Comparative Evaluation of Chemical and Photolytic Denitrosation Methods for Chemiluminescence Detection of Total N-Nitrosamines in Wastewater Samples.

N-Nitrosamines form as byproducts during oxidative water treatment and occur as impurities in consumer and industrial products. To date, two methods based on chemiluminescence (CL) detection of nitric oxide liberated from N-nitrosamines via denitrosation with acidic triiodide (HI3) treatment or ultraviolet (UV) photolysis have been developed to enable the quantification of total N-nitrosamines (TONO) in environmental water samples. In this work, we configured an integrated experimental setup to compare the performance of HI3-CL and UV-CL methods with a focus on their applicability for TONO measurements in wastewater samples. With the use of a large-volume purge vessel for chemical denitrosation, the HI3-CL method achieved signal stability and detection limits comparable to those achieved by the UV-CL method which utilized a microphotochemical reactor for photolytic denitrosation. Sixty-six structurally diverse N-nitroso compounds (NOCs) yielded a range of conversion efficiencies relative to N-nitrosodimethylamine (NDMA) regardless of the conditions applied for denitrosation. On average, TONO measured in preconcentrated raw and chloraminated wastewater samples by the HI3-CL method were 2.1 ± 1.1 times those measured by the UV-CL method, pointing to potential matrix interferences as further confirmed by spike recovery tests. Overall, our comparative assessment of the HI3-CL and UV-CL methods serves as a basis for addressing methodological gaps in TONO analysis.

Stability, biological treatment and UV photolysis of 18 bisphenols under laboratory conditions.

The limited knowledge on the stability, removal, and the fate of bisphenol A analogues in the aqueous environment led us to assess the removal by hydrolysis, adsorption, biological treatment and UV photolysis of eighteen common bisphenol compounds (BPs). Hydrolysis of BPs does not occur. The main factor affecting their stability in wastewater samples is storage time, and safe storage conditions were found to be -20 °C or 4 °C for up to four weeks. The results also revealed no significant reduction in the levels of BPs standards when stored in either methanol or ultrapure water. BPE was found to be the most stable, followed by BPF isomers, BPS and BPF, while BP26DM was the least stable and BPM, BPPH, BPP, BPBP and BPFL were quickly adsorbed. For most BPs, the removal efficiency of biological treatment was >85%, and there was no difference between the suspended activated sludge and moving bed bioreactors. Different adsorption affinities of the BPs to biomass were observed and reflect the differences in their Kow. In terms of degradability, direct UV photolysis in water produced three groups of BPs: (A) highly removable (RE > 94%), (B) moderately removable (RE 50-80%) and (C) poorly removable (RE 25-45%). In nearly all cases degradation followed pseudo-first-order kinetics.

Degradation kinetics and pathways of ß-cyclocitral and ß-ionone during UV photolysis and UV/chlorination reactions.

ß-cyclocitral and ß-ionone are ones of major algal odorants produced by oxidation of the ß-carotene that exists in algae cells. These compounds degraded the quality of drinking water therefore it needed to be treated in drinking water treatment by advanced oxidation processes. In this study, UV photolysis and UV-chlorination reactions along with chlorination to remove these odorants in water were compared. Kinetics of three reactions were well fitted at pseudo-first order model. Among three reactions, UV-chlorination was the most effective due to generation of OH and Cl radicals. ß-ionone showed faster degradation compared to ß-cyclocitral due to the existence of double bond in the alkyl carbon chain. In addition, radical contributions of degradation of odorants were examined. During UV-chlorination, UV photolysis contributed around 50% of removal for two odorants. OH radical took part of 36% removal of ß-ionone and 50% removal of ß-cyclocitral. Unlike ß-ionone, ß-cyclocitral was not degraded by reactive chlorine species during UV-chlorination. Acidic pH was favorable for UV-chlorination due to different quantum yield and radical scavenging effect by chlorine species. Formation of trace amount of chloroform was observed during UV-chlorination. The methyl ketone group of ß-ionone was the main site for chloroform production. Several byproducts during UV photolysis and UV-chlorination of ß-ionone were identified by GC-MS, and these were degraded with further reaction by UV-induced isomerization, OH radical, and bond scission mechanisms. ß-cyclocitral was formed as byproducts during UV-chlorination of ß-ionone. Based on degradation byproducts, the degradation pathways of ß-ionone and ß-cyclocitral of UV photolysis and UV-chlorination were suggested based on the identified byproducts. This study showed UV-chlorination process can be applied for degrading odorants like ß-cyclocitral and ß-ionone.

Mechanistic Insight into the Degradation of Nitrosamines via Aqueous-Phase UV Photolysis or a UV-Based Advanced Oxidation Process: Quantum Mechanical Calculations.

Nitrosamines are a group of carcinogenic chemicals that are present in aquatic environments that result from byproducts of industrial processes and disinfection products. As indirect and direct potable reuse increase, the presence of trace nitrosamines presents challenges to water infrastructures that incorporate effluent from wastewater treatment. Ultraviolet (UV) photolysis or UV-based advanced oxidation processes that produce highly reactive hydroxyl radicals are promising technologies to remove nitrosamines from water. However, complex reaction mechanisms involving radicals limit our understandings of the elementary reaction pathways embedded in the overall reactions identified experimentally. In this study, we perform quantum mechanical calculations to identify the hydroxyl radical-induced initial elementary reactions with N-nitrosodimethylamine (NDMA), N-nitrosomethylethylamine, and N-nitrosomethylbutylamine. We also investigate the UV-induced NDMA degradation mechanisms. Our calculations reveal that the alkyl side chains of nitrosamine affect the reaction mechanism of hydroxyl radicals with each nitrosamine investigated in this study. Nitrosamines with one- or two-carbon alkyl chains caused the delocalization of the electron density, leading to slower subsequent degradation. Additionally, three major initial elementary reactions and the subsequent radical-involved reaction pathways are identified in the UV-induced NDMA degradation process. This study provides mechanistic insight into the elementary reaction pathways, and a future study will combine these results with the kinetic information to predict the time-dependent concentration profiles of nitrosamines and their transformation products.

Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol and its implications for the Archean atmosphere.

Sulfur-isotopic anomalies have been used to trace the evolution of oxygen in the Precambrian atmosphere and to document past volcanic eruptions. High-precision sulfur quadruple isotope measurements of sulfate aerosols extracted from a snow pit at the South Pole (1984-2001) showed the highest S-isotopic anomalies (Δ(33)S = +1.66‰ and Δ(36)S = +2‰) in a nonvolcanic (1998-1999) period, similar in magnitude to Pinatubo and Agung, the largest volcanic eruptions of the 20th century. The highest isotopic anomaly may be produced from a combination of different stratospheric sources (sulfur dioxide and carbonyl sulfide) via SOx photochemistry, including photoexcitation and photodissociation. The source of anomaly is linked to super El Niño Southern Oscillation (ENSO) (1997-1998)-induced changes in troposphere-stratosphere chemistry and dynamics. The data possess recurring negative S-isotope anomalies (Δ(36)S = -0.6 ± 0.2‰) in nonvolcanic and non-ENSO years, thus requiring a second source that may be tropospheric. The generation of nonvolcanic S-isotopic anomalies in an oxidizing atmosphere has implications for interpreting Archean sulfur deposits used to determine the redox state of the paleoatmosphere.

Efficacy of UV-C photolysis of bisphenol A on transcriptome alterations of genes in zebrafish embryos.

The purpose of this study was to investigate the efficacy of UV-C direct photolysis of bisphenol A (BPA) as a remediation method of BPA contamination. We used zebrafish embryos as a model organism to test the toxicity and residual biological activity by measuring cytochrome P4501A1 (CYP1A), aromatase B (Aro B) and heat shock proteins (HSP-70) transcript levels. The mRNA levels of CYP1A gene increased about two fold while exposure of zebrafish embryos at 72 hpf resulted in significant induction (P = 0.048) of Aro B at 100 µg/L of BPA. Exposure of zebrafish embryos at 72 hpf to increasing concentrations of BPA resulted in significant induction (P = 0.0031) of HSP-70 transcript level. UV treatment of BPA resulted in a significant reduction in toxicity by reducing mortality of zebrafish embryos. The results suggest that UV-C direct photolysis may be an effective method for remediation of BPA contamination. Further studies will be necessary for better understanding of the identity and relative activity of the UV degradation by-products.

Modeling the photocatalytic mineralization in water of commercial formulation of estrogens 17-ß estradiol (E2) and nomegestrol acetate in contraceptive pills in a solar powered compound parabolic collector.

Endocrine disruptors in water are contaminants of emerging concern due to the potential risks they pose to the environment and to the aquatic ecosystems. In this study, a solar photocatalytic treatment process in a pilot-scale compound parabolic collector (CPC) was used to remove commercial estradiol formulations (17-ß estradiol and nomegestrol acetate) from water. Photolysis alone degraded up to 50% of estradiol and removed 11% of the total organic carbon (TOC). In contrast, solar photocatalysis degraded up to 57% of estrogens and the TOC removal was 31%, with 0.6 g/L of catalyst load (TiO2 Aeroxide P-25) and 213.6 ppm of TOC as initial concentration of the commercial estradiols formulation. The adsorption of estrogens over the catalyst was insignificant and was modeled by the Langmuir isotherm. The TOC removal via photocatalysis in the photoreactor was modeled considering the reactor fluid-dynamics, the radiation field, the estrogens mass balance, and a modified Langmuir-Hinshelwood rate law, that was expressed in terms of the rate of photon adsorption. The optimum removal of the estrogens and TOC was achieved at a catalyst concentration of 0.4 g/L in 29 mm diameter tubular CPC reactors which approached the optimum catalyst concentration and optical thickness determined from the modeling of the absorption of solar radiation in the CPC, by the six-flux absorption-scattering model (SFM).

Elucidating the performance of UV-based photochemical processes for the removal of trace organic contaminants: Degradation and toxicity evaluation.

In this study, the performance of standalone ultraviolet (UV) photolysis and UV-based advanced oxidation processes (AOPs), namely, UV/hydrogen peroxide, UV/chlorine, UV/persulphate, and UV/permonosulphate, were investigated for the degradation of 31 trace organic contaminants (TrOCs). Under the tested conditions, standalone UV photolysis did not achieve effective removal of TrOCs. To improve the degradation efficiency of UV photolysis, four different oxidants were added individually to the test solution. The effect of these oxidants in the absence of UV irradiation was also explored and only chlorine showed promising degradation of some contaminants. During the chlorination of 31 investigated TrOCs, only six demonstrated greater than 50% degradation. The combined UV-based AOPs demonstrated much improved degradation (ranging from 65 to 100%) depending on TrOC-structure and oxidant concentration. The UV/hydrogen peroxide process showed similar degradation of TrOCs, irrespective of the functional groups (i.e., electron withdrawing groups, EWGs and electron donating groups, EDGs) present in their structures. Conversely, the UV/sulphate and UV/chlorine based processes achieved better degradation of the TrOCs with EDGs in their structures. TrOCs degradation improved up to 40% when oxidants concentrations were increased from 0.1 to 1 mM, and further increasing the concentration to 2 mM did not improve degradation. Toxicity evaluation using bioluminescence test (BLT assay) demonstrated that except for UV/hydrogen peroxide, all UV-based AOPs increased the toxicity of the treated effluent, indicating generation of toxic by-products. This study elucidates the performance of four different UV-based AOPs for the removal of commonly detected diverse TrOCs for the first time.

UV-induced photodegradation of emerging para-phenylenediamine quinones in aqueous environment: Kinetics, products identification and toxicity assessments.

Substituted para-phenylenediamine quinones (PPD-quinones) are a class of emerging contaminants frequently detected in the aqueous environment. One of them, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine quinone (6PPD-Q), was found to cause acute toxicities to aquatic species at extremely low environmental levels. The ubiquitousness and ecotoxicity of such pollutants underscore the importance of their transformation and elimination. In this work, we demonstrated effective removals of five PPD-quinones in aqueous environments under UV irradiation, with up to 94% of 6PPD-Q eliminated after a 40-min treatment. By applying high-resolution mass spectrometry (HRMS) non-targeted screening in combination with isotope labeling strategies, a total of 22 transformation products (TPs) were identified. Coupling with the time-based dynamic patterns, potential transformation mechanisms were identified as an •OH-induced photocatalysis reaction involving bond cleavage, hydroxylation, and oxidation. Computational toxicity assessment predicted lower aquatic toxicity of the TPs than their parent PPD-quinones. Our results in parallel evidenced an obvious reduction of PPD-quinones accompanied by the presence of their TPs in the effluent after UV disinfection in real municipal wastewater. This work builds a comprehensive understanding of the fate, transformation products, and related toxicological characteristics of emerging PPD-quinone contaminants in the aqueous environment.

Aquatic photolysis of high-risk fluorinated liquid crystal monomers: Kinetics, toxicity evaluation, and mechanisms.

Despite the frequent detection of fluorinated liquid-crystal monomers (FLCMs) in the environment, the level of understanding of their fate, toxicity, and transformation remains insufficient. Herein, we investigated the degradation kinetics and mechanism of an FLCM (4-cyano-3-fluorophenyl 4-ethylbenzoate, CEB-F) under ultraviolet (UV) photolysis in aquatic environment. Our findings demonstrated that the UV photolysis of CEB-F followed first-order kinetics. Photodegradation products were identified using liquid chromatography with mass spectrometry, and detailed reaction pathways were proposed. It is postulated that through the attack of reactive oxygen species, hydroxylation, and CO/C-F bond cleavage, CEB-F gradually degraded into small molecular compounds, releasing fluorine ions. Acute immobilization tests with Daphnia magna (D. magna) revealed significant acute toxicity of CEB-F, with LC50 values ranging from 1.023 to 0.0536 µM over 24 to 96 h, emphasizing the potential high risk of FLCMs in aquatic ecosystems if inadvertently discharged. Interestingly, we found that the toxicity of CEB-F photolysis reaction solutions was effectively reduced. Through catalase and acetylcholinesterase activities analysis along with molecular docking simulation, we proposed differences in the underlying toxicity mechanisms of CEB-F and its photolysis products to D. magna. These findings highlight the potential harmful effects of FLCMs on aquatic ecosystems and enrich our understanding of the photolysis behavior of FLCMs.

Direct UV photodegradation of nalidixic acid in aqueous solutions: A mechanistic study.

Mechanism of direct UV photolysis of nalidixic acid (NA), a model quinolone antibiotic, was revealed using a combination of steady-state photolysis coupled with high resolution LC-MS and DFT quantum-chemical calculations. Both quantum yields of photodegradation and detailed identification of final products were performed for the first time for two main forms of NA: neutral and anionic. The quantum yield of NA photodegradation is 0.024 and 0.0032 for the neutral and anionic forms in the presence of dissolved oxygen and 0.016/0.0032 in deoxygenated solutions, respectively. The main process is photoionization with the formation of a cation radical, which undergoes transformation into three different neutral radicals and further into final photoproducts. It is shown that the triplet state does not play a role in the photolysis of this compound. The main products of photolysis are the products of the loss of carboxyl, methyl and ethyl groups in the NA molecule, as well as the dehydrogenation of the ethyl group. The results obtained may be important for understanding the fate of pyridine herbicides in the processes of disinfection by UV and in natural waters under the action of sunlight.

Treatment of synthetic dye containing textile raw wastewater effluent using UV/Chlorine/Br photolysis process followed by activated carbon adsorption.

This study investigated the efficiency and feasibility of ultraviolet (UV)-assisted photolysis of synthetic dye containing textile raw wastewater effluent. For a said purpose, in-house developed UV/Chlorine/Br process was followed in the presence of activated carbon (AC) which additionally facilitate the dye adsorption. In UV/Chlorine process Cl•, Cl2•-, and HO• are generated in the solution and destroyed compounds that cannot be oxidized by the conventional oxidant. In this process, free bromine is formed and photolyzed by UV radiation and generate Br• and Br2•- that can enhance the rate of pollutant degradation. In the present study, the dye removal efficiency was contributed by dark bromide (7.18%), UV irradiation (26.8%), dark chlorination (78.67%), and UV/Chlorine/Br (87.01%), respectively. With increasing pH from 3.0 to 8.30, the dye removal efficiency was enhanced but decreased by further increasing pH values. In addition, magnetized activated carbon from pomegranate husk using dual-stage chemical activation was used for post-adsorption of the residual dye and its degradation byproducts. The adsorption of the dye residues by AC followed the second-order kinetics with the rate constant of 1.7 × 10-3. The phytotoxicity of the treated textile wastewater by UV irradiation, dark chlorination, and UV/Chlorine/Br was assessed by seed germination of Lepidium sativum seeds. The highest inhibition effect on seed germination was related to treated wastewater by UV irradiation (more than 90% inhibition) that alleviated to less than 10% when this effluent diluted to 5% v/v. The highest germination was observed when the seeds were irrigated by the effluent of the UV/Chlorine/Br process. The significant reduction in the toxicity of the treated wastewater revealed that the UV/Chlorine/Br process has a considerable potential to effectively detoxify textile wastewater. Graphical abstract.

Advanced oxidation mechanism of UV photolysis of electrochemically generated free bromine.

In recent times, some researchers have successfully demonstrated the efficacy of UV photolysis of electrochemically generate free chlorine (UV/electro-chlorine) as for an advanced oxidation process. Since bromine as well as chlorine is an element belonging to halogen, it is expected that UV photolysis of electrochemically generated free bromine (UV/electro-bromine) also shows an advanced oxidation effect. To elucidate the feasibility of UV/electro-bromine system, its advanced oxidation mechanism was investigated using radical probes of 1,4-dioxane and nitrobenzene. In contrast to the UV/electro-chlorine system, the advanced oxidation effect of UV/electro-bromine system was inhibited under acidic conditions due to the accumulation of photochemically inert Br2. The most abundant radical in UV/electro-bromine system was dibromine radical anion (Br2˙-) and the second-order reaction rate constant of Br2˙- with 1,4-dioxane was estimated to be 2.4 × 105 M-1 s-1. As a result of the abundance and the reactivity of Br2˙-, it was the main contributor to 1,4-dioxane degradation. On the other hand, nitrobenzene was mainly decomposed by direct UV photolysis because Br2˙- does not react with nitrobenzene. The contribution of hydroxyl radical (HO˙) to 1,4-dioxane degradation was much lower than that of Br2˙- because its concentration was 4-5 order of magnitude lower than that of Br2˙-. However, the HO˙ concentration elevated with a decrease in the concentration of bromide ion (Br-). Consequently, the reactivity of Br2˙- with pollutants and the Br- concentration have critical impacts on the advanced oxidation performance of UV/electro-bromine system.

Propiconazole degradation and its toxicity removal during UV/H2O2 and UV photolysis processes.

Propiconazole (PRO) is a triazole fungicide that is frequently detected in the water. In this study, we investigated the kinetics and degradation mechanism of PRO during the UV photolysis and UV/H2O2 processes. PRO was removed by the pseudo-first-order kinetics in both processes. The removal of PRO was enhanced by increasing H2O2 concentration in the UV/H2O2 process. The highest removal under neutral conditions, and lower removal of PRO were observed in acidic and alkaline pHs in the UV/H2O2 process. The presence of natural water ingredients such as Cl-, NO3-, humic acid acted as radical scavengers, but HCO3- ion acted as both radical promoter and scavenger in the UV/H2O2 process. The transformation products (TPs) of PRO during both processes were identified using LC-QTOF/MS. Four TPs ([M+H]+ = 238, 256, 306, and 324) were identified during UV photolysis, and six TPs ([M+H]+ = 238, 256, 306, 324, 356, and 358) were identified in the UV/H2O2 process. Among the identified TPs, TP with [M+H]+ values of 356 and 358 were newly identified in the UV/H2O2 process. In addition, ionic byproducts, such as Cl-, NO3-, formate (HCOO-), and acetate (CH3COO-), were newly identified, indicating that significant mineralization was achieved in the UV/H2O2 process. Based on the identified TPs and ionic byproducts, the degradation mechanisms of PRO during two processes were proposed. The major reactions in both processes were ring cleavage and cyclization, and hydroxylation by OH radicals. The Microtox test with Vibrio fischeri showed that, while the toxicity of the reaction solution increased first, then gradually decreased during UV photolysis, the UV/H2O2 process initially increased toxicity at 10 min due to the production of TPs, but toxicity was completely removed as the reaction progressed. The results obtained in this study imply that the UV/H2O2 process is an effective treatment for eliminating PRO, its TPs, and the resulting toxicity in water.

Abiotic Formation of Calcium Oxalate under UV Irradiation and Implications for Biomarker Detection on Mars.

A major objective in the exploration of Mars is to test the hypothesis that the planet has ever hosted life. Biogenic compounds, especially biominerals, are believed to serve as biomarkers in Raman-assisted remote sensing missions. However, the prerequisite for the development of these minerals as biomarkers is the uniqueness of their biogenesis. Herein, tetragonal bipyramidal weddellite, a type of calcium oxalate, is successfully achieved by UV-photolyzing pyruvic acid (PA). The as-prepared products are identified and characterized by micro-Raman spectroscopy and field emission scanning electron microscopy. Persistent mineralization of weddellite is observed with altering key experimental parameters, including pH, Ca2+ and PA concentrations. In particular, the initial concentration of PA can significantly influence the morphology of weddellite crystal. Oxalate acid is commonly of biological origin; thus calcium oxalate is considered to be a biomarker. However, our results reveal that calcium oxalate can be harvested by a UV photolysis pathway. Moreover, prebiotic sources of organics (e.g., PA, glycine, alanine, and aspartic acid) have been proven to be available through abiotic pathways. Therefore, our results may provide a new abiotic pathway of calcium oxalate formation. Considering that calcium oxalate minerals have been taken as biosignatures for the origin and early evolution of life on Earth and astrobiological investigations, its formation and accumulation by the photolysis of abiological organic compounds should be taken into account.

Direct UV photodegradation of herbicide triclopyr in aqueous solutions: A mechanistic study.

Mechanism of direct UV photolysis of pyridine herbicide triclopyr (TRI) was revealed by the combination of nanosecond laser flash photolysis, steady-state photolysis coupled with high resolution LC-MS and DFT quantum-chemical calculations. Both the detection of short-lived intermediates and the detailed identification of final products were done for the first time. The quantum yield of TRI photodegradation is about 4% at both UVC (254 nm) and UVB (308 nm) excitation. The primary stage is the heterolytic cleavage of C-Cl bond in dissociative triplet state of TRI with the formation of phenyl cation followed by a fast nucleophilic attack by a solvent molecule. The minor channel is the photohydrolysis leading to the formation of 3,5,6-trichloropyridin-2-ol. Primary photoproducts undergo secondary photolysis by the mechanism similar to initial TRI with the formation of products of acetic group elimination, sequential substitution of chlorine atoms to hydroxyl groups and, finally, oxidation and opening of the pyridine ring. Obtained results can be important for understanding the fate of pyridine herbicides in the processes of UVC disinfection and in natural waters under action of the sunlight.

Degradation of N-nitrosamines and 1,4-dioxane using vacuum ultraviolet irradiation (UV254+185 nm or UV172 nm).

Advanced oxidation processes (AOPs) play a vital role in attenuating contaminants of emerging concern (CECs) during potable water reuse. AOPs are conventionally performed by irradiating with a 254-nm low-pressure (LP) mercury-vapor (Hg) ultraviolet (UV) lamp along with chemical treatment. Compared with UV-C light treatment (200-280 nm), vacuum-UV (V-UV) light treatment (100-200 nm) is advantageous in terms of hydroxyl radical generation without the requirement for chemical treatment. This study assessed the potential of V-UV (172-nm Xe2 excimer or 185 + 254-nm LP-Hg) lamps on the destruction of two major CECs in potable water reuse, namely N-nitrosodimethylamine (NDMA) and 1,4-dioxane. Direct irradiation using UV254 nm or UV185+254 nm lamps achieved ≥94% removal of N-nitrosamines, including NDMA, at a UV dose of 900 mJ/cm2. In contrast, the Xe2 excimer lamp (UV172 nm) was less effective for N-nitrosamine removal, achieving up to 82% removal of NDMA. The removal of 1,4-dioxane by V-UV lamps at a UV dose of 900 mJ/cm2 reached 51% (UV172 nm) and 28% (UV185+254 nm), both of which results were superior to that obtained using a conventional UV254 nm lamp (10%). The addition of hydrogen peroxide during UV254 nm or UV185+254 nm irradiation was found to enhance the removal of 1,4-dioxane, while UV172 nm irradiation without hydrogen peroxide addition still exhibited greater efficiencies than those UV254 nm lamps-based AOPs. Overall, this study demonstrated that the removal of both NDMA and 1,4-dioxane can be successfully achieved using either a UV254+185 nm lamp with hydrogen peroxide or a UV172 nm Xe2 excimer lamp without hydrogen peroxide.

Activation of organic chloramine by UV photolysis: A non-negligible oxidant for micro-pollutant abatement and disinfection by-product formation.

Due to the wide-presence of organic amines in natural waters, organic chloramines are commonly formed during (pre-)chlorination. With the increasing application of UV disinfection in water treatment, both the activation mechanism of organic chloramine by UV photolysis and its subsequent impact on water quality are not clear. Using sarcosine (Sar) as an amine group-containing compound, it was found that organic chloramines (i.e., Cl-Sar) would be firstly formed during chlorination even in the presence of natural organic matter. Compared with self-decay of Cl-Sar, UV photolysis accelerated Cl-Sar decomposition and induced NCl bond cleavage. Using metoprolol (MTP) as a model micro-pollutant, UV-activated Cl-Sar (UV/Cl-Sar) can accelerate micro-pollutant degradation, attributed to reactive radicals formation. HO• and Cl• were important contributors, with a total contribution of 45%‒64%. Moreover, the degradation rate of MTP by UV/Cl-Sar was pH-dependent, which monotonically increased from 0.044 to 0.065 min‒1 under pHs 5.5‒8.5. Although the activation of organic chloramine by UV could accelerate micro-pollutant degradation, UV/Cl-Sar treatment could also enhance disinfection by-products formation. Trichloromethane (TCM) formation was observed during MTP degradation by UV/Cl-Sar. After post-chlorination, TCM, 1,1-dichloropropanone, 1,1,1-trichloropropanone, and dichloroacetonitrile were detected. Their individual and total concentrations were all positively proportional to UV/Cl-Sar treatment time. The total concentration with 30 min treatment (66.93 µg L‒1) was about 2.3 times that with 1 min treatment (28.76 µg L‒1). Finally, the accelerated effect was verified with Cl-glycine and Cl-alanine. It is expected to unravel the non-negligible role of organic chloramine on water quality during UV disinfection.

A coupled UV photolysis-biodegradation process for the treatment of decabrominated diphenyl ethers in an aerobic novel bioslurry reactor.

The commercial flame retardant is an emerging contaminant (EC) commonly found in soils and sediments. A coupled UV-photolysis-biodegradation process was used to decompose decabromodiphenyl ether (BDE-209) in clay slurries. A novel bioslurry bioreactor (NBB) was employed in which BDE-209 degradation was maximized by the simultaneous application of LED UVA irradiation and biodegradation by a mixed bacterial culture. The rate of BDE-209 degradation decreased in the order: coupled UV photolysis-biodegradation (1.31 × 10-2 day-1) > UV photolysis alone (1.10 × 10-2 day-1) > biodegradation alone (1.00 × 10-2 day-1). Degradation intermediates detected included hydroxylated polybrominated diphenylethers, partially debrominated PBDE congeners and polybrominated dibenzofuran. The UV-resistant bacterial strains isolated that could utilize BDE-209 as a sole carbon source included Stenotrophomonas sp., Pseudomonas sp., and Microbacterium sp. These strains encoded important functional genes such as dioxygenase and reductive dehalogenases. Continuous UV irradiation during the NBB process affected various biochemical oxidative reactions during PBDEs biodegradation. Simultaneous photolysis and biodegradation in the NBB system described reduces operational time, energy, expense, and maintenance-demands required for the remediation of BDE-209 when compared to sequential UV-biodegradation process or to biodegradation alone.

Photocatalytic mechanisms of 2,4-dinitroanisole degradation in water deciphered by C and N dual-element isotope fractionation.

In surface water environments, photodegradation may be an important process for the natural attenuation of 2,4-dinitroanisole (DNAN). Understanding the photolysis and photocatalysis mechanisms of DNAN is difficult because the photosensitivity of nitro groups and the behavior of DNAN as a potential photosensitizer are unclear in aqueous solutions. Here, we investigate the degradation mechanisms of DNAN under UV-A (λ ~ 350 nm) and UV-C (λ ~ 254 nm) irradiation in a photolysis reactor where aqueous solution was continuously recycled through a UV-irradiated volume from a non-irradiated external reservoir. By tracking C and N isotopic fractionation in DNAN and its reaction products, we observed normal 13C fractionation (εC = -3.34‰) and inverse 15N fractionation (εN = +12.30‰) under UV-A (λ ~ 350 nm) irradiation, in contrast to inverse 13C fractionation (εC = +1.45‰) and normal 15N fractionation (εN = -3.79‰) under UV-C (λ ~ 254 nm) irradiation. These results indicate that DNAN can act as a photosensitizer and may follow a product-to-parent reversion mechanism in surface water environments. The data also indicate that photocatalytic degradation of DNAN in aqueous systems can be monitored via C and N stable isotope analysis.