Department of Environmental Analytical Chemistry, Institute of Atmospheric and Environmental Sciences, Goethe-University Frankfurt am Main, Frankfurt am Main, Germany.
Chemosphere. 2010 Feb;78(8):958-64. doi: 10.1016/j.chemosphere.2009.12.027. Epub 2010 Jan 13.
To investigate seasonal fluctuations and trends of organophosphate (flame retardants, plasticizers) concentrations in rain and snow, precipitation samples were collected in 2007-2009 period at a densely populated urban sampling site and two sparsely populated rural sampling sites in middle Germany. In addition, storm water runoff was sampled from May 2008 to April 2009 at an urban storm water holding tank (SWHT). Samples were analyzed for tris(2-chloroethyl) phosphate (TCEP), tris(2-chloro-1-methylethyl) phosphate (TCPP), tris(1,3-dichloro-2-propyl) phosphate (TDCP), tris(2-butoxyethyl) phosphate (TBEP), tri-iso-butyl phosphate (TiBP), and tri-n-butyl phosphate (TnBP) by gas chromatography-mass spectrometry after solid phase extraction. Among the six analyzed organophosphates (OPs), TCPP dominated in all precipitation and SWHT water samples with maximum concentrations exceeding 1000ngL(-1). For all analytes, no seasonal trends were observed at the urban precipitation sampling site, although atmospheric photooxidation was expected to reduce particularly concentrations of non-chlorinated OPs during transport from urban to remote areas in summer months with higher global irradiation. In the SWHT a seasonal trend with decreasing concentrations in summer/autumn is evident for the non-chlorinated OPs due to in-lake degradation but not for the chlorinated OPs. Furthermore, an accumulation of OPs deposited in SWHTs was observed with concentrations often exceeding those observed in wet precipitation. Median concentrations of TCPP (880ngL(-1)), TDCP (13ngL(-1)) and TBEP (77ngL(-1)) at the SWHT were more than twice as high as median concentrations measured at the urban precipitation sampling site (403ngL(-1), 5ngL(-1), and 21ngL(-1) respectively).
为了研究有机磷（阻燃剂、增塑剂）在雨雪中的季节性波动和趋势，在德国中部一个人口密集的城市采样点和两个人口稀少的农村采样点收集了 2007-2009 年期间的降水样本。此外，在 2008 年 5 月至 2009 年 4 月期间，还从一个城市雨水蓄水箱（SWHT）中采集了雨水径流样本。样品经过固相萃取后，用气相色谱-质谱法分析了三（2-氯乙基）磷酸酯（TCEP）、三（2-氯-1-甲基乙基）磷酸酯（TCPP）、三（1,3-二氯-2-丙基）磷酸酯（TDCP）、三（2-丁氧基乙基）磷酸酯（TBEP）、三异丁基磷酸酯（TiBP）和三正丁基磷酸酯（TnBP）。在所分析的六种有机磷酸酯（OPs）中，TCPP 在所有降水和 SWHT 水样中均占主导地位，最大浓度超过 1000ngL(-1)。对于所有分析物，在城市降水采样点没有观察到季节性趋势，尽管大气光氧化预计会在夏季月份减少非氯化 OPs 的浓度，因为在全球辐射较高的情况下，它们从城市向偏远地区运输时会被氧化。在 SWHT 中，由于湖泊内降解，非氯化 OPs 的浓度在夏季/秋季呈下降趋势，但氯化 OPs 则没有。此外，还观察到 SWHT 中沉积的 OPs 积累，其浓度常常超过湿沉降中的浓度。SWHT 中 TCPP（880ngL(-1)）、TDCP（13ngL(-1)）和 TBEP（77ngL(-1)）的中位数浓度分别比城市降水采样点的中位数浓度（分别为 403ngL(-1)、5ngL(-1)和 21ngL(-1)）高出两倍以上。
