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Fast liquid chromatography-tandem mass spectrometry methodology for the analysis of alkylphenols and their ethoxylates in wastewater samples from the tank truck cleaning industry
Analytical and Bioanalytical Chemistry ( IF 4.3 ) Pub Date : 2019-02-04 , DOI: 10.1007/s00216-019-01623-6
Mélanie Mignot , Maarten Nagels , Sven Poelmans , Alexander Kensert , Jan Dries , Raf DewiI , Deirdre Cabooter

A fast methodology to quantify 4-tert-octylphenol (4-t-OP) and 4-nonylphenol (4-NP) and their mono- and di-ethoxylates was developed, validated, and applied to real wastewater samples. Dispersive liquid-liquid microextraction was employed as a sample preparation step, leading to a pre-concentration factor of roughly 30. Analysis was carried out by liquid chromatography-tandem mass spectrometry with electrospray ionisation in multiple reaction monitoring mode. Average recoveries were generally between 80 and 120% for both the alkylphenols and their mono- and di-ethoxylates in influent and effluent wastewater. A minimum of 5 concentration levels per compound, ranging between 1 and 500 ng/mL, were prepared to construct calibration curves making use of isotopically labelled internal standards. The method presented good linearity and repeatability over the whole range of concentrations. Taking into account the concentration factor, and the recovery of the compounds, lower limits of quantification obtained in effluent wastewater were 0.04 ng/mL for 4-t-OP and 0.14 ng/mL for 4-NP, complying with European regulations, and between 0.03 ng/mL and 0.39 ng/mL for the ethoxylates. In influent wastewater, these limits were slightly higher. The total run time of 5 min for the alkylphenols and 8 min for the ethoxylates ensured high throughput. The developed method was applied to determine 4-t-OP and 4-NP and their mono- and di-ethoxylates in wastewater from several tank truck cleaning companies, which was subjected to ozonation and/or biological treatment. It was demonstrated that ozonation was best applied after the biological treatment, since in this case, the biological treatment could degrade most of the biodegradable organic matter, after which ozone could react directly with the recalcitrant organic pollutants. In this case, the concentrations of the target compounds in the wastewater of the investigated company decreased below the legally allowed concentration of the European water legislation.



中文翻译:

快速液相色谱-串联质谱法分析油罐车清洗行业废水样品中的烷基酚及其乙氧基化物

快速定量4-叔叔的方法-辛基苯酚(4-t-OP)和4-壬基苯酚(4-NP)以及它们的单和二乙氧基化物已开发,验证并应用于实际废水样品。分散液-液微萃取被用作样品制备步骤,导致预浓缩系数约为30。在多反应监测模式下,通过液相色谱-串联质谱分析和电喷雾电离进行分析。进水和出水废水中烷基酚及其单乙氧基和二乙氧基化物的平均回收率通常在80%至120%之间。使用同位素标记的内标,制备每种化合物的最低5个浓度水平,范围在1至500 ng / mL之间,以构建校正曲线。该方法在整个浓度范围内均表现出良好的线性和可重复性。考虑到浓缩因子和化合物的回收率,废水排放量的下限为4-t-OP为0.04 ng / mL,4-NP为0.14 ng / mL(符合欧洲法规),介于0.03 ng / mL和0.39 ng / mL的乙氧基化物。在进水废水中,这些限值略高。烷基酚的总运行时间为5分钟,乙氧基化物的总运行时间为8分钟,可确保高通量。所开发的方法用于测定来自多家加油车清洁公司的废水中的4-t-OP和4-NP及其单乙氧基和二乙氧基化物,并对其进行臭氧处理和/或生物处理。事实证明,臭氧处理是生物处理后的最佳选择,因为在这种情况下,生物处理可以降解大部分可生物降解的有机物,之后,臭氧可以直接与难降解的有机污染物发生反应。在这种情况下,被调查公司的废水中目标化合物的浓度降至低于欧洲水法规的法定允许浓度。

更新日期:2019-02-04
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