血液与头发中PFAS暴露特征及关联性研究

李丽; 赵祖兰; 黄璐璐; 曹雪; 秦瑞欣; 张释义; 谢春; 廖其龙; 郑晶

PDF(2089 KB)

中国环境科学 ›› 2025, Vol. 45 ›› Issue (12) : 6996-7007.

环境毒理与健康

血液与头发中PFAS暴露特征及关联性研究

李丽^1,2, 赵祖兰^1,2, 黄璐璐^1,2, 曹雪^2,3, 秦瑞欣^2,4,5, 张释义^2,4,5, 谢春¹, 廖其龙², 郑晶^1,2

作者信息 +

Exposure characteristics and associations of per- and polyfluoroalkyl substances in paired blood and hair samples

LI Li^1,2, ZHAO Zu-lan^1,2, HUANG Lu-lu^1,2, CAO Xue^2,3, QIN Rui-xin^2,4,5, ZHANG Shi-yi^2,4,5, XIE Chun¹, LIAO Qi-long², ZHENG Jing^1,2

Author information +

文章历史 +

摘要

本文以24名电子垃圾拆解女工为研究对象,通过间隔3个月的两次血液和头发配对采样,分析了血液和头发中PFAS的浓度水平、组成特征及关联性,并评估了该职业人群的暴露特征及头发作为非侵入性生物标志物的可行性.结果显示,女工血清中共检测到27种PFAS,总浓度范围为42.8~228ng/mL,中值为108ng/mL;头发中共检测到13种PFAS,总浓度范围为2.92~37.1ng/g,中值为6.53ng/g;全氟辛酸(PFOA)是血清与头发中含量最高的PFAS,占比分别为47.0%和39.5%.在同一采样时间节点,配对血清与头发样本中PFOA、全氟壬酸(PFNA)、全氟十一酸(PFUdA)、全氟辛烷磺酸(PFOS)、6:2氯代全氟醚磺酸(6:2Cl-PFESA)呈剂量依赖性相关,当上述PFAS血清浓度分别处于第75百分位数时,与血清浓度处于第10百分位数相比,头发中浓度分别上升299.88%、522.14%、166.98%、276.97%和323.34%个标准差,暂未观察到头发中PFAS浓度与采样节点前3个月血清PFAS浓度之间的关联.Spearman和Mann-Whitney U分析表明工作年限和工作场所对PFAS浓度无显著影响.本研究揭示了头发在表征PFAS人体内负荷的价值,为PFAS环境暴露风险评估和非侵入性监测方法的开发提供了科学依据.

Abstract

Per- and polyfluoroalkyl substances (PFAS) are typical emerging contaminants with persistence, bioaccumulation, and toxicity (PBT) properties. Female e-waste dismantling workers are at heightened risk because of their occupational activities. To characterize exposure patterns and explore the potential of hair as a non-invasive biomarker, we longitudinally evaluated 24 female workers via two sampling rounds separated by three months. Serum and hair samples were analyzed for PFAS concentrations, compositional profiles, and inter-matrix correlations. Twenty-seven PFAS were quantified in serum (median total concentration: 108ng/mL; range: 42.8~228ng/mL), while thirteen PFAS were detected in hair (median total concentration: 6.53ng/g; range: 2.92~37.1ng/g). Perfluorooctanoic acid (PFOA) dominated both matrices, accounting for 47.0% of total PFAS in serum and 39.5% in hair. Positively dose-dependent relationships were observed between contemporaneous serum and hair concentrations for PFOA, perfluorononanoic acid (PFNA), perfluoroundecanoic acid (PFUdA), perfluorooctane sulfonic acid (PFOS), and 6:2 chlorinated polyfluoroalkyl ether sulfonate (6:2Cl-PFESA). When serum levels increased from the 10th to the 75th percentile, corresponding hair concentrations rose by 299.88%, 522.14%, 166.98%, 276.97% and 323.34%, respectively. In contrast, no significant associations were found between current hair PFAS levels and serum levels measured three months earlier. Employment duration and workplace type did not significantly influence PFAS burdens. These results validate hair as a practical, non-invasive matrix for PFAS exposure assessment and provide critical evidence for environmental health risk evaluation in this high-exposure occupational group.

导出引用

李丽, 赵祖兰, 黄璐璐, 曹雪, 秦瑞欣, 张释义, 谢春, 廖其龙, 郑晶. 血液与头发中PFAS暴露特征及关联性研究[J]. 中国环境科学. 2025, 45(12): 6996-7007

LI Li, ZHAO Zu-lan, HUANG Lu-lu, CAO Xue, QIN Rui-xin, ZHANG Shi-yi, XIE Chun, LIAO Qi-long, ZHENG Jing. Exposure characteristics and associations of per- and polyfluoroalkyl substances in paired blood and hair samples[J]. China Environmental Science. 2025, 45(12): 6996-7007

中图分类号： X503.1

参考文献

[1] Cao Y X, Ng C. Absorption, distribution, and toxicity of per-and polyfluoroalkyl substances (PFAS) in the brain: A review [J]. Environmental Science: Processes & Impacts, 2021,23(11):1623-1640.
[2] Ojo A F, Peng C, Ng J C. Assessing the human health risks of per-and polyfluoroalkyl substances: A need for greater focus on their interactions as mixtures [J]. Journal of Hazardous Materials, 2021,407: 124863.
[3] Soheimi S, Rahman A A, Abd Latip N, et al. Understanding the impact of perfluorinated compounds on cardiovascular diseases and their risk factors: a meta-analysis study [J]. International Journal of Environmental Research and Public Health, 2021,18(16),8345.
[4] Sunderland E M, Hu X, Dassuncao C, et al. A review of the pathways of human exposure to poly-and perfluoroalkyl substances (PFASs) and present understanding of health effects [J]. Journal of Exposure Science and Environmental Epidemiology, 2019,29(2):131-147.
[5] Li Y, Fletcher T, Mucs D, et al. Half-lives of PFOS, PFHxS and PFOA after end of exposure to contaminated drinking water [J]. Occupational and Environmental Medicine, 2018,75(1):46-51.
[6] Rosato I, Bonato T, Fletcher T, et al. Estimation of per-and polyfluoroalkyl substances (PFAS) half-lives in human studies: a systematic review and meta-analysis [J]. Environmental Research, 2024,242:117743.
[7] 陈绩,李彤,吴限好,等.全氟和多氟烷基化合物暴露特征与健康效应研究进展 [J]. 环境与职业医学, 2023,40(8):958-964. Chen J, Li T, Wu X H, et al. Review on exposure characteristics and health effects of per-and poly-fluoroalkyl substances [J]. Journal of Environmental and Occupational Medicin, 2023,40(8):958-964.
[8] 王晓岚.多部门联合发文:禁止生产、流通、使用和进出口林丹等农药 [J]. 现代农药, 2019,18(2):44. Wang X L. Multi -department jointly issued a document: banning the production, circulation, use, and import and export of pesticides such as lindane [J]. Modern Agrochemicals, 2019,18(2):44.
[9] 重点管控新污染物清单(2023年版) [J]. 中华人民共和国国务院公报, 2023,(5):19-24. List of new pollutants subject to key control (2023 Edition) [J]. Gazette of the State Council of the People's Republic of China, 2023,(5):19-24.
[10] 傅建捷,王亚韡,周麟佳,等.我国典型电子垃圾拆解地持久性有毒化学污染物污染现状 [J]. 化学进展, 2011,23(8):1755-1768. Fu J J, Wang Y W, Zhou L J, et al. Pollution status and perspectives of persistent toxic substances in e-waste dismantling area in China [J]. Pogress in Chemistry, 2011,23(8):1755-1768.
[11] 严骁,李淑圆,王美欢,等.电子垃圾拆解工人的肝功能和肾功能健康状况及影响因素分析:以清远市龙塘镇为例 [J]. 环境科学, 2018, 39(2):953-960. Yan X, Li S Y, Wang M H, et al. Liver and kidney function of e-waste dismantling workers and potential influencing factors [J]. Environmental Science, 2018,39(2):953-960.
[12] Glüge J, Scheringer M, Cousins I T, et al. An overview of the uses of per-and polyfluoroalkyl substances (PFAS) [J]. Environmental Science: Processes & Impacts, 2020,22(12):2345-2373.
[13] Tansel B. PFAS use in electronic products and exposure risks during handling and processing of e-waste: A review [J]. Journal of Environmental Management, 2022,316:115291.
[14] Zhao L, Cheng Z, Zhu H, et al. Electronic-waste-associated pollution of per-and polyfluoroalkyl substances: Environmental occurrence and human exposure [J]. Journal of Hazardous Materials, 2023,451: 131204.
[15] Zhang T, Zhang B, Bai X Y, et al. Health status of elderly people piving near e-waste recycling sites: association of e-waste dismantling activities with legacy perfluoroalkyl substances (PFASs) [J]. Environmental Science & Technology Letters, 2019,6(3):133-140.
[16] Chang C J, Ish J L, Chang V C, et al. Exposure to per-and polyfluoroalkyl substances and breast cancer risk: a systematic review and meta-analysis of epidemiologic studies [J]. American Journal of Epidemiology, 2024,193(8):1182-1196.
[17] Liu Y, Eliot M N, Papandonatos G D, et al. Gestational perfluoroalkyl substance exposure and DNA methylation at birth and 12years of age: a longitudinal epigenome-wide association study [J]. Environmental Health Perspectives, 2022,130(3):37005.
[18] DeLuca N M, Minucci J M, Mullikin A, et al. Human exposure pathways to poly-and perfluoroalkyl substances (PFAS) from indoor media: A systematic review [J]. Environment International, 2022,162: 107149.
[19] 江建明,李敏杰,叶铖,等.全氟和多氟烷基物质在人体生物样本中的检测方法与暴露水平研究进展 [J]. 环境化学, 2024,43(9):2881-2896. Jiang J M, Ye M J, Ye C, et al. Pogress in the determination methods and exposure levels of per-and polyfluoroalkyl substancesin human biological samples [J]. Environmental Chemistry, 2024,43(9):2881-2896.
[20] India-Aldana S, Yao M Z, Midya V, et al. PFAS exposures and the human metabolome: a systematic review of epidemiological studies [J]. Current Pollution Reports, 2023,9(3):510-568.
[21] Zhang S Y, Yan X, Tang B, et al. Human hair as a noninvasive matrix to assess exposure to micro-organic contaminants: State of the art review [J]. Science of the Total Environment, 2023,892:164341.
[22] Tang B, Zheng J, Xiong S M, et al. The accumulation of organic contaminants in hair with different biological characteristics [J]. Chemosphere, 2023,312:137064.
[23] 于云江,郑晶,罗伟铿,等.头发作为环境污染物人体暴露生物检测材料的研究进展 [J]. 科学通报, 2023,68(16):2070-2085. Yun Y J, Zheng J, Luo W K, et al. Hair as a biomonitoring tool of human exposure to environmental pollutants: a review [J]. Chinese Science Bulletin, 2023,68(16):2070-2085.
[24] 罗镇南,秦瑞欣,张释义,等.头发中多种新型有机污染物检测方法的建立 [J]. 环境化学, 2023,42(5):1509-1523. Luo Z N, Qin R X, Zhang X Y, et al. The establishment of a new method for the detection of emerging organic contaminants in hair [J]. Environmental Chemistry, 2023,42(5):1509-1523.
[25] Koch S L, Tridico S R, Bernard B A, et al. The biology of human hair: A multidisciplinary review [J]. American Journal of Human Biology, 2020,32(2):e23316.
[26] 谢琳娜,张海婧,侯沙沙,等.人血清中18种全氟烷烃化合物UPLC-MS/MS的测定 [J]. 环境卫生学杂志, 2019,9(5):494-501. Xie L N, Zhang H J, Hou S S, et al. Determination of 18 perfluoroalkyl substances in human serum by UPLC-MS/MS [J]. Journal of Environmental Hygiene, 2019,9(5):494-501.
[27] Tang B, Christia C, Malarvannan G, et al. Legacy and emerging organophosphorus flame retardants and plasticizers in indoor microenvironments from Guangzhou, South China [J]. Environment International, 2020,143:105972.
[28] You L, Kou J, Wang M D, et al. An exposome atlas of serum reveals the risk of chronic diseases in the Chinese population [J]. Nature Communications, 2024,15(1):2268.
[29] Hall S M, Zhang S R, Tait G H, et al. PFAS levels in paired drinking water and serum samples collected from an exposed community in Central North Carolina [J]. Science of the Total Environment, 2023,895:165091.
[30] Wu M, Sun R, Wang M, et al. Analysis of perfluorinated compounds in human serum from the general population in Shanghai by liquid chromatography-tandem mass spectrometry (LC-MS/MS) [J]. Chemosphere, 2017,168:100-105.
[31] Zhang B, He Y, Huang Y, et al. Novel and legacy poly-and perfluoroalkyl substances (PFASs) in indoor dust from urban, industrial, and e-waste dismantling areas: The emergence of PFAS alternatives in China [J]. Environmental Pollution, 2020,263:114461.
[32] Liao Q, Tang P, Pan D X, et al. Association of serum per-and polyfluoroalkyl substances and gestational anemia during different trimesters in Zhuang ethnic pregnancy women of Guangxi, China [J]. Chemosphere, 2022,309:136798.
[33] Liu D, Tang B, Nie S, et al. Distribution of per-and poly-fluoroalkyl substances and their precursors in human blood [J]. Journal of Hazardous Materials, 2023,441:129908.
[34] Wang Y X, Zhong Y X, Li J G, et al. Occurrence of perfluoroalkyl substances in matched human serum, urine, hair and nail [J]. Journal of Environmental Sciences, 2018,67:191-197.
[35] Ruan Y F, Lalwani D, Kwok K Y, et al. Assessing exposure to legacy and emerging per-and polyfluoroalkyl substances via hair -The first nationwide survey in India [J]. Chemosphere, 2019,229:366-373.
[36] Xu F P, Chen D, Liu X T, et al. Emerging and legacy per-and polyfluoroalkyl substances in house dust from South China: Contamination status and human exposure assessment [J]. Environmental Research, 2021,192:110243.
[37] Mishra V, Heath R J. Structural and biochemical features of human serum albumin essential for eukaryotic cell culture [J]. International Journal of Molecular Sciences, 2021,22(16):8411.
[38] Huang L L, Liao Q L, Yang J J, et al. Quantitative associations of polluting chemicals and endogenous biomolecules in hair: an observational perspective from a population-based study [J]. Environmental Science & Technology Letters, 2024,11(6):518-525.
[39] Alesio J L, Slitt A, Bothun G D. Critical new insights into the binding of poly-and perfluoroalkyl substances (PFAS) to albumin protein [J]. Chemosphere, 2022,287:131979.
[40] 黄璐璐,唐斌,廖其龙,等.广州市普通人群头发中多种有机污染物暴露评估 [J]. 环境化学, 2025,44(4):1235-1253. Huang L L,Tang B, Liao Q L, et al. Exposure assessment of various organic pollutants in the hair of the general population in Guangzhou City [J]. Environmental Chemistry, 2025,44(4):1235-1253.
[41] Piva E, Giorgetti A, Ioime P, et al. Hair determination of per-and polyfluoroalkyl substances (PFAS) in the Italian population [J]. Toxicology, 2021,458:152849.
[42] Jeon H, Shin M, Kim W, et al. Family-based exposure assessment of legacy and alternative poly-and perfluoroalkyl substances (PFASs) by multiple pathways [J]. Science of The Total Environment, 2025,969: 178735.
[43] Poothong S, Thomsen C, Padilla-Sanchez J A, et al. Distribution of novel and well-known poly-and perfluoroalkyl substances (PFASs) in human serum, plasma, and whole blood [J]. Environmental Science & Technology, 2017,51(22):13388-13396.
[44] Chen M, Guo T, He K, et al. Biotransformation and bioconcentration of 6:2and 8:2polyfluoroalkyl phosphate diesters in common carp (Cyprinus carpio): Underestimated ecological risks [J]. Science of the Total Environment, 2019,656:201-208.
[45] 吴雨晴.传统PFASs及其替代品与血清白蛋白结合机制及影响研究 [D]. 沈阳:沈阳工业大学, 2024. Wu Y Q. Binding mechanisms and effects of legacy PFASs and their alternatives on serum albumin [D]. Shenyang: Shenyang University of Technology, 2024.
[46] Ojo A F, Peng C, Ng J C. Combined effects and toxicological interactions of perfluoroalkyl and polyfluoroalkyl substances mixtures in human liver cells (HepG2) [J]. Environmental Pollution, 2020,263: 114182.
[47] Vestergren R, Cousins I T, Trudel D, et al. Estimating the contribution of precursor compounds in consumer exposure to PFOS and PFOA [J]. Chemosphere, 2008,73(10):1617-1624.
[48] 郝丽丽,张磊,宁钧宇,等. PFOS与PFOA的毒性效应及其在我国普通人群中的内暴露研究进展 [J]. 中国食品卫生杂志, 2022,34(5): 1112-1121. Hao L L, Zhang L, Ning J Y, et al. Toxic effects of PFOS/PFOA and their internal exposure in Chinese general population [J]. Chinese Journal of Food Hygiene, 2022,34(5):1112-1121.
[49] Alesio J. Protein pairing and lipid linking: physicochemical properties of poly-and perfluoroalkyl substances (PFAS) influence their unteractions with macromolecules [D]. Kingston:University of Rhode Island, 2022.
[50] Labine L M, Pereira E, Kleywegt S, et al. Sublethal Exposure of per-and polyfluoroalkyl substances of varying chain length and polar functionality results in distinct metabolic responses in daphnia magna [J]. Environmental Toxicology and Chemistry, 2023,42(1):242-256.
[51] Peng L, Xu W, Zeng Q H, et al. Exposure to perfluoroalkyl substances in waste recycling workers: Distributions in paired human serum and urine [J]. Environment International, 2022,158:106963.
[52] Kim D, Lee J, Oh J. Perfluoroalkyl acids in paired serum, urine, and hair samples: Correlations with demographic factors and dietary habits [J]. Environmental Pollution, 2019,248:175-182.
[53] 李钰涛,黄语,唐冲,等.中国人人体血清中多氟和全氟烷基化合物及其与血清生化指标的关联性研究 [J]. 生态毒理学报, 2024, 19(3):36-48. Li Y T, Huang Y, Tang C, et al. Research on relationship between traditional/emerging per/polyfluoroalkyl substances in Chinese serum and human bodyfunction indicators [J]. Asian Journal of Ecotoxicology, 2024,19(3):36-48.
[54] Rand A A, Mabury S A. Protein binding associated with exposure to fluorotelomer alcohols (FTOHs) and polyfluoroalkyl phosphate esters (PAPs) in rats [J]. Environmental Science & Technology, 2014,48 (4):2421-2429.
[55] Kucharska A, Covaci A, Vanermen G, et al. Non-invasive biomonitoring for PFRs and PSDEs: New insights in analysis of human hair externally exposed to selected flame retardants [J]. Science of the Total Environment, 2015,505:1062-1071.
[56] Li M, Tang B, Zheng J, et al. PCDD/Fs in paired hair and serum of workers from a municipal solid waste incinerator plant in South China: Concentrations, correlations, and source identification [J]. Environment International, 2020,144:106064.
[57] Lin M Q, Ma S T, Tang J, et al. Polybrominated diphenyl ethers and bromophenols in paired serum, hair, and urine samples of e-waste dismantlers: insights into hair as an indicator of endogenous exposure [J]. Science of the Total Environment, 2023,871:161980.
[58] Li J, Guo F, Wang Y, et al. Can nail, hair and urine be used for biomonitoring of human exposure to perfluorooctane sulfonate and perfluorooctanoic acid? [J]. Environment International, 2013,53:47-52.
[59] 杨娟娟.电子废弃物拆解家庭作坊工人头发中塑化剂的暴露特征及健康风险研究 [D]. 贵阳:贵州医科大学, 2024. Yang J J. Characteristics of plasticizers exposure and health risks inthe hair of e-waste disassembly home workshop workers [D]. Guiyang: Guizhou Medical University, 2024.
[60] Fu J J, Gao Y, Cui L, et al. Occurrence, temporal trends, and half-lives of perfluoroalkyl acids (PFAAs) in occupational workers in China [J]. Scientific Reports, 2016,6:38039.
[61] Tanner E M, Bloom M S, Wu Q, et al. Occupational exposure to perfluoroalkyl substances and serum levels of perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in an aging population from upstate New York: a retrospective cohort study [J]. International Archives of Occupational and Environmental Health, 2018,91(2):145-154.