Molecular insight of dissolved organic matter and chlorinated disinfection by-products in reclaimed water during chlorination with permanganate preoxidation.

Permanganate is a common preoxidant applied in water treatment to remove organic pollutants and to reduce the formation of disinfection by-products. However, the effect of permanganate preoxidation on the transformation of dissolved effluent organic matter (dEfOM) and on the formation of unknown chlorinated disinfection by-products (Cl-DBPs) during chlorination remains unknown at molecular level. In this work, the molecular changes of dEfOM during permanganate preoxidation and subsequent chlorination were characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Permanganate preoxidation was found to decrease the DBE (double bond equivalent) and AImod (modified aromaticity index) of the dEfOM. The identity and fate of over 400 unknown Cl-DBPs during KMnO4-chlorine treatment were investigated. Most Cl-DBPs and the precursors were found to be highly unsaturated aliphatic and phenolic compounds. The Cl-DBPs precursors with lower H/C and lower O/C were preferentially removed by permanganate preoxidation. Additionally, permanganate preoxidation decreased the number of unknown Cl-DBPs by 30% and intensity of unknown Cl-DBPs by 25%. One-chlorine-containing DBPs were the major Cl-DBPs and had more CH2 groups and higher DBEw than Cl-DBPs containing two and three chlorine atoms. 60% of the Cl-DBPs formation was attributed to substitution reactions (i.e., +Cl-H, +2Cl-2H, +3Cl-3H, +ClO-H, +Cl2O3-2H). This work provides detailed molecular level information on the efficacy of permanganate preoxidation on the control of overall Cl-DBPs formation during chlorination.

Effects of cupric ions on the formation of chlorinated disinfection byproducts from nitrophenol compounds during UV/post-chlorination.

Cupric ions (Cu2+) are ubiquitous in surface waters and can influence disinfection byproducts (DBPs) formation in water disinfection processes. This work explored the effects of Cu2+ on chlorinated DBPs (Cl-DBPs) formation from six representative nitrophenol compounds (NCs) during UV irradiation followed by a subsequent chlorination (i.e., UV/post-chlorination), and the results showed Cu2+ enhanced chlorinated halonitromethane (Cl-HNMs) formation from five NCs (besides 2-methyl-3-nitrophenol) and dichloroacetonitrile (DCAN) and trichloromethane (TCM) formation from six NCs. Nevertheless, excessive Cu2+ might reduce Cl-DBPs formation. Increasing UV fluences displayed different influences on total Cl-DBPs formation from different NCs, and increasing chlorine dosages and NCs concentrations enhanced that. Moreover, a relatively low pH (5.8) or high pH (7.8) might control the yields of total Cl-DBPs produced from different NCs. Notably, Cu2+ enhanced Cl-DBPs formation from NCs during UV/post-chlorination mainly through the catalytic effect on nitro-benzoquinone production and the conversion of Cl-DBPs from nitro-benzoquinone. Additionally, Cu2+ could increase the toxicity of total Cl-DBPs produced from five NCs besides 2-methyl-3-nitrophenol. Finally, the impacts of Cu2+ on Cl-DBPs formation and toxicity in real waters were quite different from those in simulated waters. This study is conducive to further understanding how Cu2+ affected Cl-DBPs formation and toxicity in chlorine disinfection processes and controlling Cl-DBPs formation in copper containing water.

Comparative analysis of chlorinated disinfection byproducts formation from 4-nitrophenol and 2-amino-4-nitrophenol during UV/post-chlorination.

Nitrophenol compounds (NCs) are widely distributed in water environments and regarded as important precursors of disinfection byproducts (DBPs). Herein, 4-nitrophenol and 2-amino-4-nitrophenol were selected as representative NCs to explore chlorinated DBPs (Cl-DBPs) formation during UV/post-chlorination. Dichloronitromethane (DCNM), trichloronitromethane (TCNM), dichloroacetonitrile (DCAN), and trichloromethane (TCM) were formed from 4-nitrophenol and 2-amino-4-nitrophenol during UV/post-chlorination, and the yields of individual Cl-DBPs from 2-amino-4-nitrophenol were higher than those from 4-nitrophenol. Meantime, increasing chlorine contact time, UV fluence, and free chlorine dose could enhance Cl-DBPs formation, while much higher values of the three factors might decrease the yields of Cl-DBPs. Besides, alkaline pH could decrease the yields of halonitromethane (HNMs) and DCAN but increase the yields of TCM. Also, higher concentrations of 4-nitrophenol and 2-amino-4-nitrophenol would induce more Cl-DBPs formation. Subsequently, the possible formation pathways of DCNM, TCNM, DCAN, and TCM form 4-nitrophenol and 2-amino-4-nitrophenol during UV/post-chlorination were proposed according to transformation products (TPs) and density functional theory (DFT) calculation. Notably, Cl-DBPs formed from 2-amino-4-nitrophenol presented higher toxicity than those from 4-nitrophenol. Among these generated Cl-DBPs, DCAN and TCNM posed higher cytotoxicity and genotoxicity, respectively. Furthermore, 4-nitrophenol, 2-amino-4-nitrophenol, and their TPs exhibited ecotoxicity. Finally, 4-nitrophenol and 2-amino-4-nitrophenol presented a high potential to produce DCNM, TCNM, DCAN, and TCM in actual waters during UV/post-chlorination, but the Cl-DBPs yields were markedly different from those in simulated waters. This work can help better understand Cl-DBPs formation from different NCs during UV/post-chlorination and is conducive to controlling Cl-DBPs formation.

Reaction mechanisms of chlorinated disinfection byproducts formed from nitrophenol compounds with different structures during chlor(am)ination and UV/post-chlor(am)ination.

Nitrophenol compounds (NCs) have high formation potentials of disinfection byproducts (DBPs) in water disinfection processes, however, the reaction mechanisms of DBPs formed from different NCs are not elucidated clearly. Herein, nitrobenzene, phenol, and six representative NCs were used to explore the formation mechanisms of chlorinated DBPs (Cl-DBPs) during chlor(am)ination and UV/post-chlor(am)ination. Consequently, the coexistence of nitro and hydroxy groups in NCs facilitated the electrophilic substitution to produce intermediates of Cl-DBPs, and the different positions of nitro and hydroxy groups also induced different yields and formation mechanisms of Cl-DBPs during the chlorination and UV/post-chlorination processes. Besides, the amino, chlorine, and methyl groups significantly influenced the formation mechanisms of Cl-DBPs during the chlorination and UV/post-chlorination processes. Furthermore, the total Cl-DBPs yields from the six NCs followed a decreasing order of 2-chloro-3-nitrophenol, 3-nitrophenol, 2-methyl-3-nitrophenol, 2-amino-4-nitrophenol, 2-nitrophenol, and 4-nitrophenol during chlorination and UV/post-chlorination. However, the total Cl-DBPs yields from the six NCs during chloramination and UV/post-chloramination followed a quite different order, which might be caused by additional reaction mechanisms, e.g., nucleophilic substitution or addition might occur to NCs in the presence of monochloramine (NH2Cl). This work can offer deep insights into the reaction mechanisms of Cl-DBPs from NCs during the chlor(am)ination and UV/post-chlor(am)ination processes.

Efficient removal of Cl-DBPs by direct-indirect continuous hydrodechlorination reduction reaction on Ti3C2X2 surface: A theoretical calculation.

Degradation of Chlorine-containing disinfection by-products(Cl-DBPs) on surface by electrocatalytic hydrodechlorination (EHDC) is considered a promising advanced water treatment method. Cl-DBPs have ecological toxicity and health risks so that it is urgent to degrade DBPs. We designed and verified the degradation performance of the EHDC of 18 kinds of DBPs (TAAs, TANs, TALs, TNMs, TAcAms, THMs) with different substituents led by the Ti3C2X2(X = O/OH) system by the first-principles. On the surface of Ti3C2(OH)2, DBPs react with atomic hydrogen (*H) by a direct-indirect continuous reduction mechanism to eliminate the Cl atom in turn. Dissociative adsorption of DBPs on the surface of Ti3C2(OH)2 simultaneously realizes the first electron transfer step and forms H vacancy, which makes its electrocatalytic activity superior to that of Ti3C2O2. Removing the six types of DBPs only needs to add -0.1 V of applied potential. In addition, we investigated the impact of substituents and chlorination degree on the reactivity of DBPs removal. The strong electron-withdrawing group is more conducive to the dechlorination reaction. Dehalogenation is much favorable in thermodynamics as the increase in chlorination degree. This study provides important insights and efficient catalysts for the degradation of DBPs and shows the potential of MXenes in eliminating chloride in water.

Novel chlorinated disinfection byproducts from tannic acid: nontargeted identification, formation pathways, and computationally predicted toxicity.

Tannic acid is ubiquitously present in various simulated and real water sources and in wastewater. Various chlorinated disinfection byproducts (Cl-DBPs) are generated via reactions with tannic acid during disinfection with chlorine. We used high-resolution mass spectrometry in combination with our self-developed halogen extraction code to selectively identify Cl-DBPs. Our strategy enabled successful detection of 35 Cl-DBP formulas formed by chlorination of tannic acid, and we identified 26 of these structures. The structures of 17 novel Cl-DBPs are firstly reported here. The reaction pathways of these Cl-DBPs were tentatively proposed. These Cl-DBPs are likely to be generated during chlorination at various chlorine doses, from 0.0 to 10.0 mg-Cl2/L, and 14 of the 26 Cl-DBPs were detected in simulated drinking water, which implies a relatively high probability of incidence. Quantitative structure-activity relationship toxicity analyses predicted that most of these Cl-DBPs would exhibit much higher acute toxicity than the common DBPs trichloromethane and monochloroacetic acid and that some of these compounds would induce developmental toxicity and be mutagenic, which further emphasizes that these Cl-DBPs should raise concerns. This study broadens our understanding of the Cl-DBPs formed from tannic acid and should prompt wider application of our analytical strategy in environmental matrices.

Effects of chlorine dose on the composition and characteristics of chlorinated disinfection byproducts in reclaimed water.

During chlorination of reclaimed water, the dose of chlorine used can influence the formation of chlorinated disinfection by-products (Cl-DBPs). We used non-targeted screening by Orbitrap mass spectrometry to identify Cl-DBPs in samples of chlorinated reclaimed water, and found that chlorination was likely to form slightly oxidized unsaturated aliphatic compounds and polycyclic aromatic compounds. Increasing the chlorine dose increased the proportion of polycyclic aromatic Cl-DBPs containing one chlorine atom (Cl1-DBPs) and highly oxidized unsaturated aliphatic Cl-DBPs containing two chlorine atoms (Cl2-DBPs). In addition, increasing the chlorine dose first decreased and then increased the proportion of Cl1-DBPs with aromatic index values >0.5 and increased the proportion of Cl2-DBPs with aromatic index values <0.5. Increasing the chlorine dose increased double bond equivalent minus oxygen values of Cl1-DBPs and decreased the double bond equivalent minus oxygen values of Cl2-DBPs, while the nominal oxidant state of carbon decreased for Cl1-DBPs and increased for Cl2-DBPs. In considering the possible precursors of Cl-DBPs and their reaction pathways, substitution reactions occurred more readily with aliphatic compounds and addition reactions occurred more readily with aromatic precursors. When the chlorine dose is increased, more Cl2-DBPs may be formed by substitution. Overall, the chlorine dose influences Cl-DBP formation and composition and should be taken into account during water treatment.

Molecular transformation of algal organic matter during sequential ozonation-chlorination: Role of pre-ozonation and properties of chlorinated disinfection byproducts.

Formation of unknown chlorinated disinfection byproducts (Cl-DBPs) during chlorination gradually raised great concern, and pre-oxidation was considered as an efficient method to minimize Cl-DBP formation. In this study, pre-ozonation of algal organic matter was investigated, to explore its impacts on Cl-DBP formation and acute toxicity during subsequent chlorination. With fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis, the conversion of algal organic matter in chlorination with/without pre-ozonation was tracked. The results show that pre-ozonation reduced the formation of trichloromethane (TCM), yet the species and intensity of unknown Cl-DBPs were significantly increased in subsequent chlorination. Meanwhile, the solution acute toxicity was higher in chlorination with pre-ozonation than in chlorination only. Besides, molecular properties of these unknown Cl-DBPs were further explored and featured. One-chlorine-containing DBPs were unsaturated high molecular-weight compounds with more CH2 structures, while two or three-chlorine-containing DBPs were mainly oxidized or saturated compounds. Of note, large amounts of one-chlorine-containing DBPs related to polycyclic aromatics and polyphenols compositions were generated, which may contribute to the high potential toxicity. Overall, the findings of this study could provide new insights into the impacts of pre-ozonation on the formation of unknown Cl-DBPs and potential toxicity during chlorination for actual application.

Nontargeted identification of chlorinated disinfection byproducts formed from natural organic matter using Orbitrap mass spectrometry and a halogen extraction code.

Natural organic matter is a major source of precursors of hazardous chlorinated disinfection byproducts (Cl-DBPs) formed during water treatment, but the majority of Cl-DBPs are still unidentified. In this study, we used a self-written halogen extraction code to identify halogen isotopic patterns in combination with the R package MFAssignR, to identify Cl-DBPs from Orbitrap mass spectra. One hundred and eighty-nine Cl-DBPs were detected during chlorination of a Suwannee River natural organic matter solution, and the structures of 20 of these compounds are reported for the first time. Kendrick mass defect analysis and structural identification confirmed that chlorinated carboxylic acids are common and likely to form during chlorination. A toxicity prediction using quantitative structure-activity relationship models indicated that most of the chlorinated carboxylic acids may be highly toxic. Our analytical strategy can identify Cl-DBPs accurately from complex mixtures and may also be applicable to the identification of other halogenated disinfection byproducts formed during water treatment.

Combination of high resolution mass spectrometry and a halogen extraction code to identify chlorinated disinfection byproducts formed from aromatic amino acids.

Chlorination can lead to the formation of hazardous chlorinated disinfection byproducts (Cl-DBPs). We identified tyrosine (Tyr) and tryptophan (Trp) as precursors of toxic Cl-DBPs and developed a halogen extraction code to complement ultra performance liquid chromatography in tandem with high resolution mass spectrometry (UPLC-HRMS) in detecting and identifying Cl-DBPs. We detected 20 and 11 Cl-DBPs formed from chlorination of Tyr and Trp, respectively, and identified the structures of 15 Cl-DBPs. Fourteen structures were previously unreported. We also proposed the tentative formation pathways of these newly identified Cl-DBPs. Their incidence in real water sources demonstrated that these Cl-DBPs are likely to form during chlorination of reclaimed water. We computationally predicted the toxicity of these Cl-DBPs, which was relatively high, indicating that these Cl-DBPs could be hazardous and were of valid concern. Combining analytical data with the halogen extraction code can identify Cl-DBPs accurately from complex compounds. This analytical method can be used to identify Cl-DBPs of water treatment procedures in further studies.