Abstract: Although disinfection by-products (DBPs) occur in complex mixtures, studies evaluating health risks have been focused in few chemicals. In the framework of an epidemiological study on cancer in 11 Spanish provinces, we describe the concentration of four trihalomethanes (THMs), nine haloacetic acids (HAA), 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX), four haloacetonitries, two haloketones, chloropicrin and chloral hydrate and estimate correlations. A total of 233 tap water samples were collected in 2010. Principal component analyses were conducted to reduce dimensionality of DBPs. Overall median (range) level of THMs and HAAs was 26.4 (0.8?98.1) and 26.4 (0.9?86.9) ?g/l, respectively (N=217). MX analysed in a subset (N=36) showed a median (range) concentration of 16.7 (0.8?54.1) ng/l. Haloacetonitries, haloketones, chloropicrin and chloral hydrate were analysed in a subset (N=16), showing levels from unquantifiable (<1 ?g/l) to 5.5 ?g/l (dibromoacetonitrile). Spearman rank correlation coefficients between DBPs varied between species and across areas, being highest between dibromochloromethane and dibromochloroacetic acid (rs=0.87). Principal component analyses of 13 DBPs (4 THMs, 9 HAAs) led 3 components explaining more than 80% of variance. In conclusion, THMs and HAAs have limited value as predictors of other DBPs on a generalised basis. Principal component analysis provides a complementary tool to address the complex nature of the mixture.

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