Changes in the components and biotoxicity of dissolved organic matter in a municipal wastewater reclamation reverse osmosis system

<p>The characteristics of dissolved organic matter (DOM) and the biotoxicity of these components were investigated in a municipal wastewater reclamation reverse osmosis (mWRRO) system with a microfiltration (MF) pretreatment unit. The MF pretreatment step had little effect on the levels of dissolved organic carbon (DOC) in the secondary effluent, but the addition of chlorine before MF promoted the formation of organics with anti-estrogenic activity. The distribution of excitation emission matrix (EEM) fluorescence constituents exhibited obvious discrepancies between the secondary effluent and the reverse osmosis (RO) concentrate. Using size exclusion chromatography, DOM with low molecular weights of approximately 1.2 and 0.98 kDa was newly formed during the mWRRO. The normalized genotoxicity and anti-estrogenic activity of the RO concentrate were 32.1 ± 10.2 μg4-NQO/mgDOC and 0.36 ± 0.08 mgTAM/mgDOC, respectively, and these values were clearly higher than those of the secondary effluent and MF permeate. The florescence volume of Regions I and II in the EEM spectrum could be suggested as a surrogate for assessing the genotoxicity and anti-estrogenic activity of the RO concentrate.</p

Dichloroacetonitrile and Dichloroacetamide Can Form Independently during Chlorination and Chloramination of Drinking Waters, Model Organic Matters, and Wastewater Effluents

The increasing usage of organic nitrogen-rich wastewater- or algal-impacted waters, and chloramines for secondary disinfection, raises concerns regarding the formation of haloacetonitriles, haloacetamides and other nitrogenous disinfection byproducts (N-DBPs). Previous research obtained contradictory results regarding the relative importance of chlorination or chloramination for promoting these byproducts, but applied chlorine and chloramines at different doses and exposure periods. Additionally, mechanistic work, mostly using model precursors, suggested that haloacetonitrile and haloacetamide formation should be correlated because hydrolysis of haloacetonitriles forms haloacetamides. In this work, the formation of dichloroacetonitrile (DCAN) and dichloroacetamide (DCAcAm) were compared across a range of chlorine and chloramine exposures for drinking waters, wastewater effluents, algal extracellular polymeric substances (EPS), NOM isolates and model precursors. While chlorination favored formation of DCAN over DCAcAm, chloramination nearly always formed more DCAcAm than DCAN, suggesting the existence of haloacetamide formation pathways that are independent of the hydrolysis of haloacetonitriles. Experiments with asparagine as a model precursor also suggested DCAcAm formation without a DCAN intermediate. Application of ¹⁵N-labeled monochloramine indicated initial rapid formation of both DCAN and DCAcAm by pathways where the nitrogen originated from organic nitrogen precursors. However, slower formation occurred by pathways involving chloramine incorporation into organic precursors. While wastewater effluents and algal EPS tended to be more potent precursors for DCAN during chlorination, humic materials were more potent precursors for DCAcAm during chlorination and for both DCAN and DCAcAm during chloramination. These results suggest that, rather than considering haloacetamides as haloacetonitrile hydrolysis products, they should be treated as a separate N-DBP class associated with chloramination. While use of impaired waters may promote DCAN formation during chlorination, use of chloramines may promote haloacetamide formation for a wider array of waters

Electron Redistribution in Iridium–Iron Dual-Metal-Atom Active Sites Enables Synergistic Enhancement for H₂O₂ Decomposition

Developing efficient heterogeneous H2O2 decomposition catalysts under neutral conditions is of great importance in many fields such as clinical therapy, sewage treatment, and semiconductor manufacturing but still suffers from low intrinsic activity and ambiguous mechanism understanding. Herein, we constructed activated carbon supported with an Ir–Fe dual-metal-atom active sites catalyst (IrFe-AC) by using a facile method based on a pulsed laser. The electron redistribution in Ir–Fe dual-metal-atom active sites leads to the formation of double reductive metal active sites, which can strengthen the metal–H2O2 interaction and boost the H2O2 decomposition performance of Ir–Fe dual-metal-atom active sites. Ir–Fe dual-metal-atom active sites show a high second-order reaction rate constant of 3.53 × 106 M–1·min–1, which is ∼106 times higher than that of Fe3O4. IrFe-AC is effective in removing excess intracellular reactive oxygen species, protecting DNA, and reducing inflammation under oxidative stress, indicating its therapeutic potential against oxidative stress-related diseases. This study could advance the mechanism understanding of H2O2 decomposition by heterogeneous catalysts and provide guidance for the rational design of high-performance catalysts for H2O2 decomposition

Toxic Impact of Bromide and Iodide on Drinking Water Disinfected with Chlorine or Chloramines

Disinfectants inactivate pathogens in source water; however, they also react with organic matter and bromide/iodide to form disinfection byproducts (DBPs). Although only a few DBP classes have been systematically analyzed for toxicity, iodinated and brominated DBPs tend to be the most toxic. The objectives of this research were (1) to determine if monochloramine (NH₂Cl) disinfection generated drinking water with less toxicity than water disinfected with free chlorine (HOCl) and (2) to determine the impact of added bromide and iodide in conjunction with HOCl or NH₂Cl disinfection on mammalian cell cytotoxicity and genomic DNA damage induction. Water disinfected with chlorine was less cytotoxic but more genotoxic than water disinfected with chloramine. For both disinfectants, the addition of Br^– and I^– increased cytotoxicity and genotoxicity with a greater response observed with NH₂Cl disinfection. Both cytotoxicity and genotoxicity were highly correlated with TOBr and TOI. However, toxicity was weakly and inversely correlated with TOCl. Thus, the forcing agents for cytotoxicity and genotoxicity were the generation of brominated and iodinated DBPs rather than the formation of chlorinated DBPs. Disinfection practices need careful consideration especially when using source waters containing elevated bromide and iodide