The occurrence of disinfection by-products (DBPs) in drinking water has become an issue of concern during the past decades. The DBPs pose health risks and are suspected to cause various cancer forms, be genotoxic and have negative developmental effects. The vast chemical diversity of DBPs makes comprehensive monitoring challenging. Only few of the DBPs are regulated and included in analytical protocols. In this study, a method for simultaneous measurement of 20 DBPs from five different structural classes (both regulated and non-regulated) was investigated and further developed for 11 DBPs using solid phase extraction and gas chromatography coupled with a halogen specific detector (XSD). The XSD was highly selective towards halogenated DBPs, providing chromatograms with little noise. The method allowed detection down to 0.05 µg/L and showed promising results for the simultaneous determination of a range of neutral DBP classes. Compounds from two classes of emerging DBPs, more cytotoxic than the “traditional” regulated DBPs, were successfully determined using this method. However, haloacetic acids (HAAs) should be analyzed separately as some HAA methyl esters may degrade giving false positives of trihalomethanes (THMs). The method was tested on real water samples from two municipal waterworks where the target DBP concentrations were found below the regulatory limits of Sweden.

Reactions between chemical disinfectants and natural organic matter (NOM) upon drinking water treatment result in formation of potentially harmful disinfection by-products (DBPs). The diversity of DBPs formed is high and a large portion remains unknown. Previous studies have shown that non-volatile DBPs are important, as much of the total toxicity from DBPs has been related to this fraction. To further understand the composition and variation of DBPs associated with this fraction, non-target analysis with ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was employed to detect DBPs at four Swedish waterworks using different types of raw water and treatments. Samples were collected five times covering a full year. A common group of DBPs formed at all four waterworks was detected, suggesting a similar pool of DBP precursors in all raw waters that might be related to phenolic moieties. However, the largest proportion (64–92%) of the assigned chlorinated and brominated molecular formulae were unique, i.e. were solely found in one of the four waterworks. In contrast, the compositional variations of NOM in the raw waters and samples collected prior to chemical disinfection were rather limited.This indicated that waterworks-specific DBPs presumably originated from matrix effects at the point of disinfection, primarily explained by differences in bromide levels, disinfectants (chlorine versus chloramine) and different relative abundances of isomers among the NOM compositions studied. The large variation of observed DBPs in the toxicologically relevant non-volatile fraction indicates that non-targeted monitoring strategies might be valuable to ensure relevant DBP monitoring in the future.

Old assumptions that chloride is inert and that most chlorinated organic matter in soils is anthropogenic have been challenged by findings of naturally formed organochlorines. Such natural chlorination has been recognized for several decades, but there are still very few measurements of chlorination rates or estimates of the quantitative importance of terrestrial chlorine transformations. While much is known about the formation of specific compounds, bulk chlorination remains poorly understood in terms of mechanisms and effects of environmental factors. We quantified bulk chlorination rates in coniferous forest soil using ³⁶Cl-chloride in tracer experiments at different temperatures and with and without molecular oxygen (O₂). Chlorination was enhanced by the presence of O₂ and had a temperature optimum at 20 °C. Minimum rates were found at high temperatures (50 °C) or under anoxic conditions. The results indicate (1) that most of the chlorination between 4 and 40 °C was biotic and driven by O₂ dependent enzymes, and (2) that there is also slower background chlorination occurring under anoxic conditions at 20 °C and under oxic conditions at 50 °C. Hence, while oxic and biotic chlorination clearly dominated, chlorination by other processes including possible abiotic reactions was also detected.

Inorganic chlorine (i.e. chloride, Clin) is generally considered inert in soil and is often used as a tracer of soil and ground water movements. However, recent studies indicate that substantial retention or release of Clin can occur in soil, but the rates and processes responsible under different environmental conditions are largely unknown. We performed 36Cl tracer experiments which indicated that short-term microbial uptake and release of Clin, in combination with more long-term natural formation of chlorinated organic matter (Clorg), caused Clin imbalances in coniferous forest soil. Extensive microbial uptake and release of Clin occurred over short time scales, and were probably associated with changes in environmental conditions. Up to 24% of the initially available Clin within pore water was retained by microbial uptake within a week in our experiments, but most of this Clin was released to the pore water again within a month, probably associated with decreasing microbial populations. The natural formation of Clorg resulted in a net immobilization of 4% of the initial pore water Clin over four months. If this rate is representative for the area where soil was collected, Clorg formation would correspond to a conversion of 25% of the yearly wet deposition of Clin. The study illustrates the potential of two Clin retaining processes in addition to those previously addressed elsewhere (e.g. uptake of chloride by vegetation). Hence, several processes operating at different time scales and with different regulation mechanisms can cause Clin imbalances in soil. Altogether, the results of the present study (1) provide evidence that Clin cannot be assumed to be inert in soil, (2) show that microbial exchange can regulate pore water Clin concentrations and (3) confirm the controversial idea of substantial natural chlorination of soil organic matter. © 2007 Elsevier Ltd. All rights reserved.

Taste and odour problems are the major causes of consumer complaints regarding drinking water in the industrialised world. Nevertheless, as yet there are no mandatory requirements to identify the compounds that are responsible for the observed off-flavour. This thesis shows that gas chromatographic analysis with mass spectrometric and sensory detection provides an efficient tool for such investigations. The enrichment that precedes the gas chromatographic analysis can normally be based on stripping volatile or semi-volatile organic compounds. Due to the low blank level obtained with the open stripping system used in the present study, well-known odorous compounds, such as geosmin, 2- methylisoborneol (MIB) and 2,4,6-trichloroanisole (2,4,6-TCA), could be detected at levels below their threshold odour concentrations. However, this thesis also shows that compounds that are too hydrophilic to be enriched by stripping can play an important role, either as precursors of odorous compounds or as the direct cause of off-flavours. In particular, we found that natural formation of 2,4,6-trichlorophenol (2,4,6-TCP) may lead to the formation of 2,4,6-TCA in the distribution system. Furthermore, a study of a municipal treatment plant showed that short-chain carboxylic acids can be formed in slow sand filters, giving the finished water a rancid or nauseating flavour. Collectively, the results of the present study clearly show the importance of regarding the entire process from raw water supply to the consumer's tap as an integrated system. Off-flavours may originate from processes in the raw water supply, during treatment and in the distribution system.

Surface water and aqueous solutions of isolated organic matter from a humic rich lake in southern Sweden were exposed to artificial UV radiation to investigate the UV light induced influence on organic matter bound chlorine in natural systems. It was found that the photodegradation of organic matter bound chlorine was more pronounced than the photodegradation of organic carbon. After 120 h of irradiation of the isolated organic matter, only 35% of the initial organochlorine was still in the solution compared to about 70% of the dissolved organic carbon (DOC). A similar result was obtained for unfractionated surface water. Furthermore, our results indicate that the loss of organic chlorine was mainly due to a mineralization of organic chlorine into chloride ions. The total decrease of organic chlorine after 120 h was 32 ╡g Clorg l-1, of which the major part disappeared in the initial irradiation phase. A similar increase was observed in the chloride concentration (34 ╡g Cl- l-1).

Photodesorption of thin films of fulvic acid adsorbed on planar iron oxide surfaces was monitored by ellipsometry. Description was first observed at 546 nm, and additional fractions of the adsorbed acid left the surfaces at 405 and 365 nm Similar kinetics for photodesorption was observed from metallic iron films and from porous iron oxide prepared electrochemically by deposition on porous silicon substrates. Soluble photoproducts leaving the surface H ere monitored by UV absorbance spectroscopy at 200 nm Gaseous products were not detected by mass spectrometry but the results seemed to indicate that net all of the photoproducts entered the liquid phase. Of the metal films tested which adsorbed fulvic acid from aqueous solution (Fe. Cr, Ni, Al, and Pt), it was only iron which exhibited a photodesorption effect. (C) 2001 Elsevier Science B.V. All rights reserved.

Platinum-oxide-silicon carbide structures change their capacitance upon gas exposure and are used as gas sensors. The decrease of the inversion capacitance within 750 to 900 degrees C due to hydrogen exposure is studied for 4H- and 6H-SiC,:both n- and p-type. A mechanism for the capacitance decrease is suggested which explains also the large change in the conductance of the structures.

A case study carried out at a municipal drinking water treatment plant in southern Sweden showed that the formation of short-chain fatty acids in slow sand filters can result in severe off-flavour problems. When an extract of the headspace of the surface layer of a sand filter was subjected to gas chromatographic analysis with sensory detection (GC sniffing), several strong, rancid odours were detected. Mass spectrometric analysis of the same extract, before and after methylation, showed that substantial amounts of butyric acid, valeric acid and isovaleric acid were present in the analysed sample. The off-flavour caused by these compounds was removed by repeated shock chlorination of the malfunctioning slow sand filter. Analysis of fatty acid esters may provide an early warning of the described off-flavour problem.