Browsing by Author "Cardoso, A.S."
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- Analysis and Identification of Trihalomethanes in Lisbon Indoor Swimming Pools: Distribution, Determinants and Human ExposurePublication . Silva, Z.; Rebelo, H.; Silva, M.M.; Alves, A.; Cabral, C.; Almeida, A.C.; Aguiar, F.; Oliveira, A.; Nogueira, A.; Pinhal, H.; Matos, A.; Ramos, C.D.; Pacheco, P.; Aguiar, P.; Cardoso, A.S.Water disinfection methods are used in swimming pools to ensure an effective protection of users against microbiological pathogens, being chlorination the most common disinfection method used worldwide. The use of chlorine based treatment techniques has one strong drawback, which is the generation of disinfection by-products (DBPs), potentially harmful products that have been associated with respiratory and ocular symptoms, bladder cancer and adverse reproductive effects. Amongst DBPs, the most better characterized are trihalomethanes (THMs): chloroform (CF), bromoform (BF), bromodichloromethane (BDCM), and chlorodibromomethane (DBCM). In Portugal a specific legislation to assess the quality of swimming pools is inexistent. The guideline value used to evaluate total THMs in water (TTHMsW) is the one established in the Law 306/2007 - 100 μg/L. Some other water/air parameters were assessed by Law 5/97, WHO guidelines for safe recreational water environments (2006) and Standard 62.1 (2006) from American Society of Heating, Refrigerating, and Air-Conditioning Engineers (ASRHAE). The main goal of this investigation was to study the occurrence, distribution and determinants of THMs in indoor swimming pools. This will also enable an evaluation of the exposure of users to THMs. In order to achieve this goals, the characterization of water quality in 30 Lisbon indoor swimming pools, using chorine based treatment techniques, was made during a six month period. Several parameters such as TTHMs, CF, BDCM, DBCM, BF levels in water, free residual chlorine (FrCl), pH, TW, Tair, Hu, chemical oxygen demand (COD), and other, were determined in each pool, once a month. Statistical analysis was performed using the SPSS 17.0 software. Descriptive analysis was applied to all variables. Student’s t-test, Mann-Whitney tests and Spearman’s rank correlation coefficient were also used. Large variation in TTHMs and CF water levels between the pools was obtained, being CF the THM obtained in higher concentrations, with sporadic higher values than the allowed. In air, CF level (CFair) also presented occasional higher levels. There was a clear positive linear correlation between CFW and TTHMsW (R>0.95, p<0.01), CFW and CFair (R> 0.5; p<0.05), CFW and FrCl (R>0.2; p<0.05) and, CFw and Tw (R>0.2; p<0.05). Good correlations were also obtained between other THMs: BDCM and DBCM (R>0.5, p<0.01) and BF and DBCM (R>0.6; p<0.05). The strong positive correlation obtained between CFW and TTHMsW was expected, since, usually, CFW has the higher contribution to TTHMsW. CFW is often considered as a good indicator of TTHMs concentration in water. Therefore correlations between TTHMs and CFair, FrCl, and Tw were expected and observed: TTHMsW vs CFair (R>0.5; p<0.05), TTHMsW vs FrCl (R>0.2; p<0.05) and TTHMsW vs TW (R>0.2; p<0.01). In conclusion, reasonable water and air quality was obtained in the studied Lisbon swimming pools, although some pools presented high TTHMsW, CFW and CFair. These results clearly demonstrate that THMs monitoring is particularly important and that, in a near future, this should be extended to other DBPs. Furthermore, for conscious use of swimming pools, appropriate and targeted information about safe practices should be provided to pool users.
- Drinking water contaminants: toxicity of halogenated polycyclic aromatic hydrocarbonsPublication . José, S.S.; Pinto, M.; Antunes, A.M.M.; Louro, H.; Jordão, Luísa; Silva, M.J.; Cardoso, A.S.Food may be contaminated with polycyclic aromatic hydrocarbons (PAHs) in the process of smoking or heating. These contaminants or their derivatives can also be present in drinking water when raw water contacts with discharges of untreated industrial/waste water effluents, forest fires or by solubilisation of organic material from contaminated soils. A few studies have shown that water disinfection can lead to halogenated derivatives of PAHs (HPAHs) as chlorinated and brominated derivatives, and there are evidences that these compounds may have greater mutagenicity than the parent PAHs. In this study the cytotoxic and genotoxic effects of chlorinated/brominated derivatives of pyrene (Pyr) and benzo[a]anthracene (BaA), 1-ClPyr, 1-BrPyr and 7-ClBaA, which can be formed as water disinfection by-products, were studied in HepG2 cells to assess their potential hazard to human health. The formation of 1-ClPyr, 1-BrPyr and 7-ClBaA under aqueous disinfection conditions in waters contaminated with Pyr and BaA, was confirmed with an optimized gas chromatography method. Cells exposed (24h) to several concentrations of BaA and 7-ClBaA (1 to 200μM) displayed a dose-related and significant increase of cytotoxicity (neutral red assay) with IC50 values of 3.37 and 12.63µM respectively. For Pyr, 1-ClPyr and 1-BrPyr (10 to 200μM), a lower but significant dose-related cytotoxicity was observed. At non-cytotoxic concentrations (10 and 15µM), 7-ClBaA was able to induce a significantly higher level of oxidative DNA damage in HepG2 cells than its parent compound, as assessed by the FPG-modified comet assay. Under these conditions neither Pyr nor its derivatives were genotoxic. In conclusion, the disinfection process may give rise to genotoxic HPAHs with potential impact on human health and it should be performed in raw waters with minimal content of total organic carbon. In real conditions, humans may be exposed to a mixture of these organic compounds and thus their combined toxic effects should be further evaluated.
- Formation of emerging disinfection byproducts in water and evaluation of potential genotoxic effects: the case of halogenated polycyclic aromatic hydrocarbonsPublication . Pinto, M.; Antunes, A.M.M.; José, S.S.; Alves, A.C.; Louro, H.; Silva, M.J.; Cardoso, A.S.Disinfection byproducts (DBPs) are formed when disinfectants used in water treatment plants (WTPs) react with natural (or anthropogenic) organic matter present in the source water. Many studies have addressed health risks posed by a life-time exposure to DBPs through chlorinated drinking water or through dermal or inhalation exposure routes. Experimental studies have revealed genotoxic and carcinogenic effects of some DBPs and epidemiological studies evidenced potential associations between chlorinated drinking water and bladder or colorectal cancer. In addition, a possible link between chlorinated drinking water and reproductive/developmental effects has been hypothesized. Many DBPs have been identified in chlorinated water, which justifies the growing concern about the potential health effects of emerging unregulated DBPs, some of which appear to be more genotoxic, in some assays, than the regulated DBPs. Polycyclic aromatic hydrocarbons (PAHs) are among the most persistent contaminants detected in environmental samples such as river sediments and tap water. A few studies have already proven that water disinfection can lead to the formation of halogenated derivatives of PAHs, such as chlorinated (Cl-PAHs) and brominated PAHs (Br-PAHs). The available toxicological studies have shown that these compounds possess, in general, greater mutagenicity than the corresponding parent PAHs. Our investigation group have also showed that exposure of HepG2 cells to a dose-range of 6-Cl-benzo[a]pyrene (6-Cl-BaP) and BaP resulted in cytotoxicity above 50 µM and that, at the equimolar doses of 100 and 125 µM, 6-Cl-BaP was able to induce a significantly higher level of DNA damage than BaP. The present study had two main objectives: 1) identification of the major chlorinated and brominated derivatives of benzo[a]anthracene (BaA) and pyrene (Pyr) formed as disinfection by-products and 2) evaluation of their potential hazard to humans, through the characterization of their potential cytotoxic and genotoxic effects in a human cell line. To synthesize Cl-PAHs and Br-PAHs the method of Mitchell was developed for BaA and Pyr. 1-Cl-Pyr and 1-Br-Pyr were obtained as the major chlorinated and brominated derivatives of Pyr, and 7-Cl-BaA and 7-Br-BaA as the reaction products of BaA. Cell viability and DNA integrity of those derivatives were assessed by the neutral red uptake (NR) and the comet assay, respectively, allowing the comparison of their genotoxic potential. Although health risks of DBPs are small compared to the health risks of waterborne diseases, the formation of hazardous halogenated-PAHs in chlorinated water water emphasizes the need of development of new and safer water disinfection methods.
- Halogenated polycyclic aromatic hydrocarbons associated with drinking water disinfectionPublication . José, S. S.; Pinto, M.; Antunes, A.M.M.; Louro, H.; Silva, M.J.; Cardoso, A.S.Introduction: Disinfection by-products (DBPs) have been identified in chlorinated water. This fact justifies the growing concern about the potential health effects of emerging unregulated DBPs, some of which appear to be more genotoxic than the regulated DBPs[1]. Polycyclic aromatic hydrocarbons (PAHs) are among the most persistent contaminants detected in environmental samples such as river sediments and tap water. A few studies have already proven that water disinfection can lead to the formation of halogenated derivatives of PAHs, such as chlorinated and brominated PAHs[2] . The available toxicological studies have shown that these compounds possess, in general, greater mutagenicity than the corresponding parent PAHs. Our research group has also shown that exposure of HepG2 cells to a dose-range of 6-Cl-benzo[a]pyrene (6-ClBaP) and BaP resulted in cytotoxicity above 50 µM and that, at the equimolar doses of 100 and 125 µM, 6-ClBaP was able to induce a significantly higher level of DNA damage than BaP[3] . The present study had two main objectives: 1) identification of the major chlorinated and brominated derivatives of benzo[a]anthracene (BaA) and pyrene (Pyr) formed as disinfection by-products and 2) evaluation of their potential hazard to humans, through the characterization of their potential cytotoxic and genotoxic effects in a human cell line.
- Halogenated polycyclic aromatic hydrocarbons associated with drinking water disinfectionPublication . Cardoso, A.S.; José, S.S.; Pinto, Miguel; Antunes, A.M.M.; Louro, H.; Silva, M.J.
- Removal of polycyclic aromatic hydrocarbons by biosorbentsPublication . José, Sílvia S.; Cardoso, A.S.; Silva, S.P.; Mestre, A.S; Carvalho, A.P.Introduction: - Polycyclic aromatic hydrocarbons (PAHs) are a group of environmental carcinogens. They are formed during the incomplete combustion of organic matter. Humans are exposed to PAHs by various sources, including occupational environments, cigarette smoke, vehicle exhaust, and dietary sources as grilled and flame-broiled food. - In vivo studies in animals proved that PAHs are associated to cancer, and epidemiologic studies with exposed workers, especially in coke ovens and aluminium smelters, have shown clear excess of lung cancer and highly suggestive excesses of bladder cancer. - These compounds can enter in drinking water sources by precipitation and runoff on the earth’s surface. - Portuguese legislation for water for human consumption (DL 306/2007) proposes the determination of five PAHs; limits of the maximum concentration are 0.10 µg/L for total BghiP, BbF, BkF, IcdP, and 0.010 µg/L for BaP.
- Trihalomethanes in Lisbon Indoor Swimming Pools: Occurrence and Determining FactorsPublication . Silva, Z.; Rebelo, H.; Silva, M.M.; Alves, A.; Cabral, C.; Almeida, A.C.; Aguiar, F.; Oliveira, A.; Nogueira, A.; Pinhal, H.; Matos, A.; Ramos, C.D.; Pacheco, P.; Aguiar, P.; Cardoso, A.S.The presence of water disinfection by-products (DBPs) in swimming pools constitutes today a public health concern, particularly because swimming is an activity used by a high percentage of the population, namely elderly and young children. Moreover, several adverse short-term and long-term health effects have been associated with these compounds (Lakind et al., 2010; Zwiener et al., 2007). Water disinfection methods are used in all swimming pools, namely in public pools, to ensure an adequate and effective protection of users against microbiological pathogens. Chlorination is the most common disinfection method used worldwide, because it is low cost, easy to use, efficient against a broad spectrum of microorganisms, and enables the maintenance of a residual protection. The use of chlorine based treatment techniques has one strong drawback, which is the generation of several DBPs, potentially harmful products, that can be absorbed by ingestion, inhalation and absorption through the skin (Nieuwenhuijsen et al., 2009; Caro and Gallego, 2007). DBPs comprise several compounds that are formed through the reaction of chlorine with organic matter present in water. Amongst DBPs, the most relevant and better characterized are trihalomethanes (THMs): chloroform (CF), bromoform (BF), bromodichloromethane (BDCM), and chlorodibromomethane (DBCM). These compounds have been associated with health effects such as respiratory, ocular and cutaneous symptoms and also with some long-term health effects such as bladder cancer and adverse reproductive outcomes (Lee et al., 2009; Zwiener et al., 2007). Accurate exposure assessments to THMs in indoor pool environment is particularly difficult because their formation depends on many factors such as water and air temperature (Tw and Tair), humidity (Hu), pH, free residual chlorine (FrCl), total organic content and number of pool users (Lee et al., 2009). In Portugal a specific legislation to assess the quality of swimming pool waters is inexistent. The guideline value used in this study for total THMs (TTHMs) was the one established in the Portuguese Law 306/2007, for drinking water quality - 100 μg/L. Some other water parameters determined in swimming pools such as Tw turbidity (Turb), pH, FrCl, total residual chlorine, conductivity (Cond), permanganate index (COD) and isocyanuric acid were assessed by Portuguese Law 5/97, regarding technical and safety conditions of closed environments with water diversions. WHO guidelines for safe recreational water environments (2006) were also used to assess some water and air parameters in pools. Standard 62.1 (2006) from American Society of Heating, Refrigerating, and Air-Conditioning Engineers (ASRHAE) was also used to assess pool air parameters. The main goal of this investigation project was to study the occurrence, distribution and determinants of THMs in indoor swimming pools. This will enable an evaluation of swimming pool users’ exposure to THMs. In order to achieve this goal, the characterization of water quality of 30 Lisbon indoor swimming pools, using chorine based treatment techniques, was made during a six month period. Because of laboratory working restrictions, CF concentration in pool air was studied only in 6 swimming pools, at the same period. Several parameters such as TTHMs concentration, CF, BDCM, DBCM, BF concentration in water, FrCl, combined residual chlorine (CrCl), pH, Tw and Tair, Hu, COD, Cond, Turb and chloride (Cl) were determined in each pool, once a month. THMs water sampling was made in duplicates in two pool water spots, physicochemical parameters were determined in one of the THMs water sampling spots and THMs air sampling was made in two pool spots, considered to be representative of the swimming pool air. All sampling procedures were performed by specialized sampling technicians from Lisbon Health Centres Group (ACES). Statistical analysis was performed using the SPSS 17.0 software. Descriptive analysis was applied to all variables in order to determine mean, median, standard deviation, minimum and maximum. Student’s t-test and Mann-Whitney tests were used to compare numerical variables and Spearman’s rank correlation coefficient were used to examine correlation between all environmental parameters. TTHMs water level ranged from 10 to 160 μg/L, while CF water level typically ranged from 5 to 150 μg/L, with occasional higher levels detected. Regarding other THMs levels in pool water, BDCM ranged from 0.5 to 15 μg/L, DBCM from 0.4 to 10 μg/L and BF was obtained in concentrations less than 2 μg/L. Moreover, in some pools, DBCM and BF were not detected. From these results, it can be concluded that there was a large variation in TTHMs and CF water levels between the pools and that CF was the THM obtained in higher concentrations. These results are in agreement with studies presented by other authors (Lee et al., 2009; Chu and Nieuwenhuijsen, 2002). In air, CF level ranged from 40 to 200 μg/m3, with occasional higher levels detected. Tw presented less variation (27 to 31 ºC) than Tair (21 to 33 ºC), although sporadic higher values were found. FrCl and Cond presented higher values than the guidelines from DR 5/97 only in a small number of pools. Turb and COD values were within the guidelines from DR 5/97. pH varied from 7 to 8.5, with only a small number of pools having values higher than 7.8. As referred in WHO guidelines, pH should be maintained between 7.2 and 7.8 for chlorine disinfectants to ensure efficient disinfection. Using the statistical tests mentioned before, it was possible to obtain some interesting results. There was a clear positive linear correlation between CF water concentration (CFW) and TTHMs water concentration (R>0.98, p<0.01), good correlation other THMs, there was a clear positive linear correlation between BDCM and DBCM water concentration (R>0.78, p<0.01) and good correlation between TTHMs water concentration and Tw (R>0.45, p<0.05). These results are in agreement with Lee et al. (2009) which obtained positive linear correlations between CFW and COD and with Chu and Nieuwenhuijsen (2002) which also obtained correlations between TTHMs water concentration and Tw. In conclusion, there appears to be good water and air quality in the studied Lisbon swimming pools. Regarding THMs levels in water, some pools presented high TTHMs and CF concentrations. Moreover, CF air concentrations were also high in some swimming pools. These results clearly demonstrate that THMs monitoring is particularly important and that, in a near future, this should be extended to other DBPs. Furthermore, for a correct and conscious use of swimming pools, appropriate and targeted information about safe practices should be provided to pool users.