从黄浦江流域采集了15 份冬季水体和悬浮物样品, 利用液相色谱-质谱联用技术(liquid chromatography-mass spectroscopy-mass spectroscopy, LC-MS-MS)分析了水体和悬浮物样品中壬基酚(nonylphenol, NP)、4-t-辛基酚(4-t-octylphenol, 4-t-OP)、4-t-丁基酚(4-t-butylphenol, 4-t-BP)和双酚A(bisphenol A, BPA)的质量浓度分布. 结果表明, 黄浦江流域水体和悬浮物样品中的酚类环境激素质量浓度范围分别为47.25356.43 ng/L 和2.2948.50 mg/g, 平均值分别为167.69 ng/L 和20.81 mg/g. 因子分析结果说明, 黄浦江水域中酚类环境激素主要以NP, 4-t-OP 和BPA 为主, 局部水域伴有4-t-BP 的高残留. 生态风险评价结果显示, 黄浦江流域水体中的酚类环境激素的危害商数均小于1, 表明不存在严重和频发的酚类环境激素生态毒理风险, 但其生物富集效应不容忽视.
Transformation and distribution characteristics of phenolic environmental hormones in 15 winter water and suspended solids samples from Huangpu River were studied. Pollution levels, spatial distributions of nonylphenol (NP), 4-t-octylphenol (4-t-OP), 4-tbutylphenol (4-t-BP) and bisphenol A (BPA) in water and suspended solids were analyzed by liquid chromatography-mass spectroscopy-mass spectroscopy (LC-MS-MS). The results showed that concentration of the above 4 phenolic environmental hormones in water and suspended solids were 167.69 ng/L with a range of 47.25356.43 ng/L, and 20.81 mg/g with a range of 2.2948.50 mg/g, respectively. The factor analysis showed that the principal pollutants were NP, 4-t-OP and BPA, with a high concentration of 4-t-BP in some
basins. Ecological risk assessment showed that hazard quotient were below 1 in the above 4 phenolic environmental hormones, and no ecological risk was found. Special attention should be paid to the potential hazard caused by algae accumulation.
[1] Ying G G, Williams B, Kookana R. Environmental fate of alkylphenols and alkylphenol ethoxylates—a review [J]. Environment Internationa, 2002, 28 (2): 15-26.
[2] Manzano M A, Perales J A, Sales D, et al. The effect of temperature on the biodegradation of a nonylphenol polyethoxylate in river water [J]. Water Research, 1999, 33(11): 2593-2600.
[3] Sharman M, Honeybone C A, Jickells S M, et al. Detection of residues of the epoxy adhesive component bisphenol A diglycidyl ether (BADGE) in microwave susceptors and its migration into food [J]. Food Additives and Contaminants, 1995, 12(6): 779-787.
[4] Gorga M P, Barcelo D M. Multi-residue analytical method for the determination of endocrine disruptors and related compounds in river and waste water using dual column liquid
chromatography switching system coupled to mass spectrometry [J]. Journal of Chromatography A, 2013, 1295: 57-66.
[5] Vega-Morales T, Sosa-Ferrera Z, Santana-Rodriguez J J. Determination of various estradiol mimicking-compounds in sewage sludge by the combination of microwave-assisted extraction and LC-MS/MS [J]. Talanta, 2011, 85(4): 1825-1834.
[6] Liu S Y, Zhao G G, Chen J L, et al. Trace analysis of 28 steroids in surface water, wastewater and sludge samples by rapid resolution liquid chromatography-electrospray ionization tandem mass spectrometry [J]. Journal of Chromatography A, 2011, 1218(10): 1367-1378.
[7] Wu M, Wang L, Xu G, et al. Seasonal and spatial distribution of 4-tert-octylphenol, 4-nonylphenol and bisphenol A in the Huangpu River and its tributaries, Shanghai, China [J].
Environmental Monitoring and Assessment, 2013, 185(4): 3149-3161.
[8] 黄卫国, 唐建辉, 陈颖军, 等. 山东半岛典型海湾及邻近河流中烷基酚和双酚A初步研究[J]. 海洋环境科学, 2011, 31(3): 358-363.
[9] 范奇元, 金泰, 将学之, 等. 我国部分地区环境中壬基酚的检测[J]. 中国公共卫生, 2002, 18(11): 1372-1373.
[10] S´anchez-Avila J, Tauler R, Lacorte S. Organic micropollutants in coastal waters from NW Mediterranean Sea: sources distribution and potential risk [J]. Environment International,
2012, 46(2): 50-62.
[11] Rocha M J, Cruzeiro C, Reis M, et al. Determination of 17 endocrine disruptor compounds and their spatial and seasonal distribution in the Sado River Estuary (Portugal) [J]. Toxicological & Environmental Chemistry, 2013, 95(2): 237-253.
[12] Petrovic M, Barcel´o D. Inputs of pharmaceuticals and endocrine disrupting compounds in the Llobregat River basin [M]. The Llobregat: Springer, 2012: 151-65.
[13] 那广水, 高会, 方小丹, 等. 黄渤海近岸海域酚类内分泌干扰物分布特征及其来源解析[J]. 中国科学: 化学, 2013, 43(7): 911-918.
[14] 沈钢, 张祖麟, 余刚, 等. 夏季海河与渤海湾中壬基酚和辛基酚污染的状况[J]. 中国环境科学, 2005, 25(6): 733-736.
[15] 陈兵, 麦碧娴, 陈社军, 等. 珠江三角洲河流沉积物中的壬基酚[J]. 中国环境科学, 2005, 25(4): 484-486.
[16] 段菁春, 陈兵, 麦碧娴, 等. 洪季珠江三角洲水系烷基酚污染状况研究[J]. 中国环境科学, 2004, 24(3): 48-52.
[17] L¨u X, Zhai S. Distributions and sources of organic biomarkers in surface sediments from the Changjiang (Yangtze River) estuary, China [J]. Continental Shelf Research, 2006, 26(1): 1-14.
[18] 傅明珠, 李正炎, 王波. 夏季长江口及其临近海域不同环境介质中壬基酚的分布特征[J]. 海洋环境科学, 2008(6): 561-565.
[19] Remberger M, Kaj L, Palm A, et al. Screening tertiary butylphenols, methylphenols, and long-chain alkylphenols in the Swedish environment [R]. Swedish: IVL, 2004.
[20] Staples C A, Dorn P B, Klecka G M, et al. Bisphenol A concentrations in receiving waters near US manufacturing and processing facilities [J]. Chemosphere, 2000, 40(5): 521-525.
[21] Shao B, Hu J, Yang M, et al. Nonylphenol and nonylphenol ethoxylates in river water, drinking water, and fish tissues in the area of Chongqing, China [J]. Archives of Environmental
Contamination and Toxicology, 2005, 48(4): 467-473.
[22] Tsuda T, Takino A, Muraki K, et al. Evaluation of 4-nonylphenols and 4-tert-octylphenol contamination of fish in rivers by laboratory accumulation and excretion experiments [J]. Water
Research, 2001, 35(7): 1786-1792.
[23] Jonsson B. Risk assessment on butylphenol, octylphenol and nonylphenol, and estimated human exposure of alkylphenols from Swedish fish [M]. Ekotoxikologiska Avdelningen: Uppsala Universitet, 2006.
[24] Belfroid A, Van Velzen M, Van Der Horst B, et al. Occurrence of bisphenol A in surface water and uptake in fish: evaluation of field measurements [J]. Chemosphere, 2002, 49(1): 97-
103.
[25] Jiang W, Yan Y, Ma M, et al. Assessment of source water contamination by estrogenic disrupting compounds in China [J]. Journal of Environmental Sciences-China, 2012, 24(2): 320-328.
