Simultaneous Determination of Disinfection By-products in Water Samples from Advanced Membrane Treatments by Headspace Solid Phase Microextraction and Gas Chromatography-Mass Spectrometry

Abstract

A headspace-solid phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) method has been developed for the simultaneously determination of 20 disinfection by-products (DBPs) in water samples from reverse osmosis (RO) membranes. Selected compounds belong to different families including: trihalomethanes (THMs), halogenated acetonitriles (HANs), halogenated nitromethanes (HNMs), halogenated ketones (HKs) and other halogenated DBPs. Four commercial fibres with different polarities were tested for the extraction of the compounds and the main variables affecting HS-SPME such as extraction time, extraction temperature and pH of the samples were optimized by applying a central composite design. The method showed good detection limits in the range of 0.003 mg l^-1 up to 0.010 mg l^-1 for most of the compounds with reasonable linearity with r² higher than 0.991. Moreover, the repeatability of the method, expressed as relative standard deviation (RSD) was lower than 13% (n = 5, 1 mg l^-1) in brackish and wastewater samples. The validated method has been applied for the determination of the target DBPs in RO water samples from application research units, which treated water from various origins (wastewater, brackish water and sea water), showing good performance in the different types of studied samples. The analysis revealed the presence of several DBPs regarding different families, such as trichloromethane (with concentrations up to 0.36 μg l^-1), chloroiodomethane (0.5-1.44 μg l^-1), dibromochloromethane (found at concentrations up to 0.76 μg l^-1) and tribromoacetaldehyde (at concentrations up to 11 μg l^-1 in the influent samples). The tendency of most of them indicated a trend of removal by reverse osmosis treatments, especially the total concentration of THMs which decreased below the limit of detection.