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题名: 城市污水处理厂中典型PPCPs的分布特性及迁移转化规律研究
作者: 袁向娟
学位类别: 博士
答辩日期: 2015-05
授予单位: 中国科学院研究生院
授予地点: 北京
导师: 强志民
关键词: 药物及个人护理品 ; 城市污水处理厂 ; 分布特性 ; 迁移转化 ; 生态风险,Pharmaceuticals and personal care products ; wastewater treatment plants ; occurrence ; fate ; ecological risk
其他题名: Occurrence, distribution and fate of typical PPCPs in different wastewater treatment plants
学位专业: 环境工程
中文摘要:       药物及个人护理品(PPCPs)作为环境中新型微量污染物,已成为各国环境学者和公众关注的焦点问题,其引起的人类健康和生态环境安全风险受到了越来越多 的关注。目前国内有关城市污水处理厂中PPCPs的研究还处于起步阶段,而复杂的污水及污泥成分对其精确检测造成了极大的基质干扰,研究主要集中在进出水 浓度的检测,往往只能获得随机的零散的浓度数据及表观去除率,但是对于PPCPs在城市污水处理厂全处理流程中的迁移转化规律缺乏系统、深入的研究,因此 迫切需要对我国城市污水处理厂中多种PPCPs污染浓度水平进行长期连续的调查和系统的全相分析,明确其在不同污水处理工艺中的行为、迁移转化规律及相分 配基质,解析其归趋,最后对污水和污泥排放的生态风险进行评价。主要开展工作如下:
      采用超声溶剂萃取(USE)和固相萃取(SPE)组合的前处理方法,通过优化USE的萃取液和SPE淋洗液的选择,有效低减少了基质对PPCPs的分析干 扰,达到样品中多种PPCPs的同步萃取、富集和净化的目的;通过优化UPLC及MS/MS参数,提高多类目标物检测的选择性和灵敏度,同时结合内标物进 行定量,建立了城市污水处理厂污水和污泥中9类30种PPCPs的UPLC/MS/MS同步分析及精确定量的检测方法。通过对标准曲线、方法回收率、日内 及日间标准偏差、方法检测限和定量限等指标的分析,验证了该方法具有较好的准确度、灵敏度及稳定性。将该方法应用于北京市某污水处理厂进出水和回流污泥中 PPCPs的检测,27和21种PPCPs在进出水和污泥样品中被检出。
      对无锡市、青岛市和北京市5座污水处理厂不同生物处理工艺(A/A/O-MBBR、C-Orbal OD、A/A/O、和MBR等)的进水、出水和剩余污泥中30种PPCPs进行连续10个月的采样分析,考察多种PPCPs在不同城市污水处理厂的浓度和 组成分布、季节变化规律,同时对不同工艺的生物处理和深度处理效果进行对比。结果表明,高达27和21种目标PPCPs均能在不同污水处理厂的污水和污泥 样品中检测出,进水、二沉出水和剩余污泥中目标物的平均浓度范围分别为0.99~19.53 μg/L、0.55~523.79 ng/L、2.44~12130 μg/kg,其中多种物质具有100%的检出率。PPCPs具有明显的时空分布特性,在不同污水处理厂进水中表现出明显的季节变化规律,不同地区进水中目 标物浓度差异较大。不同污水处理工艺对目标物的去除效果差异较大,去除率在“负去除率”至完全去除范围内波动,与污水处理工艺、工艺运行参数(SRT、 HRT和pH等)、目标物理化性质、采样方式和气候条件等有关。
      在上述研究的基础上,通过对无锡市2座污水处理厂(Plant A和Plant B)全流程采样,研究多种PPCPs在典型污水处理工艺(A/AO-MBBR和C-orbal OD)中的迁移转化规律和主要去除途径。结果显示,Plant A中PPCPs的总质量负荷的去除率为94.3%,明显高于Plant B的84.5%。不同污水处理厂中的一级处理和深度处理单元对多种PPCPs的去除效果有限,其去除主要集中在生物处理单元。MBBR强化了生物段去除, 同时较长的SRT也一定程度上提高了PPCPs的去除效果。通过质量平衡分析发现,SAs、多数MLs和Others主要通过微生物降解去除,而FQs、 TCs和AZN在污水处理厂主要去除机制为污泥吸附。
      最后以城市污水处理厂出水与污泥的安全性为目标,采用MEC/PNEC风险综合评估体系,评估城市污水处理厂出水和剩余污泥排放的潜在生态风险。结果显 示,SMX、OLF、CIP、CLA和ERY-H2O在出水中对藻类的RQ大于1,对藻类具有高的风险。剩余污泥中,OLF的RQ值大于1,SMX、 CIP和CLA的RQ值大于0.1,表明其对藻类存在中-高风险。UV、UV/H2O2、O3和O3/H2O2工艺对城市污水处理厂出水中多种PPCPs 和高风险物质的降解实验结果表明,O3和O3/H2O2工艺对二沉出水中多种PPCPs均有较好的去除效果,O3投加量为7.5 mg/L时,多数PPCPs的去除率可达到90%以上,去除效果明显优于UV和UV/H2O2,为PPCPs减量化及风险控制提供理论基础和技术支持。
英文摘要:
      Pharmaceuticals and personal care products (PPCPs) have received growing attentions in recent years as emerging contaminants for their persistent input and potential threat to ecological environment and human health. So far, there are few published reports of PPCPs in wastewater treatment plants (WWTPs) in China, because the analysis of PPCPs in WWTPs represents a difficult task due to the high complexity of the wastewater and sludge matrices. To date, most studies focus on the analysis of PPCPs present in wastewater and could only obtain the apparent removal of some PPCPs; whereas the fate and mass load of multiple PPCPs in both wastewater and sludge in WWTPs are rarely reported. Therefore, it is urgent to investigate the occurrence and behavior of multiple PPCPs in a long-term scale in different WWTPs. It is important to perform mass balance analysis to clarify the fate of PPCPs and to explore their potential removal pathways. Moreover, it is essential to assess the ecological risks induced by residual PPCPs to aquatic environment based on calculated risk quotients (RQs).
      A highly selective and sensitive analytical method was developed for simultaneous determination of nine types of thirty PPCPs in both wastewater and sludge. Ultrasonic solvent extraction (USE) and solid-phase extraction (SPE) were applied in sequence for the exhaustive extraction and pre-concentration of target PPCPs and the cleanup of complex matrix. Thirty PPCPs were then separated and analyzed by ultra high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Four internal standards were applied for the precise quantification of target PPCPs. The calibration curves, absolute recoveries, inter-day and intra-day precisions and the limits of detection and quantification were all determined. The developed method demonstrated its selectivity, sensitivity, and reliability for detecting multiple-class pharmaceuticals in complex matrices such as municipal wastewater and sludge. Subsequently, this method was validated and applied for residual pharmaceuticals analysis in a WWTP located in Beijing, China. Up to 27 and 21 PPCPs were detected in all the wastewater and sludge samples.
      The occurrence, seanal variations and removal efficiencies of 30 PPCPs of multiple classes were investigated in five WWTPs from three cities, including A/A/O-MBBR, C-Orbal OD, A/A/O and MBR processes. A total of 27 and 21 pharmaceuticals were detected in wastewater and sludge, and the average concentrations of the influent, secondary effluent and sludge were in the range of 0.99~19.53 μg/L, 0.55~523.79 ng/L and 2.44~12130 μg/kg, respectively. Target PPCPs showed obvious temporal and spatial trends. The seasonal variations were detected in the influents from different WWTPs, and the concentrations of target PPCPs in the influent changed a lot in different regions. The removal efficiencies of target PPCPs in both WWTPs varied largely from “negative” to 99.9%, depending on the wastewater treatment process adopted, the operational parameters (SRT, HRT, and pH), their physicochemical properties, the sampling method used and the climate conditions.  
      The fate and mass load of target PPCPs were studied in two typical WWTPs (referred as Plant A and Plant B) located in Wuxi City. The mass balance analysis was performed to clarify the fate of target PPCPs and to explore their potential removal pathways. The removal of the total mass load of target pharmaceuticals in Plant A reached 94.3%, much higher than the 84.5% removal in Plant B. The removal efficiencies of the primary and tertiary treatment were generally low in both WWTPs, most of the target PPCPs were removed in the biological treatment processes. MBBR to some extent strengthened the removal of the biological treatment, and longer SRT in Plant A also improve the removal efficiencies of target PPCPs. Mass balance analysis showed that biodegradation primarily accounted for the removal of SAs, most MLs, and Others,  while  adsorption  onto   sludge  was  the  primary  removal pathway for FQs, TCs, and AZN during biological treatment.
     Finally, considering  the safety on the  discharge of WWTPs  effluent and sludge, the  potential ecological  risks  of  the effluent  and  sludge in  different  WWTPs  were comprehensively assessed.  Results indicated that  five PPCPs (SMX,  OLF, CIP, CLA and ERY-H2O) in the effluent, one  compound (OLF) in the sludge, and the mixture  of all target  PPCPs  in both  effluent and  sludge  could pose  a high  risk to  algae in  the aquatic environment.  The degradation  of target  PPCPs  in the  secondary effluent  by UV,  UV/H2O2, O3  and  O3/H2O2 treatments  were  investigated in  this  study. Results showed O3  and O3/H2O2 treatments  achieved great  effects on target  PPCPs removal, especially on the high risk compounds. With the  O3 dose of 7.5 mg/L, more than 90% of  majority PPCPs  could  be  eliminated by  O3  and  O3/H2O2  treatments, exhibiting better  removal  performance  than  UV  and  UV/H2O2  treatments.  This  study  helps understand the occurrence, behavior and fate of PPCPs in different WWTPs as well as the ecological risks induced  by effluent discharge and sludge disposal, thus  providing useful information for better control of micro-pollutants in WWTPs.
 
内容类型: 学位论文
URI标识: http://ir.rcees.ac.cn/handle/311016/34538
Appears in Collections:环境水质学国家重点实验室_学位论文

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Recommended Citation:
袁向娟. 城市污水处理厂中典型PPCPs的分布特性及迁移转化规律研究[D]. 北京. 中国科学院研究生院. 2015.
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