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Development of an ultra-high-performance liquid chromatography-tandem mass spectrometry method for high throughput determination of organophosphorus flame retardants in environmental water

机译:超高效液相色谱-串联质谱法开发用于高通量测定环境水中的有机磷阻燃剂

摘要

Widely used as flame retardants, organophosphate esters (OPEs) are now broadly present in the indoor and outdoor environments. Currently available liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods share some drawbacks with gas chromatography (GC) methods, including time consuming, limited target OPEs, incomplete separation capability for some OPEs and low throughput. In this study, a fast and high throughput LC-MS/MS method was developed. For the first time, all the twelve OPEs that have been studied in literature, ranging from the very polar and volatile trimethyl phosphate to the very hydrophobic and non-volatile tris(2-ethylhexyl) phosphate, were separated within 11 min. Different from previous studies, we found that the blank contamination was mainly from organic mobile phase rather than the enrichment process, and it can be efficiently eliminated by using acetonitrile rather than methanol as the organic phase of the mobile phase. The signal to noise ratio (S/N) was significantly improved by using 0.1% formic acid as an organic modifier. The method exhibited high throughput and sensitivity and can baseline separate 11 of the 12 OPEs studied within 11 min with LOQs ranging from 2 to 6 ng/L. The relative standard deviations were in the range of 2-10%. For both reagent water and river water, the spiked recoveries of OPEs ranged from 70 to 110%, except for the very polar and volatile trimethyl phosphate that has recovery below 10%. The developed procedure was successfully applied to study the OPE contamination of the Songhua River, and it was found that all the target OPEs were detected with total concentrations of around 1 mu g/L in the river waters. (C) 2011 Elsevier B.V. All rights reserved.
机译:有机磷酸酯(OPE)广泛用作阻燃剂,现在广泛存在于室内和室外环境中。当前可用的液相色谱-串联质谱分析(LC-MS / MS)方法与气相色谱(GC)方法具有一些缺点,包括耗时,目标OPE有限,某些OPE的分离能力不完全以及通量低。在这项研究中,开发了一种快速且高通量的LC-MS / MS方法。首次在11分钟内分离出了文献中已研究的所有十二种OPE,从极极性和挥发性的磷酸三甲酯到极疏水和非挥发性的磷酸三(2-乙基己基)酯。与以前的研究不同,我们发现空白污染主要来自有机流动相而不是富集过程,并且可以通过使用乙腈而不是甲醇作为流动相的有机相来有效地消除空白污染。通过使用0.1%甲酸作为有机改性剂,信噪比(S / N)得到了显着改善。该方法显示出高通量和灵敏度,并且可以在11分钟内将研究的12个OPE中的11个作为基线,LOQ范围为2至6 ng / L。相对标准偏差在2-10%的范围内。对于试剂水和河水,除高极性和易挥发的磷酸三甲酯的回收率低于10%外,OPE的加标回收率范围为70%至110%。所开发的程序已成功地用于研究松花江的OPE污染,发现所有目标OPE均在河水中被检测出,总浓度约为1μg/ L。 (C)2011 Elsevier B.V.保留所有权利。

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