沈阳市典型城市河流优先控制污染物筛选及生态环境风险评估

王立阳; 李斌; 李佳熹; 刘瑞霞; 曾萍; 宋永会; 杨洋

doi:10.13198/j.issn.1001-6929.2018.09.02

编者按:

辽河流域是国家重大水专项实施的重点流域之一. “辽河流域有毒有害物污染控制技术与应用示范研究”课题组，针对辽河流域有毒有害物污染现状不明和缺乏有效控制技术的问题，以构建和完善有毒有害物治理技术体系、保证河流健康为目标，开展辽河流域有毒有害物现状调研和生态环境风险评估，以及风险控制技术的研发、集成和工程示范研究.现将部分研究成果在该专栏刊出，另有一篇综述性文章发在本期“进展”栏目，以期为我国流域型毒害物污染控制提供参考.

沈阳市典型城市河流优先控制污染物筛选及生态环境风险评估

doi: 10.13198/j.issn.1001-6929.2018.09.02

王立阳^{1, 3,},
李斌¹,
李佳熹¹,
刘瑞霞^{1, 3, ,},
曾萍¹,
宋永会¹,
杨洋²

1.
中国环境科学研究院, 北京 100012
2.
东北制药集团股份有限公司, 辽宁沈阳 110027
3.
北京师范大学水科学研究院, 北京 100875

基金项目:

国家水体污染控制与治理科技重大专项 2012ZX07202-002

详细信息

作者简介:
王立阳(1990-), 男, 甘肃兰州人, darktee@163.com

通讯作者:
刘瑞霞(1963-), 女, 河北石家庄人, 研究员, 博士, 博导, 主要从事水污染过程与控制技术研究, liurx@craes.org.cn

中图分类号: X522
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- 被引次数: 0
出版历程
- 收稿日期: 2018-03-19
- 修回日期: 2018-08-16
- 刊出日期: 2019-01-25

Priority Pollutants and Their Ecological Risk in Typically Urbanized River of Shenyang

WANG Liyang^{1, 3
,},
LI Bin¹,
LI Jiaxi¹,
LIU Ruixia^{1, 3
, ,},
ZENG Ping¹,
SONG Yonghui¹,
YANG Yang²

1.
Chinese Research Academy of Environmental Sciences, Beijing 100012, China
2.
Northeast Pharmaceutical Co., Ltd., Shenyang 110027, China
3.
College of Water Sciences, Beijing Normal University, Beijing 100875, China

Funds:

National Major Science and Technology Program for Water Pollution Control and Treatment, China 2012ZX07202-002

摘要

摘要: 细河和蒲河接纳了沈阳市工业废水的排放，水体中有毒、有害污染物不容忽视.为了明确河流中优先控制污染物，评价实际暴露水平下优先控制污染物对该水系生态环境的风险，选择细河和蒲河表层水为研究对象，开展了平水期、丰水期和枯水期的采样及有机污染物的检测分析；通过改进的潜在危害指数法对水体中检出的52种有机污染物打分排序，筛选了优先控制污染物；将效应评价外推法与商值法结合评价了优先控制污染物的生态环境风险.结果表明：52种有机污染物在细河中检出的平均质量浓度范围为9.20×10^-6~1.37×10^-1 mg/L，在蒲河中检出的平均质量浓度范围为4.30×10^-6~3.03×10^-2 mg/L.细河或蒲河中这些污染物的危害指数总分值（R）在22分以上的分别有12和13种，其中，PAEs（酞酸酯类）占6种，苯酚类污染物占4种.在细河中，DBP（邻苯二甲酸二丁酯）、苯酚、对甲基苯酚、2，4-二甲基苯酚和2，4，6-三甲基苯酚的R_q（风险商）>1，表明这些污染物存在较大的生态环境风险；在蒲河中，DBP、DEHP[邻苯二甲酸二（2-乙基己基）酯]和苯酚的R_q>1，表明这些污染物存在较高生态环境风险水平.研究显示，在细河、蒲河中PAEs和苯酚类有机物为优先控制污染物，其中部分优先控制污染物具有较高的生态环境风险，可为该流域有毒、有害物污染控制方案的制定提供参考和指导.
- 优先控制污染物 /
- 改进的潜在危害指数法 /
- 酞酸酯类 /
- 苯酚类 /
- 生态环境风险
Abstract: In recent years, the water quality (indicated by COD, BOD and NH₃-N) in Liao River Basin (LRB) has been improved year by year, however, there have been more concerns regarding the level and ecological risk of trace toxic substances in the water bodies. The Xi and Pu Rivers are typically urbanized rivers in Shenyang City, receiving the effluences from industrial wastewaters, which led to contamination of the water bodies by toxic and hazardous substances. The objectives of this study are to identify the priority pollutants in the rivers and to assess the ecological risk of the pollutants. The surface waters were collected from the Xi and Pu Rivers during the normal, wet and dry seasons, sequentially, 52 organic pollutants in the rivers were detected. By the method of improved potential hazardous index, these organic pollutants were scored and sequenced for screening the priority pollutants. Using the extrapolation method of effect evaluation coupled with the risk quotient (R_q) approach, the ecological risk of the priority pollutants was assessed. The results showed that the average concentrations of 52 organic pollutants were in the range of 9.20×10^-6-1.37×10^-1 mg/L in the Xi River and 4.30×10^-6-3.03×10^-2 mg/L in the Pu River. Thirteen or twelve of 52 organic pollutants in Xi or Pu Rivers had a total score of the potential hazardous index over 22, including 6 phthalic acid esters (PAEs) and 4 phenols. The R_q values of dibutyl phthalate (DBP), phenol, 4-methylphenol, 2, 4-dimethylphenol and 2, 4, 6-trimethylphenol in the Xi River, and those of DBP, diphenyl phthalate (2-ethylhexyl) ester (DEHP) and phenol in the Pu River were higher than 1. Those results indicated that PAEs and phenols were identified as the priority organic pollutants, some of them showing relatively high ecological risks. Those results provide not only a theoretical basis for the formulation of pollution control countermeasures and management schemes for the whole river basin and the typical river section, but also data support for the treatment technology of the emission point source.
- priority pollutants /
- modified potential hazardous index /
- phthalates /
- phenols /
- ecological risk
注释:

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图 1 采样点分布

注：XR1~XR8为细河采样点；PR1~PR11为蒲河采样点.

Figure 1. Sketch map of sampling locations

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表 1 周围多介质环境目标值与A、B的关系

Table 1. Relation between ambient multi-media environment target value and A, B

一般化学物质的ρ(AMEG_AH)/(μg/m³)	A
>200	1
＜200	2
＜40	3
＜2	4
＜0.02	5
>20	1
＜20	2
＜2	3
＜0.2	4
＜0.02	5

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表 2 细河潜在危害指数赋分标准

Table 2. Score standard of potential hazardous index in Xi River

级别	潜在危害指数范围(N)	赋值(N')
Ⅰ级	4.0~6.6	1
Ⅱ级	6.7~9.2	2
Ⅲ级	9.3~11.8	3
Ⅳ级	11.9~14.4	4
Ⅴ级	14.5~17.0	5

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表 3 细河检出平均质量浓度评分标准

Table 3. Scoring criteria for average detected concentration of pollutants in Xi River

级别	检出平均质量浓度范围/(mg/L)	赋值(C_w)
Ⅰ级	9.20×10^-6~6.28×10^-5	1
Ⅱ级	6.28×10^-5~4.29×10^-4	2
Ⅲ级	4.29×10^-4~2.93×10^-3	3
Ⅳ级	2.93×10^-3~1.99×10^-2	4
Ⅴ级	1.99×10^-2~1.37×10^-1	5

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表 4 细河平均检出率评分标准

Table 4. Scoring criteria for detection frequency of pollutants in Xi River

级别	平均检出率范围/%	赋值(F_w)
Ⅰ级	66.7~73.3	1
Ⅱ级	73.4~80.0	2
Ⅲ级	80.1~86.7	3
Ⅳ级	86.8~93.3	4
Ⅴ级	93.4~100.0	5

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表 5 细河有机污染物评分结果

Table 5. Scoring result among detected organic pollutants in Xi River

序号	化合物	潜在危害指数(N)	潜在危害指数赋值(N')	检出平均质量浓度/(mg/L)	检出平均质量浓度赋值(C_w)	平均检出率/%	平均检出率赋值(F_w)	危害指数总分值(R)
1	硝基苯	15.0	5	8.67×10^-3	4	100.0	5	24
2	3, 5-二甲基苯酚	15.0	5	8.41×10^-3	4	100.0	5	24
3	2, 4-二甲基苯酚	15.0	5	4.73×10^-3	4	100.0	5	24
4	2, 3-二甲基苯酚	15.0	5	4.60×10^-3	4	100.0	5	24
5	2, 4, 6-三甲基苯酚	16.0	5	1.09×10^-3	3	100.0	5	23
6	DEHP 〔邻苯二甲酸二(2-乙基己基)酯〕	15.5	5	2.10×10^-3	3	95.8	5	23
7	DBP (邻苯二甲酸二丁酯)	15.0	5	1.55×10^-3	3	100.0	5	23
8	DIBP (邻苯二甲酸二异丁酯)	15.0	5	2.81×10^-3	3	100.0	5	23
9	DMP (邻苯二甲酸二甲酯)	15.0	5	2.15×10^-3	3	100.0	5	23
10	六六六	17.0	5	2.17×10^-4	2	100.0	5	22
11	DNOP (邻苯二甲酸二正辛酯)	15.0	5	1.05×10^-4	2	100.0	5	22
12	DEP (邻苯二甲酸二乙酯)	15.0	5	3.09×10^-4	2	100.0	5	22
13	3-氯苯胺	14.0	4	3.24×10^-3	4	100.0	5	21
14	莠去津/阿特拉津	13.0	4	4.11×10^-3	4	100.0	5	21
15	灭除威	12.0	4	4.16×10^-3	4	100.0	5	21
16	2, 4-二叔丁基苯酚	12.0	4	2.22×10^-4	2	100.0	5	19
17	对甲基苯酚	10.0	3	2.20×10^-2	5	100.0	5	19
18	苯酚	10.0	3	1.36×10^-1	5	100.0	5	19
19	N-乙基苯胺	12.0	4	1.92×10^-4	2	83.3	3	17
20	3-乙酰吡啶	12.0	4	2.34×10^-4	2	83.3	3	17
21	N-异丙基苯胺	11.5	3	2.09×10^-4	2	100.0	5	16
22	1, 2, 3-三氯苯	10.0	3	5.71×10^-4	3	90.0	4	16
23	苯甲酸苄酯	10.0	3	2.18×10^-4	2	100.0	5	16
24	1-金刚烷醇	8.0	2	2.82×10^-2	5	100.0	5	16
25	1-金刚烷胺	8.0	2	1.37×10^-1	5	100.0	5	16
26	萘	9.0	2	1.24×10^-2	4	100.0	5	15
27	苯乙酮	8.0	2	8.99×10^-3	4	100.0	5	15
28	苯并噻唑	8.0	2	8.13×10^-3	4	100.0	5	15
29	6-甲基喹啉	8.0	2	4.39×10^-3	4	100.0	5	15
30	2-硝基甲苯	8.0	2	1.50×10^-2	4	100.0	5	15
31	2-甲基萘	8.0	2	4.66×10^-3	4	100.0	5	15
32	2-甲基喹啉	8.0	2	2.95×10^-3	4	100.0	5	15
33	4-硝基甲苯	8.0	2	8.06×10^-4	3	100.0	5	14
34	4-甲基喹啉	8.0	2	8.82×10^-4	3	100.0	5	14
35	3-硝基甲苯	8.0	2	6.04×10^-4	3	100.0	5	14
36	1-甲基异喹啉	8.0	2	1.13×10^-3	3	100.0	5	14
37	胡椒环	8.0	2	2.37×10^-3	3	93.3	4	13
38	1, 2-二甲氧基苯	8.0	2	3.46×10^-4	2	100.0	5	13
39	1, 2, 4-三氯苯	9.0	2	1.15×10^-4	1	96.7	5	12
40	1, 4-二氯苯	5.0	1	1.28×10^-3	3	100.0	5	11
41	乙基苯	4.0	1	5.97×10^-2	5	86.7	3	11
42	邻二甲苯	4.0	1	5.91×10^-2	5	83.3	3	11
43	氯苯	4.0	1	1.74×10^-3	3	100.0	5	11
44	苯乙烯	4.0	1	1.79×10^-3	3	100.0	5	11
45	1, 2, 4, 5-四甲基苯	5.0	1	2.13×10^-4	2	93.3	5	10
46	1, 2, 3, 4-四甲基苯	4.0	1	1.90×10^-4	2	100.0	5	10
47	1, 3-二氯苯	4.0	1	4.22×10^-5	1	66.7	1	5
48	邻氨基苯乙酮	—	—	8.47×10^-3	4	100.0	5	—
49	2-甲硫基苯并噻唑	—	—	1.25×10^-2	4	100.0	5	—
50	1-溴金刚烷	—	—	1.63×10^-3	3	100.0	5	—
51	1-金刚烷甲酮	—	—	1.64×10^-3	3	100.0	5	—
52	2, 6-二-叔-丁基-4-乙基苯酚	—	—	7.59×10^-5	2	100.0	5	—

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表 6 蒲河检出平均质量浓度评分标准

Table 6. Scoring criteria for average detected concentration of pollutants in Pu River

级别	检出平均质量浓度范围/(mg/L)	赋值(C_w)
Ⅰ级	4.30×10^-6~2.53×10^-5	1
Ⅱ级	2.53×10^-5~1.49×10^-4	2
Ⅲ级	1.49×10^-4~8.75×10^-4	3
Ⅳ级	8.75×10^-4~5.14×10^-3	4
Ⅴ级	5.14×10^-3~3.03×10^-2	5

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表 7 蒲河平均检出率评分标准

Table 7. Scoring criteria for detection frequency of pollutants in Pu River

级别	平均检出率范围/%	赋值(F_w)
Ⅰ级	22.5~38.0	1
Ⅱ级	38.1~53.5	2
Ⅲ级	53.6~69.0	3
Ⅳ级	69.1~84.5	4
Ⅴ级	85.6~100.0	5

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表 8 蒲河有机污染物评分结果

Table 8. Scoring result among organic pollutants in Pu River

序号	化合物	潜在危害指数(N)	潜在危害指数赋值(N')	检出平均质量浓度/(mg/L)	检出平均质量浓度赋值(C_w)	平均检出率/%	平均检出率赋值(F_w)	危害指数总分值(R)
1	DIBP	15.0	5	5.43×10^-3	5	100.0	5	25
2	DBP	15.0	5	2.28×10^-3	4	100.0	5	24
3	DMP	15.0	5	9.84×10^-4	4	100.0	5	24
4	DEHP	15.5	5	4.18×10^-3	4	100.0	5	24
5	2, 4, 6-三甲基苯酚	16.0	5	2.45×10^-4	3	100.0	5	23
6	硝基苯	15.0	5	6.33×10^-4	3	100.0	5	23
7	DEP	15.0	5	1.67×10^-4	3	100.0	5	23
8	3, 5-二甲基苯酚	15.0	5	1.70×10^-4	3	100.0	5	23
9	2, 4-二甲基苯酚	15.0	5	1.00×10^-4	3	100.0	5	23
10	2, 3-二甲基苯酚	15.0	5	1.77×10^-4	3	100.0	5	23
11	六六六	17.0	5	5.23×10^-5	2	100.0	5	22
12	DNOP	15.0	5	1.03×10^-4	2	100.0	5	22
13	莠去津/阿特拉津	13.0	4	8.29×10^-3	5	100.0	5	22
14	3-氯苯胺	14.0	4	1.94×10^-4	3	100.0	5	20
15	灭除威	12.0	4	1.59×10^-4	3	100.0	5	20
16	2, 4-二叔丁基苯酚	12.0	4	2.04×10^-4	3	100.0	5	20
17	苯酚	10.0	3	4.59×10^-3	4	100.0	5	18
18	对甲基苯酚	10.0	3	3.36×10^-4	3	100.0	5	17
19	苯甲酸苄酯	10.0	3	1.29×10^-4	3	100.0	5	17
20	N-乙基苯胺	12.0	4	8.25×10^-5	2	47.1	2	16
21	3-乙酰吡啶	12.0	4	7.24×10^-5	2	39.9	2	16
22	N-异丙基苯胺	11.5	3	1.12×10^-4	2	100.0	5	16
23	萘	9.0	2	1.58×10^-3	4	100.0	5	15
24	苯乙酮	8.0	2	2.71×10^-3	4	100.0	5	15
25	苯并噻唑	8.0	2	1.03×10^-3	4	100.0	5	15
26	2-甲基萘	8.0	2	1.20×10^-3	4	100.0	5	15
27	1-金刚烷胺	8.0	2	4.96×10^-3	4	100.0	5	15
28	4-硝基甲苯	8.0	2	2.04×10^-4	3	100.0	5	14
29	3-硝基甲苯	8.0	2	1.60×10^-4	3	100.0	5	14
30	2-硝基甲苯	8.0	2	2.37×10^-4	3	100.0	5	14
31	2-甲基喹啉	8.0	2	4.42×10^-4	3	100.0	5	14
32	1-金刚烷醇	8.0	2	4.14×10^-4	3	100.0	5	14
33	1-甲基异喹啉	8.0	2	2.24×10^-4	3	100.0	5	14
34	胡椒环	8.0	2	1.35×10^-4	2	92.5	5	13
35	6-甲基喹啉	8.0	2	1.72×10^-4	2	100.0	5	13
36	4-甲基喹啉	8.0	2	1.70×10^-4	2	100.0	5	13
37	1, 2-二甲氧基苯	8.0	2	1.26×10^-4	2	100.0	5	13
38	1, 4-二氯苯	5.0	1	1.21×10^-3	4	97.2	5	12
39	乙基苯	4.0	1	3.03×10^-2	5	68.9	4	12
40	邻二甲苯	4.0	1	2.93×10^-2	5	69.2	4	12
41	1, 2, 3-三氯苯	10.0	3	4.30×10^-6	1	20.6	1	11
42	1, 2, 4-三氯苯	9.0	2	4.42×10^-6	1	81.4	4	11
43	苯乙烯	4.0	1	4.10×10^-4	3	100.0	5	11
44	1, 2, 3, 4-四甲基苯	4.0	1	1.53×10^-4	3	100.0	5	11
45	1, 2, 4, 5-四甲基苯	5.0	1	8.48×10^-5	2	86.9	5	10
46	氯苯	4.0	1	5.23×10^-5	2	100.0	5	10
47	邻氨基苯乙酮	—	—	2.02×10^-3	4	100.0	5	—
48	2-甲硫基苯并噻唑	—	—	1.17×10^-3	4	100.0	5	—
49	1-溴金刚烷	—	—	4.19×10^-5	2	100.0	5	—
50	1-金刚烷甲酮	—	—	1.31×10^-4	2	100.0	5	—
51	2, 6-二-叔-丁基-4-乙基苯酚	—	—	1.00×10^-4	2	100.0	5	—
52	1, 3-二氯苯	4.0	1	8.81×10^-5	2	30.7	1	6

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表 9 水体中PAEs生态环境风险评价

Table 9. Ecological risk assessment results of PAEs in surface water

化合物	P_PNEC/(mg/L)	细河		蒲河
化合物	P_PNEC/(mg/L)	P_EEC/(mg/L)	R_q	P_EEC/(mg/L)	R_q
DMP	9.60×10^-2	4.21×10^-3	4.20×10^-2	2.17×10^-3	2.10×10^-2
DEP	9.60×10^-2	7.10×10^-4	1.40×10^-2	3.42×10^-4	1.00×10^-2
DBP	5.00×10^-4	3.17×10^-3	6.35	5.02×10^-3	10.00
DEHP	1.54×10^-3	1.27×10^-3	0.83	4.16×10^-3	2.73
注: P_PNEC为预测无效应质量浓度. P_EEC为实际监测质量浓度.下同.

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表 10 细河与蒲河水体中苯酚类污染物生态环境风险评价

Table 10. Ecological risk assessment results of phenols in surface water

化合物	P_PNEC/(mg/L)	细河		蒲河
化合物	P_PNEC/(mg/L)	P_EEC/(mg/L)	R_q	P_EEC/(mg/L)	R_q
苯酚	1.18×10^-3	3.39×10^-1	2.87×10²	9.48×10^-3	8.04
对甲基苯酚	1.00×10^-2	5.49×10^-2	5.49	7.20×10^-4	7.00×10^-2
2, 4-二甲基苯酚	3.98×10^-3	1.17×10^-2	2.95	3.30×10^-4	8.00×10^-2
2, 4, 6-三甲基苯酚	1.00×10^-3	2.63×10^-3	2.63	5.30×10^-4	5.30×10^-1

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