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.

Exposure to Trihalomethanes through Different Water Uses and Birth Weight, Small for Gestational Age, and Preterm Delivery in Spain

BACKGROUND Evidence associating exposure to water disinfection by-products with reduced birth weight and altered duration of gestation remains inconclusive. OBJECTIVE We assessed exposure to trihalomethanes (THMs) during pregnancy through different water uses and evaluated the association with birth weight, small for gestational age (SGA), low birth weight (LBW), and preterm delivery. METHODS Mother-child cohorts set up in five Spanish areas during the years 2000-2008 contributed data on water ingestion, showering, bathing, and swimming in pools. We ascertained residential THM levels during pregnancy periods through ad hoc sampling campaigns (828 measurements) and regulatory data (264 measurements), which were modeled and combined with personal water use and uptake factors to estimate personal uptake. We defined outcomes following standard definitions and included 2,158 newborns in the analysis. RESULTS Median residential THM ranged from 5.9 μg/L (Valencia) to 114.7 μg/L (Sabadell), and speciation differed across areas. We estimated that 89% of residential chloroform and 96% of brominated THM uptakes were from showering/bathing. The estimated change of birth weight for a 10% increase in residential uptake was -0.45 g (95% confidence interval: -1.36, 0.45 g) for chloroform and 0.16 g (-1.38, 1.70 g) for brominated THMs. Overall, THMs were not associated with SGA, LBW, or preterm delivery. CONCLUSIONS Despite the high THM levels in some areas and the extensive exposure assessment, results suggest that residential THM exposure during pregnancy driven by inhalation and dermal contact routes is not associated with birth weight, SGA, LBW, or preterm delivery in Spain.

Development of a simple analytical method for determining trihalomethanes in beer using a headspace solid-phase microextraction technique

We developed a simple, rapid, and solventless method for analyzing trihalomethanes in beer samples using headspace solid-phase microextraction. The effects of varying experimental parameters, such as extraction temperature and time, addition of sodium chloride, and agitation speed, on extraction yield were studied using a univariate experimental design. Limits of detection between 0.22 and 0.46 µg L- 1 and wide linear ranges were achieved for trihalomethanes. We measured the trihalomethane recoveries and precision (as the standard deviation of repeat measurements) and demonstrated the applicability of the proposed method by analyzing 32 beer samples.

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.

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.

Toxicological aspects of treatment to remove cyanobacterial toxins from drinking water determined using the heterozygous P53 transgenic mouse model

The presence of toxic cyanobacteria in drinking water reservoirs renders the need to develop treatment methods for the 'safe' removal of their associated toxins. Chlorine has been shown to successfully remove a range of cyanotoxins including microcystins, cylindrospermopsin and saxitoxins. Each cyanotoxin requires specific treatment parameters, particularly solution pH and free chlorine residual. However, currently there has not been any investigation into the toxicological effect of solutions treated for the removal of these cyanotoxins by chlorine. Using the P53(def) transgenic mouse model mate and female C57BL/6J hybrid mice were used to investigate potential cancer inducing effects from such oral dosing solutions. Both purified cyanotoxins and toxic cell-free extract cyanobacterial solutions were chlorinated and administered over 90 and 170 days (respectively) in drinking water. No increase in cancer was found in any treatment. The parent cyanotoxins, microcystins, cylindrospermopsin and saxitoxins were readily removed by chlorine. There was no significant increase in the disinfection byproducts trihalomethanes or haloacetic acids, levels found were well below guideline values. Histological examination identified no effect of treatment solutions except male mice treated with chlorinated cylindrospermopsin (as a cell free extract). In this instance 40% of males were found to have fatty vacuolation in their livers, cause unknown. It is recommended that further toxicology be undertaken on chlorinated cyanobacterial solutions, particularly for non-genotoxic carcinogenic compounds, for example the Tg. AC transgenic mouse model. (C) 2003 Elsevier Science Ltd. All rights reserved.

Avaliação de compostos halogenados em água e ar de piscinas

A procura de piscinas para a prática de atividades desportivas, recreativas e/ou terapêuticas tem sofrido um aumento gradual ao longo do tempo. No entanto, nas piscinas existem vários perigos associados à sua utilização. Relativamente aos perigos químicos, a utilização de desinfetantes à base de cloro, bromo ou compostos derivados vai, por um lado, inativar microrganismos patogénicos mas, por outro, dar origem a subprodutos ao reagir com compostos orgânicos presentes na água. Os trihalometanos são um exemplo de subprodutos que se podem formar e, entre os compostos principais, estão o clorofórmio (TCM), bromodiclorometano (BDCM), clorodibromometano (CDBM) e bromofórmio (TBM). Este trabalho teve como objetivo o desenvolvimento de uma metodologia analítica para a determinação de trihalometanos em água e ar de piscinas e a sua aplicação a um conjunto de amostras. Para a análise dos compostos, foi utilizada a microextração em fase sólida no espaço de cabeça (HS-SPME) com posterior quantificação dos compostos por cromatografia gasosa com detetor de captura eletrónica (GC-ECD). Foi realizada uma otimização das condições de extração dos compostos em estudo em amostras de água, através da realização de dois planeamentos experimentais. As condições ótimas são assim obtidas para uma temperatura de extração de 45ºC, um tempo de extração de 25 min e um tempo de dessorção de 5 min. Foram analisadas amostras de águas de piscina cedidas pelo Centro de Estudos de Águas, sendo avaliada a aplicação da técnica HS-SPME e o efeito de matriz. O modo como se manuseiam as soluções que contêm os compostos em estudo influencia os resultados devido ao facto destes serem bastante voláteis. Concluiu-se também que existe efeito de matriz, logo a concentração das amostras deverá ser determinada através do método de adição de padrão. A caraterização da água de piscinas interiores permitiu conhecer a concentração de trihalometanos (THMs). Foram obtidas concentrações de TCM entre 4,5 e 406,5 μg/L sendo que apenas 4 das 27 amostras analisadas ultrapassam o valor limite imposto pelo Decreto-Lei nº306/2007 (100 μg/L) no que diz respeito a águas de consumo humano e que é normalmente utilizado como valor indicativo para a qualidade das águas de piscina. Relativamente à concentração obtida no ar de uma piscina interior, foi detetada uma concentração média de 224 μg/m3 de TCM, valor muito abaixo dos 10000 μg/m3 impostos pelo Decreto-lei nº24/2012, como valor limite para exposição profissional a agentes químicos.

Caracterização da matéria orgânica natural em águas para consumo humano

O tratamento de água para consumo humano tem por objectivos não só a sua qualidade em termos de parâmetros químicos e físicos, como também microbiológicos. Considerando que a MON pode afectar os sistemas de tratamento, a sua redução minimiza a formação de subprodutos de desinfecção, como por exemplo os trihalometanos e diminui o crescimento de microrganismos ao longo do sistema de distribuição. Nesse sentido tem havido recentemente uma grande evolução na investigação relativamente à remoção de matéria orgânica natural. O principal objectivo deste trabalho foi o de caracterizar a matéria orgânica presente na água bruta e ao longo do processo de tratamento, assim como a sua evolução sazonal. Os dados obtidos a partir desta caracterização poderão contribuir para uma futura optimização no processo de tratamento de águas de consumo. O processo utilizado baseou-se na sorção da matéria orgânica dissolvida em diferentes tipos de resinas de permuta iónica, DAX-8, DAX-4 e IRA-958, permitindo a sua separação em várias fracções: ácidos muito hidrofóbicos (VHA), ácidos ligeiramente hidrofóbicos (SHA), compostos hidrofílicos carregados (CHA) e hidrofílicos neutros (NEU). De acordo com os resultados obtidos apenas a fracção NEU demonstrou ter uma tendência sazonal, apresentando valores máximos no Verão, nos pontos de amostragem referentes à água bruta superficial (PA802) e água bruta superficial após pré-tratamento por filtração (PA800). Os valores de COD não mostraram uma variação sazonal para as amostras de água bruta superficial que rondaram os 2 mg C/L ao longo do período de amostragem (Julho a Outubro), durante o qual se verificou uma baixa pluviosidade e temperaturas médias muito semelhantes. Os compostos NEU predominam em todos os pontos de amostragem não apresentando uma tendência definida ao longo do tratamento. Observou-se uma diminuição das fracções SHA e CHA ao longo do tratamento. Não se pode indicar uma tendência definida relativamente à fracção VHA. Verifica-se globalmente uma diminuição do teor de MON ao longo do tratamento. Este trabalho demonstrou que na água bruta superficial existe uma predominância dos compostos NEU, seguidos dos SHA, dos VHA e finalmente dos compostos CHA. Na água bruta captada no sub-leito do rio, verifica-se apenas a existência dos compostos NEU, sendo as restantes fracções praticamente nulas. Os valores mais elevados de TSUVA254nm foram obtidos para as amostras que não sofreram qualquer tratamento, água bruta do sub-leito (PA903) e superficial (PA802), e água bruta após pré-filtração (PA800). Nos restantes pontos de amostragem, apesar de se verificarem valores inferiores, não se observa uma diminuição deste parâmetro ao longo do tratamento, nem uma variação sazonal. Os valores de TSUVA254nm obtidos são geralmente inferiores a 3 L.mgC-1.m-1, correspondendo a materiais não húmicos, que são considerados biodegradáveis. Para as amostras de água tratada os valores oscilam entre os 1,23 e 1,58 L.mgC-1.m-1, valores inferiores a 2 L.mgC-1.m-1, o que é considerado um valor de referência ao nível do tratamento, segundo a USEPA.

Recuperação parcial da água de lavagem dos filtros utilizados no tratamento da água de piscinas de uso público

Mestrado em Engenharia Química. Ramo optimização energética na indústria química

Risc i efectes a la salut de la desinfecció de l'aigua: una aproximació a la relació entre els subproductes de la cloració de l'aigua i el càncer colorectal

Aquest projecte es centra en l'estimació del risc ambiental que suposen els subproductes de la desinfecció de l'aigua (amb els trihalometans com a marcadors) per a la incidència de càncer colorectal. Això s'estudia mesurant les exposicions i usos de l'aigua d'un grup de casos i controls a diversos llocs de l'Estat Espanyol, comparant els nivells de trihalometans d'aquestes ciutats, estimant-ne l'absorció i, per últim, calculant-ne el risc mitjançant la odds ratio (probabilitat de patir la malaltia dividit per la probabilitat de no desenvolupar-la). Per assolir-ho és vital l'acurada estimació de l'exposició de la població a aquests productes, ja que, tot i que l'aigua de xarxa és una exposició ubiqua i, per tant, ambiental, hi ha persones més exposades que d'altres. Comparant els nivells de trihalometans arreu d'Espanya, la qualitat de l'aigua de consum varia molt als diferents llocs d'estudi, essent Barcelona la de pitjor qualitat ambiental i Guipúscoa la millor. La primera estimació al risc (l'estudi oficial, dut a terme pel Centre de Recerca en Epidemiologia Ambiental, no està conclòs) dóna positiu en la majoria d'exposicions, amb l'excepció de l'assistència a piscines durant l'hivern.

Uimahallien vedestä haihtuvat epäpuhtaudet ja niiden leviäminen allastilassa

Uimaveden klooridesinfioinnissa syntyy sivutuotteena haihtuvia ja haitallisia halogeeniyhdisteitä, kuten trihalometaaneja ja triklooriamiinia, jotka voivat heikentää allas-tilan sisäilman laatua merkittävästi. Tämän tutkimuksen tavoitteena oli kartoittaa näiden desinfioinnin sivutuotteiden pitoisuuksia suomalaisissa uimahalleissa sekä selvittää epäpuhtauksien kulkeutumista allastiloissa. Lisäksi pyrittiin löytämään merkittävimmät veden laatu- ja käsittelyparametrit sekä ilmanvaihtotekniset tekijät, jotka vaikuttavat vedestä haihtuvien epäpuhtauksien pitoisuuksiin hallitiloissa. Mittaukset tehtiin kymmenessä eri puolilla Suomea sijaitsevassa uimahallissa. Mittausten perusteella havaittiin, että allastilojen kloroformipitoisuudet vaihtelivat välillä 8,9-84,0 ¿g/m3. Terapia-allasostoilta mitatut pitoisuudet olivat pääallastiloista mitattuja pitoisuuksia suurempia ja aamulla mitattu pitoisuus alhaisempi kuin illalla mitattu. Lisäksi ilmastoiduista valvomoista mitatut pitoisuudet olivat merkittävästi allastilojen pitoisuuksia pienempiä. Triklooriamiininäytteistä suurin osa oli alle määritysrajan. Sisäilman kloroformipitoisuuden havaittiin korreloivan veden lämpötilan sekä ilman kosteuden kanssa. Triklooriamiinille tilastollista analyysiä ei voitu tehdä mm. määritys-rajan alle jääneiden näytteiden suuren osuuden vuoksi. Teknisten kyselyiden ja ilmanvaihtomittausten perusteella todettiin, että uimahallien ilmanvaihto toimii lämmitystarpeen vuoksi sekoittavana ja epäpuhtauksien leviämistä allastilassa ei voida käytännössä katsoen estää. Ilman virtausnopeudet pääaltaiden reunoilla olivat pieniä ja ilman virtauskenttien ei todettu vaikuttavan epäpuhtauksien kulkeutumiseen allastiloissa. Mittauskohteiden vähyydestä ja vedenkäsittelyn hallikohtaisista erityispiirteistä johtuen luotettavia johtopäätöksiä vedenkäsittelymenetelmien vaikutuksesta allasveden ja allastilan ilman laatuun ei pystytty tekemään.

Practical applications of a systematic approach to the chemical abatement of pollutants in water and air

The present dissertation is devoted to the systematic approach to the development of organic toxic and refractory pollutants abatement by chemical decomposition methods in aqueous and gaseous phases. The systematic approach outlines the basic scenario of chemical decomposition process applications with a step-by-step approximation to the most effective result with a predictable outcome for the full-scale application, confirmed by successful experience. The strategy includes the following steps: chemistry studies, reaction kinetic studies in interaction with the mass transfer processes under conditions of different control parameters, contact equipment design and studies, mathematical description of the process for its modelling and simulation, processes integration into treatment technology and its optimisation, and the treatment plant design. The main idea of the systematic approach for oxidation process introduction consists of a search for the most effective combination between the chemical reaction and the treatment device, in which the reaction is supposed to take place. Under this strategy,a knowledge of the reaction pathways, its products, stoichiometry and kinetics is fundamental and, unfortunately, often unavailable from the preliminary knowledge. Therefore, research made in chemistry on novel treatment methods, comprisesnowadays a substantial part of the efforts. Chemical decomposition methods in the aqueous phase include oxidation by ozonation, ozone-associated methods (O3/H2O2, O3/UV, O3/TiO2), Fenton reagent (H2O2/Fe2+/3+) and photocatalytic oxidation (PCO). In the gaseous phase, PCO and catalytic hydrolysis over zero valent ironsare developed. The experimental studies within the described methodology involve aqueous phase oxidation of natural organic matter (NOM) of potable water, phenolic and aromatic amino compounds, ethylene glycol and its derivatives as de-icing agents, and oxygenated motor fuel additives ¿ methyl tert-butyl ether (MTBE) ¿ in leachates and polluted groundwater. Gas-phase chemical decomposition includes PCO of volatile organic compounds and dechlorination of chlorinated methane derivatives. The results of the research summarised here are presented in fifteenattachments (publications and papers submitted for publication and under preparation).

Aplicação de SPME (Solid Phase Micro-Extraction) na análise de águas potáveis de três localidades do estado de São Paulo

The technique of solid phase microextraction (SPME) was used for the extraction of halogenated contaminants of water samples from three cities of the State of São Paulo and the extracts were submitted to gas chromatographic analysis with electron capture detection (GC-ECD). In the samples of water collected at the city of São Paulo the detected level of trihalomethanes (THM) expressed as the sum of chloroform, dibromochloromethane and dichlorobromomethane, were higher than the permissible limit established by the Brazilian regulation. In the samples collected at the two other cities the level of any of the three THM remained below the sensitivity of the ECD.

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.