In vitro bioacessibility and transport across Caco-2 monolayers of haloacetic acids in drinking water.

Water disinfection plays a crucial role in water safety but it is also a matter of concern as the use of disinfectants promotes the formation of disinfection by-products (DBPs). Haloacetic acids (HAAs) are one of the major classes of DBPs since they are frequently found in treated water, are ubiquitous, pervasive and have high water solubility, so a great concern emerged about their formation, occurrence and toxicity. Exposure to HAAs is influenced by consumption patterns and diet of individuals thus their bioavailability is an important parameter to the overall toxicity. In the current study the bioacessibility of the most representative HAAs (chloroacetic acid - MCAA, bromoacetic acid - MBAA, dichloroacetic acid - DCAA, dibromoacetic acid - DBAA, and trichloroacetic acid - TCAA) after simulated in vitro digestion (SIVD) in tap water and transport across Caco-2 monolayers was evaluated. Compounds were monitored in 8 points throughout the digestion phases by an optimized LC-MS/MS methodology. MCAA and MBAA were not bioaccessible after SIVD whereas DCAA, DBAA and TCAA are highly bioaccessible (85 ± 4%, 97 ± 4% and 106 ± 7% respectively). Concerning transport assays, DCAA and DBAA were highly permeable throughout the Caco-2 monolayer (apparent permeability and calculated fraction absorbed of 13.62 × 10(-6) cm/s and 90% for DCAA; and 8.82 × 10(-6) cm/s and 84% for DBAA), whereas TCAA showed no relevant permeability. The present results may contribute to efficient risk analysis studies concerning HAAs oral exposure from tap water taking into account the different biological behaviour of these chemically similar substances.

Water quality concerns due to forest fires: polycyclic aromatic hydrocarbons (PAH) contamination of groundwater from mountain areas.

Water quality alterations due to forest fires may considerably affect aquatic organisms and water resources. These impacts are cumulative as a result of pollutants mobilized from fires, chemicals used to fight fire, and postfire responses. Few studies have examined postfire transport into water resources of trace elements, including the polycyclic aromatic hydrocarbons (PAH), which are organic pollutants produced during combustion and are considered carcinogenic and harmful to humans. PAH are also known to adversely affect survival, growth, and reproduction of many aquatic species. This study assessed the effects of forest wildfires on groundwater from two mountain regions located in protected areas from north and central Portugal. Two campaigns to collect water samples were performed in order to measure PAH levels. Fifteen of 16 studied PAH were found in groundwater samples collected at burned areas, most of them at concentrations significantly higher than those found in control regions, indicating aquifer contamination. The total sum of PAH in burned areas ranged from 23.1to 95.1 ng/L with a median of 62.9 ng/L, which is one- to sixfold higher than the average level measured in controls (16.2 ng/L). In addition, in control samples, the levels of light PAH with two to four rings were at higher levels than heavy PAH with five or six rings, thus showing a different profile between control and burned sites. The contribution of wildfires to groundwater contamination by PAH was demonstrated, enabling a reliable assessment of the impacts on water quality and preparation of scientifically based decision criteria for postfire forest management practices.

Groundwater from infiltration galleries used for small public water supply systems: contamination with pesticides and endocrine disruptors.

Infiltration galleries are among the oldest known means used for small public water fountains. Owing to its ancestral origin they are usually associated with high quality water. Thirty-one compounds, including pesticides and estrogens from different chemical families, were analysed in waters from infiltration galleries collected in Alto Douro Demarcated Wine region (North of Portugal). A total of twelve compounds were detected in the water samples. Nine of these compounds are described as presenting evidence or potential evidence of interfering with the hormone system of humans and wildlife. Although concentrations of the target analytes were relatively low, many of them below their limit of quantification, four compounds were above quantification limit and two of them even above the legal limit of 0.1 µg/L: dimethoate (30.38 ng/L), folpet (64.35 ng/L), terbuthylazine-desethyl (22.28 to 292.36 ng/L) and terbuthylazine (22.49 to 369.33 ng/L).

Quantification of endocrine disruptors and pesticides in water by gas chromatography-tandem mass spectrometry. Method validation using weighted linear regression schemes.

A multi-residue methodology based on a solid phase extraction followed by gas chromatography-tandem mass spectrometry was developed for trace analysis of 32 compounds in water matrices, including estrogens and several pesticides from different chemical families, some of them with endocrine disrupting properties. Matrix standard calibration solutions were prepared by adding known amounts of the analytes to a residue-free sample to compensate matrix-induced chromatographic response enhancement observed for certain pesticides. Validation was done mainly according to the International Conference on Harmonisation recommendations, as well as some European and American validation guidelines with specifications for pesticides analysis and/or GC-MS methodology. As the assumption of homoscedasticity was not met for analytical data, weighted least squares linear regression procedure was applied as a simple and effective way to counteract the greater influence of the greater concentrations on the fitted regression line, improving accuracy at the lower end of the calibration curve. The method was considered validated for 31 compounds after consistent evaluation of the key analytical parameters: specificity, linearity, limit of detection and quantification, range, precision, accuracy, extraction efficiency, stability and robustness.