华南地区城市内河水体、沉积物及鱼类中有机磷阻燃剂的污染特征及健康风险评估
Pollution Characteristics and Health Risk Assessment of Organophosphorus Flame Retardants in Water, Sediments, and Fish from An Urban Inland River in South China
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摘要: 本研究采集了华南地区城市内河上下游不同点位水体、沉积物及配对的21份鱼体样本,分析了14种有机磷阻燃剂(organophosphorus flame retardants, OPFRs)在环境和生物样本中的污染特征,并探讨了鱼体中OPFRs的潜在来源及贡献,进一步评估了水体及鱼体中OPFRs的人体暴露健康风险。结果显示OPFRs在水、沉积物及鱼体中的总浓度分别为0.92~356.76 ng·L-1、1 023.18~33 491.16 ng·g-1 (以干质量计)和14.34~723.71 ng·g-1 (以干质量计),中值浓度分别为52.60 ng·L-1、11 195.67 ng·g-1 (以干质量计)、49.38 ng·g-1 (以干质量计)。其中水、沉积物和鱼的检出率为100%的化合物分别是磷酸三(2-氯乙基)酯(TCEP)、磷酸三乙酯(TEP)和磷酸三(2-丁氧乙基)酯(TBOEP),磷酸三(1,3-二氯异丙基)酯(TDCIPP)、磷酸三丁酯(TNBP)和磷酸三(2-丁氧乙基)酯(TBOEP),磷酸三(2-氯乙基)酯(TCEP)、磷酸三苯酯(TPHP)、磷酸三丙酯(TIPRP)、磷酸三乙酯(TEP)、磷酸三丁酯(TNBP)和磷酸三(2-丁氧乙基)酯(TBOEP)。在靠近人口密集的HH点位,罗非鱼和鲮鱼体内污染物的浓度有着显著性差异,另外,HH点位和人口稀疏的LTYC点位的同种鱼类(罗非鱼)相比,也存在显著性差异。通过主成分分析(principal component analysis, PCA)和正定矩阵因子分解(positive definite matrix factorization, PMF)模型对鱼中的OPFRs进行来源解析,建筑材料、塑料制品以及电子产品在生产、消费或处置过程的污染排放对鱼OPFRs的贡献相对较高,这可能与城市内河周边人类活动及相关产业分布密切相关。鱼体中OPFRs的生物富集潜力较低。水体和鱼中OPFRs的致癌及非致癌风险远低于安全阈值,表明该地区居民对摄入水和鱼的健康风险较小,但长期摄入导致的累积暴露所带来的潜在健康风险不容忽视。Abstract: In this study, water samples, sediment samples, and 21 paired fish samples were collected at multiple points in the upper and the lower reaches of urban inland rivers, South China. The pollution characteristics of 14 organophosphorus flame retardants (OPFRs) in the environmental samples and biological samples were evaluated, and the potential sources and the contributions of each OPFR in fish samples were investigated. Furthermore, the associated human exposure health risks of OPFRs in water and fish were assessed. The findings of this study showed that the total concentrations of OPFRs in water, sediment, and fish ranged from 0.92 to 356.76 ng·L-1, 1 023.18 to 33 491.16 ng·g-1 (dry mass), and 14.34 to 723.71 ng·g-1 (dry mass), respectively. The median concentrations were 52.60 ng·L-1, 11 195.67 ng·g-1 (dry mass), and 49.38 ng·g-1 (dry mass), respectively. The compounds with 100% detection frequencies were tris(2-chloroethyl) phosphate (TCEP), triethyl phosphate (TEP) and tris(2-butoxyethyl) phosphate (TBOEP) in water, tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), tributyl phosphate (TNBP) and tris(2-butoxyethyl) phosphate (TBOEP) for sediment, and tris(2-chloroethyl) phosphate (TCEP), triphenyl phosphate (TPHP), trisopropyl phosphate (TIPRP), triethyl phosphate (TEP), tributyl phosphate (TNBP) and tris(2-butoxyethyl) phosphate (TBOEP) for fish. A significant difference was observed in the concentrations of OPFRs between tilapia and dace in the HH site with dense population. Additionally, a significant difference was found in tilapia between the HH site and the LTYC site with sparse population. Principal component analysis (PCA) and positive definite matrix factorization (PMF) models were employed to identify the sources of OPFRs in fish. OPFRs in fish were largely attributed to the building materials, plastic products, and electronic products during their production, consumption, and disposal processes. This can be closely related to the human activities and the industrial activities along the urban inland river. The bioaccumulation potential of OPFRs in fish was relatively low. Both the carcinogenic and non-carcinogenic risks of OPFRs in water and fish were remarkably below the safety threshold. This suggested that the health risks of local residents associated with the ingestion of water and fish were minor. Nevertheless, the potential cumulative exposure health risks due to the long-term ingestion should not be neglected.
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