Determination of non-ionic surfactants and polar degradation products in influent and effluent water samples and sludges of sewage treatment plants by a generic solid-phase extraction protocol

Abstract

Non-ionic polyethoxylated surfactants (nonylphenol polyethoxylates, alcohol polyethoxylates), their breakdown products (polyethylene glycol, polyethoxylated nonylphenol carboxylates and polyethoxylated alcohol carboxylates) and other compounds were identified and measured in various waste-water treatment samples (influent, effluent and sludge). A generic protocol involving the use of sequential solid-phase extraction (SSPE) with octadecylsilica and styrene–divinylbenzene cartridges in series and differential elution was used. Fractionated extracts were analyzed by liquid chromatography-mass spectrometry (LC-MS) using atmospheric pressure chemical ionization (APCI) in the positive and negative ionization modes. For sewage treatment plant (STP) sludge, the extraction protocol involved lyophilization of the sludge followed by sonication with MeOH–CH₂Cl₂ (7 + 3) and final clean-up using the SSPE protocol. Limits of detection for target analytes ranging from 1.1 to 4.1 μg L⁻¹ for water samples and from 0.11 to 0.28 mg kg⁻¹ for sludge were achieved. The results obtained demonstrated the inefficient removal of the target analytes in physico-chemical STPs whereas their elimination factors in STPs with biological treatment reached average values of 77, 92 and 98% for alcohol polyethoxylates, nonylphenol polyethoxylates (NPEOs) and polyethylene glycols (PEGs), respectively. Quantitative elimination of coconut fatty acid diethanolamide (CDEA) surfactants in the activated sludge process occurred. In contrast, total removal of NPEOs led to the formation of persistent and toxic metabolites such as nonylphenol which was present in treated effluent as well as in sludge samples with average concentrations ranging from 15.0 to 251.2 μg L⁻¹ and from 13.5 to 74.2 mg kg⁻¹, respectively. Polyethoxylated carboxylates and short chain NPEOs were also detected at similar levels in the effluents and sludges. In addition, a linear correlation between the total phenolic concentration (Total Ph) measured by the 4-aminoantipyrine method and the total concentration of nonylphenolic compounds (Total NP) measured by SSPE-LC-APCI-MS was observed.