Phototransformation of Brominated Disinfection Byproducts and Toxicity Elimination in Sunlit-Ozonated Reclaimed Water.

Ozonation is universally used during water treatment but can form hazardous brominated disinfection byproducts (Br-DBPs). While sunlight exposure is advised to reduce the risk of Br-DBPs, their phototransformation pathways remain insufficiently understood. Here, sunlight irradiation was found to reduce adsorbable organic bromine by 63%. Applying high-resolution mass spectrometry, the study investigated transformations of dissolved organic matter in sunlit-ozonated reclaimed water, revealing the number and abundance of assigned formulas decreased after irradiation. The Br-DBPs with O/C < 0.6 and MW > 400 Da were decreased or removed after irradiation, with the majority being CHOBr compounds. The peak intensity reduction ratio of CHOBr compounds correlated positively with double bound equivalent minus oxygen ratios but negatively with O/C, suggesting that photo-susceptible CHOBr compounds were highly unsaturated. Mass difference analysis revealed that the photodegradation pathways were mainly oxidation aligned with debromination. Three typical CHOBr molecular structures were resolved, and their photoproducts were proposed. Toxicity estimates indicated decreased toxicity in these photoproducts compared to their parent compounds, in line with experimentally determined values. Our proposed phototransformation pathways for Br-DBPs enhance our comprehension of their degradation and irradiation-induced toxicity reduction in reclaimed water, further illuminating their transformation under sunlight in widespread environmental scenarios.

Toxicity of Ozonated Wastewater to HepG2 Cells: Taking Full Account of Nonvolatile, Volatile, and Inorganic Byproducts.

Wastewater ozonation forms various toxic byproducts, such as aldehydes, bromate, and organic bromine. However, there is currently no clear understanding of the overall toxicity changes in ozonated wastewater because pretreatment with solid phase extraction cannot retain inorganic bromate and volatile aldehydes, yet contributions of known ozonation byproducts to toxicity are unknown. Moreover, compared with bromate, organic bromine did not receive widespread attention. This study evaluated the toxicity of ozonated wastewater by taking aldehydes, bromate, and organic bromine into consideration. In the absence of bromide, formaldehyde contributed 96-97% cytotoxicity and 92-95% genotoxicity to HepG2 cells among the detected known byproducts, while acetaldehyde, propionaldehyde, and glyoxal had little toxicity. Both formaldehyde and dibromoacetonitrile drove toxicity among the known byproducts when bromide was present. Toxicity assays in HepG2 cells showed that when secondary effluents contained no bromide, the cytotoxicity of the nonvolatile organic fraction (NVOF) was reduced by 56-70%, and genotoxicity was completely removed after ozonation. However, the formed aldehydes (volatile organic fraction, VOF) led to increased overall toxicity. In the presence of bromide, compared with the secondary effluent, ozonation increased the cytotoxicity of the NVOFBr from 3.4-4.0 mg phenol/L to 10.3-13.9 mg phenol/L, possibly due to the formation of organic bromine. In addition, considering the toxicity of VOFBr (VOF in the presence of bromide, including aldehydes, tribromomethane, etc.), the overall cytotoxicity and genotoxicity became much higher than those of the secondary effluent. Although bromate had a limited impact on cytotoxicity and genotoxicity, it caused an increase in oxidative stress in HepG2 cells. Therefore, when taking full account of nonvolatile, volatile, and inorganic fractions, ozonation generally increases the toxicity of wastewater.

Increased formation of brominated disinfection by-products and toxicities during low-H2O2-mediated ozonation of reclaimed water.

Reusing reclaimed water requires stringent disinfection but inevitably generates disinfection by-products (DBPs). H2O2/O3 treatment is an efficient and environmentally benign disinfection method. For the first time, our bioassay results elucidate that low H2O2/O3 ratio (molar) treated water increased unignorable toxicity effect compared to that of the high H2O2/O3 ratio. To clarify this finding, individual organic brominated DBPs (Br-DBPs), bromate, and adsorbable organic bromine (AOBr) were considered due to their potential risk. Organic Br-DBPs were mainly generated from ozone-induced pathways. Individual organic Br-DBPs were not the primary concern in this scenario because they are typically only produced in observable quantities at bromide concentrations exceeding 500 µg/L, and even then, they often remain below detection limits when treated with H2O2/O3. On the contrary, both bromate and AOBr were detectable at low H2O2/O3 ratios. Furthermore, bromate is produced from HOBr and bromine radicals induced by HO•. Moreover, bromate formation was promoted because of increased HO• formation, particularly at H2O2/O3 ratios <0.24. To prevent HO•-induced pathways from being dominant, higher H2O2/O3 ratios (>0.48) were required. Toxicity assays revealed that AOBr-included organic extracts of ozonated reclaimed water induced more toxic effects. The toxicity induced by the organic fraction resulted from its decreased oxidation level, which was, in turn, driven by the increased formation of bromate. Enhanced toxicity effects were observed when cells were exposed to a bromate and organic extract mixture. It indicates that both the AOBr and bromate present in low-H2O2-O3-treated reclaimed water pose potential risks, and their coexistence further elevates these risks. Increasing the H2O2/O3 ratio markedly decreased the generation of intracellular oxidative substances and oxidative damage. In conclusion, when treated with H2O2/O3, shifting from HO•-induced pathways to ozone-induced pathways by a relatively high H2O2/O3 ratio decreased the amounts of DBPs produced and controlled the toxic effects to ensure the safety of ozonated reclaimed water.

Changes in toxicity and adsorbable organic bromine concentrations in ozonated reclaimed water irradiated with sunlight.

Disinfecting reclaimed water for safe reuse can produce toxic disinfection by-products such as adsorbable organic bromine (AOBr). Irradiating stored reclaimed water with sunlight is a "green" and free method for eliminating some toxic disinfection by-products, but the effects of irradiation with sunlight on ozonated reclaimed water containing bromide are not well understood. In this study, AOBr was found at concentrations of 171-180 (µg Br)/L in ozonated reclaimed water containing bromide at a concentration of 2 (mg Br)/L and dissolved organic carbon at a concentration of ∼5 (mg C)/L. Irradiation with sunlight degraded 53-74% of the AOBr in two reclaimed water samples in 8 h, and the pseudo-first-order rate constants (k) were 0.09-0.17 h-1. The concentration of tribromomethane, a typical Br-containing disinfection by-product, was decreased by >96% by irradiation for 8 h (k = 0.42-0.47 h-1). Irradiation with sunlight decreased the toxicity of ozonated reclaimed water to Chinese hamster ovary cells. Irradiation with sunlight decreased the degree of intracellular oxidative stress and oxidative damage caused by ozonated reclaimed water. Irradiation with sunlight for 8 h decreased cytotoxicity of the ozonated reclaimed water samples by 79% and 65%. The change in AOBr concentration correlated with the change in toxicity (R2=0.69, p<0.05). The relationships between sunlight wavelength and decreases in the AOBr concentration and toxicity were assessed, and it was found that UV in sunlight was predominantly responsible for decreasing the AOBr concentration and toxicity by reclaimed water. During irradiation for 8 h, UV was responsible for 65%-66% of the decrease in the AOBr concentration and 65-79% of the decrease in reclaimed water induced cytotoxicity. Irradiation with sunlight is a promising method for degrading AOBr and detoxifying ozonated reclaimed water during storage to allow the water to be reused.

Comparative molecular transformations of dissolved organic matter induced by chlorination and ammonia/chlorine oxidation process.

The ammonia/chlorine oxidation process can greatly degrade PPCPs in water. However, its effect on molecular transformations of natural organic matter (NOM) and effluent organic matter (EfOM) are still poorly understood. In this study, molecular transformations of NOM and EfOM occurring during ammonia/chlorine were explored and compared with those occurred during chlorination, using spectroscopy and mass spectrometry. Phenolic and highly unsaturated aliphatic compounds together with aliphatic compounds were found to be predominant in both NOM and EfOM samples, all of which were significantly degraded after two processes. The ammonia/chlorine process led to greater decreases in the molecular weights of such components but lower reductions in aromaticity. Compared with chlorination, ammonia/chlorine was found to be more likely to degrade compounds while remaining fluorophores or chromophores. The CH(N)O(S) precursors were found to be similar for both processes but their products were quite different. The CH(N)O(S) precursors that only found in ammonia/chlorine had higher molecular weights and greater degrees of oxidation but lower degrees of saturation. In contrast, the unique CH(N)O(S) products that only found in ammonia/chlorine exhibited lower molecular weights and lower degrees of oxidation degrees together with higher degrees of saturation. Lower total abundance of chlorinated byproducts was found by ammonia/chlorine compared with chlorination, although the former process provided a richer diversity. In all water samples, chlorinated byproducts were mainly generated by substitution reactions during ammonia/chlorine and chlorination. Overall, the findings of this study could provide new insights into the transformations of NOM and EfOM induced by ammonia/chlorine and chlorination.

Vacuum ultraviolet irradiation for reduction of the toxicity of wastewater towards mammalian cells: Removal mechanism, changes in organic compounds, and toxicity alternatives.

Vacuum ultraviolet (VUV, 185 + 254 nm) irradiation performs well for oxidation of model pollutants. However, oxidation of pollutants does not necessarily lead to a reduction in toxicity. Currently, a comprehensive understanding of the effect of VUV irradiation on the toxicity of real wastewater is still lacking. In this study, the influence of VUV irradiation on the toxicity of secondary effluents to Chinese hamster ovary (CHO) cells was investigated. The induction units of endogenous reactive oxygen species (ROS) and 8-hydroxyguanosine (8-OHdG) in cells continuously decreased with prolonged irradiation time. After 36 min of irradiation, the cytotoxicity and the genotoxicity of the secondary effluents were reduced by 57%-63% and 56%-61%, respectively. The UV (254 nm), •OH, and other substances generated during the VUV irradiation directly drive toxicity changes of wastewater. The contribution of •OH generated during VUV irradiation to the reductions in cytotoxicity and genotoxicity of the secondary effluents reached 72%-78% and 77%-84%, respectively. Hydroxyl radicals generated during VUV irradiation played an important role in the detoxification. The relative signal intensity of dissolved organic carbon (DOC) > 500 Da was partially removed, whereas that of DOC < 500 Da was small changed. Since the content of DOC > 500 Da in the samples was much lower than that of DOC < 500 Da, the removal of total DOC was only 15.8%-20.0% after 36 min of irradiation. The UV254 values and the fluorescence intensity values for different molecular weights (MWs) were all reduced effectively by VUV irradiation. Electron-rich organic compounds of all MWs were all sensitive to VUV irradiation. There were mono-linear relationships between changes in chemical indexes and changes in cytotoxicity or genotoxicity. The total fluorescence intensity (Ex: 220-420 nm, Em: 280-560 nm) was identified as the best indicator of the reduction in toxicity.