典型药物及个人护理品在黄东海海域水体中的检测、分布规律及其风险评估

目前对沿海地区存在的药物及个人护理品(PPCPs)的了解十分有限,建立能同时精确检测海水样品中多种PPCPs的方法至关重要.本研究选取非甾体类消炎药、抗生素、脂质调节剂和兴奋剂等类别的9种PPCPs作为检测对象,建立固相萃取-高效液相色谱-质谱联用方法(SPE-HPLC-MS),确定了固相萃取柱的填料、洗脱液组成及用量等最佳实验条件.结果表明,萃取柱为CNW HLB,洗脱液为甲醇∶乙腈(1∶1,体积比),洗脱液体积为6 m L,水样pH为7,流速为5 m L·min~(-1),螯合剂EDTA-Na_2添加量为1 g,且浓缩倍数为500倍时,萃取效果最佳.9种PPCPs的线性回归方程均具有良好线性,相关性系数均大于0. 999,回收率在82%～106%之间,相对标准偏差在1. 6%～14%之间,检出限在0. 01～2 ng·L~(-1)之间,满足海水中痕量分析的要求.于2018年夏季对黄东海表层水体中PPCPs的分布特性、来源和分布规律进行研究.9种PPCPs均被检出,主要污染物是NAP、IBU、GEM、CAF和ASA.在空间分布上,PPCPs浓度整体呈现河口近岸高,远海海域较低的趋势,黄海海域中PPCPs浓度高于东海,这与黄海海域污染源多、其水交换能力与东海相比较弱有关.主成分分析结果显示,表层海水中的PPCPs浓度与盐度和pH之间具有负相关性,与叶绿素a具有一定正相关性,表明PPCPs的主要来源为陆源输入.运用风险熵值法对该海域的PPCPs进行环境风险评估,9种PPCPs的RQ均小于1,其中IBU和NAP的RQ大于0. 1,可能对该海域产生中度风险危害,其余PPCPs的RQ均小于0. 1,表明其目前对黄海及东海海域基本没有危害.

Detection Method, Distribution, and Risk Assessment of Pharmaceuticals and Personal Care Products in the Yellow Sea and the East China Sea

At present, research findings on pharmaceuticals and personal care products (PPCPs) in coastal areas are still unclear, and there is a need to develop a method to detect more PPCPs simultaneously in seawater. In this study, nine compounds of non-steroidal anti-inflammatory drugs, antibiotics, lipid regulators. and stimulants were selected as analytes. Solid phase extraction (SPE) was used to extract the compounds, which were then analyzed by high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS). The optimum experimental conditions, such as the filler, eluent, pH, flow rate, and the reduction of matrix effect were optimized during the SPE. The results showed that the best extraction column was CNW HLB, the best eluent was methanol:acetonitrile (1:1, volume ratio), the best eluent volume was 6 mL, the best pH was 7, the best flow rate was 5 mL·min^-1, the amount of EDTA-Na₂ added was 1 g, and the best concentration multiple was 500. The linear regression equations of all PPCPs had good linearity. Correlation coefficients were>0.999, recovery rates were between 82%-106%, relative standard deviations were between 1.6%-14%, and detection limits were between 0.01-2 ng·L^-1, thus satisfying the requirement of trace analysis in seawater. Distribution characteristics and sources of PPCPs were studied in the Yellow Sea and the East China Sea during summer 2018. All nine PPCPs were detected and the main pollutants were NAP, IBU, GEM, CAF, and ASA. High concentrations of PPCPs were generally detected in the nearshore area and displayed conspicuous decreasing tendencies from the inshore towards the offshore. The concentrations of PPCPs in the Yellow Sea were higher than of those in the East China Sea, and this was related to there being more sources of pollutions and poor water exchange capacity in the Yellow Sea. Principal component analysis showed that the main source of PPCPs was terrestrial input. The environmental risk assessment of PPCPs indicated that risk quotients (RQs) of IBU and NAP (0.1-1) posed a medium risk to the aquatic environment, while others posed low risk to organisms.