Effervescence-assisted spiral hollow-fibre liquid-phase microextraction of trihalomethanes, halonitromethanes, haloacetonitriles, and haloketones in drinking water.

A new analytical method was optimized to determine 18 disinfection by-products (DBPs) in drinking water, including four different chemical groups. For this purpose, spiral-shaped hollow-fibre liquid phase microextraction with 1-octanol as the acceptor solvent assisted by effervescence was applied using a homemade supporting device that was specifically designed for this application. The device was printed in a 3D printer and allows for an increased fibre surface even with a low sample volume, which significantly facilitates the extraction. The samples were analysed by gas chromatography coupled to both an electron capture detector and a mass spectrometer for the quantification and unequivocal identification of the analytes, respectively. Effervescence was generated using citric acid and bicarbonate at a molar ratio 1:2, which significantly improves the extraction efficiency and reduces mechanical operations, since stirring and modifiers are not required. The results showed enrichment factors ranging from 13.1 to 140.1. Satisfactory recoveries (80-113 %) were obtained, with relative standard deviations from 3 to 15 % and good linearity. The detection limits (ng L-1) ranged from 10 to 35 (trihalomethanes), 12 to 220 (halonitromethanes), 17 to 79 (haloacetonitriles) and 10 to 16 (haloketones). The applicability of the method was assessed in 6 local water distribution systems.

Seasonal and spatial evolution of trihalomethanes in a drinking water distribution system according to the treatment process.

This paper comparatively shows the influence of four water treatment processes on the formation of trihalomethanes (THMs) in a water distribution system. The study was performed from February 2005 to January 2012 with analytical data of 600 samples taken in Aljaraque water treatment plant (WTP) and 16 locations along the water distribution system (WDS) in the region of Andévalo and the coast of Huelva (southwest Spain), a region with significant seasonal and population changes. The comparison of results in the four different processes studied indicated a clear link of the treatment process with the formation of THM along the WDS. The most effective treatment process is preozonation and activated carbon filtration (P3), which is also the most stable under summer temperatures. Experiments also show low levels of THMs with the conventional process of preoxidation with potassium permanganate (P4), delaying the chlorination to the end of the WTP; however, this simple and economical treatment process is less effective and less stable than P3. In this study, strong seasonal variations were obtained (increase of THM from winter to summer of 1.17 to 1.85 times) and a strong spatial variation (1.1 to 1.7 times from WTP to end points of WDS) which largely depends on the treatment process applied. There was also a strong correlation between THM levels and water temperature, contact time and pH. On the other hand, it was found that THM formation is not proportional to the applied chlorine dose in the treatment process, but there is a direct relationship with the accumulated dose of chlorine. Finally, predictive models based on multiple linear regressions are proposed for each treatment process.

Application of hollow fiber liquid phase microextraction for simultaneous determination of regulated and emerging iodinated trihalomethanes in drinking water.

Trihalomethanes (THMs) are regulated disinfection by-products (DBPs) most commonly analyzed in quality control water supply due to their harmful effects on health. However, few data exist about the content of emerging iodo-trihalomethanes (I-THMs) which are present in drinking water at very low concentrations (in the order of ngL(-1)). For this reason a two-phase hollow fiber liquid phase microextraction method for the simultaneous determination of four regulated trihalomethanes and six emerging iodo-trihalomethanes using GC-µECD and GC-MS with detection limits in the range of few ngL(-1) has been developed. A central composite design was used to optimize conditions for simultaneous extraction. The best extraction recovery was obtained with 19.2min at 27.1°C and 900rpm, without salt addition, using a supported hollow fiber membrane of 10.5cm (0.6mm id) and 1-octanol as acceptor phase. The limits of detection for the regulated THMs and I-THMs were 3-44ngL(-1) and 1-3ngL(-1), respectively. The calibration curves showed good linearity (R(2)>0.995) and good repeatibility (3-22%). The relative recoveries in water were between 96.5% and 105.2%. The method was applied for the simultaneous determination of trihalomethanes in supply water samples from seven water distribution systems (WDS) in the Huelva area, located at the southwest Spain, which use different water-treatment processes. The highest concentrations of I-THMs, particularly CHBrClI and CHCl2I, were detected in water treated with advanced treatment process using pre-ozonation, however these compounds were not detected or decreased along distribution system. In the samples of treated water with conventional treatment, using pre-oxidation by permanganate and distribution network, CHCl2I, CHBrClI, CHClI2, CHBrI2 and CHI3 were detected at very low concentrations (1-18ngL(-1)). Finally, in water samples from underground origin without oxidation treatment, in which only disinfection with sodium hypochlorite was applied, I-THMs were not detected.