北京市典型湖泊中对羟基苯甲酸酯类化合物污染特征

孟甜; 王晓伟; 汪素芳; 董淮晋; 冯学良; 何连生

doi:10.12153/j.issn.1674-991X.20210383

北京市典型湖泊中对羟基苯甲酸酯类化合物污染特征

doi: 10.12153/j.issn.1674-991X.20210383

中国环境科学研究院

基金项目: 国家重点研发计划项目(2020YFC1807903)

详细信息

作者简介:
孟甜(1993—)，女，硕士研究生，主要从事环境污染物检测分析，mengtian@craes.org.cn

通讯作者:
王晓伟(1978—)，男，高级工程师，主要从事环境污染物研究，wang.xiaowei@craes.org.cn

中图分类号: X524
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出版历程
- 收稿日期: 2021-08-05

Pollution characteristic analysis of parabens compounds in typical lakes in Beijing

Chinese Research Academy of Environmental Sciences

摘要

摘要:
通过在冬季和春季分别采集北京市某典型湖泊11个点位的湖水样品，采用固相萃取-液相色谱-三重四极杆串接质谱法测定样品中14种对羟基苯甲酸酯类化合物（PBs），进而对该湖泊PBs的污染水平和分布特征进行分析。结果表明：湖水中共检出10种PBs，其中对羟基苯甲酸甲酯（MeP）和对羟基苯甲酸丙酯（ PrP）浓度较高，分别为24.8、44.8 ng/L；同一采样点检出的PBs浓度随季节性变化而变化，与冬季相比，氯代对羟基苯甲酸酯（氯代-PBs）在春季浓度偏低，冬季靠近污水处理厂排污口水样中，氯代-PBs浓度高于其他采样点；外来污水是湖水中PBs的主要来源，春季电厂排水口MeP浓度（24.8 ng/L）高于冬季（1.30 ng/L）。调查结果显示，该湖泊中PBs种类和浓度水平与其他国家地表水相比，属中等浓度水平，湖泊中PBs主要来源于周边污水排放，不同季节PBs浓度变化较大。
- 对羟基苯甲酸酯类化合物(PBs) /
- 湖泊 /
- 季节变化 /
- 氯代对羟基苯甲酸酯(氯代-PBs) /
- 污染水平
Abstract:
In order to study the pollution level and distribution characteristics of parabens (PBs) in lakes, the pollution status of 14 PBs in typical lakes in Beijing was investigated and analyzed. The water samples of a lake in Beijing were collected in both winter and summer, and detected by solid-phase extraction and liquid chromatography-triple quadrupole tandem mass spectrometry. The results showed that ten kinds of PBs were detected with high level in the lake, among which methylparaben (MeP, 24.8 ng/L) and propylparaben (PrP, 44.8 ng/L) were the dominant compounds. The concentrations of the target compounds detected at the same sampling site changed seasonally, and the concentrations of chlorinated parabens in spring were lower than those in winter. However, in the winter near the outlet of the wastewater treatment plant, the concentrations of chlorinated parabens were higher than those at other sampling sites. The external sewage was the main source of PBs in the lake water, and the concentration of MeP at the sampling site of the outlet of the power plant in spring (24.8 ng/L) was higher than that in winter (1.30 ng/L). The survey results showed that the species and concentration level of PBs in the lake were medium comparing with those reported in the researches of other nations. The pollution of PBs in the lake mainly came from the surrounding sewage discharge, and the concentration of PBs varied greatly in different seasons.
- parabens (PBs) /
- lake /
- seasonal variation /
- chlorinated parabens /
- pollution level

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图 1 对羟基苯甲酸酯的分子结构

Figure 1. Molecular structure of PBs

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图 2 采样点位置

Figure 2. Location of sampling sites

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图 3 浓度为500 μg/L的14种PBs的标准色谱

Figure 3. Standard chromatogram of 14 PBs at 500 μg/L

1—MeP；2—EtP；3—PrP；4—BuP；5—PeP；6—HeP；7—OcP；8—BzP；9—PHBA；10—3-Cl-MeP；11—3,5-2Cl-MeP； 12—3-Cl-EtP；13—3,5-2Cl-EtP；14—3,5-2Cl-PrP

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图 4 湖泊水样中PBs及氯代-PBs浓度（n=3）

Figure 4. Concentration of PBs and Chlorinated PBs in the sampling sites of the lake (n=3)

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表 1 PBs的化学性质

Table 1. Chemical property of PBs

化合物	分子式	分子量	lg K_o/w	pK_a
MeP	C₈H₈O₃	152.16	1.66^[9]	8.17^[9]
EtP	C₉H₁₀O₃	166.18	2.19^[9]	8.22^[9]
PrP	C₁₀H₁₂O₃	180.21	2.71^[9]	8.35^[9]
BuP	C₁₁H₁₄O₃	194.23	3.24^[9]	8.37^[9]
对羟基苯甲酸戊酯（PeP）	C₁₂H₁₆O₃	208.25	3.48
对羟基苯甲酸庚酯（HeP）	C₁₄H₂₀O₃	236.31	4.41
对羟基苯甲酸辛酯（OcP）	C₁₅H₂₂O₃	250.34	4.88
对羟基苯甲酸苄酯(BzP)	C₁₄H₁₂O₃	228.24	3.54^[16]	8.18^[16]
对羟基苯甲酸(PHBA)	C₇H₆O₃	138.12	1.39^[17]	8.4
3-氯-4-羟基苯甲酸甲酯 (3-Cl-MeP)	C₈H₇ClO₃	186.59	2.27
3,5-二氯-4-羟基苯甲酸甲酯(3,5-2Cl-MeP)	C₈H₆Cl₂O₃	221.04	2.88
3-氯-4-羟基苯甲酸乙酯 (3-Cl-EtP)	C₉H₉ClO₃	200.62
3,5-二氯-4-羟基苯甲酸乙酯(3,5-2Cl-EtP)	C₉H₈Cl₂O₃	235.06	3.32
3,5-二氯-4-羟基苯甲酸丙酯(3,5-2Cl-PrP)	C₁₀H₁₀Cl₂O₃	249.10
注：K_o/w为正辛醇-水分配系数；pK_a为酸度系数。

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表 2 质谱检测条件

Table 2. Experimental condition of mass spectrometry

化合物	母离子(m/z)	子离子(m/z)	入口电压/V	解簇电压/V	碰撞入口电压/V	碰撞能量/eV	碰撞出口电压/V
MeP	151.0	91.9	−5	−27	−7	−26	−10
EtP	165.0	93.0	−5	−25	−14	−30	−10
PrP	179.0	93.0	−5	−30	−8	−28	−10
BuP	193.0	91.9	−5	−30	−8	−35	−10
PeP	207.1	91.9	−10	−35	−9	−34	−10
HeP	235.1	92.0	−5	−40	−12	−38	−10
OcP	249.1	136.0	−5	−45	−10	−27	−10
BzP	227.0	91.9	−5	−25	−8	−34	−10
PHBA	137.0	93.0	−5	−23	−8	−20	−10
3-Cl-MeP	185.0	126.0	−5	−30	−7	−26	−13
3,5-2Cl-MeP	218.9	160.0	−5	−40	−8	−28	−15
3-Cl-EtP	199.0	170.9	−5	−32	−7	−20	−15
3,5-2Cl-EtP	232.9	161.1	−5	−36	−8	−30	−16
3,5-2Cl-PrP	246.8	160.0	−9	−45	−10	−32	−16
MeP-d₄	155.0	96.1	−10	−25	−10	−28	−10
EtP-d₅	170.0	91.9	−5	−26	−8	−30	−10
PrP-d₇	186.1	91.9	−5	−30	−8	−33	−10
BuP-d₉	202.1	91.9	−5	−30	−8	−34	−10
BzP-d₇	233.9	135.9	−9	−40	−10	−20	−13
PHBA-d₄	141.0	97.1	−5	−23	−8	−18	−10

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表 3 14种PBs的线性范围和检出限

Table 3. Linear range and limit of detection of 14 PBs

化合物	替代物	相关系数（R²）	线性范围/（μg/L）	检出限/（μg/L）
MeP	MeP-d₄	0.998 5	0.1~500	0.10
EtP	EtP-d₅	0.996 2	0.1~500	0.08
PrP	PrP-d₇	0.998 1	0.5~500	0.27
BuP	BuP-d₉	0.998 2	0.05~500	0.05
PeP	BuP-d₉	0.998 4	0.5~500	0.43
HeP	BuP-d₉	0.999 1	0.5~500	0.04
OcP	BuP-d₉	0.999 0	0.05~500	0.04
BzP	BzP-d₇	0.998 3	0.1~500	0.07
PHBA	PHBA-d₄	0.993 4	0.5~500	0.16
3-Cl-MeP	MeP-d₄	0.998 6	0.5~500	0.27
3,5-2Cl-MeP	MeP-d₄	0.999 2	0.5~500	0.10
3-Cl-EtP	EtP-d₅	0.998 3	0.5~500	0.35
3,5-2Cl-EtP	EtP-d₅	0.999 8	0.5~500	0.40
3,5-2Cl-PrP	PrP-d₇	0.999 1	0.1~500	0.06

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表 4 S6采样点回收试验结果

Table 4. Result of recovery test at S6 sampling site

化合物	2020年11月采样			2021年5月采样
化合物	浓度/ (ng/L)	加标浓度/ (ng/L)	回收率/ %	浓度/ (ng/L)	加标浓度/ (ng/L)	回收率/ %
MeP	3.94	49.3	90.7	8.48	52.4	87.8
EtP	ND	46.3	92.6	ND	42.9	85.8
PrP	ND	43.2	86.4	ND	43.1	86.2
BuP	ND	43.7	87.4	ND	42.9	85.8
PeP	ND	44.2	88.4	ND	41.4	82.8
HeP	ND	43.6	87.2	ND	46.9	93.8
OcP	ND	42.4	84.8	ND	40.5	81.0
BzP	ND	44.6	89.2	ND	43.9	87.8
PHBA	ND	46.6	93.2	259	302	86.0
3-Cl-MeP	ND	45.9	91.8	ND	43.6	87.2
3,5-2Cl-MeP	19.7	64.2	89.0	3.18	48.3	90.2
3-Cl-EtP	ND	46.6	93.2	0.60	45.7	90.2
3,5-2Cl-EtP	15.0	61.3	92.6	10.3	55.9	91.2
3,5-2Cl-PrP	11.1	54.5	86.8	6.52	50.6	88.2
注：ND表示未检出。

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表 5 湖泊水样中PBs浓度

Table 5. Concentration of PBs in water samples of the lake

化合物	最大浓度/ (ng/L)	最小浓度/ (ng/L)	平均浓度/ (ng/L)	中位值/ (ng/L)	检出率/ %
MeP	24.8	0.45	7.89	7.1	100
EtP	4.66	ND	0.29	ND	6.25
PrP	44.8	ND	5.67	2.47	68.8
BuP	3.82	ND	0.35	ND	25
PeP	ND	ND	ND	ND	ND
HeP	ND	ND	ND	ND	ND
OcP	0.13	ND	0.01	ND	6.25
BzP	0.55	ND	0.03	ND	6.25
PHBA	1023	ND	379	292	68.8
3-Cl-MeP	ND	ND	ND	ND	ND
3,5-2Cl-MeP	19.7	2.12	6.09	3.16	100
3-Cl-EtP	0.60	ND	0.04	ND	6.25
3,5-2Cl-EtP	28.0	8.94	14.5	13.5	100
3,5-2Cl-PrP	11.1	2.4	7.16	7.44	100
注：ND表示未检出。采样点数量（n）为16个。

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参考文献(23)

[1]	LEE H B, PEART T E, SVOBODA M L. Determination of endocrine-disrupting phenols, acidic pharmaceuticals, and personal-care products in sewage by solid-phase extraction and gas chromatography-mass spectrometry[J]. Journal of Chromatography A,2005,1094(1/2):122-129.
[2]	Final amended report on the safety assessment of methylparaben, ethylparaben, propylparaben, isopropylparaben, butylparaben, isobutylparaben, and benzylparaben as used in cosmetic products[M/OL]. [2021-08-10].https://journals.sagepub.com/doi/10.1177/109158180802704s01.
[3]	林忠洋, 马万里, 齐迹, 等.对羟基苯甲酸酯类防腐剂的人体暴露[J]. 化学进展,2015,27(5):614-622. LIN Z Y, MA W L, QI J, et al. Human exposure to parabens[J]. Progress in Chemistry,2015,27(5):614-622.
[4]	蔺远, 傅建捷, 高常安, 等.对羟基苯甲酸酯雌激素活性物种差异的理论研究[J]. 环境化学,2011,30(2):399-404. LIN Y, FU J J, GAO C A, et al. Insight into specie difference in estrogenic activities of selected parabens by computer modeling[J]. Environmental Chemistry,2011,30(2):399-404.
[5]	GUO Y, KANNAN K. A survey of phthalates and parabens in personal care products from the United States and its implications for human exposure[J]. Environmental Science & Technology,2013,47(24):14442-14449.
[6]	王亮, 毛茜慧, 袁守军, 等.气相色谱-质谱联用法同时测定污水中对羟基苯甲酸酯和甾体雌激素[J]. 环境化学,2016,35(1):49-56. doi: 10.7524/j.issn.0254-6108.2016.01.2015081901 WANG L, MAO Q H, YUAN S J, et al. Simultaneous determination of parabens and steroid estrogens in sewage water using gas chromatography-mass spectrometry[J]. Environmental Chemistry,2016,35(1):49-56. doi: 10.7524/j.issn.0254-6108.2016.01.2015081901
[7]	林贞贤, 汝少国.环境内分泌干扰物促进乳腺细胞增殖的分子机制研究进展[J]. 环境科学研究,2018,31(5):796-804. doi: 10.13198/j.issn.1001-6929.2018.03.03 LIN Z X, RU S G. Research advances on the molecular mechanism of environmental endocrine disrupting chemicals on promoting breast cell proliferation[J]. Research of Environmental Sciences,2018,31(5):796-804. doi: 10.13198/j.issn.1001-6929.2018.03.03
[8]	SONI M G, CARABIN I G, BURDOCK G A. Safety assessment of esters of p-hydroxybenzoic acid (parabens)[J]. Food and Chemical Toxicology,2005,43(7):985-1015. doi: 10.1016/j.fct.2005.01.020
[9]	岳强.对羟基苯甲酸酯在人体中的暴露研究进展[J]. 北方环境,2011,23(3):161-165. YUE Q. Advances in human exposure of parabens[J]. Northern Environment,2011,23(3):161-165.
[10]	金相灿, 王圣瑞, 席海燕.湖泊生态安全及其评估方法框架[J]. 环境科学研究,2012,25(4):357-362. doi: 10.13198/j.res.2012.04.4.jinxc.005 JIN X C, WANG S R, XI H Y. Lake ecological security and assessment methodology framework[J]. Research of Environmental Sciences,2012,25(4):357-362. doi: 10.13198/j.res.2012.04.4.jinxc.005
[11]	BENIJTS T, LAMBERT W, de LEENHEER A. Analysis of multiple endocrine disruptors in environmental waters via wide-spectrum solid-phase extraction and dual-polarity ionization LC-ion trap-MS/MS[J]. Analytical Chemistry,2004,76(3):704-711. doi: 10.1021/ac035062x
[12]	GORGA M, PETROVIC M, BARCELÓ D. Multi-residue analytical method for the determination of endocrine disruptors and related compounds in river and waste water using dual column liquid chromatography switching system coupled to mass spectrometry[J]. Journal of Chromatography A,2013,1295:57-66. doi: 10.1016/j.chroma.2013.04.028
[13]	PENG X Z, YU Y Y, TANG C M, et al. Occurrence of steroid estrogens, endocrine-disrupting phenols, and acid pharmaceutical residues in urban riverine water of the Pearl River Delta, South China[J]. Science of the Total Environment,2008,397(1/2/3):158-166.
[14]	WEI F, MORTIMER M, CHENG H F, et al. Parabens as chemicals of emerging concern in the environment and humans: a review[J]. Science of the Total Environment,2021,778:146150. doi: 10.1016/j.scitotenv.2021.146150
[15]	姜琦, 席海燕, 焦立新, 等.我国湖泊管理的思考[J]. 环境工程技术学报,2012,2(1):44-50. doi: 10.3969/j.issn.1674-991X.2012.01.008 JIANG Q, XI H Y, JIAO L X, et al. Some thinkings on lake management in China[J]. Journal of Environmental Engineering Technology,2012,2(1):44-50. doi: 10.3969/j.issn.1674-991X.2012.01.008
[16]	YAMAMOTO H, TAMURA I, HIRATA Y, et al. Aquatic toxicity and ecological risk assessment of seven parabens: individual and additive approach[J]. Science of the Total Environment,2011,410/411:102-111. doi: 10.1016/j.scitotenv.2011.09.040
[17]	WANG L, KANNAN K. Alkyl protocatechuates as novel urinary biomarkers of exposure to p-hydroxybenzoic acid esters (parabens)[J]. Environment International,2013,59:27-32. doi: 10.1016/j.envint.2013.05.001
[18]	CRISTINA JARDIM V, de PAULA MELO L, SOARES DOMINGUES D, et al. Determination of parabens in urine samples by microextraction using packed sorbent and ultra-performance liquid chromatography coupled to tandem mass spectrometry[J]. Journal of Chromatography B,2015,974:35-41. doi: 10.1016/j.jchromb.2014.10.026
[19]	赵佳慧, 冯精兰, 席楠楠, 等.超高效液相色谱-三重四极杆质谱测定沉积物中6种对羟基苯甲酸酯及其代谢产物[J]. 分析化学,2018,46(2):260-264. doi: 10.11895/j.issn.0253-3820.170330 ZHAO J H, FENG J L, XI N N, et al. Determination of paraben and its metabolite in sediments by ultra performance liquid chromatography-triple quadrupole tandem mass spectrometry[J]. Chinese Journal of Analytical Chemistry,2018,46(2):260-264. doi: 10.11895/j.issn.0253-3820.170330
[20]	李闯修, 赵晓丽, 高立红, 等.高效液相色谱-串联质谱法测定地表水样品中5种有机磷酸酯代谢物[J]. 分析测试学报,2016,35(2):194-199. doi: 10.3969/j.issn.1004-4957.2016.02.010 LI C X, ZHAO X L, GAO L H, et al. Determination of five organophosphate ester metabolites in surface water samples by LC-MS/MS[J]. Journal of Instrumental Analysis,2016,35(2):194-199. doi: 10.3969/j.issn.1004-4957.2016.02.010
[21]	GONZÁLEZ-MARIÑO I, QUINTANA J B, RODRÍGUEZ I, et al. Simultaneous determination of parabens, triclosan and triclocarban in water by liquid chromatography/electrospray ionisation tandem mass spectrometry[J]. Rapid Communications in Mass Spectrometry,2009,23(12):1756-1766. doi: 10.1002/rcm.4069
[22]	TERASAKI M, TAKEMURA Y, MAKINO M. Paraben-chlorinated derivatives in river waters[J]. Environmental Chemistry Letters,2012,10(4):401-406. doi: 10.1007/s10311-012-0367-1
[23]	JONKERS N, KOHLER H P E, DAMMSHÄUSER A, et al. Mass flows of endocrine disruptors in the Glatt River during varying weather conditions[J]. Environmental Pollution,2009,157(3):714-723. ◇ doi: 10.1016/j.envpol.2008.11.029