上海市电镀企业周边地表水中全氟和多氟烷基物质(PFASs)的污染特征

郑平平; 陈晓倩; 沈璐; 吴强; 刘敏

doi:10.13198/j.issn.1001-6929.2022.06.12

上海市电镀企业周边地表水中全氟和多氟烷基物质(PFASs)的污染特征

doi: 10.13198/j.issn.1001-6929.2022.06.12

郑平平^{1, 3,},
陈晓倩²,
沈璐²,
吴强³,
刘敏^2, ,

1.
上海市安全生产科学研究所，上海　200233
2.
上海市检测中心生物与安全检测实验室，上海　201203
3.
上海电力大学环境与化学工程学院，上海市电力材料防护与新材料重点实验室，上海　200090

基金项目: 上海浦东新区科技发展基金(No.PCK2020-C001)

详细信息

作者简介:
郑平平（1992-），女，河南周口人，助理工程师，硕士，主要从事有毒有害物质分析与安全生产管理研究，zheng2237798573@163.com

通讯作者:
刘敏(1980-)，女，江西永新人，正高级工程师，博士，主要从事新污染物分析与化学品风险评估研究，lium@apm.sh.cn

中图分类号: X522
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出版历程
- 收稿日期: 2022-04-19
- 修回日期: 2022-06-07

Pollution Characteristics of Per- and Polyfluoroalkyl Substances (PFASs) in Adjacent Surface Water of Electroplating Industries in Shanghai

ZHENG Pingping^{1, 3
,},
CHEN Xiaoqian²,
SHEN Lu²,
WU Qiang³,
LIU Min^{2
, ,}

1.
Shanghai Institute of Work Safety Science, Shanghai 200233, China
2.
Bioassay and Safety Assessment Laboratory, Shanghai Academy of Public Measurement, Shanghai 201203, China
3.
Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, College of Environmental and Chemical Engineering, Shanghai University of Electric Power, Shanghai, 200090, China

Funds: Science and Technology Development Foundation of Pudong New District, Shanghai, China (No.PCK2020-C001)

摘要

摘要: 电镀是全氟和多氟烷基物质(PFASs)污染的主要来源之一. 目前关于电镀企业周边地表水中的PFASs污染特征报道较为缺乏. 为了解上海市电镀企业周边地表水中PFASs的污染特征与生态风险水平，选取全氟烷基羧酸(PFCAs)、全氟烷基磺酸(PFSAs)、磺酸调聚物以及1-氯-全氟烷基醚磺酸钾(F-53B)等26种典型PFASs为对象，调查其在上海市电镀企业周边地表水中的污染特征，探讨其污染来源并开展初步的生态风险评估. 结果表明：上海市电镀企业周边地表水中∑PFASs浓度范围为93.3~1 334 ng/L，其中大部分地表水中∑PFASs浓度小于300 ng/L，污染最严重的地表水分布于金山区，∑PFASs浓度是背景值的14.8倍. 地表水中全氟辛酸(PFOA)为普遍的主要污染物，其次为短链PFCAs和PFSAs. 1H,1H,2H,2H-全氟辛烷磺酸钠(6∶2 FTS)和F-53B也普遍存在于地表水中，但只在少数地表水中具有较高浓度，尤其是F-53B，其中金山区采样点浓度高达968 ng/L，主要与镀铬业务有关. 这表明短链PFCAs和PFSAs、PFOA、6∶2 FTS及F-53B等均可能已应用于电镀领域. 据污染源特征分析，地表水中PFASs除了受电镀行业的污染外，同时还可能来源于表面处理工业、前体化合物生物降解等. 初步的生态风险评估结果表明，上海市大部分电镀企业周边地表水中生态风险较低，但个别镀铬企业周边地表水中F-53B污染可能产生高生态风险. 研究显示，上海市电镀企业周边地表水中存在一定程度的PFASs污染，污染水平与特征差异较大；其中PFOA是电镀企业周边地表水中普遍存在的主要污染物，但生态风险较低；而F-53B在个别采样点中具有高残留、高生态风险，需加强污染防控.
- 全氟和多氟烷基物质 /
- 地表水 /
- 电镀 /
- 全氟辛酸(PFOA) /
- 1-氯-全氟烷基醚磺酸钾(F-53B) /
- 替代
Abstract: Electroplating industry is one of the main sources for per-and polyfluoroalkyl substances (PFASs). At present, there are few reports on PFASs pollution characteristics in surface water around electroplating enterprises. In order to understand the pollutant characteristics and potential ecological risk levels in the surface water around electroplating enterprises in Shanghai, 26 typical PFASs including perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkyl sulfonic acids (PFSAs), sulfonic acid telomeres and potassium 1-chloro-perfluoroalkyl sulfonate (F-53B), were analyzed. The pollution characteristics, source analysis and ecological risk of PFASs were further investigated. The results show that the concentration of ∑PFASs ranged from 93.3-1334 ng/L in the surface water, and ∑PFASs were less than 300 ng/L in most surface water. The most contaminated area was located in Jinshan, where the concentration of ∑PFASs was 14.8 times the background value. The concentration of ∑PFASs was comparable to those of surface water around electroplating enterprises in Guangdong; chemical industry park and airports in Shanghai; and Huangpu River except for a few sampling points; higher than those of the Yellow River and Pearl River with non-potential pollution sources. Perfluorooctanoic acid (PFOA) was the main pollutant in almost all surface water, followed by short-chain PFCAs and PFSAs. It indicates that short-chain PFCAs, PFSAs and PFOA were used in electroplating. While 1H,1H,2H,2H- sodium perfluorooctane sulfonate (6∶2 FTS) and F-53B were ubiquitous in surface water, but there were only a few with high concentration, especially F-53B concentration was 968 ng/L in the sample site of Jinshan due to chrome plating business. Although perfluorooctanesulfonate (PFOS) was prevalent in surface water, the concentration was lower than perfluorobutanesulfonate (PFBS) and perfluorohexanesulfonate (PFHxS), with the average concentration of 5.89 ng/L; which showed PFOS should be partly substituted by the two alternatives. All sampling points were divided into five categories with different pollution characteristics. Principal component analysis (PCA) of PFASs indicates that PFBS, PFHxS, PFBA, PFHxA, PFPeA, PFOA and F-53B were the main pollutants with a contribution rate of 35.7%. Spearman correlation analysis showed that PFBS and PFHxS were positively correlated with most PFCAs, indicating that highly relevant PFASs might come from similar sources. F-53B showed positive correlation with PFHpS, PFOS, 6∶2 FTS, which could be released from similar sources, such as chrome plating. According to the characteristics analysis of pollution source, PFASs came not only from electroplating industry, but also from surface treatment industries and biodegradation of precursor compounds. Preliminary ecological risk assessment shows that there is low ecological risk to most surface water, but it exhibits high ecological risk to the surface adjacent a few chrome-plating enterprises with high concentration of F-53B. The research showed that there was pollution in the surface water around electroplating enterprises in Shanghai with different level and characteristics. PFOA was a main pollutant in most surface water, but with low ecological risk. However, there was high F-53B residue and ecological risk in a few sampling sites. It is necessary to strengthen pollution prevention and control.
- per and polyfluoroalkyl substances /
- surface water /
- electroplating /
- perfluorooctanoic acid (PFOA) /
- potassium 1-chloro-perfluoroalkyl sulfonate (F-53B) /
- alternatives

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图 1 上海市地表水采样点分布

Figure 1. Sampling sites of surface water in Shanghai

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图 2 上海市重点电镀企业周边地表水中PFASs浓度分布

Figure 2. The concentration distribution of PFASs in surface water around main electroplating enterprises in Shanghai

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图 3 上海市不同区域电镀企业周边地表水中PFASs浓度

注：图中数值单位为ng/L.

Figure 3. Concentration of PFASs in adjacent surface water of electroplating industries of different districts in Shanghai

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图 4 上海市重点电镀企业周边地表水中PFASs的主成分分析(PCA)

Figure 4. Principal component analysis (PCA) of PFASs in adjacent surface water of main electroplating industries in Shanghai

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表 1 不同城市电镀企业周边地表水以及其他地表水中PFASs的浓度比较

Table 1. Concentration comparison of PFASs in surface water adjacent electroplating industries and others ng/L

研究地点	PFBA	PFPeA	PFHxA	PFHpA	PFOA	PFNA	PFDA	PFUdA	PFBS	PFHxS	PFOS	F-53B	11Cl-PF3OUdS	∑PFASs	数据来源
上海市¹⁾	17.7~29.3	37.6~75.1	17.6~37.3	0.09~12.1	85.7~525	nd	nd	—	27.6~53.4	nd	nd	—	—	221~705	文献[7]
深圳市¹⁾	16.9~48.9	7.03~23.8	5.70~16.7	4.04~8.93	22.8~99.4	0.69~2.46	0.27~0.54	nd~0.04	105~202	3.79~23.7	54.8~621	1.63~12.6	nd~0.03	224~983	文献[13]
广东省¹⁾	1.96~84.2	0.97~30.8	0.66~21.1	0.74~13.2	0.41~43.8	0.38~5.5	0.56~2.46	—	0.3~150.52	0.12~24.2	0.11~32.52	nd~0.97	—	5.33~248.73	文献[14]
长江	0.93~9.61	0.21~3.6	0.33~38.2	0.29~4.43	3.48~36.5	0.15~2.75	0.03~1.59	nd~0.07	0.22~4.68	0.92~85.8	0.36~12.1	0.12~12.94	—	7.04~212	文献[17]
黄河	1.2~7.38	0.04~1.13	0.1~1.57	0.02~0.74	0.15~4.92	0.05~0.76	nd~0.31	nd~0.06	0.71~1.86	0.15~0.37	0.95~5.37	0.01~0.29	—	3.38~24.8
淮河	3.91~22.8	0.58~1.25	0.89~1.97	0.72~1.30	4.24~9.06	0.77~1.35	1.13~0.42	0.03~0.15	0.52~1.59	0.09~1.52	0.48~3.72	0.36~21.38	—	13.7~66.5
珠江	0.88~9.40	0.15~3.68	0.34~2.99	0.07~2.11	0.40~52.8	0.22~1.28	0.06~0.87	0.04~0.30	0.21~21.51	0.09~4.17	1.38~23.57	0.13~11.06	—	3.97~134
辽河	2.53~7.52	0.71~1.46	0.91~1.73	0.69~1.30	5.28~12.3	0.48~0.90	0.06~0.36	LOQ~0.15	0.43~2.16	0.23~0.84	2.26~5.66	0.24~2.29	—	13.8~36.7
巢湖	5.17~11.7	2.29~6.82	3.41~10.8	1.36~2.35	7.00~10.5	1.19~1.65	0.28~2.02	0.06~0.61	1.50~81.5	0.23~14.34	1.96~29.7	0.69~52.2	—	25.1~224
太湖	0.88~12.9	0.27~2.74	0.36~198	0.37~3.05	3.15~44.5	0.41~5.73	0.19~5.75	0.10~0.94	0.17~4.85	0.11~292	0.22~15.2	0.21~27.6	—	6.44~613
汉江	2.56~6.31	1.14~2.54	0.98~2.38	0.55~1.45	1.84~4.53	0.47~0.85	0.17~0.81	0.07~0.16	1.34~3.17	1.39~4.68	1.08~3.86	0.02~0.06	—	11.6~30.8
泰晤士河	4.62~9.79	10.1~19.9	7.32~15.0	2.58~5.19	5.56~11.7	0.77~1.71	0.52~1.22	0.03~0.10	3.26~6.75	4.96~11.3	8.12~18.8	0.01~0.08	—	47.9~102
莱茵河	0.84~6.17	0.42~4.04	0.83~4.56	0.20~1.99	0.86~3.66	0.09~0.67	0.07~1.02	LOQ~0.18	0.46~146	0.12~3.90	0.23~8.56	0.02~0.38	—	4.14~182
德拉瓦河	1.47~6.51	1.72~11.0	1.89~15.5	0.93~5.70	2.12~14.9	0.76~4.81	0.15~1.84	0.10~3.06	0.52~4.20	0.65~2.63	0.97~6.92	LOQ~0.08	—	11.3~77.2
梅拉伦湖	1.69~3.01	1.00~3.17	0.89~2.92	0.55~1.32	1.07~3.34	0.24~0.76	0.09~−0.67	LOQ~0.38	0.75~1.92	0.56~2.79	0.99~8.23	LOQ~0.05	—	7.83~28.6
渤海	0.15~1.5	0.31~3.0	0.40~4.0	0.19~2.2	2.3~106	0.09~0.23	0.02~0.02	—	0.12~0.28	0.05~0.33	0.33~0.12	—	—	3.8~118	文献[18]
小清河	1 400~4 100	860~2 820	1 570~4 300	1 320~3 500	18 250~69 500	58.2~374	14.1~180	1.47~21.2	2.24~9.32	2.44~27.7	17.3~93.3	—	—	24 400~84 400	文献[20]
黄浦江	nd~13.7	nd~6.3	nd~161.2	nd~26.1	1.0~402.7	nd~20.8	nd~13.7	nd~3.3	nd~51.6	nd~28.5	nd~286.0	—	—	39.8~596.2	文献[16]
上海市	0.54~1.1	1.8~3.2	4.0~7.9	0.5~1.7	20~44	0.70~1.8	0.27~0.99	0.070~1.14	5.1~8.4	0.62~1.1	0.78~5.2	—	—	38.72~71.93	文献[19]
上海市	2.32~9.08	7.4~59.16	8.72~38.04	1.68~6.12	21.89~104.66	0.67~3.64	LOD~1.32	—	14.28~276.28	0.88~27.51	2.89~13.07	—	—	113.38~362.37	文献[15]
上海市	3.06~83.2	1.24~121	10.5~39.5	1.39~24.5	29.0~160	0.34~26.0	0.22~1.99	0.19~9.75	3.9~22.9	2.85~31.5	0.75~20.1	2.06~968	nd~14.1	86~1 299	该研究
注：1)表示电镀企业周边地表水. —表示未给出相应数据；LOQ表示定量限；nd表示未检出.

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表 2 上海市重点电镀企业周边地表水中PFASs浓度的Spearman相关性分析

Table 2. Spearman correlation analysis among the concentration of PFASs in adjacent surface water of main electroplating industries in Shanghai

化合物	PFBA	PFPeA	PFHxA	PFHpA	PFOA	PFNA	PFDA	PFUdA	PFDoA	PFTrDA	PFPrS	PFBS	PFHxS	PFHpS	PFOS	6:2 FTS	8:2 FTS	F-53B
PFBA	1
PFPeA	0.571^*	1
PFHxA	−0.019	0.501^*	1
PFHpA	0.313	0.654^**	0.094	1
PFOA	0.708^**	0.683^**	0.217	0.490^*	1
PFNA	0.268	0.599^**	0.356	0.725^**	0.281	1
PFDA	0.361	0.793^**	0.612^**	0.617^**	0.467	0.841^**	1
PFUdA	−0.033	0.642^**	0.264	0.550^*	0.194	0.423	0.524^*	1
PFDoA	−0.082	−0.476^*	−0.008	−0.599^**	−0.251	−0.413	−0.283	−0.367	1
PFTrDA	−0.205	−0.233	−0.388	0.173	−0.068	−0.176	−0.319	−0.080	−0.096	1
PFPrS	−0.056	−0.355	0.033	−0.301	−0.188	0.037	0.087	−0.455	0.692^**	−0.121	1
PFBS	0.374	0.596^**	0.212	0.629^**	0.390	0.379	0.393	0.284	−0.651^**	0.164	−0.591^**	1
PFHxS	0.151	0.541^*	0.319	0.703^**	0.257	0.782^**	0.689^**	0.326	−0.572^*	−0.079	−0.180	0.674^**	1
PFHpS	0.011	0.189	0.350	−0.344	0.086	−0.219	−0.027	0.150	0.106	−0.489^*	−0.245	0.086	−0.059	1
PFOS	−0.298	−0.227	0.296	−0.500^*	−0.250	−0.217	−0.191	−0.238	0.204	−0.308	−0.035	0.040	0.042	0.742^**	1
6:2 FTS	0.489^*	0.332	0.041	0.123	0.392	0.034	0.097	−0.029	−0.427	−0.228	−0.351	0.542^*	0.166	0.307	0.129	1
8:2 FTS	0.521^*	0.392	0.270	0.171	0.321	0.399	0.472^*	0.285	0.238	−0.218	0.178	0.117	0.129	0.169	−0.092	0.178	1
F-53B	0.136	0.109	0.079	−0.053	0.152	0.014	0.178	0.080	0.217	0.074	0.207	0.167	0.073	0.408	0.305	0.288	0.370	1
注：*表示P<0.01；表示P<0.05.

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