Genotoxicity Induced by Low Dose and Mixed Exposure to Haloacetaldehydes,an Emerging Class of Drinking Water Disinfection By-products

Haloacetaldehydes(HALs)are the third largest disinfection by-products(DBPs)class by mass in drinking water.Most of them alone in high doses are more cytotoxic and genotoxic than regulated DBPs.However,the toxic effects of mixed exposure to HALs at environmentally relevant levels are still unknown.Given that genotoxicity is critical for risk assessment,we employed multiple genotoxic tests including the Salmonella typhimurium revertant mutation assay(Ames assay),the single cell gel electrophoresis(SCGE)assay,the cytoplasmic blocking micronucleus(CBMN)assay,and theγ-H2AX assay to investigate the genotoxicity of HALs based on the HALs concentrations and components detected in the finished drinking water of Shanghai,China.The results demonstrated the concentrations of HALs were low,ranging from 0.04µg/L to 4.47µg/L,and the total concentration was 10.85µg/L.Although the mutagenicity of HALs was negative even at 1000-fold concentrations in the real world,mixed exposure to 100 and 1000-fold concentrations HALs resulted in DNA and chromosomal damage in human hepotocyte(HepG2)cells.HALs significantly increased the levels of reactive oxygen species(ROS)andγ-H2AX and activated nuclear factor erythroid-derived factor 2-related factor 2(NRF2)pathway-related protein expressions in HepG2 cells.The antioxidant NAC could ameliorate NRF2 pathway-related protein expression and DNA damage caused by HALs,suggesting that the genotoxicity of mixed exposure to HALs involved cellular oxidative stress and NRF2 pathway activation.

Formation of iodo-trihalomethanes, iodo-haloacetic acids, and haloacetaldehydes during chlorination and chloramination of iodine containing waters in laboratory controlled reactions

Iodine containing disinfection by-products（I-DBPs） and haloacetaldehydes（HALs） are emerging disinfection by-product（DBP） classes of concern. The former due to its increased potential toxicity and the latter because it was found to be the third most relevant DBP class in mass in a U.S. nationwide drinking water study. These DBP classes have been scarcely investigated, and this work was performed to further explore their formation in drinking water under chlorination and chloramination scenarios. In order to do this, iodo-trihalomethanes（I-THMs）,iodo-haloacetic acids（I-HAAs） and selected HALs（mono-HALs and di-HALs species, including iodoacetaldehyde） were investigated in DBP mixtures generated after chlorination and chloramination of different water matrices containing different levels of bromide and iodide in laboratory controlled reactions. Results confirmed the enhancement of I-DBP formation in the presence of monochloramine. While I-THMs and I-HAAs contributed almost equally to total I-DBP concentrations in chlorinated water, I-THMs contributed the most to total I-DBP levels in the case of chloraminated water. The most abundant and common I-THM species generated were bromochloroiodomethane, dichloroiodomethane, and chlorodiiodomethane. Iodoacetic acid and chloroiodoacetic acid contributed the most to the total I-HAA concentrations measured in the investigated disinfected water. As for the studied HALs, dihalogenated species were the compounds that predominantly formed under both investigated treatments.

Relationships between regulated DBPs and emerging DBPs of health concern in U.S. drinking water

A survey was conducted at eight U.S. drinking water plants, that spanned a wide range of water qualities and treatment/disinfection practices. Plants that treated heavily-wastewaterimpacted source waters had lower trihalomethane to dihaloacetonitrile ratios due to the presence of more organic nitrogen and HAN precursors. As the bromide to total organic carbon ratio increased, there was more bromine incorporation into DBPs. This has been shown in other studies for THMs and selected emerging DBPs(HANs), whereas this study examined bromine incorporation for a wider group of emerging DBPs(haloacetaldehydes, halonitromethanes). Moreover, bromine incorporation into the emerging DBPs was, in general, similar to that of the THMs. Epidemiology studies that show an association between adverse health effects and brominated THMs may be due to the formation of brominated emerging DBPs of heath concern. Plants with higher free chlorine contact times before ammonia addition to form chloramines had less iodinated DBP formation in chloraminated distribution systems, where there was more oxidation of the iodide to iodate(a sink for the iodide) by the chlorine. This has been shown in many bench-scale studies(primarily for iodinated THMs), but seldom in full-scale studies(where this study also showed the impact on total organic iodine. Collectively, the THMs, haloacetic acids, and emerging DBPs accounted for a significant portion of the TOCl, TOBr, and TOI;however, ~50% of the TOCl and TOBr is still unknown. The correlation of the sum of detected DBPs with the TOCl and TOBr suggests that they can be used as reliable surrogates.