The impact of iodinated X-ray contrast agents on formation and toxicity of disinfection by-products in drinking water.

The presence of iodinated X-ray contrast media (ICM) in source waters is of high concern to public health because of their potential to generate highly toxic disinfection by-products (DBPs). The objective of this study was to determine the impact of ICM in source waters and the type of disinfectant on the overall toxicity of DBP mixtures and to determine which ICM and reaction conditions give rise to toxic by-products. Source waters collected from Akron, OH were treated with five different ICMs, including iopamidol, iopromide, iohexol, diatrizoate and iomeprol, with or without chlorine or chloramine disinfection. The reaction product mixtures were concentrated with XAD resins and the mammalian cell cytotoxicity and genotoxicity of the reaction mixture concentrates was measured. Water containing iopamidol generated an enhanced level of mammalian cell cytotoxicity and genotoxicity after disinfection. While chlorine disinfection with iopamidol resulted in the highest cytotoxicity overall, the relative iopamidol-mediated increase in toxicity was greater when chloramine was used as the disinfectant compared with chlorine. Four other ICMs (iopromide, iohexol, diatrizoate, and iomeprol) expressed some cytotoxicity over the control without any disinfection, and induced higher cytotoxicity when chlorinated. Only iohexol enhanced genotoxicity compared to the chlorinated source water.

Transformation of iopamidol during chlorination.

The transformation of the iodinated X-ray contrast media (ICM) iopamidol, iopromide, iohexol, iomeprol, and diatrizoate was examined in purified water over the pH range from 6.5 to 8.5 in the presence of sodium hypochlorite, monochloramine, and chlorine dioxide. In the presence of aqueous chlorine, only iopamidol was transformed. All other ICM did not show significant reactivity, regardless of the oxidant used. Chlorination of iopamidol followed a second order reaction, with an observed rate constant of up to 0.87 M(-1) s(-1) (±0.021 M(-1) s(-1)) at pH 8.5. The hypochlorite anion was identified to be the reactive chlorine species. Iodine was released during the transformation of iopamidol, and was mainly oxidized to iodate. Only a small percentage (less than 2% after 24 h) was transformed to known organic iodinated disinfection byproducts (DBPs) of low molecular weight. Some of the iodine was still present in high-molecular weight DBPs. The chemical structures of these DBPs were elucidated via MSn fragmentation and NMR. Side chain cleavage was observed as well as the exchange of iodine by chlorine. An overall transformation pathway was proposed for the degradation of iopamidol. CHO cell chronic cytotoxicity tests indicate that chlorination of iopamidol generates a toxic mixture of high molecular weight DBPs (LC50 332 ng/µL).

Formation of DBPs and halogen-specific TOX in the presence of iopamidol and chlorinated oxidants.

Iopamidol is a known direct precursor to iodinated and chlorinated DBP formation; however, the influence of iopamidol on both iodo/chloro-DBP formation has yet to be fully investigated. This study investigated the effect of iopamidol on the formation and speciation of halogen-specific total organic halogen (TOX), as well as iodo/chloro-DBPs, in the presence of 3 source waters (SWs) from Northeast Ohio and chlorinated oxidants. Chlorination and chloramination of SWs were carried out at pH 6.5-9.0 and, different iopamidol and dissolved organic carbon (DOC) concentrations. Total organic iodine (TOI) loss was approximately equal (22-35%) regardless of SW. Total organic chlorine (TOCl) increased in all SWs and was substantially higher in the higher SUVA254 SWs. Iopamidol was a direct precursor to chloroform (CHCl3), trichloroacetic acid (TCAA), and dichloroiodomethane (CHCl2I) formation. While CHCl3 and TCAA exhibited different formation trends with varying iopamidol concentrations, CHCl2I increased with increasing iopamidol and DOC concentrations. Low concentrations of iodo-acids were detected without discernible trends. Total trihalomethanes (THMs), total haloacetic acids (HAAs), TOCl, and unknown TOCl (UTOCl) were correlated with fluorescence regional volumes and SUVA254. The yields of all these species showed a strong positive correlation with fulvic, humic, and combined humic and fulvic regions, as well as SUVA254. Iopamidol was then compared to the 3 SWs with respect to DBP yield. Although the SUVA254 of iopamidol was relatively high, it did not produce high yields of THMs and HAAs compared to the 3 SWs. However, chlorination of iopamidol did result in high yields of TOCl and UTOCl.