常州市水环境中精神活性物质污染特征与生态风险

邓洋慧; 郭昌胜; 殷行行; 罗莹; 徐建

doi:10.13198/j.issn.1001-6929.2021.10.19

常州市水环境中精神活性物质污染特征与生态风险

doi: 10.13198/j.issn.1001-6929.2021.10.19

邓洋慧^1,,
郭昌胜^{1, 2},
殷行行¹,
罗莹¹,
徐建^{1, 2, ,}

1.
中国环境科学研究院环境健康风险评估与研究中心，北京　100012
2.
中国环境科学研究院，国家环境保护化学品生态效应与风险评估重点实验室，北京　100012

基金项目: 国家自然科学基金项目(No.42177382)；国家水体污染控制与治理科技重大专项(No.2017ZX07302001，2017ZX07301005)

详细信息

作者简介:
邓洋慧（1993-），女，浙江衢州人，1306535971@qq.com

通讯作者:
徐建(1978-)，男，安徽来安县人，研究员，博士，博导，主要从事污染物环境化学及生态效应研究，xujian@craes.org.cn

中图分类号: X524
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- 被引次数: 0
出版历程
- 收稿日期: 2021-08-30
- 修回日期: 2021-10-26
- 网络出版日期: 2022-03-07

Pollution Characteristics and Risk Assessment of Psychoactive Substances in Aqueous Environment of Changzhou City

DENG Yanghui^1
,,
GUO Changsheng^{1, 2},
YIN Xingxing¹,
LUO Ying¹,
XU Jian^{1, 2
, ,}

1.
Center for Environmental Health Risk Assessment and Research, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
2.
State Environmental Protection Key Laboratory of Ecological Effect and Risk Assessment of Chemicals, Chinese Research Academy of Environmental Sciences, Beijing 100012, China

Funds: National Natural Science Foundation of China (No.42177382)；National Major Science and Technology Program for Water Pollution Control and Treatment，China (No.2017ZX07302001，2017ZX07301005)

摘要

摘要: 为评估精神活性物质(psychoactive substances，PSs)在常州市水环境中的污染特征、潜在来源及生态风险，利用超高效液相色谱-质谱联用(UPLC-MS/MS)方法，检测了地表水(湖泊、河流及饮用水源水)中13种典型PSs的污染水平和分布特征. 结果表明：常州市湖泊、河流及饮用水源水三类地表水中甲基苯丙胺(methamphetamine，METH)、苯丙胺(amphetamine，AMP)、3,4-亚甲基二氧基苯丙胺(3,4-methylenedioxy amphetamine，MDA)、海洛因(heroin，HR)、氯胺酮(ketamine，KET)、美沙酮(methadone，MET)及麻黄碱(ephedrine，EPH)均有不同程度检出. ∑PSs (13种典型PSs)的检出浓度范围为0.67~39.03 ng/L，其中在河流中的检出频率和浓度较高，EPH (0.23~21.98 ng/L)和METH (nd~8.47 ng/L)是检出浓度和频率较高的单体目标物. 采用主成分分析对PSs的来源进行解析，发现医院、生活污水的直接排放以及污水处理厂出水可能是常州水体中PSs的主要来源. 对常州市水环境中PSs进行生态风险评估，发现新浮山水库及长荡湖中MET对水生生物具有低风险〔0.01<RQ(risk quotient)<0.1〕，其余采样点的RQ<0.01. 研究显示，常州市水环境中的主要滥用药物为EPH和METH，虽然PSs对水生生物产生的生态风险可忽略不计，但是PSs对水生生态系统的长期风险仍需引起关注.
- 精神活性物质(PSs) /
- 污染特征 /
- 源解析 /
- 环境风险
Abstract: In order to assess the contamination characteristics, potential sources and ecological risks of psychoactive substances (PSs) in the water environment of Changzhou City, the contamination levels and distribution characteristics of 13 typical psychoactive substances in surface water (lakes, rivers and drinking water) in Changzhou were analyzed using ultra performance liquid chromatography-mass spectrometry (UPLC-MS/MS). Methamphetamine, amphetamine, 3,4-methylenedioxy amphetamine, heroin, ketamine, methadone and ephedrine were detected to varying degrees. The detected concentrations of ∑PSs in the three types of surface waters ranged from 0.67 ng/L to 39.03 ng/L, and the frequency and concentration of ∑PSs in surface waters and rivers were higher than in drinking water. The monomer target with the highest detection concentration and frequency was EPH (0.23-21.98 ng/L), followed by METH (nd-8.47 ng/L). Among all sampling locations, the Wunan River located in the lower reaches of Gehu Lake had the highest detection concentration (EPH at 21.98 ng/L). Principal component analysis was used to analyze the sources of PSs, indicating that the direct discharge of hospitals and domestic sewage and the effluent from sewage treatment plants may be the main sources of PSs in Changzhou′s water bodies. The ecological risk assessment of PSs in the water environment of Changzhou City showed that MET in Xinfushan Reservoir and Changdang Lake had low risk to aquatic organisms (0.01<(risk quotient, RQ)<0.1), and the risk quotients in the remaining locations were less than 0.01. This research shows that the main drugs of abuse in the water environment of Changzhou City were EPH and METH. The ecological risks of PSs to aquatic organisms are negligible, but the long-term risks of PSs to aquatic ecosystems still need attention.
- psychoactive substances /
- pollution characteristics /
- source identification /
- risk assessment

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图 1 常州市水环境采样点分布

Figure 1. Location of the sampling sites in the water environment of Changzhou City

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图 2 常州市水环境中PSs的组成特征

Figure 2. Composition of PSs in the water environment of Changzhou City

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图 3 常州市水环境中PSs的因子载荷与主成分得分

Figure 3. Loading and score plot of PCA of PSs in the water environment of Changzhou City

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图 4 常州市水环境中PSs存在的生态风险

Figure 4. RQ values of PSs in the surface water in Changzhou City

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表 1 PSs的理化性质

Table 1. Basic physicochemical properties of PSs

化合物	结构式	分子式	分子量	CAS登记号	pKa	水溶性/(g/L)
EPH		C₁₀H₁₅NO	165	299-42-3	10.3^[3]	—
AMP		C₉H₁₃N	135	300-62-9	10.1^[3]	28.03
METH		C₁₀H₁₅N	149	4846-07-5	9.9^[3]	4.28
MC		C₁₀H₁₃NO	163	5650-44-2	8.0^[3]	—
MDA		C₁₀H₁₃NO₂	179	4764-17-4	9.67^[36]	15.87
MDMA		C₁₁H₁₅NO₂	193	42542-1-9	9.9^[36]	7.03
NK		C₁₂H₁₄ClNO	223	35211-10-0	—	1.80
KET		C₁₃H₁₆ClNO	238	6740-88-1	7.5^[3]	3.87
BE		C₁₆H₁₉NO₄	289	519-09-5	10.1^[36]	1.61
COC		C₁₇H₂₁NO₄	303	50-36-2	8.61^[36]	1.30
MET		C₂₁H₂₇NO	309	76-99-3	8.94^[36]	—
HR		C₂₁H₂₃NO₅	369	561-27-3	7.95^[36]	—
COD		C₁₈H₂₁NO₃	299	76-57-3	8.21^[36]	12.15

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表 2 目标物质的洗脱梯度

Table 2. Elution gradient of target substance

时间/min	流速/ (mL/min)	流动相/%		进样量/μL
时间/min	流速/ (mL/min)	A(0.1%甲酸水)	B(乙腈)	进样量/μL
0	0.45	98	2	5
0~0.5	0.45	98	2	5
0.5~4.5	0.45	50	50	5
4.5~4.6	0.45	2	98	5
4.6~6.0	0.45	2	98	5
6.0~6.2	0.45	98	2	5
6.2~7.0	0.45	98	2	5

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表 3 目标物质的特征选择离子及质谱条件

Table 3. Analyte ions for UPLC-MS /MS monitoring, and conditions of collision voltage and declustering potential

目标物	保留时间/ min	母离子 (m/z)	去簇电压/ V	定量离子		定性离子
目标物	保留时间/ min	母离子 (m/z)	去簇电压/ V	碰撞电压/V	子离子 (m/z)	碰撞电压/V	子离子 (m/z)
EPH	1.3	166.0	35	20	133.2	3	148.0
AMP	1.8	136.1	14	14	91.0	9	119.1
METH	2.0	150.1	22	16	91.0	10	119.1
MC	1.6	164.1	20	18	131.0	22	105.0
MDA	1.9	180.0	22	20	105.0	16	135.4
MDMA	2.0	194.1	22	12	163.0	24	105.0
NK	2.2	224.0	28	24	125.0	50	89.2
KET	2.3	232.0	16	24	125.0	16	179.0
BE	2.3	290.0	20	20	168.1	28	105.0
COC	2.7	304.1	6	18	182.1	28	82.1
MET	3.9	310.1	4	24	105.0	48	77.1
HR	2.6	370.0	34	48	165.1	26	268.1
COD	1.7	300.0	28	26	215.1	35	165.1
METH-d8	1.9	158.1	16	22	93.1	12	124.0

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表 4 常州市水环境中PSs的LOD、LOQ、回收率以及入常州市水环境中其检出浓度

Table 4. LOD, LOQ, detection rates and concentrations of PSs in the water environment of Changzhou City

化合物	回收率/%			LOD/ (ng/L)	LOQ/ (ng/L)	浓度/(ng/L)
化合物	Milli-Q水	自来水	地表水	LOD/ (ng/L)	LOQ/ (ng/L)	最小值	最大值	中值
AMP	101.5±7.7	98.7±18.3	85.6±24.0	0.010	0.015	nd	0.53	0.46
METH	107.2±24.1	107.5±27.7	105.5±13.4	0.005	0.010	nd	8.47	0.34
MC	87.4±28.5	85.0±25.9	100.3±12.7	0.400	0.450	nd	0.38	0.37
MDA	95.2±7.9	92.1±6.6	80.7±32.4	0.150	0.200	nd	7.96	0.15
MDMA	106.9±13.8	101.9±9.1	90.6±16.9	0.200	0.250	nd	0.20	0.19
NK	105.1±18.4	108.2±17.1	104.1±9.0	0.010	0.020	nd	<LOD	nd
KET	107.0±28.0	101.4±26.2	105.3±23.6	0.020	0.050	nd	3.29	0.30
BE	100.0±35.8	103.0±25.1	105.6±21.2	0.005	0.010	nd	nd	nd
COC	101.2±27.1	113.9±21.1	107.2±33.8	0.300	0.350	nd	0.34	0.28
MET	110.3±19.5	111.5±23.0	105.2±21.5	0.400	0.450	nd	4.67	0.48
HR	96.1±22.0	98.4±15.1	104.2±17.4	0.010	0.020	nd	3.83	0.29
COD	100.8±24.7	92.0±20.9	82.7±22.2	0.050	0.010	nd	0.15	nd
EPH	105.5±9.7	112.0±16.9	94.5±12.5	0.010	0.015	0.23	21.98	0.41
∑PSs	—	—	—	—	—	0.23	51.80	3.27
注：LOD为检出限，LOQ为定量限，nd表示未检出. 下同.

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表 5 国内外地表水中AMP、METH、MET和KET的浓度

Table 5. Concentrations of AMP, METH, MET and KET in surface water from different regions ng/L

采样区域	METH	AMP	COC	BE	HR	KET	MDA	MDMA	MET
中国鄱阳湖^[12]	0.37	0.15	<LOD	<LOD	0.31	0.55	<LOD	0.01	<LOD
中国巢湖^[12]	0.90	<LOD	<LOD	<LOD	<LOD	0.60	<LOD	<LOD	<LOD
中国太湖^[12]	0.20	<LOD	<LOD	<LOD	<LOD	0.70	<LOD	<LOD	<LOD
中国海河^[14]	2.92	<LOD	3.62	2.82	<LOD	0.08	<LOD	<LOD	0.04
中国黄河^[14]	8.14	<LOD	202.00	206.00	<LOD	6.27	<LOD	<LOD	<LOD
西班牙^[9]	<LOD	2.34	2.47	31.33	<LOD	<LOD	0.60	1.82	1.05
意大利^[2]	<LOD	<LOD	16.20	64.60	<LOD	<LOD	0.80	0.80	3.30
英国^[2]	0.30	<LOD	4.40	19.00	<LOD	21.3	1.25	6.15	5.00
比利时^[11]	<LOD	<LOD	15.30	96.00	<LOD	<LOD	<LOD	<LOD	<LOD

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表 6 常州市水环境中PSs浓度的相关性

Table 6. Relevance of PSs concentrations in Changzhou City

项目	AMP 浓度	METH 浓度	MDA 浓度	KET 浓度	MET 浓度	HR 浓度	EPH 浓度
AMP浓度	1
METH浓度	−0.38^*	1
MDA浓度	−0.34	0.97^**	1
KET浓度	0.12	0.09	−0.08	1
MET浓度	−0.02	−0.07	−0.13	−0.10	1
HR浓度	0.09	−0.09	−0.07	−0.08	0.20	1
EPH浓度	−0.39^*	0.97^**	0.98^**	−0.09	−0.08	−0.08	1
注：*表示在0.01水平上(双尾)显著相关；表示在0.05水平上(双尾)显著相关.

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表 7 12种PSs的半数致死(效应)浓度L(E)C₅₀和PNEC值

Table 7. Half effect concentration L(E)C₅₀ and PNEC values of 12 psychoactive substance

目标物	L(E)C₅₀/(mg/L)			AF	PNEC/(mg/L)	数据来源
目标物	藻类	水溞	鱼类	AF	PNEC/(mg/L)	数据来源
COC	2.28	4.90	13.00	1 000	2.28×10⁻³	ECOSAR软件
BE	12 041.67	6 805.16	33 458.81	1 000	6.81×10⁰	ECOSAR软件
EPH	3.91	3.62	56.00	1 000	3.62×10⁻³	文献[53]
MDMA	2.30	0.22	24.18	1 000	2.20×10⁻⁴	ECOSAR 软件
AMP	3.80	2.22	28.80	1 000	2.22×10⁻³	ECOSAR 软件
METH	1.97	2.51	20.51	1 000	1.97×10⁻³	文献[54]
HR	7.63	11.22	2.93	1 000	2.93×10⁻³	ECOSAR软件
MET	0.17	0.34	2.24	1 000	1.70×10⁻⁴	ECOSAR软件
COD	18.36	18.83	171.79	1 000	1.84×10⁻²	ECOSAR 软件
MC	4.00	—	—	1 000	4.00×10⁻³	ECOSAR 软件
MDA	4.60	—	—	1 000	4.60×10⁻³	ECOSAR 软件
KET	0.72	1.13	8.34	1 000	7.20×10⁻⁴	ECOSAR 软件

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