Organophosphorus Flame Retardants and Plasticizers in Rain and Snow from Middle Germany

The role of precipitation as an important source of, and entry pathway for, organophosphates (OPs) into the aquatic environment was investigated. Rainwater and snow samples (53 and 4:3, respectively) collected between November 2007 and April 2008 from urban and remote areas of middle Germany were analyzed for OPs by gas chromatography-mass spectrometry (GC-MS) after solid phase extraction (SPE). The analytes 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) were detected in almost all rain and snow samples. TCPP was the most abundant chlorinated alkyl-phosphate ester in urban rainwater, with concentrations ranging from 46 to 2659 ng L-1. In general, concentrations of OPs in urban rainwater were 3 to 4 times higher than those at background monitoring stations, e.g., Schmucke and Thuringian Forest. Variable concentrations of chlorinated flame retardants were found in precipitation, but their occurrence was not correlated with air temperature. The results of the study indicate that volatilization of OPs from objects protected by flame retardants, including vehicles and buildings, causes these compounds to reach the aquatic environment via washout from the atmosphere, despite their reported short atmospheric half-lives (< 24 h).