Occurrence characteristics and risk assessment of halogenated flame retardants in soils of Hefei City

doi:10.3969/j.issn.1000-5641.2024.06.014

Abstract

Abstract:

The contents of halogenated flame retardants (HFRs) in 31 surface soil samples collected from different areas of Hefei City were measured by gas chromatography-mass spectrometry. Their composition characteristics, spatial distribution, and sources were explored. The results showed that the mean concentrations of ∑₂₃PBDEs, ∑₂₂ABFRs, and ∑₁₁DECs in the surface soils of Hefei City were (6.490 ± 13.221), (26.375 ± 101.928), and (0.815 ± 0.760) ng/g, respectively. DBDPE is the main homologue among alternative flame retardants, accounting for 84.4%. In terms of spatial distribution, the hotspots of HFRs were mostly located in manufacturing concentrated areas, such as urban development zones and high-tech zones. Source analysis revealed that the use of commercial polybrominated diphenyl ethers and alternative flame retardants in the study area were the main emission sources, followed by the production, transportation, and environmental degradation process of HFRs. Non-carcinogenic risk assessment was carried out based on hazard index method. The results showed that the non-carcinogenic risk index of the target objects in the study area were less than 1, which were within the acceptable range, indicating that there was no non-carcinogenic risk.

Key words: soils, halogenated flame retardants, spatial distribution, risk assessment

CLC Number:

X144

Dingye YANG, Jing YANG, Ruihe JIN, Fangfang DING, Yuxin ZHANG, Min LIU. Occurrence characteristics and risk assessment of halogenated flame retardants in soils of Hefei City[J]. Journal of East China Normal University(Natural Science), 2024, 2024(6): 161-177.

Figures/Tables 15

Fig.1

Table 1

Concentrations of halogenated flame retardants in the surface soils of Hefei City"

类别	化合物	名称	最小值/(ng/g)	最大值/(ng/g)	平均值/(ng/g)	检出率/%
PBDEs	BDE17	2,2’,4-三溴联苯醚	ND	1.032	0.054 ± 0.181	29.0
	BDE28/33	2,4,4’-三溴联苯醚	ND	0.132	0.027 ± 0.039	83.9
	BDE49	2,2’,4,4’-四溴联苯醚	ND	1.047	0.086 ± 0.183	35.5
	BDE47	2,2’,4,5’-四溴联苯醚	ND	0.327	0.039 ± 0.069	58.1
	BDE66	2,3’,4,4’-四溴联苯醚	ND	0.212	0.012 ± 0.037	51.6
	BDE100	2,2’,3,4,4’-五溴联苯醚	ND	0.398	0.021 ± 0.069	74.2
	BDE99	2,2’,4,4’,5-五溴联苯醚	ND	0.933	0.170 ± 0.257	64.5
	BDE85	2,2’,4,4’,6-五溴联苯醚	ND	0.650	0.061 ± 0.114	74.2
	BDE154	2,2’,3,4,4’,5’-六溴联苯醚	ND	1.985	0.097 ± 0.367	74.2
	BDE153	2,2’,4,4’,5,5’-六溴联苯醚	ND	2.045	0.073 ± 0.360	9.7
	BDE138	2,2’,4,4’,5,6’-六溴联苯醚	ND	1.055	0.060 ± 0.182	16.1
	BDE183	2,2’,3,4,4’,5’,6-七溴联苯醚	ND	3.127	0.121 ± 0.549	83.9
	BDE190	2,3,3’,4,4’,5,6-七溴联苯醚	ND	0.792	0.047 ± 0.138	41.9
	BDE202	2,2’,3,3’,4,4’,5,6’-八溴联苯醚	ND	0.986	0.121 ± 0.168	74.2
	BDE201	2,2’,3,3’,4,4’,6,6’-八溴联苯醚	ND	2.391	0.148 ± 0.417	71.0
	BDE197	2,2’,3,3’,4,5’,6,6’-八溴联苯醚	ND	1.532	0.100 ± 0.264	74.2
	BDE203	2,2’,3,3’,5,5’,6,6’-八溴联苯醚	ND	0.943	0.071 ± 0.161	90.3
	BDE196	2,2’,3,4,4’,5,5’,6-八溴联苯醚	ND	1.277	0.075 ± 0.220	93.5
	BDE208	2,2’,3,3’,4,4’,5,5’,6-九溴联苯醚	ND	1.542	0.123 ± 0.267	71.0
	BDE207	2,2’,3,3’,4,4’,5,6,6’-九溴联苯醚	0.042	2.420	0.254 ± 0.412	100
	BDE206	2,2’,3,3’,4,5,5’,6,6’-九溴联苯醚	0.018	1.944	0.210 ± 0.349	96.8
	BDE209	十溴联苯醚	0.999	51.134	4.520 ± 8.748	100
	Σ₂₂PBDEs	多溴联苯醚 (无BDE209)	0.400	26.742	1.970 ± 4.561
	Σ₂₃PBDEs	多溴联苯醚 (含BDE209)	1.399	77.876	6.490 ± 13.221
ABFRs	TBP	三溴苯酚	0.337	34.728	2.256 ± 6.062	100
	ATE	2,4,6-三溴苯基烯丙基醚	ND	0.171	0.033 ± 0.044	80.6
	TBECH	1,2-二溴乙基环己烷	ND	0.358	0.183 ± 0.077	96.8
	TBPX	2,3,5,6-四溴对二甲苯	ND	0.025	0.006 ± 0.005	51.6
	PBBZ	五溴苯	ND	0.071	0.034 ± 0.016	74.2
ABFRs	TBCO	1,2,5,6-四溴环辛烷	ND	0.092	0.013 ± 0.017	38.7
	TBOCT	四溴邻氯甲苯	0.014	0.490	0.093 ± 0.092	100
	PBT	五溴甲苯	ND	0.038	0.014 ± 0.009	58.1
	PBEB	五溴乙苯	ND	0.034	0.007 ± 0.008	61.3
	HBBZ	六溴苯	0.118	0.292	0.180 ± 0.041	100
	BB101	2,2’,4,5,5’-五溴联苯	ND	0.398	0.017 ± 0.070	22.6
	PBBA	丙烯酸五溴苄酯	ND	0.410	0.030 ± 0.079	45.2
	HCDBCO	六氯二溴辛烷	ND	3.470	0.690 ± 0.860	96.8
	EHTBB	2-乙基己基-2,3,4,5-四溴苯甲酸酯	ND	0.240	0.043 ± 0.047	9.7
	BB153	2,2’,4,4’,5,5’-六溴联苯	ND	2.394	0.166 ± 0.432	6.5
	BTBPE	2,4,6-三溴苯氧基乙烷	ND	1.447	0.080 ± 0.252	51.6
	TBPH	2-乙基己基四溴邻苯二甲酸	ND	0.727	0.104 ± 0.127	87.1
	DBDPE	十溴二苯乙烷	0.871	544.305	22.260 ± 95.702	100
	BATBPE	2-溴烯丙基-2,4,6-三溴苯醚	ND	0.011	0.005 ± 0.003	32.3
	DPTE	2,3-二溴丙基-2,4,6-三溴苯基)醚	ND	0.083	0.033 ± 0.009	3.2
	TBC	三(2,3-二溴丙基)异氰脲酸酯	ND	0.493	0.082 ± 0.096	22.6
	OBIND	八溴-1,1,3-三甲基-3-苯基苯胺	ND	0.152	0.045 ± 0.020	3.2
	Σ₂₂ABFRs	替代型溴代阻燃剂	2.159	582.652	26.375 ± 101.928
DECs	HCPN	1,2,3,4,7,7-六氯-5-苯基-2-降冰片烯	ND	0.406	0.106 ± 0.092	83.9
	DEC-602	得克隆602	ND	1.585	0.106 ± 0.275	83.9
	Cplus	氯丁加	ND	0.115	0.021 ± 0.026	32.3
	DEC-604CB	得克隆604 组分 B	ND	0.107	0.012 ± 0.017	3.2
	DEC-603	得克隆603	ND	0.318	0.030 ± 0.054	38.7
	DEC-604	得克隆604	ND	3.150	0.124 ± 0.553	58.1
	Cl10-DP	Cl10-得克隆	ND	0.460	0.108 ± 0.104	67.7
	DEC-601	得克隆601	ND	0.070	0.010 ± 0.013	29.0
	Syn-DP	顺式得克隆	ND	0.529	0.030 ± 0.092	29.0
	Cl11-DP	Cl11-得克隆	0.035	0.523	0.178 ± 0.132	100
	Anti-DP	反式得克隆	ND	0.644	0.089 ± 0.122	90.3
	Σ₁₁DECs	得克隆及其类似物	0.250	4.217	0.815 ± 0.760

Table 1

Fig.2

Fig.3

Fig.4

Fig.5

Fig.6

Fig.7

Fig.8

Fig.9

Table 2

Table 3

Fig.10

Table 4

Fig.11

References 41

1	IQBAL M, SYED J H, KATSOYIANNIS A, et al.. Legacy and emerging flame retardants (FRs) in the freshwater ecosystem: A review. Environmental Research, 2017, 152, 26- 42.
2	HOU R, LIN L, LI H X, et al.. Occurrence, bioaccumulation, fate, and risk assessment of novel brominated flame retardants (NBFRs) in aquatic environments−A critical review. Water Research, 2021, 198, 117168.
3	张文睿, 辛正豪, 曾冬娟, 等.. 高含卤阻燃剂污染特征及分析方法研究进展. 科学技术与工程, 2024, 24 (3): 897- 915.
4	王钦, 李晨光, 尹诗琪, 等.. 新型溴代阻燃剂(NBFRs)的生态毒性效应研究进展. 生态毒理学报, 2023, 18 (2): 212- 223.
5	LING S Y, LU C, PENG C, et al.. Characteristics of legacy and novel brominated flame retardants in water and sediment surrounding two e-waste dismantling regions in Taizhou, eastern China. Science of the Total Environment, 2021, 794, 148744.
6	LING S Y, ZHOU S Q, TAN J Q, et al.. Brominated flame retardants (BFRs) in sediment from a typical e-waste dismantling region in Southern China: Occurrence, spatial distribution, composition profiles, and ecological risks. Science of the Total Environment, 2022, 824, 153813.
7	YADAV I C, DEVI N L, LI J, et al.. Environmental concentration and atmospheric deposition of halogenated flame retardants in soil from Nepal: Source apportionment and soil-air partitioning. Environmental Pollution, 2018, 233, 642- 654.
8	翁君贺, 沈其艳, 谈建国, 等.. 持久性有机污染物土气交换过程影响因素分析. 长江流域资源与环境, 2021, 30 (4): 879- 888.
9	中华人民共和国生态环境部. 土壤环境监测技术规范: HJ/T 166-2004 [S]. 北京: 中国环境出版社, 2004.
10	SHI S X, ZHANG L F, YANG W L, et al.. Levels and spatial distribution of polybrominated diphenyl ethers (PBDEs) in surface soil from the Yangtze River Delta, China. Bulletin of Environmental Contamination and Toxicology, 2014, 93 (6): 752- 757.
11	赵丹丹. 长三角城市发展带土壤PBDEs污染特征及与经济发展的耦合关系 [D]. 上海: 华东师范大学, 2020.
12	SUN J T, PAN L L, ZHAN Y, et al.. Contamination of phthalate esters, organochlorine pesticides and polybrominated diphenyl ethers in agricultural soils from the Yangtze River Delta of China. Science of the Total Environment, 2016, 544, 670- 676.
13	向鑫鑫, 鲁垠涛, 阮起炀, 等.. 中国东北沈抚地区土壤中PBDEs的残留、来源及风险评价. 环境科学, 2020, 41 (1): 368- 376.
14	谢薇, 孙天河, 韩鹏, 等.. 青藏高原中部地区表层土壤中多溴联苯醚的分布特征及影响因素. 现代地质, 2012, 26 (5): 917- 925.
15	KORCZ W, CZAJA K, LISZEWSKA M, et al.. Decabromodifenyl ether (BDE-209) in surface soils from warsaw and surrounding areas: Characterization of non-carcinogenic risk associated with oral and dermal exposure. Molecules, 2024, 29 (10): 2335.
16	李文龙. 亚洲五国土壤和大气中溴代阻燃剂的时空分布和健康风险 [D]. 哈尔滨: 哈尔滨工业大学, 2016.
17	DEMIRTEPE H, IMAMOGLU I.. Levels of polybrominated diphenyl ethers and hexabromocyclododecane in treatment plant sludge: Implications on sludge management. Chemosphere, 2019, 221, 606- 615.
18	SHEN K H, LI L, LIU J Z, et al.. Stocks, flows and emissions of DBDPE in China and its international distribution through products and waste. Environmental Pollution, 2019, 250, 79- 86.
19	XIAN H, HAO Y F, LV J Y, et al.. Novel brominated flame retardants (NBFRs) in soil and moss in Mt Shergyla, southeast Tibetan Plateau: Occurrence, distribution and influencing factors. Environmental Pollution, 2021, 291, 118252.
20	HU G C, XU Z C, DAI J Y, et al.. Distribution of polybrominated diphenyl ethers and decabromodiphenylethane in surface sediments from Fuhe River and Baiyangdian Lake, North China. Journal of Environmental Science, 2010, 22 (12): 1833- 1839.
21	YAMADA T, TAKAHAMA Y, YAMADA Y.. Biodegradation of 2,4,6-tribromophenol by sp strain TB01. Bioscience, Biotechnology and Biochemistry, 2008, 72 (5): 1264- 1271.
22	FENG H R, RUAN Y F, WU R B, et al.. Occurrence of disinfection by-products in sewage treatment plants and the marine environment in Hong Kong. Ecotoxicology and Environmental Safety, 2019, 181, 404- 411.
23	DALANGGUD M, LV Y, LIU C, et al.. Dechlorane Plus in environmental samples and human serum samples from new and old electronic waste dismantling areas in East China: Levels, composition profiles, and human exposure. Science of the Total Environment, 2024, 906, 167571.
24	MA J, QIU X H, LIU D, et al.. Dechlorane Plus in surface soil of North China: Levels, isomer profiles, and spatial distribution. Environmental Science and Pollution Research, 2014, 21 (14): 8870- 8877.
25	YU Z Q, LU S Y, GAO S T, et al.. Levels and isomer profiles of Dechlorane Plus in the surface soils from e-waste recycling areas and industrial areas in South China. Environment Pollution, 2010, 158 (9): 2920- 2925.
26	SHEN L, REINER E J, MACPHERSON K A, et al.. Dechloranes 602, 603, 604, Dechlorane Plus, and Chlordene Plus, a newly detected analogue, in tributary sediments of the Laurentian Great Lakes. Environmental Science and Technology, 2011, 45 (2): 693- 699.
27	SVERKO E, TOMY G T, MARVIN C H, et al.. Dechlorane Plus levels in sediment of the lower Great Lakes. Environmental Science and Technology, 2008, 42 (2): 361- 366.
28	WANG P, ZHANG Q H, ZHANG H D, et al.. Sources and environmental behaviors of Dechlorane Plus and related compounds−A review. Environment International, 2016, 88, 206- 220.
29	CHEN S J, TIAN M, WANG J, et al.. Dechlorane Plus (DP) in air and plants at an electronic waste (e-waste) site in South China. Environment Pollution, 2011, 159 (5): 1290- 1296.
30	RAFF J D, HITES R A.. Deposition versus photochemical removal of PBDEs from lake superior air. Environmental Science and Technology, 2007, 41 (19): 6725- 6731.
31	高景顺, 朱培.. “灭蚁灵”防治山地白蚂蚁技术总结. 经济林研究, 1996, (S1): 47.
32	AN Q, YANG L N, YANG S C, et al.. Legacy and novel brominated flame retardants in agricultural soils of eastern China (2011-2021): Concentration level, temporal trend, and health risk assessment. Journal of Hazardous Materials, 2023, 446, 130631.
33	SVERKO E, TOMY G T, REINER E J, et al.. Dechlorane Plus and related compounds in the environment: A review. Environmental Science and Technology, 2011, 45 (12): 5088- 5098.
34	VENIER M, MA Y N, HITES R A.. Bromobenzene flame retardants in the Great Lakes atmosphere. Environmental Science and Technology, 2012, 46 (16): 8653- 8660.
35	MALLIARI E, KALANTZI O I.. Children’s exposure to brominated flame retardants in indoor environments−A review. Environment International, 2017, 108, 146- 169.
36	MA Y N, VENIER M, HITES R A.. Tribromophenoxy flame retardants in the Great Lakes atmosphere. Environmental Science and Technology, 2012, 46 (24): 13112- 13117.
37	JOHNSON-RESTREPO B, KANNAN K.. An assessment of sources and pathways of human exposure to polybrominated diphenyl ethers in the United States. Chemosphere, 2009, 76 (4): 542- 548.
38	LUO P, BAO L J, WU F C, et al.. Health risk characterization for resident inhalation exposure to particle-bound halogenated flame retardants in a typical E-Waste Recycling Zone. Environmental Science and Technology, 2014, 48 (15): 8815- 8822.
39	TAO F, SJÖSTRÖM Y, DE WIT C A, et al.. Organohalogenated flame retardants and organophosphate esters from home and preschool dust in Sweden: Pollution characteristics, indoor sources and intake assessment. Science of the Total Environment, 2023, 896, 165198.
40	Environment Canada. Federal environmental quality guidelines: Polybrominated diphenyl ethers (PBDEs) [EB/OL]. (2013-02-01)[2024-07-01]. https://www.canada.ca/content/dam/eccc/migration/ese-ees/05df7a37-60ff-403f-bb37-0cc697dbd9a3/feqg_pbde_en.pdf.
41	HU Y X, LI Z R, XIONG J J, et al.. Occurrence and ecological risks of brominated flame retardants and dechlorane plus in sediments from the Pearl River Estuary and Daya Bay, South China. Marine Polution Bulletin, 2022, 185, 114- 182.

目标物	PC1	PC2	PC3	PC4	PC5
BDE28/33	0.389	–0.139	0.048	0.033	0.708
BDE47	0.698	–0.052	0.043	0.314	0.398
BDE66	0.976	–0.041	0.075	0.063	0.168
BDE100	0.982	–0.041	0.061	0.038	0.133
BDE99	0.440	–0.118	0.301	0.191	0.568
BDE85	0.933	–0.034	0.078	–0.051	0.197
BDE154	0.941	0.285	0.041	0.067	0.093
BDE183	0.984	–0.048	0.041	0.039	0.131
BDE202	0.933	0.134	0.112	0.052	0.109
BDE201	0.979	0.104	0.042	0.078	0.087
BDE197	0.985	–0.015	0.047	0.048	0.068
BDE203	0.983	–0.057	0.039	0.040	0.119
BDE196	0.987	–0.028	0.038	0.050	0.092
BDE208	0.963	0.098	0.049	0.112	0.123
BDE207	0.934	0.007	0.230	0.081	0.175
BDE206	0.910	0.047	0.027	0.141	0.155
BDE209	0.966	–0.067	0.051	0.072	0.081
TBP	0.018	0.940	–0.008	0.191	–0.122
ATE	0.485	0.041	0.063	–0.034	0.633
TBECH	0.156	0.026	0.092	0.439	0.346
TBPX	–0.036	–0.005	0.914	0.087	0.136
PBBZ	0.018	0.266	0.235	0.805	–0.058
TBOCT	0.709	–0.046	0.100	–0.035	0.513
PBT	0.392	0.353	0.705	0.253	–0.050
PBEB	0.115	–0.055	0.855	0.030	0.070
HBBZ	0.150	0.079	0.291	0.196	–0.340
HCDBCO	0.544	–0.171	–0.135	–0.104	0.266
BTBPE	0.984	–0.061	0.049	0.039	0.079
TBPH	0.903	–0.104	–0.008	0.030	0.147
DBDPE	0.051	0.953	–0.011	0.118	–0.089
HCPN	–0.041	0.030	0.223	0.501	–0.061
DEC-602	0.057	–0.076	–0.062	–0.134	–0.084
DEC-604	0.987	–0.037	0.043	0.045	0.125
Cl10-DP	–0.135	0.767	0.132	–0.382	0.075
Cl11-DP	0.203	–0.112	0.023	0.849	0.113
Anti-DP	0.096	0.244	–0.091	–0.035	0.024

人群	年龄/岁	DIR/(g/d)	BSA/cm²	BW/kg	SAS/(mg/(cm²·d))	AF/%	OEF/%
成人	≥ 20	0.05	4615	62.9	0.096	3	12.5
青少年	[12,19]	0.05	3692	52.0	0.096	3	12.5
儿童	[6,11]	0.05	3067	25.2	0.096	3	20.8
幼儿	[1,5]	0.10	2564	16.0	0.096	3	20.8
婴儿	< 1	0.02	801	5.0	0.096	3	12.5

[1]	Chenming GU, Jing YANG, Ye LI, Ye HUANG, Yan WU, Guoyu YIN, Ruihe JIN, Yi YANG, Min LIU. Advances in research on multimedia fate, risks, and simulation of contaminants of emerging concern in urban agglomerations [J]. Journal of East China Normal University(Natural Science), 2024, 2024(6): 24-38.
[2]	Jing YANG, Yan WU, Yue LI, Xia LIU, Dingye YANG, Yuanyuan CHEN, Ruihe JIN, Ye LI, Min LIU. Occurrence characteristics and healthy risk assessment of hexabromocyclododecane in agricultural soils in Shanghai [J]. Journal of East China Normal University(Natural Science), 2024, 2024(6): 178-187.
[3]	Yuyi WANG, Ye HUANG, Jing YANG, Fangfang DING, Tianhao HE, Yushan LI, Lin HUANG, Ye LI, Min LIU. Spatiotemporal differential distribution characteristics and ecological risk assessment of antibiotics in the Yangtze River Estuary and offshore areas [J]. Journal of East China Normal University(Natural Science), 2024, 2024(6): 136-150.
[4]	Ying LI, Ye HUANG, Ye LI, Min LIU. Spatiotemporal distribution characteristics and respiratory exposure risk of PCDD/Fs in Shanghai, China [J]. Journal of East China Normal University(Natural Science), 2024, 2024(6): 124-135.
[5]	Tiefeng CUI, Daoji LI. Progress and critical issues in research on micro- and nanoplastics in human body [J]. Journal of East China Normal University(Natural Science), 2024, 2024(6): 1-13.
[6]	Zhifu LI, Yonghong WU, Xuemei LIU, Dan LI. Assessment of water quality and heavy metal contamination of sediments after rice harvesting in a rice-shrimp co-cropping system [J]. Journal of East China Normal University(Natural Science), 2024, 2024(1): 122-133.
[7]	WANG Huaxiang, CHU Xiaoye, CHEN Ying, XU Lu, YANG Kai. A study on temporal and spatial distribution characteristics of dissolved oxygen in surface water of megacities [J]. Journal of East China Normal University(Natural Science), 2020, 2020(6): 154-163.
[8]	YANG Yun-ping, LI Yi-tian, HAN Jian-qiao. Temporal and spatial variation law of momentum coefficients in the Yangtze Estuary [J]. Journal of East China Normal University(Natural Sc, 2013, 2013(5): 9-17.
[9]	NIU Hai-yan, LIU Min, LU Min, QUAN Rui-song, ZHANG Li-jia,WANG Jing-jing, XU Shi-yuan. Risk assessment of typhoon hazard factors in China coastal areas [J]. Journal of East China Normal University(Natural Sc, 2011, 2011(6): 20-25,35.
[10]	ZHANG Li-jia;LIU Min;QUAN Rui-song;LU Min;WANG Jing-jing;XU Shi-yuan . Characteristics and disaster evaluation of the tropical cyclonesin southeast coastal areas of China （Chinese） [J]. Journal of East China Normal University(Natural Sc, 2009, 2009(2): 41-49.
[11]	CHEN Cheng;CHEN Hua-lin;HUANG Min-sheng. Adsorption properties of humic acid and pyrene on paddy soils and its extracts(Chinese) [J]. Journal of East China Normal University(Natural Sc, 2008, 2008(6): 51-55,1.
[12]	MENG Fei;;LIU Min;HOU Li-jun;CHANG Jing;JIANG Hai-yan;WANG He-yi. Heavy Metals in Urban Dusts and Soils of Shanghai and Its Pollution Assessment(Chinese) [J]. Journal of East China Normal University(Natural Sc, 2007, 2007(4): 56-63.
[13]	CHEN Li-qiao;LI Yun-kai;HOU Jun-li;LI Kai;CHEN Yong. A Survey of Managements of Non-indigenous Species via Ballast Water Transport(Chinese) [J]. Journal of East China Normal University(Natural Sc, 2005, 2005(5/6): 40-48.
[14]	ZHAO Qin-na;XU Qi-xin;YANG Kai. Application of Potential Ecological Risk Index in Soil Pollution of Typical Polluting Industries(Chinese) [J]. Journal of East China Normal University(Natural Sc, 2005, 2005(1): 111-116.