污水处理厂废水中苯胺类化合物的测定及生态风险分析
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摘要
本研究建立了固相萃取结合高效液相色谱-串联质谱法测定水样中苯胺类化合物的方法,水样前处理使用PCX固相萃取小柱吸附苯胺类化合物,以甲醇溶剂洗脱,采用ZORBAX Eclipse Plus C18色谱柱,电喷雾质谱正离子模式,以乙腈-0. 2%甲酸水为流动相,梯度洗脱,同时测定水样中12种苯胺类化合物。结果显示,进水中12种苯胺类化合物加标回收率62.3%～119%,日内精密度为2.55%～11.8%,日间精密度为4.17%～13.6%;出水中12种苯胺类化合物加标回收率为70.5%～115%,日内精密度为2.49%～10.5%,日间精密度为3.01%～15.5%;12种物质的检出限为0.25～1.97μg/L。该方法操作简单、结果准确,能够满足水样中12种苯胺类化合物的定性定量测定,可同时处理大批样品。用该方法对江苏省淮安市18家污水处理厂的进、出水样进行了测定,12种苯胺类化合物在18个采样点均能检出,其中N,N-二乙基间甲苯胺检出水平最高,平均值为15.29ng/L,2,6-二甲基苯胺同样检出水平最低,平均值为5.22 ng/L。采用风险商值法评估对12种苯胺类化合物进行了生态风险评估,结果表明二苯胺、苯胺和间甲苯胺为中等潜在生态风险,其他均为低生态风险。
This study builds an analysis method based on solid phase extraction(SPE) coupled with liquid chromatography electrospray ionization tandem mass spectrometry(LC-ESI-MS/MS) with has been developed for measuring of 12 aniline compounds in environmental water samples. The target compounds were pretreated by PCX solid phase extraction column and elution with methanol, separated on ZORBAX Eclipse Plus C18(3.5μm,2.1×150 mm) column with multiple reactions monitoring(MRM)and positive ionization mode, the mobile phases containing acetonitrile and 2 mmol/L aqueous ammonium formate. Recovery experiments concentrations varied from 2 ～20μg/L. The recovery rates for target compounds in influent were in the range of 62.3% ～119%, RSDr 2.55% ～11.8%, RSDR4.17% ～13.6%(n=3), recovery rates in effluent were in the range of 70.5% ～115%, RSDr 2.49% ～10.5%, RSDR3.01%～15.5% respectively. The limit of determination of 12 aniline compounds were ranged from 0.25μg/L to 1.97 μg/L. The method is simple and accurate, suitable for the qualitative and quantitative determination of 12 aniline compounds in water samples, useful for massive of samples at the same time. Base on the analysis method, the water samples in wastewater treatment plants of Huai'an at 18 sampling sites were analyzed. All target compounds were determined in the water, while N,N-diethyl-m-toluidine was performed at highest level with 15.29 ng/L,2, 6-dimethylaniline was performed at lowest level with 5.22 ng/L. Risk quotient method was utilized to evaluate the environmental risks for 12 aniline compounds, in addition to the medium risk levels of diphenylamine, aniline and m-toluidine were, others were at low risk levels.
This study builds an analysis method based on solid phase extraction(SPE) coupled with liquid chromatography electrospray ionization tandem mass spectrometry(LC-ESI-MS/MS) with has been developed for measuring of 12 aniline compounds in environmental water samples. The target compounds were pretreated by PCX solid phase extraction column and elution with methanol, separated on ZORBAX Eclipse Plus C18(3.5μm,2.1×150 mm) column with multiple reactions monitoring(MRM)and positive ionization mode, the mobile phases containing acetonitrile and 2 mmol/L aqueous ammonium formate. Recovery experiments concentrations varied from 2 ～20μg/L. The recovery rates for target compounds in influent were in the range of 62.3% ～119%, RSDr 2.55% ～11.8%, RSDR4.17% ～13.6%(n=3), recovery rates in effluent were in the range of 70.5% ～115%, RSDr 2.49% ～10.5%, RSDR3.01%～15.5% respectively. The limit of determination of 12 aniline compounds were ranged from 0.25μg/L to 1.97 μg/L. The method is simple and accurate, suitable for the qualitative and quantitative determination of 12 aniline compounds in water samples, useful for massive of samples at the same time. Base on the analysis method, the water samples in wastewater treatment plants of Huai'an at 18 sampling sites were analyzed. All target compounds were determined in the water, while N,N-diethyl-m-toluidine was performed at highest level with 15.29 ng/L,2, 6-dimethylaniline was performed at lowest level with 5.22 ng/L. Risk quotient method was utilized to evaluate the environmental risks for 12 aniline compounds, in addition to the medium risk levels of diphenylamine, aniline and m-toluidine were, others were at low risk levels.
引文
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[10]Pradenas J, Galarce-Bustos O, Henríquez-Aedo K, et al.Occurrence of biogenic amines in beers from Chilean market[J]. Food Control, 2016, 70:138-144.
[11]Boulahlib S, Boudina A, Siahmed K, et al. Development and validation of a fast and simple HPLC method for the simultaneous determination of aniline and its degradation products in wastewater[J]. Analytical Methods, 2016, 8(30).
[12]Xiong J, Qian S, Xie Y H, et al. Simultaneous Determination of Acrylamide, Aniline and Benzidine in Water Sam-ple by High Performance Liquid Chromatography-Tandem Mass Spectrometry[J]. Chinese Journal of Analytical Chemistry,2014, 42(1):93-98.
[13]European C. Technical Guidance Document in Support of Commission Directive 93/67/EEC on Risk Assessment for New Notified Substances and Commission Regulation(EC)No 1488/94 on Risk Assessment for Existing Subs-tances,Part II[Z]. 2003.
[14]Klimisch H J, Andreae M, Tillmann U. A Systematic Approach for Evaluating the Quality of Experimental Toxico-logical and Ecotoxicological Data[J]. Regulatory Toxicology&Pharmacology, 1997, 25(1):1-5.
[15]李亚莹,许玉萍,王薇,等.城镇污水处理厂出水中苯胺类化合物测定的影响因素探讨[J].科学咨询:科技·管理,2011(28):84-85.
[2]Jurado-Sánchez B, Ballesteros E, Gallego M. Occurrence of aromatic amines and N-nitrosamines in the different steps of a drinking water treatment plant[J]. Water Research, 2012,46(14):4543-4555.
[3]Nitisakulkan T, Oku S, Kudo D, et al. Degradation of chloroanilines by toluene dioxygenase from Pseudomonas putida T57[J]. Journal of Bioscience&Bioengineering. 2014,117(3):292-297.
[4]周文敏,傅德黔.水中优先控制污染物黑名单[J].中国环境监测, 1990(4):3-5.
[5]蒋建国,刘朝文.印染行业苯胺类污染急需控制[Z].201555.
[6]古文,周林军,刘济宁,等. 3种苯胺类化学品在好氧污水处理模拟系统中的降解特性[J].环境科学, 2016(1):240-246.
[7]Yin X H, Shi W J, Shen X, et al.[Spectrophotometric determination of aromatic amino compounds with J-acid][J].Guang pu xue yu guang pu fen xi=Guang pu, 2015, 35(1):193-197.
[8]Wang C C, Sung L Y, Wu P L, et al. An Analytical Method for the Field Investigation of Environmental Amines Released by Industrial Processes[J]. Process Safety&Environmental Protection, 2016, 102:328-335.
[9]Kim Y H, Kim K H. A novel quantitation approach for maximizing detectable targets for offensive/volatile odoran-ts with diverse functional groups by thermal desorption-gas chromatography-mass spectrometry[J]. Scientific Rep-orts,2016, 6.
[10]Pradenas J, Galarce-Bustos O, Henríquez-Aedo K, et al.Occurrence of biogenic amines in beers from Chilean market[J]. Food Control, 2016, 70:138-144.
[11]Boulahlib S, Boudina A, Siahmed K, et al. Development and validation of a fast and simple HPLC method for the simultaneous determination of aniline and its degradation products in wastewater[J]. Analytical Methods, 2016, 8(30).
[12]Xiong J, Qian S, Xie Y H, et al. Simultaneous Determination of Acrylamide, Aniline and Benzidine in Water Sam-ple by High Performance Liquid Chromatography-Tandem Mass Spectrometry[J]. Chinese Journal of Analytical Chemistry,2014, 42(1):93-98.
[13]European C. Technical Guidance Document in Support of Commission Directive 93/67/EEC on Risk Assessment for New Notified Substances and Commission Regulation(EC)No 1488/94 on Risk Assessment for Existing Subs-tances,Part II[Z]. 2003.
[14]Klimisch H J, Andreae M, Tillmann U. A Systematic Approach for Evaluating the Quality of Experimental Toxico-logical and Ecotoxicological Data[J]. Regulatory Toxicology&Pharmacology, 1997, 25(1):1-5.
[15]李亚莹,许玉萍,王薇,等.城镇污水处理厂出水中苯胺类化合物测定的影响因素探讨[J].科学咨询:科技·管理,2011(28):84-85.