过程中壬基酚的迁移转化行为研究

采用SPE—GC—MSD-SIM方法，分析了壬基酚在污水再生处理全过程中的迁移转化行为与归宿。研究表明，在污水二级生物处理流程中，壬基酚主要来源为原污水和泥区回流液；壬基酚的去除途径有一沉池生污泥的吸附迁移作用和曝气池单元的生物降解转化作用，其中一沉池生污泥的吸附去除29．8％，曝气池生物降解54．4％，NP总去除率为84．2％。絮凝、过滤和消毒的污水再生深度处理工艺对壬基酚的迁移转化作用不明显。     

Evaluation of municipal sewage treatment systems for pollutant removal efficiency by measuring levels of micropollutants

In order to evaluate the municipal sewage treatment systems used at Harbin municipal sewage treatment plant for their pollutant removal efficiency, raw sewage and effluent samples at different treatment stages from the sewage treatment systems were taken, priority pollutants (PPs) were identified and quantified using gas chromatography-mass spectrometry (GC-MS) and inductively coupled plasma-atomic emission spectrograph (ICP-AES). The test results indicated that there were one hundred and fifty species of organic pollutants identified in the raw sewage sample, and only ten species of PPs in all the sewage samples. The levels of dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), di-n-octyl phthalate (DnOP) in the sewage samples were 0.779-0.111 microg l(-1), 1.977-0.022 microg l(-1), 6.411-2.194 microg l(-1) and 7.152-2.953microg l(-1), respectively, and most of these phthalate esters (PAEs) were removed through anaerobic/aerobic (A/O) process; The levels of alachlor, acetochlor, atrazine were 0.074-0.021 microg l(-1), 0.160-0.096 microg l(-1) and 0.238-0.184 microg l(-1), respectively, and the total removal efficiency of atrazine was poorest through the sewage treatment systems. The levels of Cu, Cr, Se, Hg, Ni and Zn were 0.0030-0.2327 mg l(-1). It is therefore concluded from these results that the sewage treatment systems were efficient in removing most of the organic and inorganic compounds in this study, and so, the discharged effluent could cause little of the secondary pollution of the aquatic environment.     

Biodegradation of phthalate esters in polluted soil by using organic amendment

This study investigated the biodegradation of the phthalate esters (PAEs) di-n-butyl phthalate (DBP) and di-(2-ethyl hexyl) phthalate (DEHP) in sludge and sludge-amended soil. DBP (100 mg kg(-1)) and DEHP (100 mg kg(-1)) were added to sewage sludge, which was subsequently added to soil. The results showed that sewage sludge can degrade PAEs and the addition of sewage sludge to soil enhanced PAE degradation. Sludge samples were separated into fractions with various particle size ranges, which spanned 0.1-0.45 μm to 500-2000 μm. The sludge fractions with smaller particle sizes demonstrated higher PAE degradation rates. However, when the different sludge fractions were added to soil, particle size had no significant effect on the rate of PAE degradation. The results from this study showed that microbial strains F4 (Rhodococcus sp.) and F8 (Microbacterium sp.) were constantly dominant in the mixtures of soil and sludge.     

东莞地下水邻苯二甲酸酯分布特征及来源探讨

在广东东莞地区采集了59组地下水水样和9组地表水水样,采用气相色谱-质谱联用技术进行测定,结果表明,地下水中邻苯二甲酸酯(PAEs)的检出率为39.0％,6种PAEs的质量浓度在未检出～6.70 μg/L.其中,邻苯二甲酸双(2-乙基己基)酯(DEHP)检出率最高,为22.O％,最大值为6.20 μg/L；邻苯二甲酸二...     

Biodegradation of phthalate esters in polluted soil by using organic amendment

This study investigated the biodegradation of the phthalate esters (PAEs) di-n-butyl phthalate (DBP) and di-(2-ethyl hexyl) phthalate (DEHP) in sludge and sludge-amended soil. DBP (100 mg kg^?1) and DEHP (100 mg kg^?1) were added to sewage sludge, which was subsequently added to soil. The results showed that sewage sludge can degrade PAEs and the addition of sewage sludge to soil enhanced PAE degradation. Sludge samples were separated into fractions with various particle size ranges, which spanned 0.1–0.45 μm to 500–2000 μm. The sludge fractions with smaller particle sizes demonstrated higher PAE degradation rates. However, when the different sludge fractions were added to soil, particle size had no significant effect on the rate of PAE degradation. The results from this study showed that microbial strains F4 (Rhodococcus sp.) and F8 (Microbacterium sp.) were constantly dominant in the mixtures of soil and sludge.     

Occurrence and microbial degradation of phthalate esters in Taiwan river sediments

Concentrations and microbial degradation rates were measured for eight phthalate esters (PAEs) found in 14 surface water and six sediment samples taken from rivers in Taiwan. The tested PAEs were diethyl phthalate (DEP), dipropyl phthalate (DPP), di-n-butyl phthalate (DBP), diphenyl phthalate (DPhP), benzylbutyl phthalate (BBP), dihexyl phthalate (DHP), dicyclohexyl phthalate (DCP), and di-(2-ethylhexyl) phthalate (DEHP). In all samples, concentrations of DEHP and DBP were found to be higher than the other six PAEs. DEHP concentrations in the water and sediment samples ranged from ND to 18.5 μg/l and 0.5 to 23.9 μg/g, respectively; for DBP the concentration ranges were 1.0–13.5 μg/l and 0.3–30.3 μg/g, respectively. Concentrations of DHP, BBP, DCP and DPhP were below detection limits. Under aerobic conditions, average degradation half-lives for DEP, DPP, DBP, DPhP, BBP, DHP, DCP and DEHP were measured as 2.5, 2.8, 2.9, 2.6, 3.1, 9.7, 11.1 and 14.8 days, respectively; under anaerobic conditions, respective average half-lives were measured as 33.6, 25.7, 14.4, 14.6, 19.3, 24.1, 26.4 and 34.7 days. In other words, under aerobic conditions we found that DEP, DPP, DBP, DPhP and BBP were easily degraded, but DEHP was difficult to degrade; under anaerobic conditions, DBP, DPhP and BBP were easily degraded, but DEP and DEHP were difficult to degrade. Aerobic degradation rates were up to 10 times faster than anaerobic degradation rates.     

Biodegradation of four phthalate esters in sludge

This study investigated the effects of ultrasonic pretreatment and various treatments on the aerobic degradation of four phthalic acid esters (PAEs) such as diethyl phthalate (DEP), benzyl butyl phthalate (BBP), di-n-butyl phthalate (DBP) and di-(2-ethyl hexyl)phthalate (DEHP) in sludge. The effect on PAE degradation of treating sludge with a 20 min sonication period at a power level of 0.1 W ml(-1) was evaluated. The degradation rates of the four PAEs were DBP>BBP>DEP>DEHP. Degradation rate constants (k(1)) and half-lives (t(1/2)) for the four PAEs (50 mg kg(-1)) ranged from 0.182 to 0.379 day(-1) and 1.8 to 3.8 days, respectively. The optimal pH for PAE degradation in sludge was 7.0 at 30 degrees C. PAE degradation was enhanced by the addition of yeast extract, brij 30 or brij 35 and inhibited by the addition of hydrogen peroxide. Our results show that a combination of ultrasonic pretreatment and biodegradation can effectively remove PAE from sludge.     

A risk assessment of selected phthalate esters in North American and Western European surface waters

Potential risks to aquatic organisms by four commercial phthalate esters, dimethyl (DMP), diethyl (DEP), di-n-butyl (DBP), and butylbenzyl (BBP), were assessed using measured and calculated concentrations in North American and Western European surface waters. Predicted no effect concentrations (PNECs) were calculated using statistical extrapolation procedures and the large aquatic toxicity database. Surface water concentrations of DMP, DEP, DBP, and BBP were calculated using reported emissions to US surface waters from the toxics release inventory (TRI). Monitoring data obtained from the US EPA STORET database and literature surveys from North America and Western Europe show that DMP, DEP, DBP, and BBP are infrequently detected in surface water. Calculated and measured concentrations of DMP, DEP, DBP, and BBP are typically several orders of magnitude below their respective PNECs, indicating that these phthalate esters do not pose a ubiquitous threat to aquatic organisms in North American and Western European surface waters.     

Anaerobic degradation of diethyl phthalate, di-n-butyl phthalate, and di-(2-ethylhexyl) phthalate from river sediment in Taiwan

We investigated anaerobic degradation rates for three phthalate esters (PAEs), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), and di-(2-ethylhexyl) phthalate (DEHP), from river sediment in Taiwan. The respective anaerobic degradation rate constants for DEP, DBP, and DEHP were observed as 0.045, 0.074, and 0.027 1/day, with respective half-lives of 15.4, 9.4, and 25.7 days under optimal conditions of 30 °C and pH 7.0. Anaerobic degradation rates were enhanced by the addition of the surfactants brij 35 and triton N101 at a concentration of 1 critical micelle concentration (CMC), and by the addition of yeast extract. Degradation rates were inhibited by the addition of acetate, pyruvate, lactate, FeCl₃, MnO₂, NaCl, heavy metals, and nonylphenol. Our results indicate that methanogen, sulfate-reducing bacteria, and eubacteria are involved in the degradation of PAEs.     

Biodegradation of phthalate esters by two bacteria strains

In this study two aerobic phthalic acid ester (PAE) degrading bacteria strains, DK4 and O18, were isolated from river sediment and petrochemical sludge, respectively. The two strains were found to rapidly degrade PAE with shorter alkyl-chains such diethyl phthalate (DEP), dipropyl phthalate (DPrP), di-n-butyl phthalate (DBP), benzylbutyl phthalate (BBP) and diphenyl phthalate (DPP) are very easily biodegraded, while PAE with longer alkyl-chains such as dicyclohexyl phthalate (DCP) and dihexyl phthalate (DHP) and di-(2-ethylhexyl) phthalate (DEHP) are poorly degraded. The degradation rates of the eight PAEs were higher for strain DK4 than for strain O18. In the simultaneous presence of strains DK4 and O18, the degradation rates of the eight PAEs examined were enhanced. When the eight PAEs were present simultaneously, degradation rates were also enhanced. We also found that PAE degradation was delayed by the addition of nonylphenol or selected polycyclic aromatic hydrocarbons (PAHs) at a concentration of 1 microg/g in the sediment. The bacteria strains isolated, DK4 and O18, were identified as Sphigomonas sp. and Corynebacterium sp., respectively.     

Occurrence of organic contaminants in sewage sludges from eleven wastewater treatment plants, China

This study presents the occurrence of 43 semi-volatile organic compounds (SVOCs) listed as priority pollutants by both China and the United States Environmental Protection Agency, in sewage sludges collected from eleven wastewater treatment plants (WWTPs) of mainland and Hong Kong, China. Thirty-six SVOCs were detected by gas chromatography coupled with mass spectrometer (GC-MS) and at least 14 in each sample. The most abundant compounds were phthalic acid esters (PAEs) and polycyclic aromatic hydrocarbons (PAHs) with total concentrations ranging from 10 to 114mgkg(-1) dry weight (d.w.) (with a mean of 30mgkg(-1) d.w.) and from 1.4 to 33mgkg(-1)d.w. (with a mean of 16mgkg(-1) d.w.), respectively, followed by chlorobenzenes, nitroaromatics, haloethers and halogenated hydrocarbons which occurred generally at concentrations lower than 10mgkg(-1) d.w. Large variations were observed between the concentrations of individual compounds as well as their total concentrations in sludge samples from different WWTPs. The highest values of sum concentration of 16 PAHs and of 6 PAEs were found in sewage sludge from Beijing. The mean total concentration of each class of SVOCs in sewage sludge from mainland was remarkably higher than that from Hong Kong. The concentrations of di(2-ethylhexyl) phthalate in 91% sludge samples met the limit (100mgkg(-1)d.w.) proposed by the Europe Union for land application, whereas the PAH concentrations of 64% sludge samples exceeded the maximum permissible concentration (6.0mgkg(-1)d.w.). The occurrence of SVOCs in this study are compared with other studies and their sources are discussed.