上海市水源中药品及个人护理品污染现状分析及生态风险评价
Pollution analysis and ecological risk assessment of pharmaceutical and personal care products in water sources of Shanghai
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摘要:
背景 药品和个人护理品（PPCPs）作为一类新型的污染物，种类繁多，且广泛存在于自然水体中。近年来PPCPs受到广大群众和科研工作者的关注。上海作为国际化大都市，饮用水安全是一项重要的民生问题。
目的 本研究分析上海市水源中PPCPs的污染特征，并对其进行生态风险评价。
方法 采集上海市2017年丰水季4个水源地水样，采用全自动固相萃取对水样中的33种PPCPs进行富集浓缩后，经超高效液相色谱-三重四级杆质谱进行定量分析。利用熵值法对质量浓度较高的PPCPs进行生态风险评估。
结果 33种PPCPs中，未检出、部分检出和100%检出的PPCPs各约占1/3。其中安乃近的代谢产物4-乙酰氨基安替比林（4-AMP）和磺胺类抗生素等兽药为主要污染物，检出率均为100%，质量浓度分别为30.44~344.35、7.38~65.39 ng/L，占PPCPs总量的79.69%~97.69%。被检出的磺胺类药物主要为磺胺嘧啶、磺胺吡啶、磺胺二甲嘧啶和磺胺甲恶唑，其最高质量浓度分析别为22.18、3.70、28.45、8.67 ng/L。喹诺酮类抗生素的检出率及检出质量浓度均较低，除氧氟沙星和沙拉沙星外，质量浓度均低于1 ng/L。人用药物中，高血压及抗抑郁药美托洛尔和卡马西平也在所有水源中被检出，但相对含量较低，最高质量浓度分别仅为3.44、5.69 ng/L。4个水源中PPCPs的组成特征存在一定的异同点。4-AMP均为各水源中主要污染物。地处长江支流的水源D中PPCPs含量是其他3个水源的2.55~10.35倍；污染物质量浓度普遍高于其他水源，尤其是4-AMP和甲氰咪胍，质量浓度分别344.35、88.49 ng/L。其他水源中PPCPs的总量差异主要来源于4-AMP。生态风险评价结果表明，4-AMP尽管质量浓度较大，但生态毒性较低，风险熵值为2.77×10-3~3.13×10-2，风险较低。磺胺甲恶唑为主要的风险来源，为优先污染物。水源D中，总磺胺所致风险熵值为0.51，其余3个水源为0.18~0.33。
结论 上海市水源中存在一定的PPCPs污染，主要以磺胺类抗生素及4-AMP等兽药为主。其中地处长江支流的水源受PPCPs污染最为严重。初步风险评估结果表明个别抗生素具有一定的潜在生态风险，应加强优先污染物的管控。
Abstract:Background Pharmaceutical and personal care products (PPCPs), as a new type of pollutants, contain a wide range of chemicals and are widely found in natural water bodies. In recent years, PPCPs have drawn considerable attentions from the masses and researchers. Drinking water safety is an important livelihood issue in Shanghai as an international metropolis.
Objective This study is designed to analyze the pollution characteristics of PPCPs in water sources of Shanghai and assess the ecological risk.
Methods Water samples were collected in wet reason of 2017 from four water sources of Shanghai, and 33 PPCPs were quantitatively analyzed by ultra high performance liquid chromatography-triple quadrupole mass spectrometry after automatic solid phase extraction. Risk quotient was applied to assess the ecological risk of high-concentration PPCPs.
Results Around one third of the 33 PPCPs studied were detected in all, partial, and no samples respectively. The main pollutants were veterinary drugs such as analginum metabolite 4-acetamidoantipyrine (4-AMP) and sulfanilamides, both detection rates were 100%, the concentrations were 30.44-344.35 ng/L and 7.38-65.39 ng/L respectively, and they accounted for 79.69%-97.69% of the total PPCPs. The detected sulfanilamides mainly included sulfadiazine, sulfapyridine, sulfadimidine, and sulfamethoxazole with highest concentrations of 22.18, 3.70, 28.45, and 8.67ng/L, respectively. Quinolones showed low detection rates and concentrations, and their concentrations were below 1 ng/L except ofloxacin and sarafloxacin. For human medicines, antihypertensive and antidepressive drugs like metoprolol and carbamazepine were also detected in all the water sources, and their concentrations were relatively low with maximum concentrations of 3.44 and 5.69 ng/L respectively. There were some similarities and differences among the constituent features of PPCPs from the selected four water sources. The main pollutant in all water sources was 4-AMP. The concentration of PPCPs in water source D, one branch of the Yangtze River, was 2.55-10.35 times higher than the concentrations in the other water sources; the concentrations of each PPCPs detected in water source D were generally higher than those in the other water sources, especially 4-AMP and cimetidine at concentrations of 344.35 and 88.49 ng/L respectively. The difference among the other three water sources mainly lied on the concentration of 4-AMP. The results of ecological risk assessment indicated a low ecological risk with risk quotients ranging from 2.77×10-3 to 3.13×10-2 due to the low ecotoxicity of 4-AMP in spite of its high concentration. The main risk resulted from sulfamethoxazole as a priority pollutant. In water source D, the risk quotient contributed by sulfanilamides was 0.51, and in the other three water sources, the values were between 0.18 and 0.33.
Conclusion PPCPs contamination is found in the water sources of Shanghai, mainly veterinary drugs such as sulfanilamides and 4-AMP. The water source on the branch of the Yangtze River is the most polluted. The preliminary risk assessment results show that individual PPCPs exhibit potential ecological risks, calling for strengthening regulations for such priority pollutants.
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