上海市16区县水产品全氟和多氟烷基物质污染及膳食暴露评估

Contamination of per- and polyfluoroalkyl substances in aquatic products and dietary risk assessment across 16 districts of Shanghai, China

  • 摘要:
    背景 全氟化合物(PFAS)是全球关注的环境内分泌干扰物,我国污染问题突出,人群暴露普遍。膳食,尤其是水产品等动物源性食物,是其最主要的来源。
    目的 在人群PFAS暴露水平较高的上海地区调查当地水产品PFAS污染水平,并对当地多年龄段人群进行水产品和饮用水暴露风险及健康风险评估,为上海市居民膳食指导和我国PFAS风险管理提供基础数据。
    方法 在上海市16个区县随机选取采样点,采集有代表性的四类水产品,包括淡水鱼(n=28)、海水鱼(n=27)、虾类(n=18)和蟹类(n=17),定量测定四类食物中13种PFAS水平,包括3种短链全氟烷基羧酸(PFCA)和5种长链PFCA、2种短链全氟烷基磺酸(PFSA)和3种长链PFSA。选取国内外重点关注的3种PFAS同系物(全氟辛酸(PFOA)、全氟辛烷磺酸(PFOS)和全氟壬酸(PFNA),评估上海地区人群平均消费量人群和高消费量人群通过水产品和饮用水摄入PFAS的日均摄入量。分别基于国际常用人群安全限值——美国毒物与疾病登记署(ATSDR)制订的PFAS日均摄入最小风险值(MRL)和欧洲食品安全署(EFSA)制订的每周摄入限值(TWI),使用危害指数法计算健康风险。
    结果 在四类水产品所检测的13种PFAS同系物中,每类水产品均检出9~10种PFAS同系物,主要集中在PFOS和5种长链PFCA(检出率均超过50%)。四类水产品中,PFAS检出质量分数(后简称为浓度)(Σ13PFAS)中位数由高到低依次为:蟹类6.314 ng·g−1(以湿重计,余同),虾类(2.313 ng·g−1),淡水鱼(0.833 ng·g−1),海水鱼(0.808 ng·g−1)。不同水产品PFAS浓度分布存在差异:淡水鱼和海水鱼中,PFOS检出浓度最高,中位数分别为0.238和0.145 ng·g−1;虾类和蟹类中,全氟十一烷酸(PFUA)检出浓度最高,中位数分别为0.840和1.439 ng·g−1。当地平均消费量人群通过水产品和饮用水摄入Σ3PFAS日均摄入量范围为0.455~1.129 ng·kg−1·d−1(以体重计,余同);当地高消费量人群通过水产品和饮用水摄入Σ3PFAS日均摄入量范围为1.129~2.939 ng·kg−1·d−1。总体而言,成年人(18~岁)和儿童(<12岁),尤其是低龄儿童(<9岁),PFAS暴露风险最大;且无论是哪个年龄段的人群,对人群暴露风险贡献最大的PFAS同系物均为PFOS。根据ATSDR制订的MRL,上海地区各年龄段平均消费量人群均无健康风险危害指数(HI)<1,除成年人外的高消费量人群均存在健康风险(HI>1)。相比于更为严格的EFSA制订的TWI,当地居民均存在健康风险:平均消费量人群HI为1.17~2.46,高消费量人群HI为3.56~6.09。
    结论 上海地区水产品PFAS检出普遍,整体而言,PFOS检出浓度高于其他PFAS同系物。四类水产品中,PFAS检出浓度由高到低依次为:蟹类、虾类、淡水鱼、海水鱼。当地居民,尤其是成年人和低龄儿童(<9岁)通过水产品和饮用水摄入PFAS可能存在一定的健康风险,水产品是PFAS重要来源。建议优化调整水产品摄入种类以减少人群PFAS摄入风险。

     

    Abstract:
    Background Per- and polyfluoroalkyl substances (PFAS) are globally concerning environmental endocrine disruptors, with prominent pollution issues in China, and have been widely detected in humans. Diet, especially animal-derived foods such as aquatic products, is the main source of PFAS.
    Objective To investigate the contamination of PFAS in local aquatic products in Shanghai that reported high PFAS exposure, evaluate PFAS exposure through aquatic products and drinking water, and perform risk assessments for individuals of different age groups in Shanghai, providing evidence for dietary recommendations for Shanghai residents and risk management of PFAS in China.
    Methods Four aquatic product species, including freshwater fish (n=28), marine fish (n=27), shrimps (n=18), and crabs (n=17), were purchased from randomly selected sampling sites in 16 districts and counties of Shanghai. The concentrations of 13 PFAS congeners were measured, including 3 short-chain perfluoroalkyl carboxylic acids (PFCAs), 5 long-chain PFCAs, 2 short-chain perfluoroalkyl sulfonic acids (PFSAs), and 3 long-chain PFSAs. The assessment of local residents' exposure risk to PFAS was conducted by combining their consumption of aquatic products and drinking water with the most widely concerned three PFAS congeners (perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS), and perfluorononanoate (PFNA) in both average consumers and high consumers. Hazard index was applied to evaluate human health risks according to the oral minimal risk levels (MRL) of PFAS established by Agency for Toxic Substances and Disease Registration (ATSDR) and the tolerable weekly intake (TWI) established by European Food Safety Authority (EFSA).
    Results Nine to ten PFAS congeners were positive in each of the four aquatic product species out of the 13 PFAS congeners, and the most frequently positive PFAS congeners were PFOS and five long-chain PFCA (the positive rates were > 50%). The highest concentration of Σ13PFAS (median) was detected in crabs 6.314 ng·g−1 (wet weight, thereafter), followed by shrimps (2.313 ng·g−1), freshwater fish (0.833 ng·g−1), and marine fish (0.808 ng·g−1). The distribution of PFAS congeners varied in four aquatic food species: freshwater fish and marine fish showed the leading median concentrations of PFOS (0.238 and 0.145 ng·g−1), respectively, while shrimps and crabs showed the leading median concentrations of perfluoroundecanoate (PFUA) (0.840 and 1.439 ng·g−1), respectively. The average daily intake of Σ3PFAS through aquatic products and drinking water by average consumers ranged from 0.145 to 1.129 ng·kg−1·d−1 (in terms of body weight, thereafter), and by high consumers from 1.129 to 2.939 ng·kg−1·d−1, respectively. Adults (>18 years) and children (<12 years), especially those under 9 years old, were more likely exposed to PFAS, and PFOS contributed the most across all age groups. According to the MRL established by ATSDR, there was no health risk for average consumers of all ages in Shanghai hazard index (HI) <1, but there were health risks for all ages in high consumers except for adults (HI>1). Meanwhile, after comparing with the more stringent TWI formulated by EFSA, there were health risks for all ages in both average consumers and high consumers in Shanghai: HI for average consumers was from 1.17 to 2.46, and HI for high consumers from 3.56 to 6.09.
    Conclusion In Shanghai, PFAS is frequently detected in aquatic products. In general, PFOS concentrations are higher than those of other PFAS congeners. The PFAS levels of four aquatic food species from high to low are crabs, shrimps, freshwater fish, and marine fish. Potential health risks are found in local residents, especially adults and young children (less than 9 years old), via aquatic products and drinking water, and aquatic products are the primary source. It is recommended to optimize the types of aquatic products consumed to reduce the risk of PFAS intake for the local population.

     

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