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题名: 水中PPCPs与极性农药的分析方法与分布规律研究
作者: 孙静
学位类别: 博士
答辩日期: 2015-11
授予单位: 中国科学院研究生院
授予地点: 北京
导师: 王子健 ; 罗茜
关键词: 药物,个人护理用品,极性农药,水源地,分析方法 ; Pharmaceutical, Personal care product, Polar pesticide, Drinking water source, Analytical method.
其他题名: Analytical methods and distribution patterns of pharmaceuticals, personal care products and polar pesticides in environmental waters
学位专业: 环境科学
中文摘要:       药物和个人护理品(PPCPs),由于持续不断地消费和极性化学性质,在水环境中常被称作是“假持久性”的有机污染物。由于药物和个人护理用品的种类多,物化性质各异,在地表水中的存在浓度水平低(ng/L-μg/L级),目前很难对水中的多种类别的 PPCPs进行同时测定。农药被广泛的应用于农业生产活动中,容易对水环境造成污染。某些极性较强且具有潜在的生态毒理效应的农药,如乙酰甲胺磷、甲胺磷等,由于缺少合适的分析方法,在水环境研究中容易被忽略。本研究旨在建立有效的分析方法用于测定地表水尤其是水源水中多类别的  PPCPs类及极性农药,并对在地表水和水源水中的分布规律进行研究,并考察在饮用水处理工艺工程中 PPCPs及极性农药的变化规律。
    基于固相萃取(SPE)—超高效液相色谱串联质谱(UPLC-MS/MS)技术,建立了同时测定环境水样中 135种  PPCPs类化合物的分析方法。经过优化实验条件确定为采用 Oasis WAX串联  Oasis HLB柱为固相萃取小柱,碱性甲醇和酸性甲醇分别为洗脱溶剂,调节水样的 pH值为6-8时,能够使得116种PPCPs在饮用水基质中的回收率范围为 50-150%之间,分析方法的方法检出限范围为0.004-11 ng/L。
    基于建立的多类别 PPCPs的分析方法,在  2012年至  2013年期间调查了五大重点流域典型水源地中多类别 PPCPs类化合物。结果显示,共有  70种药物被检出,检出频率最高的化合物包括磺胺类、大环内酯类、镇痫剂、消炎药及 β-阻断剂等。检出浓度较高的化合物有林可霉素、磺胺甲恶唑、对乙酰氨基酚和1,7-二甲基黄嘌呤等,检出最高浓度可达 134 ng/L。检出浓度较低的化合物主要
有美托洛尔、苯海拉明、文拉法新、萘啶酸和雄烯二酮,其浓度未超过  1 ng/L。卡马西平和避蚊胺在所有样点中都有检出,浓度范围分别为 0.8-10.2 ng/L和0.01-3.5 ng/L。典型药物有季节分布规律,可替宁在暖季中浓度水平大于在冷季中的浓度水平,而林可霉素相反。从原因来看,水源地中的药物的检出率主要跟分析方法的检测限、国内原料药的生产状况有关。
    本文基于建立的多类别 PPCPs的分析方法,在  2014年期间对中国典型流域的极性有机污染物进行了分布状况调查。结果显示,根据采样点检出的污染物的种类可以推测该采样点可能的污染源。例如,“兰州”样点中检测出多类别的医药品,如抗生素类、只能用于医药行业的可待因、非甾体类消炎药对乙酰氨基酚及激素类药物宝丹酮和美雄酮等,推测该样点可能受到附近区域医院污水排放的影响。大运河流域样点检出的几百 ng/L的喹诺酮类、大环内酯类、林可霉素等类别抗生素,可能与当地有污染源有关。
    对饮用水处理工艺过程中的多类别药物和农药的变化规律进行了研究。以连云港市自来水厂为例,常规处理工艺对絮凝、沉淀对药物和农药转化产物等新型污染物无明显的去除效果,氯消毒对部分化合物有去除效果,但对这些微量污染物的去除起主要作用的处理工艺为臭氧和生物活性炭工艺。
    采用固相萃取(SPE)-超高效液相色谱串联质谱(UPLC-MS/MS)技术,建立了同时测定环境水样中痕量浓度多极性的 35种高关注农药及转化产物的方法。优化的前处理方法为:串联 HLB和活性炭小柱用于富集水样,10mL乙腈为HLB柱洗脱溶剂,10 mL20 mmol/L乙酸铵-甲醇作为活性炭柱的洗脱溶剂,将洗脱溶液混合、浓缩、溶剂转化和定容,定容溶剂为 10 mmol/L乙酸铵的乙腈-水的混合溶液(1:1,v/v)流动相分别为 5 mmol/ L甲酸铵-甲酸缓冲溶液(pH   3.5)和乙腈进行UPLC色谱分离,质谱用多反应监测(MRM)模式进行分析测定。实验结果表明,目标物在 0. 5 ~200 μg/L含量范围内线性良好(R2≥0.9802),检出限范围为0.01 ~0.8ng/ L,回收率在 60% ~120%之间。本研究构建的 SPE-UPLC-MS/ MS方法灵敏可靠,可用于对地表水中 ng/L级极性不同的多种农药及转化产物的测定。
英文摘要:       Pharmaceuticals and personal care products (PPCPs) are so-called“pseudo-persistent” contaminants in aquatic environments because of their consistent consumption and their polar and non-volatile properties. Since various kinds of PPCPs have different physic-chemical properties, and moreover, the concentrations of PPCPs in environmental water vary vary from low ng/L to thousands of ng/L, it is a challenge to determine various kinds of PPCPs simutaniously using one SPE procedure. Pesticides were used widely in agricultural activities, so it is obvious that environmental waters can be contaminanted from the agricultural areas. Some polar pesticides with polar proterties which have the ecotoxicological potential, such as acephate and mathaminophos, were often ignored in aquatic environment due to lack of analytical method. The objective of this dissertation was to develop analytical methods effectively to determine multiple-classes of pharmaceuticals and polar pesticides in environmental waters, especially in drinking water sources and distribution waters. These methods were applied to investigate the occurrences of phamaceuticals in drinking water sources of major watersheds in China. They were also applied to investigate multiple classes of pharmaceuticals and polar pesticides in surface waters of key watersheds in China. Based on the analytical methods, the occurrences of pharmaceuticals and polar pesticides during drinking water treatment were also investigated.
      A survey for multi-class pharmaceuticals in drinking water sources (DWSs) of five major river watersheds in China was conducted from 2012 to 2013. Samples were collected from 25 sampling sites in rivers and reservoirs. 135 pharmaceuticals were analyzed using solid-phase extraction and ultra-performance liquid chromatography tandem mass spectrometry. The results showed that a total of 70 pharmaceuticals were present in the samples, and the most frequently detected ones included sulfonamides,macrolides, antiepileptic drugs, anti-inflammatory drugs, and β-blockers, etc.
      Amongst these, maximum concentrations of lincomycin, sulfamethoxazole,acetaminophen and paraxanthine were between 44 ng/L and 134 ng/L, and those of metoprolol, diphenhydramine, venlafaxine, nalidixic acid and androstenedione were less than 1 ng/L. Concentrations of the two that were most persistent,diethyltoluamide (DEET) and carbamazepine, were 0.8-10.2 ng/L and 0.01-3.5 ng/L,respectively. Higher concentrations of cotinine were observed in warm season than in cold season, while concentrations of lincomycin were the opposite. In a causality analysis, the occurrence of pharmaceuticals in DWSs depends mainly on the detection limits of the methods, their usage and the persistence in the aquatic environment.
      Based on the analytical methods, multiple classes of pharmaceuticals and polar pesticides were also surveyed in key watersheds of China during year 2014. It was found out that pollution sources were speculated based on the specific usage of certain pharmaceuticals. For instance, codeine, non-steroidal anti-inflammatory drugs, steroid
hormones which were permitted to bed used in hospitals, were found in sampling site “Lanzhou”. For another example, hundreds of ng/L concentration level for  macrolides, quinolones and lincomycin were found in sampling site F2 in the Grand Canal.
      The occurrences and distribution pattern of PPCPs and polar pesticides were investigated in conventional and advanced drinking water treatment processes of three drinking water treatment plants in Lianyungang City. Results showed that removal efficiencies were not significant during conventional processes such as flocculation and sedimentation. Prechlorination could remove some of the contaminants. However,advanced technology (ozonation combined with BAC filtration) could effectively remove the micropollutants for drinking water supply.
      A method based on solid-phase extraction combined with ultra-performance liquid chromatography-tandem mass spectrometry (SPE-UPLC-MS/MS) was established for the simultaneous determination of thirty-five pesticides and transformation products of high concern with different polarities at trace level in environmental waters. Under optimized conditions, tandem cartridges with Oasis HLB column and activated carbon were used for the enrichment of water samples.HLB column was eluted by 10 mL of    actonitrile, and activated carbon cartridge was eluted by 10 mL of methanol solution containing 20 mmol/L ammonium acetate. The elution solvents were mixed and concentrated. Finally, the elution solvent was reconstituted with a mixed solution of acetonitrile and water (1:1, V/V) containing 10
mmol/L ammonium acetate. The targets were separated by gradient elution with 5 mmol/L ammonium formate buffer and acetonitrile as mobile phases, and detected by MS/MS in the multi-reactions monitoring (MRM) mode. Under the experimental conditions, good linearity ranging form 0.5-200 μg/L was made (R2≥0.9802), and the limits of detection (LODs) were from 0.01 to 0.8 ng/L. Recovery of most targets were 60%-120%. The SPE-UPLC-MS/MS method established here is reliable and can be applied to determine ng/L level of pesticides and transformation products with different polarities in surface water.
内容类型: 学位论文
URI标识: http://ir.rcees.ac.cn/handle/311016/36955
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:
孙静. 水中PPCPs与极性农药的分析方法与分布规律研究[D]. 北京. 中国科学院研究生院. 2015.
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