Optimization of HS-SPME analytical conditions using factorial design for trihalomethanes determination in swimming pool water samples

Trihalomethanes (THMs) are widely referred and studied as disinfection by-products (DBPs). The THMs that are most commonly detected are chloroform (TCM), bromodichloromethane (BDCM), chlorodibromomethane (CDBM), and bromoform (TBM). Several studies regarding the determination of THMs in swimming pool water and air samples have been published. This paper reviews the most recent work in this field, with a special focus on water and air sampling, sample preparation and analytical determination methods. An experimental study has been developed in order to optimize the headspace solid-phasemicroextraction (HS-SPME) conditions of TCM, BDCM, CDBM and TBM from water samples using a 23 factorial design. An extraction temperature of 45 °C, for 25min, and a desorption time of 5 min were found to be the best conditions. Analysis was performed by gas chromatography with an electron capture detector (GC-ECD). The method was successfully applied to a set of 27 swimming pool water samples collected in the Oporto area (Portugal). TCM was the only THM detected with levels between 4.5 and 406.5 μg L−1. Four of the samples exceeded the guideline value for total THMs in swimming pool water (100 μgL−1) indicated by the Portuguese Health Authority.

Risk assessment of trihalomethanes from tap water in Fortaleza, Brazil

The cancer risks (CR) by oral ingestion, dermal absorption, and inhalation exposure of trihalomethanes (THM) from tap water of ten districts in Fortaleza, Brazil were estimated. The mean levels of THM compounds were obtained in Fortaleza tap water as follow: 63.9 mu g L(-1) for chloroform (CHCl(3)), 40.0 mu g L(-1) for bromodichloromethane (CHBrCl(2)), and 15.6 mu g L(-1) for dibromochloromethane (CHBr(2)Cl). Bromoform (CHBr(3)) was not detected. The mean CR for THMs in tap water is 3.96 x 10(-4). The results indicate that Fortaleza residents have a higher CR by inhalation than dermal absorption and oral ingestion. The CR for CHCl(3) contributes with 68% as compared with the total CR, followed by CHBrCl(2) (21%), and CHBr(2)Cl (11%). The hazard index (HI) is about ten times lower than unity, not indicating non-cancer effects.

Prediction of chlorine and trihalomethanes concentration profile in bulk drinking water distribution systems from laboratory data

Nearly all drinking water distribution systems experience a "natural" reduction of disinfection residuals. The most frequently used disinfectant is chlorine, which can decay due to reactions with organic and inorganic compounds in the water and by liquid/solids reaction with the biofilm, pipe walls and sediments. Usually levels of 0.2-0.5 mg/L of free chlorine are required at the point of consumption to maintain bacteriological safety. Higher concentrations are not desirable as they present the problems of taste and odour and increase formation of disinfection by-products. It is usually a considerable concern for the operators of drinking water distribution systems to manage chlorine residuals at the "optimum level", considering all these issues. This paper describes how the chlorine profile in a drinking water distribution system can be modelled and optimised on the basis of readily and inexpensively available laboratory data. Methods are presented for deriving the laboratory data, fitting a chlorine decay model of bulk water to the data and applying the model, in conjunction with a simplified hydraulic model, to obtain the chlorine profile in a distribution system at steady flow conditions. Two case studies are used to demonstrate the utility of the technique. Melbourne's Greenvale-Sydenham distribution system is unfiltered and uses chlorination as its only treatment. The chlorine model developed from laboratory data was applied to the whole system and the chlorine profile was shown to be accurately simulated. Biofilm was not found to critically affect chlorine decay. In the other case study, Sydney Water's Nepean system was modelled from limited hydraulic data. Chlorine decay and trihalomethane (THM) formation in raw and treated water were measured in a laboratory, and a chlorine decay and THM model was derived on the basis of these data. Simulated chlorine and THM profiles agree well with the measured values available. Various applications of this modelling approach are also briefly discussed.

Management of Trihalomethanes in Finished Drinking Water Through Source Water Precursor Monitoring

Trihalomethanes are organic compounds formed in drinking water distribution systems as a result of disinfection. This capstone project researched and evaluated the statistical correlation of trihalomethanes in finished drinking water and total organic carbon in source water using data generated by Denver area utilities. Results of the study conclude that some drinking water supply systems show a slight correlation between source water total organic carbon levels and trihalomethane levels in finished water. Results of the study also verify the assertion that changes to treatment for the reduction of trihalomethanes, for the protection of human health under the Safe Drinking Water Act should be determined by each utility, using information from gathered data, seasonal trends, and small scale batch testing.

Predictive models for water sources with high susceptibility for bromine-containing disinfection by-product formation: Implications for water treatment

This study examines a matrix of synthetic water samples designed to include conditions that favour brominated disinfection by-product (Br-DBP) formation, in order to provide predictive models suitable for high Br-DBP forming waters such as salinity-impacted waters. Br-DBPs are known to be more toxic than their chlorinated analogues, in general, and their formation may be favoured by routine water treatment practices such as coagulation/flocculation under specific conditions; therefore, circumstances surrounding their formation must be understood. The chosen factors were bromide concentration, mineral alkalinity, bromide to dissolved organic carbon (Br/DOC) ratio and Suwannee River natural organic matter concentration. The relationships between these parameters and DBP formation were evaluated by response surface modelling of data generated using a face-centred central composite experimental design. Predictive models for ten brominated and/or chlorinated DBPs are presented, as well as models for total trihalomethanes (tTHMs) and total dihaloacetonitriles (tDHANs), and bromide substitution factors for the THMs and DHANs classes. The relationships described revealed that increasing alkalinity and increasing Br/DOC ratio were associated with increasing bromination of THMs and DHANs, suggesting that DOC lowering treatment methods that do not also remove bromide such as enhanced coagulation may create optimal conditions for Br-DBP formation in waters in which bromide is present.

Approche multidisciplinaire pour l’amélioration de l’estimation de l’exposition aux sous-produits de désinfection de l’eau en milieu domestique et en piscine

La désinfection de l’eau de consommation et des piscines induit la formation de sous-produits (SPD) potentiellement nocifs pour la santé, parmi lesquels les trihalométhanes (THM), les acides haloacétiques (HAA) et les chloramines (CAM). La difficulté d’estimer l’exposition humaine à ces SPD empêche de cerner précisément les risques sanitaires possiblement associés (i.e., cancérigènes, reprotoxiques, irritatifs). Nos travaux s’articulent autour d’une méthodologie consistant à intégrer des données d’occurrence environnementales à des modèles toxicocinétiques à base physiologique (TCBP) pour améliorer les mesures de l’exposition aux SPD. Cette approche multidisciplinaire veut prendre en compte de manière aussi appropriée que possible les deux composantes majeures des variations de cette exposition : les variations spatio-temporelles des niveaux de contamination environnementale et l’impact des différences inter- et intra-individuelles sur les niveaux biologiques. Cette thèse, organisée en deux volets qui explorent chacun successivement des aspects environnemental et biologique de la problématique, vise à contribuer au développement de cette stratégie innovante d’estimation de l’exposition et, plus généralement, à des meilleures pratiques en la matière. Le premier volet de la thèse s’intéresse à l’exposition en milieu domestique (i.e., résultant de l’utilisation de l’eau potable au domicile) et est consacré au cas complexe des THM, les plus abondants et volatils des SPD, absorbables par ingestion mais aussi par inhalation et voie percutanée. Les articles I et II, constitutifs de ce volet, documentent spécifiquement la question des variations inter- et intra- journalières de présence des SPD en réseau et de leurs impacts sur les estimateurs de l’exposition biologique. Ils décrivent l’amplitude et la diversité des variations à court terme des niveaux environnementaux, présentent les difficultés à proposer une façon systématique et « épidémiologiquement » pratique de les modéliser et proposent, de manière originale, une évaluation des mésestimations, somme toute modestes, des mesures biologiques de l’exposition résultant de leurs non-prise en compte. Le deuxième volet de la thèse se penche sur l’exposition aux SPD en piscine, d’un intérêt grandissant au niveau international, et se restreint au cas jugé prioritaire des piscines publiques intérieures. Ce volet envisage, pour quantifier l’exposition dans ce contexte particulier, l’extension de l’approche méthodologique préconisée, élaborée originellement pour application dans un contexte domestique : d’abord, à travers une analyse approfondie des variations des niveaux de contamination (eau, air) des SPD en piscine en vue de les modéliser (article III); puis en examinant, dans le cas particulier du chloroforme, le THM le plus abondant, la possibilité d’utiliser la modélisation TCBP pour simuler des expositions en piscine (article IV). Les résultats mettent notamment en évidence la difficulté d’appréhender précisément la contamination environnementale autrement que par un échantillonnage in situ tandis que la modélisation TCBP apparait, sur le plan toxicologique, comme l’outil le plus pertinent à ce jour, notamment au regard des autres approches existantes, mais qu’il convient d’améliorer pour mieux prédire les niveaux d’exposition biologique. Finalement, ces travaux illustrent la pertinence et la nécessité d’une approche multidisciplinaire et intégratrice et suggère, sur cette base, les pistes à explorer en priorité pour mieux évaluer l’exposition aux SPD et, in fine, cerner véritablement les risques sanitaires qui en résultent.

A comparison of the role of two blue-green algae in THM and HAA formation

The contribution of two blue-green algae species, Anabaeria flos-aquae and Microcystis aeruginosa, to the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) was investigated. The experiments examined the formation potential of these disinfection by-products (DBPs) from both algae cells and extracellular organic matter (EOM) during four algal growth phases. Algal cells and EOM of Anabaena and Microcystis exhibited a high potential for DBP formation. Yields of total THMs (TTHM) and total HAAs (THAA) were closely related to the growth phase. Reactivity of EOM from Anabaena was slightly higher than corresponding cells, while the opposite result was found for Microcystis. Specific DBP yields (yield/unit C) of Anabaena were in the range of 2-11 mu mol/mmol C for TTHM and 217 mu mol/mmol C for THAA, while those of Microcystis were slightly higher. With regard to the distributions of individual THM and HAA compounds, differences were observed between the algae species and also between cells and EOM. The presence of bromide shifted the dominant compounds from HAAs to THMs. (C) 2009 Elsevier Ltd. All rights reserved.

Speciation and variation in the occurrence of haloacetic acids in three water supply systems in England

An investigation into the speciation and occurrence of nine haloacetic acids (HAAs) was conducted during the period of April 2007 to March 2008 and involved three drinking water supply systems in England, which were chosen to represent a range of source water conditions; these were an upland surface water, a lowland surface water and a groundwater. Samples were collected seasonally from the water treatment plants and at different locations in the distribution systems. The highest HAA concentrations occurred in the upland surface water system, with an average total HAA concentration of 21.3 μg/L. The lowest HAA levels were observed in the groundwater source, with a mean concentration of 0.6 μg/L. Seasonal variations were significant in the HAA concentrations; the highest total HAA concentrations were found during the autumn, when the concentrations were approximately two times higher than in winter and spring. HAA speciation varied among the water sources, with dichloroacetic acid and trichloroacetic acid dominant in the lowland surface water system and brominated species dominant in the upland surface water system. There was a strong correlation between trihalomethanes and HAAs when considering all samples from the three systems in the same data set (r2=0.88); however, the correlation was poor/moderate when considering each system independently.

The use of polyacrylamides (PAMs) for removing natural organic matter (NOM) from Paraiba do Sul River (Brazil)

This work assesses the efficiency of polyacrylamides for natural organic matter (NOM) removal from Paraiba do Sul River (Brazil) raw water for drinking purposes. Jar tests were performed following an experimental design protocol. Three kinds of polyacrylamides (anionic, cationic, and non-ionic) at 0.2 mg L(-1) were tested. After coagulation, turbidity, DOC, UVA(254) and SCAN (UV-absorbing material) were determined. Color and pH were also measured. It was found that polyacrylamides did not reduce the amounts of alum and lime needed in the process and that the amount of alum alone for removing UV-absorbing organic matter is significantly higher. Efficiency of the coagulation process decreased as follows: non-ionic -> cationic -> anionic -> no polyacrylamide. Removal efficiencies for the best case were: 100%, 90%, 83%, and 68% for turbidity, DOC, UVA(254), and SCAN, respectively.

Avaliação em escala laboratorial da utilização do processo eletrolítico no tratamento de águas

Water treatment uses chlorine for disinfection causing formation of trihalomethanes. In this work, an electrolytic water pre-treatment was studied and applied to the water from a fountainhead. The action against microorganisms was evaluated using cast-iron and aluminum electrodes. Assays were made in laboratory using the electrolytic treatment. After 5 min of electrolysis the heterotrophic bacteria count was below 500 cfu/mL and complete elimination of total and fecal coliforms was observed. Using electrolytic treatment as a pretreatment of conventional tap water treatment is proposed.

A thin layer electrochemical cell for disinfection of water contaminated with Staphylococcus aureus

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effects of the electrolytic treatment on Bacillus subtilis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Interactions of chlorine with tropical aquatic fulvic acids and formation of intermediates observed by fluorescence spectroscopy

The interactions of tropical aquatic fulvic acids (AFA) with chlorine and formation of trihalomethanes were characterized by fluorescence spectroscopy. The aquatic humic substances (AHS) were isolated from a dark-brown stream (located in a environmental protection area near Cubatão city in São Paulo State, Brazil) by means of the collector XAD 8 according the procedure recommended by the International Humic Substances Society. The photoluminescence measurements were made by using a Perkin Elmer spectrometer; AHS, aquatic humic acids (AHA) and AFA samples were assayed. The interactions of AFA and chlorine were characterized by using different reaction times (1, 24, 48, 72 and 168 h) and chlorine concentrations (2.5, 5.0, 10.0 and 20.0 mg L-1). The relative fluorescence intensity for AFA was significantly decreased with the increasing of chlorine concentration and reaction time. The reduction of fluorescence intensity in the region of longer wavelength was interpreted as an indicative of interaction between condensed aromatic groups of AFA and chlorine.

Avaliação da atividade fotocatalítica sobre a inativação de Escherichia coli, Staphylococcus aureus e Saccharomyces cerevisiae utilizando dióxido de titânio, para aplicação em desinfecção de águas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)