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Pools and spas are enjoyed throughout the world for exercise and relaxation. However, there are no previous studies on mutagenicity of disinfected spa (hot tub) waters or comprehensive identification of disinfection byproducts (DBPs) formed in spas. Using 28 water samples from seven sites, we report the first integrated mutagenicity and comprehensive analytical chemistry of spas treated with chlorine, bromine, or ozone, along with pools treated with these same disinfectants. Gas chromatography (GC) with high-resolution mass spectrometry, membrane-introduction mass spectrometry, and GC-electron capture detection were used to comprehensively identify and quantify DBPs and other contaminants. Mutagenicity was assessed by the Salmonella mutagenicity assay. More than 100 DBPs were identified, including a new class of DBPs, bromoimidazoles. Organic extracts of brominated pool/spa waters were 1.8× more mutagenic than chlorinated ones; spa waters were 1.7× more mutagenic than pools. Pool and spa samples were 2.4 and 4.1× more mutagenic, respectively, than corresponding tap waters. The concentration of the sum of 21 DBPs measured quantitatively increased from finished to tap to pool to spa; and mutagenic potency increased from finished/tap to pools to spas. Mutagenic potencies of samples from a chlorinated site correlated best with brominated haloacetic acid concentrations (Br-HAAs) (r = 0.98) and nitrogen-containing DBPs (N-DBPs) (r = 0.97) and the least with Br-trihalomethanes (r = 0.29) and Br-N-DBPs (r = 0.04). The mutagenic potencies of samples from a brominated site correlated best (r = 0.82) with the concentrations of the nine HAAs, Br-HAAs, and Br-DBPs. Human use increased significantly the DBP concentrations and mutagenic potencies for most pools and spas. These data provide evidence that human precursors can increase mutagenic potencies of pools and spas and that this increase is associated with increased DBP concentrations.

Concerns have been raised in the scientific community regarding the environmental implications of a dramatic increase in corn-based ethanol production and associated increases in pesticide use. The use of glyphosate, a broad-spectrum herbicide, for corn production has increased considerably in recent years in Canada and the United States. The cost of measuring concentrations of organic contaminants in the environment using traditional wet chemistry methods can be prohibitive; especiallywhen large numbers of samples are required to quantify the spatial and temporal variability in contaminant concentrations. The goal of our study was to evaluate a cost-effective method to measure glyphosate concentrations in surface waters. The reliability of enzyme-linked immunosorbent assay (ELISA) results was evaluated against liquid chromatography tandem mass spectrometry, and linear regression results for 30 water samples from urban watersheds revealed a strong relationship (R2 = 0.88). These results suggest that ELISA methods, used in conjunction with traditional methods, represent a cost-effective approach to enhance the spatial and temporal resolution of a water quality monitoring study. Additionally, we measured a total of 739 surface water samples from over 150 sampling locations throughout Ontario using ELISA from April to October 2007. Concentrations exceeded the method detection limit of 0.1 microg/L in 33% of the samples, with a maximum concentration of 12.0 microg/L. Glyphosate showed a bimodal temporal distribution with peak concentrations occurring in late spring/early summer and fall, and did not exceed the Canadian Council of Ministers of the Environment (CCME) guideline for the protection of aquatic life (65 microg/L) in any of the samples.

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