title: Quantitative determination of 13 organophosphorous flame retardants and plasticizers in a wastewater treatment system by high performance liquid chromatography tandem mass spectrometry.
abstract: A method for quantitative determination of 13 organophosphorous compounds (OPs) was developed and applied to influent, primary sludge, activated sludge, biosolids, primary effluent and final effluent from a wastewater treatment plant (WWTP). The method involved solvent extraction followed by solid phase clean-up and analysis by high performance liquid chromatography positive electrospray ionization-tandem mass spectrometry (HPLC(+ESI)MS/MS). Replicate spike/recovery experiments revealed the method to have good accuracy (70-132%) and precision (<19% RSD) in all matrices. Detection limits of 0.1-5 ng/L for aqueous samples and 0.01-0.5 ng/g for solid samples were achieved. In the liquid waste stream ∑OP concentrations were highest in influent (5764 ng/L) followed by primary effluent (4642 ng/L), and final effluent (2328 ng/L). In the solid waste stream, the highest ∑OP concentrations were observed in biosolids (3167 ng/g dw), followed by waste activated sludge (2294 ng/g dw), and primary sludge (2128 ng/g dw). These concentrations are nearly 30-fold higher than ∑polybrominated diphenyl ether (BDE) concentrations in influents and nearly 200-fold higher than ∑BDE concentrations in effluents from other sites in Canada. Tetrekis(2-chlorethyl)dichloroisopentyldiphosphate (V6), tripropylphosphate (TnPrP), and Tris(2,3-dibromopropyl)phosphate (TDBPP) are investigated for the first time in a WWTP. While TnPrP and TDBB were not detected, V6 was observed at concentrations up to 7.9 ng/g in solid waste streams and up to 40.7 ng/L in liquid waste streams. The lack of removal of OPs during wastewater treatment is a concern due to their release into the aquatic environment.
authors.affiliation: AXYS Analytical Services Ltd., 2045 Mills Road West, Sidney, BC, Canada V8L 5X2. Electronic address: mwoudneh@axys.com.
authors.forename: Million B
authors.initials: MB
authors.lastname: Woudneh
authors.affiliation: AXYS Analytical Services Ltd., 2045 Mills Road West, Sidney, BC, Canada V8L 5X2.
authors.forename: Jonathan P
authors.initials: JP
authors.lastname: Benskin
authors.affiliation: AXYS Analytical Services Ltd., 2045 Mills Road West, Sidney, BC, Canada V8L 5X2.
authors.forename: Guanghui
authors.initials: G
authors.lastname: Wang
authors.affiliation: AXYS Analytical Services Ltd., 2045 Mills Road West, Sidney, BC, Canada V8L 5X2.
authors.forename: Richard
authors.initials: R
authors.lastname: Grace
authors.affiliation: AXYS Analytical Services Ltd., 2045 Mills Road West, Sidney, BC, Canada V8L 5X2.
authors.forename: M Coreen
authors.initials: MC
authors.lastname: Hamilton
authors.affiliation: AXYS Analytical Services Ltd., 2045 Mills Road West, Sidney, BC, Canada V8L 5X2.
authors.forename: John R
authors.initials: JR
authors.lastname: Cosgrove
mesh_terms: D002170:Canada; D002851:Chromatography, High Pressure Liquid; D004784:Environmental Monitoring / Q000379:methods*; D005411:Flame Retardants / Q000032:analysis*; D010968:Plasticizers / Q000032:analysis*; D012722:Sewage / Q000737:chemistry; D053719:Tandem Mass Spectrometry; D062065:Wastewater / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000032:analysis
chemical_list: D005411:Flame Retardants; D010968:Plasticizers; D012722:Sewage; D062065:Wastewater; D014874:Water Pollutants, Chemical
keywords: LC–MS/MS; Organophosphorous compounds; Wastewater treatment