Molecular-level transformations of dissolved black carbon in UV-based advanced oxidation processes.

Dissolved black carbon (DBC) released from biochar, is an essential group in the dissolved organic matter (DOM) pool and is widely distributed in aquatic environments. In various advanced oxidation processes (AOPs), DBC exhibits enhanced free radical scavenging compared to typical DOM, attributed to its smaller molecular weight and more compacted aromatic structure; however, the molecular-level transformations of DBC in different AOPs, such as UV/H2O2, UV/PDS, and UV/Chlorine, remain unclear. This study employed a DBC derived from wheat biochar for experimentation. Characterization involved ultraviolet-visible (UV-Vis) spectroscopy and fluorescence excitation-emission-matrix (EEM) spectroscopy, revealing the transformation of DBC through diminished SUVA254 values and reduced intensity of three-dimensional fluorescence peaks. Further insights into the transformation were gained through Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). After each UV-AOP treatment, a conspicuous augmentation in the oxygen content of DBC was observed. The detailed oxygenation processes were elucidated through mass difference analysis, based on 23 types of typical reactions. Results indicated that oxygenation reactions were most frequently detected in all three UV-AOP treatments. Specifically, the hydroxylation (+O) predominated in UV/H2O2, while the di-hydroxylation (+2O) prevailed in UV/PDS. UV/Chlorine treatments commonly exhibited tri-hydroxylation (+3O), with the identification of 1194 Cl-BPs of unknown structures. This study contributes to a comprehensive understanding of the molecular transformations of DBC induced by various free radicals in different UV-AOP processes, leading to a better understanding of the different fates of DBC in UV-AOP processes. In addition, the identification of DBC as a precursor of by-products will also contribute to the understanding of how to inhibit the generation of by-products.

Unveiling the activity difference cause and ring-opening reaction routes of typical radicals induced degradation of toluene.

This study employs five UV-AOPs (PMS, PDS, H2O2, NaClO and NaClO2) to produce radicals (•OH, SO4•-, ClO•, O2•- and 1O2) and further comparatively studies their activity sequence and activity difference cause in toluene degradation. The toluene mineralization efficiency as a descending order is 73 % (UV-PMS) > 71 % (UV-PDS) > 70 % (acidified-UV-NaClO) > 55 % (UV-H2O2) > 36 % (UV-NaClO) > 35 % (UV-NaClO2); that of conversion efficiency is 99 % (acidified-UV-NaClO) > 95 % (UV-PMS) > 90 % (UV-PDS) > 74 % (UV-H2O2) > 44 % (UV-NaClO) > 41 % (UV-NaClO2). Acidic pretreatment significantly boosts the reactivity of UV-NaClO. ESR combined with radical quenching tests reveals the radicals' generation and evolution, and their contribution rates to toluene conversion, i.e. ClO• > SO4•- > O2•- > 1O2 > â€¢OH. Theoretical calculations further unveil the ring-opening reaction routes and the nature of the activity difference of different radicals. The minimum energy required for ring-opening reaction is 116.77, 150.63, 168.29 and 191.92 kJ/mol with respect to ClO•, SO4•-, 1O2 and •OH, and finding that the ClO•-HO• pair is the best for toluene mineralization. The difficulty for eliminating typical VOCs by using UV-AOPs method is determined as toluene > chlorobenzene > benzene > ethyl acetate.

New insights into the transformation of effluent organic matter during Fe(II)-assisted advanced oxidation processes: Parallel factor analysis coupled with self-organizing maps.

The negative effects of effluent organic matter (EfOM) on receiving aquatic environments and advanced treatment facilities pose significant concerns. However, the effective removal of EfOM is challenging due to its chemically complex nature and its refractory characteristics. In this study, two Fe(II)-assisted oxidation processes including UV/Fe(II)/H2O2 and UV/Fe(II)/persulfate (UV/Fe(II)/PS) were investigated to promote EfOM reduction. Fe(II) was essential for promoting EfOM degradation. The mineralization rate of EfOM increased from 7 to 29% with 2 mM Fe(II) addition in the UV/H2O2 process and to 23% with 0.8 mM Fe(II) addition in the UV/PS process. A preliminary experiment was conducted to obtain the optimal molar ratio of oxidant to Fe(II) for practical applications based on different indicators. The form of Fe(III) prevalent at different pH values strongly affected Fe(II)/Fe(III) cycling, thus determining the progress of EfOM degradation. A machine learning approach consisting of parallel factor analysis coupled with self-organizing maps (PARAFAC-SOM) was employed with fluorescence spectra to visualize the degradation behavior of EfOM in the different reaction systems. Four components (i.e., two humic-like substances, one fulvic acid, and one tryptophan-like substance) were eventually identified, and their reductions reached more than 62% during the Fe(II)-assisted oxidation processes. The degradation orders for each component in the different oxidation processes were initially evaluated by SOM analysis with Fmax percentage data. The degradation behavior of EfOM in the UV/Fe(II)/H2O2 and UV/Fe(II)/PS systems exhibited different trends based on the best matching unit map and component planes. The humic-like component was more refractory than the other three components in both oxidation processes. The microbial humic-like and high-molecular-weight fulvic acid substances showed higher reactivity with SO·4- than with ·OH, while the tryptophan-like substance was more reactive in the UV/Fe(II)/H2O2 system than in the UV/Fe(II)/PS system. The outcomes of this study provide new insights into the degradation behavior of EfOM, promoting the development of advanced wastewater treatments.

Ultraviolet-coupled advanced oxidation processes for anti-COVID-19 drugs treatment: Degradation mechanisms, transformation products and toxicity evolution.

Remdesivir (RDV), dexamethasone (DEX) and hydroxychloroquine (HCQ) were widely used in the treatment of COVID-19 pneumonia, possibly causing environmental risks and drug-resistance viruses. This study elucidated the degradation mechanisms and potential toxicity risks of the three anti-COVID-19 drugs by UV and ultraviolet-coupled advanced oxidation processes (UV/AOPs). All the drugs could be degraded by more than 98% within 3 min under the following optimal conditions: pH of 5.0 and drug-to-oxidant (H2O2) molar ratio of 1:200. Combined with density functional theory (DFT) analysis and high-performance liquid chromatography quadrupole time-of-flight mass spectrometry (HPLC-QTOF-MS), twenty-four transformation products (TPs) were detected and the main degradation pathways were investigated. Based on bacterial luminescence inhibition test and the peak-area evolution of TPs, RDV and HCQ showed an obvious toxicity-increase region when TPs were generated in large quantities, while the toxicity of DEX continued to decline during degradation processes. By QSAR predictions, the main contributors to the toxicity evolution during the UV/AOPs were predicted. Halogen-containing TPs showed significantly higher toxicity than other TPs, and thus the chlorine-containing structure in HCQ presented the potential toxicity. Appropriate reaction parameters and adequate reaction time for the UV/AOPs could eliminate the toxicity of TPs and ensure environmental safety. This study could play a positive role in the treatment of anti-COVID-19 drugs and their environmental hazard assessment.

Control for chlorine resistant spore forming bacteria by the coupling of pre-oxidation and coagulation sedimentation, and UV-AOPs enhanced inactivation in drinking water treatment.

Spore forming bacteria (SFB) are strongly chlorine resistant. Their presence in drinking water may cause diseases and pose threat to public health. Three SFB strains, i.e. Bacillus alvei, Bacillus cereus, and Lysinibacillus fusiformis, were isolated and identified from the finished water of a drinking water treatment plant where bacteria colonies occasionally reached the limit value. Due to their chlorine resistance, a SFB control strategy coupling pre-oxidation, coagulation sedimentation, and UV-AOPs inactivation in water treatment process was studied in lab scale. Five minutes pre-oxidation treatment by applying Cl2 and ClO2 induced remarkable spore transformation. Longer pre-oxidation exposure time didn't have apparent improvement. Cl2 and ClO2 dosages of 0.9 mg/L and 0.5 mg/L were suggested, respectively. The formed spores can be efficiently removed by the following coagulation sedimentation treatment. At a suggested dosage combination of 20 mg/L PAC and 0.08 mg/L PAM, spore removal efficiency reached about 3.15-lg. Comparing to applying sole UV irradiation, enhanced UV inactivation by adding 0.1 mM H2O2, or Cl2, or peroxymonosulfate (PMS) substantially improved the inactivation of the most chlorine resistant SFB strain, Lysinibacillus fusiformis. UV-AOPs stably achieved 2-lg inactivation rate at UV dosage of 40 mJ/cm2. UV/H2O2, UV/Cl2 and UV/PMS inactivation kinetically enhanced 1.20 times, 1.36 times and 1.91 times over sole UV irradiation. Intracellular DNA and ATP leakages were detected, and remarkable damages of Lysinibacillus fusiformis cells' surface and ultrastructure were observed. These findings evidenced cell wall and cell membrane destructions, guaranteeing substantial SFB cells inactivation. This study was carried out based on three SFB strains isolated from a finished water, and common engineering practical operations. By providing engineeringly relevant references, the outcomes obtained would be helpful for dealing with SFB outbreak risk in drinking water treatment.

Degradation of 2,6-dichloro-1,4-benzoquinone by UV/H2O2/O3 treatment: Effectiveness, water matrix effects, and degradation mechanism.

2,6-dichloro-1,4-benzoquinone (DCBQ), a typical representative of Halobenzoquinones, is an emerging aromatic disinfection by-product (DBP) with high toxicity and carcinogenicity, generated commonly through the chlorination in the drinking water disinfection process while there is still a lack of research on its removal. In this study, the effects of ultraviolet-based advanced oxidation processes (UV-AOPs) on the degradation of DCBQ were evaluated. The results showed that UV-AOPs are effective in degrading DCBQ. The removal of DCBQ by UV/H2O2/O3 was more significant than by UV/H2O2 or UV/O3, achieving a 96.7% removal rate at both the O3 and H2O2 doses of 1 mg/L. The results also indicated the alkaline and weakly acidic environments could facilitate the degradation of DCBQ, inorganic anions could inhibit DCBQ degradation and the degree of inhibition increased as the matrix concentration increased. The degradation of DCBQ was inhibited more by the CO32- than the other matrix components, such as Cl- and NO3-. It was shown by the density functional theory simulations and the ultrahigh-performance liquid chromatography (UPLC) - Orbitrap mass spectra that the electrons in DCBQ are mainly on the chlorine atom connected to the carboatomic ring and that OH• can attack the chlorine atom to cause de-chlorination. The DCBQ degradation pathway may involve the oxidation of DCBQ to 3-hydroxy-2,6-DCBQ (HO-DCBQ) and 3,5-dichloro-1,2,4-pyrogallol, the further degradation of intermediate products by OH• to dechlorinated forms of HO-DCBQ and DCBQ.

Effect of bromide on molecular transformation of dissolved effluent organic matter during ozonation, UV/H2O2, UV/persulfate, and UV/chlorine treatments.

Ozonation and ultraviolet-based advanced oxidation processes (UV-AOPs) play important roles in advanced treatment of municipal wastewater for water reuse. Bromide is widely present in wastewater at different concentration levels (ranging from µg/L to mg/L). However, the effect of bromide on molecular transformation of dissolved effluent organic matter (dEfOM) in real wastewater during ozonation and UV-AOPs treatments still remains unclear. Herein, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) was utilized to characterize the overall molecular transformation of dEfOM and the formation of unknown halogenated byproducts (X-BPs) in ozonation, UV/H2O2, UV/persulfate (UV/PS), and UV/chlorine (UV/Cl) processes in the presence of additional bromide. Compared with the same oxidation processes without additional bromide, the degree of dEfOM oxygenation had some extent decrement with the effect of bromide. A slightly increment of the number of unknown brominated byproducts (Br-BPs) was observed during ozonation, UV/H2O2, and UV/PS treatments in the presence of additional bromide, and the largest increment of these compounds was found in UV/Cl process. A total of 82 chlorinated byproducts (Cl-BPs) and 183 Br-BPs were detected in all oxidation processes with the effect of bromide, and the number of Br-BPs was significantly higher than that of Cl-BPs. Based on mass difference analysis, 69 pairs of possible precursors/Br-BPs were identified. In addition, the additional bromide did not remarkably increase the concentrations of trihalomethanes (THMs) and haloacetic acids (HAAs) in ozonation, UV/H2O2, and UV/PS treatments, while the production of THMs and HAAs significantly decreased by 68.06% and 54.55%, respectively, during UV/Cl treatment. The calculated cytotoxicity increased to some extent for each treatment, especially for UV/Cl treatment, and the compound with largest contribution to cytotoxicity was monobromoacetic acid. This study provides new insights into the formation and transformation of X-BPs during advanced treatment of real wastewater with the effect of bromide.

The fate and transformation of iodine species in UV irradiation and UV-based advanced oxidation processes.

Iodinated disinfection byproducts (I-DBPs) formed in water treatment are of emerging concern due to their high toxicity and the tase-and-odor problems associated with iodinated trihalomethanes (I-THMs). Iodoacetic acid and dichloroiodomethane are currently regulated in Shenzhen, China and the Ministry of Health of the People's Republic of China has also been considering regulating I-DBPs. Iodide (I-), organoiodine compounds (e.g., iodinated X-ray contrast media [ICM]), and iodate (IO3-) are the three common iodine sources in aquatic environment that lead to I-DBP formation. While UV irradiation effectively inactivate a wide range of microorganisms in water, it induces the transformation of these iodine sources, enabling the formation of I-DBPs. This review focuses on the fate and transformation of these iodine sources in UV-based water treatment (i.e., UV irradiation and UV-based advanced oxidation processes [UV-AOPs]) and the formation of I-DBPs in post-disinfection. I- released in UV-based treatments of ICM and can be oxidized in subsequent disinfection to hypoiodous acid (HOI), which reacts with natural organic matter (NOM) to produce I-DBPs. Both UV and UV-AOPs are not able to fully mineralize ICM and completely oxidize the released I- to (except UV/O3). Results reveal that UV and UV-AOPs are adequate for I-DBP degradation but require high UV doses. While the ideal I-DBP mitigation strategy awaits to be developed, understanding their sources and formation pathways aids in informed selections of water treatment processes, empowers water suppliers to meet drinking water standards, and minimizes consumers' exposure to I-DBPs.

Unravelling molecular transformation of dissolved effluent organic matter in UV/H2O2, UV/persulfate, and UV/chlorine processes based on FT-ICR-MS analysis.

Ultraviolet-based advanced oxidation processes (UV-AOPs) are very promising in advanced treatment of municipal secondary effluents. However, the transformation of dissolved effluent organic matter (dEfOM) in advanced treatment of real wastewater, particularly at molecular level, remains unclear. In this study, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) coupled with multiple statistical analysis were performed to better understand the transformation of dEfOM in UV/H2O2, UV/persulfate (UV/PS), and UV/chlorine treatments. An obvious increase in oxygen content of dEfOM was observed after every UV-AOPs treatment, and the detailed oxygenation processes were further uncovered by mass difference analysis based on 24 types of typical reactions. Generally, UV/H2O2 process was subjected to the most oxygenation reactions with the typical tri-hydroxylation one (+3O), whereas di-hydroxylation reaction (+H2O2) was dominant in UV/PS and UV/chlorine processes. Additionally, the three UV-AOPs shared the majority of precursors, and more proportions of unique products were identified for each process. The precursors with lower H/C and higher aromaticity were readily degraded by UV/chlorine over UV/H2O2 and UV/PS, with the products featuring lower molecular weight. Moreover, dEfOM of high aromaticity tended to produce chlorinated byproducts through addition reactions in chlorination and UV/chlorine processes. Among these UV-AOPs, the highest reduction of both acute toxicity and specific UV absorbance at 254 nm (SUVA254) was observed for UV/chlorine, implying the potential for UV/chlorine process in advanced treatment of wastewater. In addition, acute toxicity was highly correlated with SUVA254 and CHOS compounds. This study is believed to help better understand the different fates of dEfOM in real wastewater during UV-AOPs treatment.