Unveiling the role of artificial intelligence in tetracycline antibiotics removal using UV/sulfite/phenol advanced reduction process.

UV/sulfite-based advanced reduction processes (ARP) have attracted increasing attention due to their high capability for removing a wide range of pollutants. Therefore, developing UV/sulfite ARP systems with assisted Artificial Intelligence (AI) models is considered an efficient strategy for sustainable pollutant removal. The present study delves into modeling and optimizing photodegradation of tetracycline (TC) antibiotics under UV/sulfite/рhenol reԁuсtion рroсess (UV/SPAP) using integrаteԁ Artifiсiаl Neurаl Networks (ANN), Suррort Veсtor Regression (SVR), аnԁ Genetiс Algorithm (GA). The сonсentrаtions of рhenol (X1) аnԁ sulfite (X2), рH (X3), reасtion time (X4), аnԁ TC сonсentrаtion (X5) in our exрerimentаl setuр were varied, аnԁ use the generаteԁ ԁаtа to trаin AI moԁels. The findings revealed that the AI-optimized performance is very effective in predicting and optimizing the removal of TC, thereby providing a sustainable water treatment approach. In general, SVR performed better based on scaling coefficients and ANN using different criteria indicated that X4 and X5 parameters were statistically significant. Oрtimаl rаnges for X1, X2, X3, X4, аnԁ X5 аre ԁetermineԁ to be 6.34, 3, 8.45, 80.13, аnԁ 1, resрeсtively. This аррroасh highlights the imрortаnсe of integrаting AI аnԁ ARP for sustаinаble environmentаl mаnаgement.

Dataset on the decolorization of Naphthol Green B using a UV/sulfite system: Optimization by response surface methodology.

Naphthol Green B (NGB) is a synthetic azo dye widely used in various industries, including textiles and leathers. NGB poses significant environmental and ecological concerns when released into natural water systems. This paper investigates the decolorization of NGB using UV/sulfite system. The % decolorization of NGB was optimized using 32 Full Factorial Design (FFD), and the ANOVA results show that the model has a good fit for the data (R2 = 99.54 %, R2 (adj) = 98.76 %) and the significant factors contributing to the % decolorization are A, B, A2, and B2 where A = mM sulfite and B = pH. The model predicted ≥100 % decolorization with the optimum conditions 12 mM sulfite and pH 10. An actual experiment was conducted to verify the response, resulting in 96.2 % decolorization which is in good agreement with the model.

Sorption/desorption and degradation of long- and short-chain PFAS by anion exchange resin and UV/sulfite system.

A combined sorption/desorption and UV/sulfite degradation process was investigated for achieving efficient elimination of PFAS from water. Two gel-type resins, Purolite A532E and A600, and one macroporous resin, Purolite A860, were firstly tested for the sorption of individual PFPrA, PFHxA, PFOA, PFOS, and GenX at different concentrations. Sorption data and density functional theory (DFT) calculations revealed that electrostatic interactions predominated for short-chain PFAS sorption and hydrophobic interactions played a more significant role for long-chain PFAS than for short-chain PFAS. A600 and A860 were selected for desorption tests with 0.025% NaOH, 5% NaCl, and 5% NH4Cl solution with or without 20% ethanol (EtOH) due to their high sorption capacity for all target PFAS. The mixture of 5% NH4Cl and 20% EtOH as the desorption solution typically showed the highest desorption efficiency. PFOS was the most resistant for desorption but its desorption could be enhanced by stronger mixing conditions (in 5% NaCl + 20% EtOH). Direct degradation of studied PFAS in the desorption solution (0.025% NaOH, 5% NaCl, and 5% NH4Cl) by UV/sulfite achieved 97.6-100% degradation and 46.6-86.1% defluorination. EtOH hindered degradation and thus should be separated from the water before UV/sulfite degradation.

Positive profile of natural small molecule organic matters on emerging antivirus pharmaceutical elimination in advance reduction process: A deep dive into the photosensitive mechanism of triplet excited state compounds.

Natural small molecular organic matter (NSOM), ubiquitous in natural waters and distinct from humic acid or fulvic acid, is a special type of dissolved organic matter (DOM) which is characterized as strong photosensitivity and simple molecular structure. However, little study had been directed on the role of NSOM in eliminating emerging contaminants in advanced reduction process (ARP). This study took three small molecular isomeric organic acids (p-hydroxybenzoic acid, pHBA; salicylic acid, SA; m-hydroxybenzoic acid, mHBA) as the representative substances of NSOM to explore these mechanisms on promoting Ribavirin (RBV, an anti COVID-19 medicine) degradation in ultraviolet activated sulfite (UV/Sulfite) process. The results demonstrated that the observed degradation rate constant of RBV (kobs-RBV) was 7.56 × 10-6 s-1 in UV/Sulfite process, indicating that hydrated electron (eaq-) from UV/Sulfite process could not effectively degrade RBV, while it increased by 178 and 38 times when pHBA and SA were introduced into UV/Sulfite process respectively, suggesting that pHBA and SA strongly promoted RBV degradation while mHBA had no promotion on RBV abatement in UV/Sulfite process. Transient absorption spectra and reactive intermediates scavenging experiment indicated that the triplet excited state pHBA and SA (3pHBA* and 3SA*) contributed to the degradation of RBV through non-radical process. Notably, eaq- played the role of key initiator in transforming pHBA and SA into their triplet states. The difference of kobs-RBV in UV/Sulfite/pHBA and UV/Sulfite/SA process was attributed to different generation pathways of 3pHBA* and 3SA* (high molar absorptivity at the wavelength of 254 nm and photosensitive cycle, respectively) and their second order rate constants towards RBV (kRBV-3pHBA* = 8.60 × 108 M-1 s-1 and kRBV-3SA* = 6.81 × 107 M-1 s-1). mHBA could not degrade RBV for its lack of intramolecular hydrogen bond and low molar absorptivity at 254 nm to abundantly transform into its triplet state. kobs-RBV increased as pH increased from 5.0 to 11.0 in UV/Sulfite/SA process, due to the high yield of eaq- in alkaline condition which promoted the generation of 3SA* and the stable of the absorbance of SA at 254 nm. By contrast, kobs-RBV underwent a process of first increasing and then decreasing in UV/Sulfite/pHBA process as the increase of pH, and its highest value achieved in a neutral condition. This lied in the exposure of eaq- increased as the increase of pH which promoted the generation of 3pHBA*, while the molar absorptivity of pHBA at 254 nm decreased as the increase of pH in an alkaline condition which inhibited the yield of 3pHBA*. The RBV degradation pathways and products toxicity assessment indicated that UV/Sulfite/pHBA had better detoxification performance on RBV than UV/Sulfite/SA process. This study disclosed a novel mechanism of emerging contaminants abatement through non-radical process in NSOM mediated ARP, and provide a wide insight into positive profile of DOM in water treatment process, instead of only taking DOM as a quencher of reactive intermediates.

Kinetic Model for Predicting Perfluoroalkyl Acid Degradation During UV-Sulfite Treatment.

Hydrated electron (eaq-) treatment processes show great potential in remediating recalcitrant water contaminants, including perfluoroalkyl and polyfluoroalkyl substances (PFAS). However, treatment efficacy depends upon many factors relating to source water composition, UV light source characteristics, and contaminant reactivity. Here, we provide critical insights into the complex roles of solution parameters on contaminant abatement through application of a UV-sulfite kinetic model that incorporates first-principles information on eaq- photogeneration and reactivity. The model accurately predicts decay profiles of short-chain perfluoroalkyl acids (PFAAs) during UV-sulfite treatment and facilitates quantitative interpretation of the effects of changing solution composition on PFAS degradation rates. Model results also confirm that the enhanced degradation of PFAAs observed under highly alkaline pH conditions results from changes in speciation of nontarget eaq- scavengers. Reverse application of the model to UV-sulfite data collected for longer chain PFAAs enabled estimation of bimolecular rate constants (k2, M-1 s-1), providing an alternative to laser flash photolysis (LFP) measurements that are not feasible due to the water solubility limitations of these compounds. The proposed model links the disparate means of investigating eaq- processes, namely, UV photolysis and LFP, and provides a framework to estimate UV-sulfite treatment efficacy of PFAS in diverse water sources.

Biochar and surfactant synergistically enhanced PFAS destruction in UV/sulfite system at neutral pH.

The UV/sulfite-based advanced reduction process (ARP) emerges as an effective strategy to combat per- and polyfluoroalkyl substances (PFAS) pollution in water. Yet, the UV/sulfite-ARP typically operates at highly alkaline conditions (e.g., pH > 9 or even higher) since the generated reductive radicals for PFAS degradation can be quickly sequestered by protons (H+). To overcome the associated challenges, we prototyped a biochar-surfactant-system (BSS) to synergistically enhance PFAS sorption and degradation by UV/sulfite-ARP. The degradation and defluorination efficiencies of perfluorooctanoic acid (PFOA) depended on solution pH, and concentrations of surfactant (cetyltrimethylammonium bromide; CTAB), sulfite, and biochar. At high pH (8-10), adding biochar and BSS showed no or even small inhibitory effect on PFOA degradation, since the degradation efficiencies were already high enough that cannot be differentiated. However, at acidic and neutral pH (6-7), an evident enhancement of PFOA degradation and defluorination efficiencies occurred. This is due to the synergies between biochar and CTAB that create favorable microenvironments for enhanced PFOA sorption and deeper destruction by prolonging the longevity of reductive radicals (e.g., SO3•-), which is less affected by ambient pH conditions. The performance of UV/sulfite/BSS was further optimized and used for the degradation of four PFAS. At the optimal experimental condition, the UV/sulfite/BSS system can completely degrade PFOA with >30% defluorination efficiency for up to five continuous cycles (n = 5). Overall, our BSS provides a cost-effective and sustainable technique to effectively degrade PFAS in water under environmentally relevant pH conditions. The BSS-enabled ARP technique can be easily tied into PFAS treatment train technology (e.g., advanced oxidation process) for more efficient and deeper defluorination of various PFAS in water.

Combination of adsorption/desorption and photocatalytic reduction processes for PFOA removal from water by using an aminated biosorbent and a UV/sulfite system.

Per- and polyfluoroalkyl substances (PFAS) are stable organic chemicals, which have been used globally since the 1940s and have caused PFAS contamination around the world. This study explores perfluorooctanoic acid (PFOA) enrichment and destruction by a combined method of sorption/desorption and photocatalytic reduction. A novel biosorbent (PG-PB) was developed from raw pine bark by grafting amine groups and quaternary ammonium groups onto the surface of bark particles. The results of PFOA adsorption at low concentration suggest that PG-PB has excellent removal efficiency (94.8%-99.1%, PG-PB dosage: 0.4 g/L) to PFOA in the concentration range of 10 µg/L to 2 mg/L. The PG-PB exhibited high adsorption efficiency regarding PFOA, being 456.0 mg/g at pH 3.3 and 258.0 mg/g at pH 7 with an initial concentration of 200 mg/L. The groundwater treatment reduced the total concentration of 28 PFAS from 18 000 ng/L to 9900 ng/L with 0.8 g/L of PG-PB. Desorption experiments examined 18 types of desorption solutions, and the results showed that 0.05% NaOH and a mixture of 0.05% NaOH + 20% methanol were efficient for PFOA desorption from the spent PG-PB. More than 70% (>70 mg/L in 50 mL) and 85% (>85 mg/L in 50 mL) of PFOA were recovered from the first and second desorption processes, respectively. Since high pH promotes PFOA degradation, the desorption eluents with NaOH were directly treated with a UV/sulfite system without further adjustment. The final PFOA degradation and defluorination efficiency in the desorption eluents with 0.05% NaOH + 20% methanol reached 100% and 83.1% after 24 h reaction. This study proved that the combination of adsorption/desorption and a UV/sulfite system for PFAS removal is a feasible solution for environmental remediation.

Source preventing mechanism of florfenicol resistance risk in water by VUV/UV/sulfite advanced reduction pretreatment.

To avoid the inhibition of microbial activity and the emergence of bacterial resistance, effective abiotic pretreatment methods to eliminate the antibacterial activity of target antibiotics before the biotreatment system for antibiotic-containing wastewater are necessary. In this study, the VUV/UV/sulfite system was developed as a pretreatment technique for the source elimination of florfenicol (FLO) resistance risk. Compared with the VUV/UV/persulfate and sole VUV photolysis, the VUV/UV/sulfite system had the highest decomposition rate (0.33 min‒1) and the highest defluorination (83.0%), resulting in the efficient elimination of FLO antibacterial activity with less than 2.0% mineralization, which would effectively retain the carbon sources for the sludge microorganisms in the subsequent biotreatment process. Furthermore, H• was confirmed to play a more important role in the elimination of FLO antibacterial activity by controlling the environmental conditions for the formation and transformation of reactive species and adding their scavengers. Based on the theoretical calculation and proposed photolytic intermediates, the elimination of FLO antibacterial activity was achieved by dechlorination, defluorination and removal of sulfomethyl groups. When the pretreated FLO-containing wastewater entered the biological treatment unit, the abundance of associated antibiotic resistance genes (ARGs) and the relative abundance of integrons were efficiently prevented by approximately 55.4% and 22.9%, respectively. These results demonstrated that the VUV/UV/sulfite system could be adopted as a promising pretreatment option for the source elimination of FLO resistance risk by target decomposition of its responsible structures before the subsequent biotreatment process.

Degradation of metoprolol by UV/sulfite as an advanced oxidation or reduction process: The significant role of oxygen.

The degradation of metoprolol (MTP) by the UV/sulfite with oxygen as an advanced reduction process (ARP) and that without oxygen as an advanced oxidation process (AOP) was comparatively studied herein. The degradation of MTP by both processes followed the first-order rate law with comparable reaction rate constants of 1.50×10-3sec-1 and 1.20×10-3sec-1, respectively. Scavenging experiments demonstrated that both eaq- and H• played a crucial role in MTP degradation by the UV/sulfite as an ARP, while SO4•- was the dominant oxidant in the UV/sulfite AOP. The degradation kinetics of MTP by the UV/sulfite as an ARP and AOP shared a similar pH dependence with a minimum rate obtained around pH 8. The results could be well explained by the pH impacts on the MTP speciation and sulfite species. Totally six transformation products (TPs) were identified from MTP degradation by the UV/sulfite ARP, and two additional ones were detected in the UV/sulfite AOP. The benzene ring and ether groups of MTP were proposed as the major reactive sites for both processes based on molecular orbital calculations by density functional theory (DFT). The similar degradation products of MTP by the UV/sulfite process as an ARP and AOP indicated that eaq-/H• and SO4•- might share similar reaction mechanisms, primarily including hydroxylation, dealkylation, and H abstraction. The toxicity of MTP solution treated by the UV/sulfite AOP was calculated to be higher than that in the ARP by the Ecological Structure Activity Relationships (ECOSAR) software, due to the accumulation of TPs with higher toxicity.

Revisiting UV/sulfite exposed to air: A redox process for reductive dechlorination and oxidative mineralization.

2,4-Dichlorophenol (2,4-DCP) widely exists in many industrial wastewaters and is considered a priority pollutant due to its high toxicity. In this work, we proposed a UV/sulfite process without aeration for high-efficiency dechlorination and enhanced mineralization. The UV/sulfite system significantly improved the removal of 2,4-DCP (93.33 % in 60 min) and dechlorination rate (85.13 % in 60 min) compared with UV alone and sulfite alone, and the synergistic factor was 6.59. The UV/sulfite system without aeration improved the mineralization rate (49.80 %) compared with the nitrogen aeration system. UV/sulfite was a reduction-oxidation coupled process and was more suitable for neutral and alkaline conditions. Reducing species (hydrated electrons and H•) made 2,4-DCP dechlorinate to form dechlorination products such as p-chlorophenol (4-CP), o-chlorophenol (2-CP), and phenol, which were further mineralized by oxidized species (SO4•-). UV/sulfite remained highly efficient in the presence of coexisting ions and under different water quality conditions. This process was also suitable for removing a wide range of chlorinated organic compounds. The UV/sulfite process without aeration can achieve high dechlorination and enhanced mineralization with simple operation and low cost (1.78 $·m-3 order-1), which has a broad and cost-effective application prospect in removing refractory halogenated organic pollutants.

Treatment of bromate in UV/sulfite autoxidation process enhances formation of dibromoacetonitrile during chlorination.

The integration of UV/sulfite autoxidation process (USAP, i.e., UV activation of sulfite in the presence of 5 ∼ 10 mg/L O2) into conventional water to degrade micropollutants rises extensive attention, but its impact on water quality, and especially the formation of disinfection byproducts is still unclear. Herein, the formation of dibromoacetonitrile (DBAN) from bromate (BrO3-) upon treatment with USAP followed by chlorination was evaluated, in the presence of amino acids (AAs) selected as representative organic matter in drinking water. Results revealed that hydrated electrons (eaq-) produced during USAP contribute to the reduction of BrO3- to Br-, which is then converted into HBrO/BrO- during post-chlorination. At the same time, sulfate radicals (SO4•-) and hydroxyl radicals (•OH) generated in USAP mediated AAs' conversion via α-hydrogen abstraction and NH2-hydrogen abstraction reactions to produce HN=C(CH3)‒COOH, CH3‒CH=NH, and CH3‒CN, which are released into the post-chlorination stage and therefore, enhance the bromine utilization factor (BUF) value and DBAN formation. The effects of the USAP treatment time, BrO3- concentration, AA concentration, pH, and real waters were also evaluated. Although 63.5% of BrO3- was eliminated by USAP followed by chlorination, the toxicity index (TI) was increased by 1.5-fold due to the formation of the all brominated CX3R-type nitrogenous disinfection byproducts (N-DBPs), demonstrating the potential risk of applying USAP as a treatment process in BrO3- containing waters.

Source prevention of halogenated antibiotic resistance genes proliferation: UV/sulfite advanced reduction process achieved accurate and efficient elimination of florfenicol antibacterial activity.

The production and consumption of halogenated antibiotics, such as florfenicol (FLO), remain high, accompanied by a large amount of antibiotic-containing wastewater, which would induce the potential proliferation and transmission of antibiotic resistance genes (ARGs) in conventional biological systems. This study revealed that the introduction of reductive species (mainly H) by adding sulfite during UV irradiation process accelerated the decomposition rate of FLO, increasing from 0.1379 min-1 in the single UV photolytic system to 0.3375 min-1 in the UV/sulfite system. The enhanced photodecomposition in UV/sulfite system was attributed to the improved dehalogenation performance and additional removal of sulfomethyl group at the site of the benzene ring, which were the representative structures consisting of FLO antibacterial activity. Compared with single UV photolysis, UV/sulfite advanced reduction process saved the light energy requirement by 40 % for the evolutionary suppression of floR, and its corresponding class of ARGs in subsequent biotreatment system was controlled at the level of the negative group. Compared with UV/H2O2 and UV/persulfate systems, the decomposition rate of FLO in the UV/S system was the highest and preserved the corresponding carbon source of the coexisting organic compounds for the potential utilization of microbial metabolism in subsequent biotreatment process. These results demonstrated that UV/sulfite advanced reduction process could be adopted as a promising pretreatment option for the source prevention of representative ARGs proliferation of halogenated antibiotics in subsequent biotreatment process.

Reductive removal of As(V) and As(III) from aqueous solution by the UV/sulfite process: Recovery of elemental arsenic.

The removal of arsenic (As(V) and As(III)) from contaminated water has attracted great attention. However, the generation of arsenic-containing hazardous waste by traditional methods has become an inevitable environmental problem. Herein, a UV/sulfite advanced reduction method was proposed to remove As(V) and As(III) from aqueous solution in the form of valuable elemental arsenic (As(0)), thus avoiding the generation of arsenic-containing hazardous waste. The results showed that greater than 99.9% of As(V) and As(III) were reduced to the high purity As(0) (> 99.5 wt%) with the residual arsenic concentration below 10 µg L-1. The hydrated electrons (eaq-), H• and SO3•- radicals are generated by the UV/sulfite process, of which eaq- and H• serve as reductants of As(V) and As(III) while the SO3•- radicals inhibit arsenic reduction by oxidizing arsenic. The effective quantum efficiency (Φ) for the formation of As(0) in the As(V) and As(III) removal process is approximately 0.0078 and 0.0055 mol/Einstein, respectively. The reduction of arsenic is favorable under alkaline conditions (pH > 9.0) due to the higher photolysis efficiency of SO32- than HSO3- (pKa = 7.2) and higher stability of eaq-/H• under alkaline conditions. The presence of dissolved oxygen (O2), NO2-, NO3-, CO32-, PO43- and humic acid (HA) inhibited arsenic reduction through light blocking or eaq-/H• scavenging effects while Cl-, SO42-, Ca2+ and Mg2+ had negligible effects on arsenic reduction. The proposed method can effectively remove and recover arsenic from contaminated water at a low cost, demonstrating feasibility for practical application. This study provides a novel technology for the reductive removal and recovery of arsenic from contaminated water.

Determination of total reducible organofluorine in PFAS-impacted aqueous samples based on hydrated electron defluorination.

Per- and polyfluoroalkyl substances (PFASs) is a large group of thousands of anthropogenic chemicals. Recently, measurement of total organic fluorine (TOF) to reflect the total PFASs has been recommended in limits and advisories. In this study, a total reducible organofluorine (TROF) assay is developed based on hydrated electron (eaq-) conversion of PFASs into inorganic fluorine combined with ion chromatograph, which is a common and widespread instrument. The eaq- is generated in UV/sulfite system with alkaline condition, and the concentration of TROF (CF_TROF) is the difference of fluoride concentration before and after assay. Method validation uses perfluorooctanesulfonic acid, perfluorooctanoic acid and their main alternatives, and F- recoveries are 76.6%-101%, except for perfluorobutanesulfonic acid (48.5%). Method application of TROF assay uses industrial surfactant products and fluorochemical industry-contaminated water, meanwhile, target PFAS analysis and total oxidizable precursors (TOP) assay are concurrently conducted. Concentrations of PFASs detected in target analysis and TOP assay were converted to fluorine equivalents concentrations (CF_Target and CF_TOP). ∑CF_Target and ∑CF_TOP account for 0.80%-36% of CF_TROF in industrial samples, 0.12%-54% in environmental water and 9.7%-14% in wastewater. The TROF assay can be used to initially judge whether PFASs contamination occurred near a hotspot with known sources. The CF_TROF could infer the extent of PFAS contamination in PFAS-impacted samples and estimate the fraction of uncharacterized PFAS.

Reductive degradation of perfluorooctanoic acid in complex water matrices by using the UV/sulfite process.

Hydrated electrons (e-aq,E= -2.9 V) generated by advanced reduction processes (ARPs) have been proved to be a promising approach to eliminate various per- and polyfluoroalkyl substances (PFASs) in water. In this study, the decomposition of perfluorooctanoic acid (PFOA) in a complex water matrix by e-aq generated from the UV/sulfite process was investigated. The effect of pH (9-12) and co-existing compounds (chloride, nitrate, phosphate, carbonate and humic acid) on PFOA degradation efficiency was studied. In addition, the intermediates and possible degradation pathways were analyzed by ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS). The results showed that the concentration of PFOA was below the detection limit (10 µg/L) after 1 h (conditions: C0 10 mg/L, initial pH = 10, sulfite 10 mM) while 89% defluorination was achieved after 24 h. Using a higher initial pH (pH = 12) greatly enhanced the PFOA degradation as 100% degradation and 98% defluorination were achieved after 24 h. The presence of carbonate (> 5 mM), nitrate (> 2 mM) and humic acid (> 25 mg/L) showed a significant negative effect on PFOA degradation via a UV blocking effect or quenching of hydrated electrons while the presence of chloride and phosphate had a smaller effect on PFOA degradation. Even at extremely high concentrations of chloride (1.709 M, pH = 11.25), the defluorination ratio reached 97% after 24 h of reaction time. During the process, short-chain perfluorinated carboxylic acids (PFCAs, C < 7) and hydrogen substituted compounds were detected, which implies that chain-shortening and H/F change reactions had occurred. Moreover, this confirmed the generation of sulfonated and unsaturated intermediates during the process, which disclosed valuable new mechanistic insights into PFOA degradation.

Efficient photochemical denitrification by UV/sulfite system: Mechanism and applications.

Denitrification is an effective strategy to control eutrophication caused by excessive nitrate in water. However, the comparatively low efficiency of nitrate removal and N2 selectivity remains a challenge in the denitrification process. Herein, this study proposed a novel photochemical denitrification process by introducing hydrated electron (eaq-) to reduce nitrate in UV/sulfite system. The results indicated that the optimized UV/sulfite system could effectively reduce nitrate to N2 with a nearly 100% denitrification efficiency in 90 min. eaq- was identified as the mainly reactive species to achieve rapid removal of nitrate and nitrite, and the result was verified by quenching and laser flash photolysis tests. Benefiting from the high dispersion of eaq- in water and the rapid reaction rate between eaq- and the target, the generated N2O is susceptible to be reduced, leading to a high selectivity of N2 that was confirmed by 15N-isotopic. Besides, thermodynamic results based on the density functional theory (DFT) calculations suggested that the photochemical denitrification process was exothermic process and tend to transform to N2. Significantly, UV/sulfite system applied in the nickel-plating wastewater showed high denitrification efficiency, demonstrating that the novel photochemical denitrification process is promising for practical wastewater treatment.

[Accelerated Degradation of Aqueous Recalcitrant Iodinated Contrasting Media Using a UV/SO32- Advanced Reduction Process].

Based on the formation of free radical-hydrated electrons by the activation of sulfite (SO32-), the UV/SO32- process is an advanced reduction process that can reduce pollutants. This study investigated the degradation kinetics, mechanism, influencing factors, and degradation pathways of sodium diatrizoate (DTZ), an iodinated contrasting media, during the UV/SO32- process. The degradation kinetics of DTZ were well fitted by the pseudo-first-order model, the degradation rate of which was higher than that of UV only and UV/H2 O2. The degradation rate of DTZ during the UV/SO32- process was positively correlated with the initial SO32- concentration. Weakly alkaline and alkaline conditions promoted the degradation of DTZ, while organic matter inhibited degradation during the UV/SO32- process. The degradation mechanism included direct photolysis and free radical attack, whereby free radical attack played a more important role than direct photolysis. Sulfite radicals dominated DTZ degradation efficiency, and hydrated electrons controlled the deiodination efficiency. The degradation pathways of DTZ during the UV/SO32- process included substitution, decarboxylation-hydroxylation, and amide bond cleavage.

Review on UV/sulfite process for water and wastewater treatments in the presence or absence of O2.

Based on previous reports, UV/sulfite process is generally used as an advanced reduction process (ARP) since eaq- and/or ∙H, both with strong reduction potential, could be substantially generated herein. Very recently, the combination of UV and sulfite as an advanced oxidation process (AOP) or an oxidation-reduction coupling process has attracted increasing interest due to the yield of SO4∙- and/or HO∙. Herein, the application of UV/sulfite as an ARP and AOP (or oxidation-reduction coupling process) during water and wastewater treatments is reviewed respectively. (1) In the absence of O2, UV/sulfite works as an ARP. The generation mechanism of reactive reduction species and various contaminants removal (including degradation kinetics and efficiency, decomposition mechanisms, effects of some factors, etc.) is summarized in detail and systematically. Moreover, both the application of different types of UV lights and the economic evaluation are summarized systematically. (2) In the presence of O2, UV/sulfite could be used as an AOP or oxidation-reduction coupling process. The generation mechanism of reactive oxidation species and influencing factors is also presented in detail. Moreover, two ways (including homogeneous and heterogeneous activation) used to enhance the UV/sulfite oxidation potential are summarized respectively. Moreover, several knowledge gaps and research needs for further research are proposed. Overall, this review provides an overview for in-depth understanding of UV/sulfite as an ARP or AOP (oxidation-reduction coupling process) during water and wastewater treatments.

Sulfite enhanced transformation of iopamidol by UV photolysis in the presence of oxygen: Role of oxysulfur radicals.

UV/sulfite process in the absence of oxygen was previously applied as an advanced reduction process for the removal of many halogenated organics and inorganics in water and wastewater. Here, it was found that UV/sulfite process in the presence of oxygen could act as an advanced oxidation process. Specifically, the oxysulfur radicals (including sulfate radical (SO4·-) and sulfite/peroxomonosulfate radicals (SO3·-/SO5·-)) played important roles on the degradation of iopamidol (IPM) as a typical iodinated contrast media (ICM). Furthermore, the contribution of SO4·- on IPM removal gradually increased as pH increased from 5 to 7 and that of SO3·-/SO5·- decreased. Besides, all water quality parameters (i.e., chloride (Cl-), iodide (I-) and natural organic matter (NOM)) investigated here exhibited inhibitory effect on IPM removal. Three inorganic iodine species (i.e., I-, reactive iodine species and iodate (IO3-)) were detected in UV/sulfite process in the presence of oxygen, while only I- was detected in that without oxygen. During UV/sulfite/ethanol, UV photolysis and UV/peroxydisulfate (PDS)/tert-butyl alcohol (TBA) processes, thirteen transformation products including eleven deiodinated products of IPM were identified by ultra HPLC quadrupole time of flight-mass spectrometry (UPLC-Q-TOF-MS). Besides, these products generated by direct UV photolysis, SO4·- and SO3·-/SO5·- were further distinguished. The acute toxicity assay of Vibrio fischeri indicated that transformation products by UV/sulfite under aerobic conditions were less toxic than that by direct UV photolysis.

Electrolysis-assisted UV/sulfite oxidation for water treatment with automatic adjustments of solution pH and dissolved oxygen.

Sulfite as precursor to generate sulfate radical (SO4 •-) for water treatment has gained attention. Here we report a metal-free and highly efficient electro/UV/sulfite process to produce SO4 •- for water treatment. UV/sulfite reaction induces sulfite radical (SO3 •-), which transforms into SO4 •- in the presence of oxygen generated by water electrolysis. Electro/UV/sulfite process generates a steady-state SO4 •- concentration of 0.2 to 1.1 × 10-12 M in our tests. Solution pH affects sulfite species distribution, and higher pH mediates improved yield of steady-state SO4 •- concentration. Effect of sulfite concentration exhibits a bell-shaped pattern toward SO4 •- production due to self-scavenging. The oxidation capability of electro/UV/sulfite process is manifested by removing representative micropollutants (i.e., ibuprofen, salicylic acid, and bisphenol A) and Escherichia coli model pathogen, in both synthetic and natural water matrices. This novel electro/UV/sulfite process has obvious advantages, since it bypasses metal ion catalysts, supplies reaction with electrolytically generated nascent oxygen, and overcomes the acidic pH requirement, that are challenging to traditional metal/sulfite processes. Considering the features of environmental friendliness and low cost, the proposed electro/UV/sulfite process should lead to successful applications in the future.