Octyl and nonylphenol ethoxylates and carboxylates in wastewater and sediments by liquid chromatography/tandem mass spectrometry

This work presents an LC-MS-MS-based method for the quantitation of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) in water, sediment, and suspended particulate matter, and three of their carboxylated derivatives in water. The alkylphenol ethoxylates (APEOs) were analyzed using isotope dilution mass spectrometry with [C-13(6)]-labeled analogues, whereas the carboxylated derivatives were determined by external standard quantitation followed by confirmation using standard additions. The method was used to study APEO's behavior in a wastewater treatment plant (WWTP), where total dissolved NP0-16EO concentration was reduced by approximately 99% from influent (390 mu g 1(-1)) to final effluent (4 mu g 1(-1)), and total OP0-5EO concentration decreased by 94% from 3.1 to 0.2 mu g 1(-1). In contrast, the carboxylated derivatives were formed during the process with NP0-1EC concentrations increasing from 1.4 to 24 mu g 1-1. Short-chain APEOs were present in higher proportions in particulate matter, presumably due to greater affinity for solids compared to the long-chain homologues. NP (0.49 mu g 1(-1)) and NP0-1EC (4.8 mu g 1(-1)) were the only APEO-related compounds detected in a surface water sample from a WWTP-impacted estuary; implying that 90% of the mass was in the form of carboxylated derivatives. Sediment analysis showed nonylphenol to be the single most abundant compound in sediments from the Baltimore Harbor area, where differences in homologue distribution suggested the presence of treated effluent in some of the sites and non-treated sources in the rest. (c) 2007 Elsevier Ltd. All rights reserved.