Photo-transformation of isoproturon under UV-A irradiation: The synergy of nitrite and natural organic matter.

Isoproturon (IPU), a widely utilized phenylurea herbicide, is recognized as an emerging contaminant. Previous studies have predominantly attributed the degradation of IPU in natural waters to indirect photolysis by natural organic matter (NOM). Here, we demonstrate that nitrite (NO2-) also serves as an important photosensitizer that induces the photo-degradation of IPU. Through radical quenching tests, we identify hydroxyl radicals (•OH) and nitrogen dioxide radicals (NO2•) originating from NO2- photolysis as key players in IPU degradation, resulting in the generation of a series of hydroxylated and nitrated byproducts. Moreover, we demonstrate a synergistic effect on the photo-transformation of IPU when both NOM and NO2- are present in the reaction mixture. The observed rate constant (kobs) for IPU removal increases to 0.0179 ± 0.0002 min-1 in the co-presence of NO2- (50 µM) and NOM (2.5 mgC/L), surpassing the sum of those in the presence of each alone (0.0135 ± 0.0004 min-1). NOM exhibits multifaceted roles in the indirect photolysis of IPU. It can be excited by UV and transformed to excited triplet states (3NOM*) which oxidize IPU to IPU•+ that undergoes further degradation. Simultaneously, NOM can mitigate the reaction by reducing the IPU•+ intermediate back to the parent IPU. However, the presence of NO2- alters this dynamic, as IPU•+ rapidly couples with NO2•, accelerating IPU degradation and augmenting the formation of mono-nitrated IPU. These findings provide in-depth understandings on the photochemical transformation of environmental contaminants, especially phenylurea herbicides, in natural waters where NOM and NO2- coexist.

Formation of nitrated naphthalene in the sulfate radical oxidation process in the presence of nitrite.

Polycyclic aromatic hydrocarbons (PAHs) have become a global environmental concern due to their potential hazardous implication for human health. In this study, we found that sulfate radical (SO4•-) could effectively degrade naphthalene (NAP), a representative PAH in groundwaters, generating 1-naphthol. This intermediate underwent further degradation, yielding ring-opening products including phthalic acid and salicylic acid. However, the presence of nitrite (NO2-), a prevalent ion in subsurface environments, was observed to compete with NAP for SO4•-, thus slowing down the NAP degradation. The reaction between NO2- and SO4•- generated a nitrogen dioxide radical (NO2•). Concurrently, in-situ formed 1-naphthol underwent further oxidization to the 1-naphthoxyl radical by SO4•-. The coupling of 1-naphthoxyl radicals with NO2• gave rise to a series of nitrated NAP, namely 2-nitro-1-naphthol, 4-nitro-1-naphthol, and 2,4-dinitro-1-naphthol. In addition, the in-situ formed phthalic acid and salicylic acid also underwent nitration, generating nitrophenolic products, although this pathway appeared less prominent than the nitration of 1-naphthol. When 10 µΜ NAP was subjected to heat activated peroxydisulfate oxidation in the presence of 10 µΜ NO2-, the total yield of nitrated products reached 0.730 µΜ in 120 min. Overall, the presence of NO2- dramatically altered the behavior of NAP degradation by SO4•- oxidation and contributed to the formation of toxic nitrated products. These findings raise awareness of the potential environmental risks associated with the application of SO4•--based oxidation processes for the remediation of PAHs-polluted sites in presence of NO2-.

Photo-transformation of acetaminophen sensitized by fluoroquinolones in the presence of bromide.

Fluoroquinolones (FQs) are a class of antibiotics with emerging concern. This study investigated the photochemical properties of two representative FQs, i.e., norfloxacin (NORF) and ofloxacin (OFLO). Results showed that both FQs could sensitize the photo-transformation of acetaminophen under UV-A irradiation, during which excited triplet state (3FQ*) was the main active species. In the presence of 3 mM Br‾, the photolysis rate of acetaminophen increased by 56.3% and 113.5% in the solutions with 10 µM NORF and OFLO, respectively. Such an effect was ascribed to the generation of reactive bromine species (RBS), which was verified by 3,5-dimethyl-1H-pyrazole (DMPZ) probing approach. 3FQ* reacts with acetaminophen through one-electron transfer, producing radical intermediates which then couple to each other. Presence of Br‾ did not lead to the formation of brominated products but the same coupling products, which suggests that radical bromine species, rather than free bromine, were responsible for the accelerated acetaminophen transformation. According to the identified reaction products and assisted with the theoretical computation, the transformation pathways of acetaminophen under UV-A irradiation were proposed. The results reported herein suggest that sunlight-driven reactions of FQs and Br‾ may influence the transformation of coexisting pollutants in surface water environments.

Degradation of tetracyclines by peracetic acid and UV/peracetic acid: Reactive species and theoretical computations.

As an environment-friendly oxidant and disinfectant, peracetic acid (PAA) and PAA based-advanced oxidation processes (AOPs) for the treatment of emerging micropollutants have raised increasing interest, owing to their ease of activation and less generation of harmful disinfection byproducts. Tetracyclines (TCs) antibiotics as a group of wide-spectrum antibiotics are frequently detected in sewage effluents, while the knowledge of PAA-based advanced oxidation reactions to remove the substrates is quite limited. In this work, we systematically investigated the kinetics and underlying transformation mechanisms of three TCs including tetracycline (TTC), oxytetracycline (OTC), and chlortetracycline (CTC) in the UV-activated PAA oxidation process. The results indicated that three TCs can be efficiently decayed by UV/PAA. The pseudo-first-order reaction rate constants (kobs) of TCs followed the order: kCTC (0.453 min-1) ≫ kTTC (0.164 min-1) > kOTC (0.158 min-1). Quenching experiments showed that the removal of CTC was mainly ascribed to the direct oxidation of PAA, while TTC and OTC were more susceptible to free radicals. The kobs values of the three TCs by PAA oxidation presented a fairly well correlation to the global nucleophilicity and the activation energies of the TC molecules, highlighting the structure-specific reactions of TCs to PAA. Based on product identification and theoretical calculation, N-demethylation and hydroxylation were proposed as the main pathways for TCs degradation by PAA non-radical oxidation. The combination of PAA and UV irradiation can further improve the degradation efficiency of TCs and contribute to reducing the diffusion and transmission of resistance genes in the environment.

Nitrophenolic byproducts formation during sulfate radical oxidation and their fate in simulated drinking water treatment processes.

Nitrite can be transformed to nitrophenolic byproducts in sulfate radical oxidation processes (SR-AOPs). These nitrophenols are highly mobile in subsurface and can potentially contaminate drinking water sources. However, their fate in a drinking water treatment remains ambiguous. Herein, the removal and transformation of four nitrophenolic byproducts formed during a heat activated peroxydisulfate oxidation process, i.e., 4-nitrophenol, 2,4-dinitrophenol, 5-nitrosalicylic acid, and 3,5-dinitrosalicylic acid, in a simulated drinking water treatment train were comprehensively examined. The removal of these nitrophenolic compounds in coagulation by either aluminum sulfate or ferric chloride ranged from 3.8% to 13.4%. In the chlorination process, 4-nitrophenol was removed only by 45.4% in 24 h at a chlorine dose of 5.0 mg/L. The removal of the other three nitrophenolic byproducts were less than 20%. Reaction between nitrophenolic byproducts and chlorine via electrophilic substitution gave rise to their chlorinated derivatives. Chlorinated nitrophenolic byproducts were more recalcitrant and toxic than their parent compounds, but still a tiny fraction of them could undergo further oxidation to form trichloronitromethane. This work implied that once nitrophenolic byproducts enter water source, they can penetrate the drinking water treatment train and react with the residual chlorine in distribution pipelines to form more hazardous byproducts. The findings raised additional concerns to the potential risk of the nitrophenolic byproducts formed in SR-AOPs.

Differentiation of Pathways of Nitrated Byproduct Formation from Ammonium and Nitrite During Sulfate Radical Oxidation.

Recent studies found that both nitrite (NO2-) and ammonium (NH4+) lead to nitrophenolic byproducts in SO4•- oxidation processes, during which NO2• generated through the oxidation of the inorganic nitrogen by SO4•- is the key nitrating agent. This study demonstrates that the formation of phenoxy radicals to which NO2• can be incorporated immediately is another governing factor. Two types of sites having distinct reactivities in natural organic matter (NOM) molecules can be transformed to phenoxy radicals upon SO4•- oxidation. Fast sites associated with phenolic functionalities are primarily targeted in the reaction sequence involving NO2-, because both are preferentially oxidized. Following the depletion of NO2-, NH4+ becomes the main precursor of NO2• that interacts with slow sites associated with the carboxylic functionalities. Experimental data show that the formation of total organic nitrogen in 24 h reached 6.28 µM during SO4•- oxidation of NOM (4.96 mg/L organic carbon) in the presence of both NO2- (0.1 mM) and NH4+ (1.0 mM), while the sum of those formed in the presence of each alone was only 3.52 µM. Results of this study provide further insights into the mechanisms of nitrated byproduct formation when SO4•- is applied for environmental remediation.

Transformation of amino acids and formation of nitrophenolic byproducts in sulfate radical oxidation processes.

In this study, the transformation of five amino acids (AAs), i.e., glycine (GLY), alanine (ALA), serine (SER), aspartic acid (ASP), and methionine (MET), in a heat activated peroxydisulfate (PDS) oxidation process was investigated. Experimental data showed that the nitrogen in the AA molecules was oxidized to NH4+ and nitrate (NO3-) sequentially. However, in the presence of natural organic matter (NOM), nitrophenolic byproducts including 4-nitrophenol, 2,4-dinitrophenol, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid were formed. The nitrogen dioxide radical (NO2•) generated during the transformation of NH4+ to NO3- was presumed to be the key nitrating agent. It reacted with phenolic moieties in NOM and was transformed to nitrophenolic byproducts. Among the selected AAs, SER showed the highest nitrophenolic byproducts formation potential. A total yield of 0.258 µM was observed at the condition of 0.1 mM SER, 5 mg/L (as TOC) NOM, 2 mM PDS, and pH 7.0. The formation from GLY and ALA was lowest, only 0.009 µM detected under the same conditions. The nitrophenolic byproducts formation potential of the AAs was positively related to their reactivity toward SO4•- and can be explained by the local nucleophilicity index (Nk). These findings underline the potential risks in the application of SO4•- based oxidation technology.

Photodegradation of benzophenones sensitized by nitrite.

Benzophenone UV filters (BPs) are a group of contaminants of emerging concern due to their widespread occurrence and adverse effects on aquatic ecosystems. In this study, the transformation of BPs by nitrite sensitized photodegradation was comprehensively investigated. OH and NO2 generated by nitrite photolysis reacted with BPs, forming hydroxylated and nitrated products, respectively. Kinetic modeling revealed that the steady-state concentrations of NO2 were approximately six orders of magnitude higher than those of OH in the UV/nitrite process, although the second-order rate constants of NO2 reactions with BPs were six orders of magnitude lower. With the increase in nitrite concentration, BPs degradation was accelerated, and the contribution of NO2 increased as well. At initial nitrite concentration of 10 µM, the contributions of OH and NO2 to the degradation of 2,4-dihydroxybenzophenone (BP1) were 66.1% and 21.5%, respectively. However, NO2 only contributed a tiny fraction to the degradation of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (BP4), due to the presence of an electron-withdrawing sulfonate group in the molecule. Natural organic matter (NOM) inhibited the nitrite sensitized degradation of BPs, due to light screening and radical scavenging effects. This study suggests that BPs can be effectively transformed in sunlit waters in the presence of nitrite, leading to nitrated products.

Facile one-step synthesis of 3D honeycomb-like porous chitosan bead inlaid with MnFe bimetallic oxide nanoparticles for enhanced degradation of dye pollutant.

Developing a sustainable, efficient and recyclable heterogeneous Fenton-like catalyst is important to wastewater treatment. Herein, well-dispersed MnO2 and Fe3O4 nanoparticles inlaid in chitosan beads (MnO2-Fe3O4/CH) was firstly fabricated and employed in the degradation of methylene blue (MB). The bead was prepared via a facile one-step method by dropwise addition of chitosan-metal salt solution into alkaline solution. Comparing with monometallic chitosan beads (MnO2/CH, Fe3O4/CH) and naked MnO2-Fe3O4, MnO2-Fe3O4/CH displayed significantly higher activity for MB degradation with the assistance of hydrogen peroxide (H2O2), finally removing 96.8% MB under the optimal conditions (50 mg L-1 MB, 4.0 g L-1 catalyst, 30 g L-1 H2O2, pH = 7, 60 min). Based on a series of characterizations, the large surface area (60.1 m2 g-1), well-developed porosity (0.3 cm3 g-1), and intensified electron transport of MnO2-Fe3O4/CH consequently enhanced the catalytic performance via a synergistic effect. Because the specific porous structure of MnO2-Fe3O4/CH facilitated the adsorption/diffusion of reactants and exposure of active sites. Meanwhile, the electron transfer from Mn3+ to Fe3+ accelerated the Fe3+/Fe2+ cycle, which favored the production of dominant reactive species hydroxyl radical for MB degradation. Besides, the magnetic beads could be easily collected from the solution and reused for five times with a negligible leaching.

Transformation of bisphenol A by electrochemical oxidation in the presence of nitrite and formation of nitrated aromatic by-products.

In this contribution, the electrocatalytic abatement of bisphenol A (BPA) with boron-doped diamond (BDD) anode had been conducted in NaNO2 electrolytes. Central composite design was used as statistical multivariate method to optimize the operating parameters adopted (applied current density, flow rate, concentration of NaNO2 and initial pH). The results from response surface analysis indicated that pH was the most influential factor for TOC decay, and a maximum TOC decay of 63.7% was achieved under the optimized operating conditions (9.04 mA cm-2 of applied current density, 400 mL min-1 of flow rate, 10 mM of NaNO2, 4.0 of initial pH and 60 min of electrolysis time). Besides, LC/MS technique was applied to identify the main reaction intermediates, and plenty of nitrated oligomers were detected at the end of the degradation. These by-products were generated via the coaction of coupling reaction of nitrated phenol and electrophilic substitution mediated by nitrogen dioxide radicals. Moreover, our results showed that the degree of nitration depended heavily on the employed initial nitrite concentration. This was one of the very few investigations dealing with nitrophenolic by-products in nitrite medium, and thus the findings exhibited important implications for electrochemical degradation of BPA and its related phenolic pollutants.

Electrochemical mineralization of uric acid with boron-doped diamond electrode: Factor analysis and degradation mechanism.

In the present study, the mineralization performance and pathway of uric acid (UA) on boron-doped diamond (BDD) anodes were investigated. The oxidation behavior of UA on BDD surface was firstly tested through cyclic voltammetry measurements. The individual and joint effects of four quantitative parameters (applied current density, NaHCO3 concentration, NaCl concentration and flow rate) on UA mineralization were then examined with Doehlert experimental design. The results acquired by statistical analysis revealed that NaCl concentration and applied current density displayed the most dominant roles on UA degradation, while the influences of NaHCO3 concentration and flow rate were statistically insignificant. As a result, the following optimal conditions were reached: applied current density of 7.80 mA cm-2, NaHCO3 concentration of 6.0 mM, NaCl concentration of 9.0 mM and flow rate of 600 mL min-1, which gave a TOC decay of 89.4%, a specific energy consumption of 125.36 KWh kg-1 TOC, a combustion current efficiency of 15.0% and an electrical energy per order of 35.79 KWh m-3 order-1 within 30 min of electrolysis. Further results from LC/MS analysis confirmed the ring rupture of UA during the electrolysis, due to the attack of hydroxyl radicals and active chlorine species. Accordingly, two plausible degradation pathways of UA in bicarbonate and chloride media on BDD anode were proposed respectively.

The role of nitrite in electrocatalytic oxidation of phenol: An unexpected nitration process relevant to groundwater remediation with boron-doped diamond electrode.

Using boron-doped diamond (BDD) to mineralize recalcitrant organics has been one of the hottest areas of research interest in the field of water treatment. Here we report for the first time that, in the presence of nitrite ions (NO2-), the anodic oxidation of phenol with BDD electrode will lead to the formation of nitrated by-products of phenol. These by-products include 2-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol, 2,6-dinitrophenol, 2,4,6-trinitrophenol, 2,3,4,6-tetranitrophenol, 2,3,4,5,6-pentanitrophenol, as well as a large number of dimers and trimers of nitrophenols. Increasing the concentration of NO2- will not only greatly affects the degradation and mineralization of phenol, but also enhances the formation of nitrophenols. The nitrated by-products are mainly generated via electrophilic substitution reactions mediated by nitrogen dioxide radicals and hydroxyl radicals, as well as via coupling reactions of phenol. In addition, it is found that several simple nitrophenols may also be formed in nitrate media. As a whole, formation of nitrated by-products is a novel phenomenon in anodic oxidation processes. Since nitrated aromatics are well known for their persistence in the environment, their formations in BDD anode cells should be carefully scrutinized before such technology is applied to groundwater remediation.

MicroRNA-182-5p contributes to the protective effects of thrombospondin 1 against lipotoxicity in INS-1 cells.

The dysfunction of beta cells serves an important role in the pathogenesis of type 2 diabetes mellitus (T2DM). An improved understanding of the molecular mechanisms underlying beta cell mass and failure will be useful for identifying novel approaches toward preventing and treating this disease. Recent studies have indicated that free fatty acids (FFAs) can cause beta cell dysfunction. In the present study, palmitate (Pal) was used as a FFA and its functions on cell viability and apoptosis were detected. MTT assay and flow cytometry were used and the results revealed that incubation of INS-1 cells with Pal significantly decreased cell viability and increased cell apoptosis. However, a co-incubation with thrombospondin 1 (THBS-1) protected the cells against Pal-induced toxicity. Numerous studies have demonstrated that microRNAs (miRs) are involved in fatty acid-induced beta cell dysfunction. Various studies have reported that miR-182-5p is associated with a number of diseases, including cancer, heart disease, and leukemia. However, to the best of our knowledge miR-182-5p has never been reported to be associated with diabetes. In the present study, miR-182-5p, which is predicted to target the 3'-untranslated region (UTR) of THBS-1, was detected using reverse transcription-quantitative polymerase chain reaction in INS-1 cells in response to Pal. miR-182-5p was significantly increased in Pal-treated cells compared with the control cells. Furthermore, miR-182-5p mimics significantly decreased cell viability and increased Pal-induced apoptosis in INS-1 cells. However, cell viability was increased and Pal-induced apoptosis was decreased in cells that were treated with miR-182-5p inhibitors. The present findings also revealed that overexpression of THBS-1 counteracted the effect of miR-182-5p on cell viability and apoptosis. These results suggested that miR-182-5p is involved in the mechanism of THBS 1 on the modulation of beta cell survival.

Adenovirus-mediated artificial miRNA targetting fibrinogen-like protein 2 attenuates the severity of acute pancreatitis in mice.

Severe acute pancreatitis (SAP) remains to be challenging for its unpredictable inflammatory progression from acute pancreatitis to SAP. Apoptosis is an important pathology of SAP. Fibrinogen-like protein 2 (FGL2) has been reported to be involved in apoptosis. The present study aimed to explore the therapeutic effect of an adenovirus-mediated artificial miRNA targetting FGL2 (Ad-FGL2-miRNA) in taurocholate-induced murine pancreatitis models. Sodium taurocholate was retrogradely injected into the biliopancreatic ducts of the C57/BL mice to induce SAP. FGL2 expression was measured with reverse transcription-PCR, Western blotting, and immunohistochemical staining. ELISA was used to detect the activity of amylase and the concentrations of tumor necrosis factor-α (TNF-α) and interleukin-1ß (IL-1ß). In addition, the mRNA levels of TNF-α and IL-1ß were also detected. Finally, apoptosis was assessed by terminal deoxynucleotidyl transferase mediated dUTP-biotin nick-end labeling (TUNEL) method and Western blotting. Ad-FGL2-miRNA significantly suppressed FGL2 expression and alleviated pancreatic injury. Also, Ad-FGL2-miRNA markedly inhibited a post-SAP increase in the activation of TNF-α and IL-1ß. Finally, pretreatment with Ad-FGL2-miRNA ameliorated apoptosis at the early stage of SAP by modulating cleaved caspase-3 and therefore played a protective role. These results indicated that FGL2 might be a promising target for attenuating the severity of SAP and adenovirus-mediated artificial miRNAs targetting FGL2 represented a potential therapeutic approach for the treatment of SAP.

Access to Cyano-Containing Isoxazolines via Copper-Catalyzed Domino Cyclization/Cyanation of Alkenyl Oximes.

A highly efficient copper-catalyzed cyclization/cyanation cascade of unactivated olefins bearing oximes is described. A variety of cyano-containing isoxazolines have been obtained in high yields with cheap Cu(NO3)2·3H2O as the catalyst and TMSCN as the non-metallic cyanide source. The present method provides a mild, simple, and practical access to cyano-substituted isoxazolines and is amenable to gram scale. The simultaneous construction of C(sp3)-CN and C-O bonds can be achieved in one step.