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气相色谱-负化学电离质谱法测定中国南方珠江地表水中的酚类内分泌干扰物和酸性药物。

Determination of phenolic endocrine disrupting chemicals and acidic pharmaceuticals in surface water of the Pearl Rivers in South China by gas chromatography-negative chemical ionization-mass spectrometry.

作者信息

Zhao Jian-Liang, Ying Guang-Guo, Wang Li, Yang Ji-Feng, Yang Xiao-Bing, Yang Li-Hua, Li Xu

机构信息

State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China.

出版信息

Sci Total Environ. 2009 Jan 1;407(2):962-74. doi: 10.1016/j.scitotenv.2008.09.048. Epub 2008 Nov 11.

Abstract

An analytical method for phenolic endocrine disrupting chemicals and acidic pharmaceuticals in river water was developed using gas chromatography mass spectrometry (GC-MS) coupled with negative chemical ionization (NCI) technique, and used for the determination of these compounds in the Pearl Rivers (Liuxi, Zhujiang and Shijing Rivers). Derivatization using pentafluorobenzoyl chloride (PFBOCl) and pentafluorobenzyl bromide (PFBBr) before GC-MS analysis were applied and optimized for phenolic compounds and acidic compounds, respectively. The target compounds were analyzed for river waters from the upstream to downstream of the Pearl Rivers. Phenolic compounds 4-tert-octylphenol (4-t-OP), 4-nonylphenol (4-NP), bisphenol-A (BPA), estrone (E1), estradiol (E2) and triclosan (TCS) were detected at trace or low levels in the water samples from Liuxi River and Zhujiang River. Diethylstilbestrol (DES) was not detected in the Pearl Rivers. The highest concentrations of the phenolic compounds were found in Shijing River, and they were 3150 ng/L for 4-t-OP, 11,300 ng/L for 4-NP, 1040 ng/L for BPA, 79 ng/L for E1, 7.7 ng/L for E2 and 355 ng/L for TCS, respectively. Only a few acidic pharmaceuticals were detected at low concentrations in water from Liuxi River and Zhujiang River, but the highest concentrations for the acidic pharmaceuticals were also found in Shijing River. The highest concentrations detected for clofibric acid, ibuprofen, gemfibrozil, naproxen, mefenamic acid and diclofenac were 17 ng/L, 685 ng/L, 19.8 ng/L, 125 ng/L, 24.6 ng/l and 150 ng/L, respectively. The results suggest Liuxi and Zhujiang Rivers are only slightly contaminated and can be used as drinking water sources, but Shijing River is heavily polluted by the wastewater from nearby towns.

摘要

建立了一种采用气相色谱 - 质谱联用(GC-MS)结合负化学电离(NCI)技术分析河水中酚类内分泌干扰物和酸性药物的方法,并用于珠江(流溪河、珠江和石井河)中这些化合物的测定。在GC-MS分析之前,分别采用五氟苯甲酰氯(PFBOCl)和五氟苄基溴(PFBBr)对酚类化合物和酸性化合物进行衍生化,并进行了优化。对珠江从上游到下游的河水进行了目标化合物分析。在流溪河和珠江的水样中,痕量或低水平地检测到了酚类化合物4-叔辛基苯酚(4-t-OP)、4-壬基苯酚(4-NP)、双酚A(BPA)、雌酮(E1)、雌二醇(E2)和三氯生(TCS)。在珠江中未检测到己烯雌酚(DES)。酚类化合物的最高浓度出现在石井河中,4-t-OP为3150 ng/L,4-NP为11300 ng/L,BPA为1040 ng/L,E1为79 ng/L,E2为7.7 ng/L,TCS为355 ng/L。在流溪河和珠江的水中仅检测到少量低浓度的酸性药物,但酸性药物的最高浓度也出现在石井河中。检测到的氯贝酸、布洛芬、吉非罗齐、萘普生、甲芬那酸和双氯芬酸的最高浓度分别为17 ng/L、685 ng/L、19.8 ng/L、125 ng/L、24.6 ng/L和150 ng/L。结果表明,流溪河和珠江仅受到轻微污染,可作为饮用水源,但石井河受到附近城镇废水的严重污染。

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