龚剑^1,2,3,,,
冉勇^2,,,
黄文²,
杨娟²,
陈迪云^1,3,
杨余²
1. 广州大学环境科学和工程学院 广东省放射性核素污染控制与资源化重点实验室, 广州 510006;
2. 中国科学院广州地球化学研究所 有机地球化学国家重点实验室, 广州 510640;
3. 广州大学(省部共建)珠江三角洲水质安全与保护教育部重点实验室, 广州 510006

作者简介: 龚剑(1979-),男,博士,高级实验师,研究方向为典型毒害污染物的水陆环境行为及风险研究,E-mail:gong_jian@mails.ucas.ac.cn.

通讯作者: 龚剑,gong_jian@mails.ucas.ac.cn ; 冉勇,yran@gig.ac.cn ;

基金项目: NSFC-广东联合基金(U1201235)
国家自然科学基金项目(41473103,41372364)
广州市属高校科技计划项目重点项目(1201410747)
广州市科技计划项目(201607010217)


中图分类号: X171.5

Partitioning and Risk of Endocrine-disrupting Chemicals in Multiphases of the Rivers from the Pearl River Delta, China

Gong Jian^1,2,3,,,
Ran Yong^2,,,
Huang Wen²,
Yang Juan²,
Chen Diyun^1,3,
Yang Yu²
1. Guangdong Provincial Key Laboratory of Radionuclides Pollution Control and Resources, School of Environmental Science and Engineering, Guangzhou University, Guangzhou 510006, China;
2. State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China;
3. Ministry of Education Key Laboratory of Safety and Protection of the Pearl River Delta Water Quality, Guangzhou 510006, China

Corresponding authors: Gong Jian,gong_jian@mails.ucas.ac.cn ; Ran Yong,yran@gig.ac.cn ;

CLC number: X171.5

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摘要:为探究典型内分泌干扰物(EDCs)在多相体系中的分配作用及其生态风险，利用切向流超滤、固相萃取、气相色谱-质谱联用等分析方法，对珠江广州河段和东江东莞河段水/胶体/悬浮颗粒中的辛基酚(OP)、4-壬基酚(NP)、双酚A (BPA)、雌酮(E1)、17β-雌二醇(E2)、己烯雌酚(DES)、17α-乙炔雌二醇(EE2)、雌三醇(E3)展开了研究。结果发现，约60%的酚类雌激素存在于水相，约30%存在于胶体相，约10%赋存于颗粒相。DES、E2、EE2、E3在所有样品中均未检出。此外，NP、BPA的含量与溶解性有机碳(DOC)和颗粒态有机碳(POC)含量均呈正相关关系。溶解相中OP、NP、BPA、E1的溶解有机碳归一化含量与特定紫外吸收(SUVA254)均呈正相关，表明溶解有机质与EDCs之间可能通过π-π作用相结合，其作用强度与芳香度有关。OP、NP、BPA在颗粒物/水、胶体/水间的原位有机碳归一化分配系数的对数值(logK_oc、logK_coc)分别为：4.41±0.69、4.60±0.32、4.30±0.43和5.35±0.42、5.69±0.50、5.51±0.77，显示出胶体对EDCs有更高的吸附能力。两条河流的风险商数(RQ)在0.39～2.01之间，其中珠江广州河段为高风险区(RQ平均值为1.5)，东江东莞河段为中风险区(RQ平均值为0.75)，且底层水的风险高于表层水。
关键词: 内分泌干扰物/
多相体系/
分配/
风险/
珠江

Abstract:In order to explore the multi-phase partitioning and eco-risk of EDCs in water, colloids, and suspended particulate materials (SPM) in the Zhujiang River and the Dongjiang River, Pearl River Delta, the cross-flow ultrafiltration, solid phase extraction, and gas chromatography-mass spectrometry were employed. The typical EDCs 4-tert-octylphenol (OP), 4-nonylphenol (NP), bisphenol A (BPA), estrone (E1), diethylstilbestrol (DES), 17β-estradiol (E2), estriol (E3) and 17α-ethynylestradiol (EE2) were selected as the target compounds. It was observed that about 60% of OP, NP, and BPA were soluble in water phase, 30% were bound with colloids, and 10% were associated with SPM. DES, E2, EE2, E3 were not detected in these tested samples. Moreover, NP and BPA concentrations were both positively correlated with the dissolved and particulate organic carbon (OC) contents, respectively. The dissolved OC-normalized concentrations of OP, NP, BPA, E1, respectively, were positively correlated with the specific UV absorbance at 254 nm (SUVA254) in the dissolved phase, suggesting that they can be bonded with dissolved organic matters through π-π interaction which was related with the aromaticity. Moreover, the in situ particle-water and colloid-water partition coefficients (K_oc and K_coc) were calculated. The log K_oc values for OP, NP and BPA were 4.41±0.69, 4.60±0.32 and 4.30±0.43, respectively, and their log K_coc values were 5.35±0.42, 5.69±0.50 and 5.51±0.77, respectively. The K_coc were one order of magnitude higher than the K_oc, indicating the more powerful affinity of colloids with the EDCs than that of SPM. In addition, the environmental risk quotient (RQ) approach was used to briefly assess the potential risk of the two rivers. The RQ values were in a range of 0.39~2.01, indicating that the Zhujiang River likely have the high risk with a mean value of 1.5, and the Dongjiang River contain the medium risk with an average value of 0.75. It was also found that the risk in the bottom water layer were higher than that in the surface layer.
Key words:endocrine-disrupting chemicals/
multiphases/
partitioning/
risk/
Pear River.