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

Abstract

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 43, 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), triiso-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., Schmücke 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 (a 24 h).

Occurrence, distribution and seasonal variation of organophosphate flame retardants and plasticizers in urban surface water in Beijing, China

“…This result disagreed with previous study showing no significant seasonal trends for the OPEs in urban lake water samples from Germany (Regnery and Puttmann, 2010). It has been previously demonstrated that the proportions of OPEs in condensate and internal vehicle air reveal an increase when the temperature is increased (Regnery and Püttmann, 2009). The average temperature is about 30 C in July and August (summer) in Beijing, while it is only about 10 C and 5 C in November and February (winter), respectively.…”

“…The occurrence and fate of OPEs in aquatic environment is of concern since these compounds can massively reach surface water from industrial and domestic sewage discharge (Fries and Puttmann, 2003;Martinez-Carballo et al, 2007) and atmosphere deposition (Bacaloni et al, 2008;M€ oller et al, 2011;Regnery and Püttmann, 2009). The discharge of industrial and domestic sewage is considered as the major source of OPEs in surface water (Reemtsma et al, 2008).…”

“…Some alkyl-OPEs such as trimethyl phosphate (TMP) and triethyl phosphate (TEP), have been well removed in sewage treatment plants (STPs), whereas the chlorinated-OPEs are not subjected to the significant removal, which are, thus, discharged with effluents into rivers (Bester, 2005;Marklund et al, 2005a;Meyer and Bester, 2004). Besides, atmosphere deposition has been pointed to be another important source of OPEs in surface water environment (M€ oller et al, 2011;Regnery and Püttmann, 2009). The OPEs at levels from ng L À1 to mg L À1 have been detected in many rivers in Germany (Andresen et al, 2004;Puttmann, 2001, 2003;Regnery and Puttmann, 2010), Aire River in UK (Cristale et al, 2013a), volcanic lakes in Italy (Bacaloni et al, 2008), and rivers in Austria (Martinez-Carballo et al, 2007), as well several rivers in China (Wang et al, 2015(Wang et al, , 2011.…”

Occurrence and Concentrations of Halogenated Flame Retardants in the Atmospheric Fine Particles in Chinese Cities

“…50 This can be explained by the shorter atmospheric half-life of TCPP (the calculated half-lives for the atmospheric reaction with hydroxyl radicals are 8.6 h for TCPP and 17.5 h for TCEP) or by the higher potential of TCPP to adsorb to airborne particles, which may then be removed through dry and wet deposition during long-range transport. 51 Among the chlorinated OPFRs, the range of TDCPP concentrations across all the cities was 2.1−280 pg/m 3 (39 ± 38 pg/m 3 , n = 149) in the PM 2.5 samples, which was much lower than the corresponding values for TCPP and TCEP. Most studies in the indoor environment have shown the dominance of different compounds (TCPP, TCEP, or TDCPP) due to different types, amounts, and ages of flame retardant-treated products within these environments.…”

Haloalkylphosphorus Hydrolases Purified from Sphingomonas sp. Strain TDK1 and Sphingobium sp. Strain TCM1

“…Widespread use of these flame retardants has led to their accumulation in various environments at concentrations ranging from nanograms to several micrograms per liter (1)(2)(3)(4)(5). Although these compounds are considerably less toxic than organophosphorus pesticides and chemical warfare agents, many studies have shown their diverse toxic effects (6).…”