Application of chlorine dioxide and its disinfection mechanism.

Chlorine dioxide (ClO2) is a strong oxidizing agent and an efficient disinfectant. Due to its broad-spectrum bactericidal properties, good inactivation effect on the vast majority of bacteria and pathogenic microorganisms, low resistance to drugs, and low generation of halogenated by-products, chlorine dioxide is widely used in fields such as water purification, food safety, medical and public health, and living environment. This review introduced the properties and application status of chlorine dioxide, compared the action mode, advantages and disadvantages of various disinfectants. The mechanism of chlorine dioxide inactivating bacteria, fungi and viruses were reviewed. The lethal target of chlorine dioxide to bacteria and fungi is to destroy the structure of cell membrane, change the permeability of cell membrane, and make intracellular substances flow out, leading to their death. The lethal targets for viruses are the destruction of viral protein capsids and the degradation of RNA fragments. The purpose of this review is to provide more scientific guidance for the application of chlorine dioxide disinfectants.

Performance and Mechanism of Chlorine Dioxide on BTEX Removal in Liquid and Indoor Air.

With the development of the chemical industry, benzene, toluene, ethylbenzene, and xylene (BTEX) have gradually become the major indoor air pollutants. Various gas treatment techniques are widely used to prevent the physical and mental health hazards of BTEX in semi-enclosed spaces. Chlorine dioxide (ClO2) is an alternative to chlorine as a secondary disinfectant with a strong oxidation ability, a wide range of action, and no carcinogenic effects. In addition, ClO2 has a unique permeability which allows it to eliminate volatile contaminants from the source. However, little attention has been paid to the removal of BTEX by ClO2, due to the difficulty of removing BTEX in semi-enclosed areas and the lack of testing methods for the reaction intermediates. Therefore, this study explored the performance of ClO2 advanced oxidation technology on both liquid and gaseous benzene, toluene, o-xylene, and m-xylene. The results showed that ClO2 was efficient in the removal of BTEX. The byproducts were detected by gas chromatography-mass spectrometry (GC-MS) and the reaction mechanism was speculated using the ab initio molecular orbital calculations method. The results demonstrated that ClO2 could remove the BTEX from the water and the air without causing secondary pollution.

Hydroxyl Radical Based Photocatalytic Degradation of Halogenated Organic Contaminants and Paraffin on Silica Gel.

Photochemical materials are of scientific and practical importance in the field of photocatalysis. In this study, the photochemistry of several organic contaminants, including decabromodiphenyl ether (BDE-209), halogenated phenols (C6 X5OH, X = F, Cl, Br) and paraffin, on silica gel (SG) surface was investigated under simulated solar irradiation conditions. Photolysis of these compounds at the solid/air interface proceeds with different rates yielding various hydroxylation products, and hydroxyl radical was determined as the major reactive species. According to density functional theory (DFT) calculations, the reaction of physically adsorbed water with reactive silanone sites (>Si═O) on silica was indispensable for the generation of •OH radical, where the required energy matches well with the irradiation energy of visible light. Then, the BDE-209 was selected as a representative compound to evaluate the photocatalytic performance of SG under different conditions. The SG material showed good stability in the photodegradation process, and was able to effectively eliminate BDE-209 under natural sunlight. These findings provide new insights into the potential application of SG as a solid surface photocatalyst for contaminants removal.

Antioxidant defenses and histological changes in Carassius auratus after combined exposure to zinc and three multi-walled carbon nanotubes.

With the increasing applications of carbon nanotubes (CNTs) worldwide, considerable concerns have been raised regarding their inevitable releases into natural waters and ecotoxicity. It was supposed that CNTs may interact with some existing pollutants like zinc in aquatic systems and exhibit different effects when compared with their single treatments. However, data on their possible combined toxicity on aquatic species are still lacking. Moreover, the interactions of Zn with different functionalized CNTs may be distinct and thereby lead to diverse results. It is like that functional groups play a vital role in illustrating the differences in toxicity among various CNTs. In this study, the single and joint effects of multi-walled carbon nanotubes (MWCNTs) and two MWCNTs functionalized with carboxylation (COOH-MWCNTs) or hydroxylation (OH-MWCNTs) in the absence or presence of zinc (Zn) on antioxidant status and histopathological changes in Carassius auratus were evaluated. Synergistic effect was tentatively proposed for joint-toxicity action, which was supported by apparently observed oxidative stress and histopathological changes in joint exposure groups. The integrated biomarker response index was calculated to rank the toxicity order, from which the conclusion of synergistic effect was strengthened. Regarding differences among various CNTs, our data showed that OH-MWCNTs and COOH-MWCNTs were more stressful to fish than raw MWCNTs. This finding sustained that functionalization is an important factor in nanotoxicity, which may serve as clues for future design and application of CNTs. Overall, these results provided some valuable toxicological data on the joint effects of CNTs and heavy metals on aquatic species, which can facilitate further understanding on the potential impacts of other coexisting pollutants in the culture of freshwater fish.

Ultra-short chain fluorocarboxylates exhibit wide ranging reactivity with hydrated electrons.

Recent reports demonstrate that technologies generating hydrated electrons (eaq-; e.g., UV-sulfite) are a promising strategy for destruction of per- and polyfluoroalkyl substances, but fundamental rate constants are lacking. This work examines the kinetics and mechanisms of eaq- reactions with ultra-short chain (C2-C4) fluorocarboxylates using experimental and theoretical approaches. Laser flash photolysis (LFP) was used to measure bimolecular rate constants (k2; M-1 s-1) for eaq- reactions with thirteen per-, and for the first time, polyfluorinated carboxylate structures. The measured k2 values varied widely from 5.26 × 106 to 1.30 × 108 M-1s-1, a large range considering the minor structural changes among the target compounds. Molecular descriptors calculated using density functional theory did not reveal correlation between k2 values and individual descriptors when considering the whole dataset, however, semiquantitative correlation manifests when grouping by similar possible initial reduction event such as electron attachment at the α-carbon versus ß- or γ-carbons along the backbone. From this, it is postulated that fluorocarboxylate reduction by eaq- occurs via divergent mechanisms with the possibility of non-degradative pathways being prominent. These mechanistic insights provide rationale for contradictory trends between LFP-derived k2 values and apparent degradation rates recently reported in UV-sulfite constant irradiation treatment experiments.

Process of landfill leachate pretreatment using coagulation and hydrodynamic cavitation oxidation.

Landfill leachate poses a threat to the environment and human health, and its complex composition made it difficult to treat. Among the methods for treating landfill leachate, the physicochemical combination method is considered to have significant effectiveness, low cost, and application potential. In this study, we propose a new method of coagulation and hydrodynamic cavitation/chlorine dioxide (HC/ClO2) for treating landfill leachate. The optimal conditions for coagulation and HC/ClO2 treatment were investigated experimentally. Under the optimal conditions for coagulation, the COD removal rate was 60.14%. Under the optimal HC/ClO2 treatment conditions, the COD removal rate was 58.82%. In the combined coagulation and HC/ClO2 process, the COD removal rate was 83.58%. Thus, the proposed method can significantly reduce the organic load before subsequent biological treatment processes, thereby reducing the operation cycles and cost of biological treatment.

Formation of perfluorocarboxylic acids from photodegradation of tetrahydroperfluorocarboxylic acids in water.

Tetrahydroperfluorocarboxylic acids (2H,2H,3H,3H-PFCAs) have aroused the interest of scholars worldwide due to their potential to generate perfluorinated compounds. In this work, we systematically examined the photodegradation kinetics and mechanisms of typical 2H,2H,3H,3H-PFCAs (CnF2n+1C2H4COOH, n = 6, 7, 8) in aqueous solution by a 500 W Hg lamp. The photodecomposition of 2H,2H,3H,3H-PFCAs all followed pseudo-first-order kinetics, and the photolysis rate coefficients increased with the increasing carbon chain length. Under the same reaction condition, 2H,2H,3H,3H-PFCAs degraded much faster than the corresponding PFCAs. The photodecomposition rate coefficient of C8F17CH2CH2COOH was accelerated by low pH and Fe3+ addition, but decreased by the existence of humic acid, carbonate and bicarbonate. Compared with ultrapure water, a decreased removal of 2H,2H,3H,3H-PFCAs was observed in four types of natural waters, i.e., tap water, Jiuxiang river water, primary effluent and secondary effluent. According to mass analysis, C8F17CH2CH2COOH was mainly decomposed into 8:2 fluorotelomer acid (C8F17CH2COOH), shorter-chain perfluorocarboxylic acids (PFCAs), perfluoro-1-enes (CnF2n) and perfluoroketenes (CnF2n+1CF = C = O). Thus, α-oxidation, decarboxylation and elimination reaction were proposed as reaction pathways. ECOSAR predictions showed that photolysis generally decreased the aquatic toxicity of C8F17CH2CH2COOH.

Formation of hydroxylated derivatives and coupling products from the photochemical transformation of polyfluorinated dibenzo-p-dioxins (PFDDs) on silica surfaces.

Polyfluorinated dibenzo-p-dioxins (PFDDs) are dioxin compounds that have been detected in industrial fluoroaromatic chemicals and can cause adverse effects to organisms. In this work, the photochemical behaviors of PFDDs congeners on silica was systematically investigated. The pseudo-first-order rate constants (k, h-1) of surface photolysis changed with the substitution number and position of fluorine atoms, and the tetra-fluorinated PFDDs tended to degrade more efficiently. Octafluorinated dibenzo-p-dioxin (OFDD) was selected as a representative to explore the reaction mechanisms. Product analysis showed that OFDD was decomposed into hydroxylated PFDDs (OH-PFDDs) and hydroxylated polyfluorinated diphenyl ethers (OH-PFDEs) via hydroxyl substitution and (OH radical mediated or direct) C-O bond cleavage. Coupling elimination reaction was also observed, resulting in the formation of three-membered and four-membered ring compounds. According to the extracted peak areas in mass spectra and the energy barrier in potential energy surface, direct homolysis of C-O bond occurs as the dominant reaction pathway. This work could provide some new insights into the environmental fate of dioxin compounds.

Photochemical formation of hydroxylated polychlorinated biphenyls (OH-PCBs) from decachlorobiphenyl (PCB-209) on solids/air interface.

In this work, the photochemical transformation of decachlorobiphenyl (PCB-209) on the surface of several solid particles were systematically evaluated under simulated solar irradiation. The degradation kinetics of PCB-209 were first investigated using silica as a model aerosol particulate. It was found that PCB-209 photodegradation was enhanced at small silica particle size, low surface coverage and low humidity. Electron paramagnetic resonance (EPR) analysis and radicals quenching experiments demonstrated that hydroxyl radicals contributed to PCB-209 degradation. Stepwise hydrodechlorination, hydroxyl addition and cleavage of the CC bridge bond were mainly observed in the reaction process, leading to the formation of lower chlorinated PCBs, hydroxylated PCBs (OH-PCBs) and chlorophenols. Based on density functional theory (DFT) calculation, the dissociation energy of the CCl bond requires 354.81-359.79 kJ/mol energy that corresponds to a wavelength of less than 322 nm. And the minimum activation energy of OH radicals attack on PCB-209 is only 18.12 kJ/mol. Photochemical transformation of PCB-209 can also occur on the surface of natural particles, but the rates were inhibited as compared to silica. The hydroxylation and hydrodechlorination products of PCB-209 were detected in all natural particles. This study would make significant contribution to understanding the fate of PCBs in solids/air interface.

Oxidation of flumequine in aqueous solution by UV-activated peroxymonosulfate: Kinetics, water matrix effects, degradation products and reaction pathways.

The degradation of flumequine (FLU) in aqueous solution by ultraviolet (UV)-activated peroxymonosulfate (PMS) was investigated in this work. Under the conditions of [PMS]0:[FLU]0 = 1:1, T = 25 ±â€¯2 °C, pH = 7.0 ±â€¯0.1, nearly complete removal of FLU was achieved after 60 min. The effects of various operating parameters, including oxidant doses, pH, the presence of typical ions (NH4+、Mg2+、Fe3+、Cl-、NO3-、HCO3-) and humic acid were evaluated. It was found that the pseudo-first-order rate constants of FLU degradation increased with increasing PMS dosage and decreasing solution pH. The presence of Mg2+ could accelerate FLU removal, while Fe3+, HCO3-, NO3- and HA inhibited the reaction. Moreover, the degradation of FLU in different water matrices were also explored, and the removal followed the order of Tap water > Ultrapure water > River water > Secondary clarifier effluent. According to the control and radical quenching experiment results, direct photolysis and reactive radicals (SO4- and HO) contributed mainly to FLU degradation in the UV/PMS system. Initial FLU molecule underwent reactions such as hydroxylation, hydroxyl substitution, demethylation, decarboxylation/decarbonylation and ring opening, leading to the formation of nineteen oxidation products. The effective degradation by UV/PMS suggests a feasible technology for treating FLU in waters and wastewaters.

Understanding the ozonated degradation of sulfadimethoxine, exploration of reaction site, and classification of degradation products.

Ozonation has been demonstrated to be an efficient method of water treatment. In this study, the degradation of 20 mg/L of sulfadimethoxine (SDM) in different water matrices during ozonation was investigated. At pH 7.0, 100% removal of SDM was achieved by ozonation within 10 min. The degradation of SDM was more pronounced at acidic pH than under ambient environmental conditions, and was also dependent on different water matrices. Both direct and indirect oxidation of SDM by ozone were observed, and it was also shown that both ozone molecules and hydroxyl radicals were involved in the SDM degradation process, whereas it was found that the saturated ring of SDM made it O3-recalcitrant. Seven transformation products (TPs) were identified during SDM ozonation, allowing three degradation pathways to be proposed. Additionally, the main reaction sites, including N (7) and C (2) on the aniline ring, and the __S__N__ bond, were confirmed both experimentally and theoretically. The toxicity evolution during the degradation process was investigated, and the results showed no toxic intermediate products obtained during ozonation.

The laccase-like reactivity of manganese oxide nanomaterials for pollutant conversion: rate analysis and cyclic voltammetry.

Nanostructured manganese oxides, e.g. MnO2, have shown laccase-like catalytic activities, and are thus promising for pollutant oxidation in wastewater treatment. We have systematically compared the laccase-like reactivity of manganese oxide nanomaterials of different crystallinity, including α-, ß-, γ-, δ-, and ɛ-MnO2, and Mn3O4, with 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulfonate) (ABTS) and 17ß-estradiol (E2) as the probing substrates. The reaction rate behaviors were examined with regard to substrate oxidation and oxygen reduction to evaluate the laccase-like catalysis of the materials, among which γ-MnO2 exhibits the best performance. Cyclic voltammetry (CV) was employed to assess the six MnOx nanomaterials, and the results correlate well with their laccase-like catalytic activities. The findings help understand the mechanisms of and the factors controlling the laccase-like reactivity of different manganese oxides nanomaterials, and provide a basis for future design and application of MnOx-based catalysts.

Thermal- and photo-induced degradation of perfluorinated carboxylic acids: Kinetics and mechanism.

Perfluorinated carboxylic acids (PFCAs) of different carbon chain lengths are chemicals of concern to human health and their removal, using conventional remediation technologies, is challenging. The present paper pursuits thermal and photo-induced degradation of PFCAs (F(CF2)nCOOH, n = 1-9) under various concentrations of four different acids (HNO3, H2SO4, HCl, and H3PO4) covering a range of strong acidic to basic pH. For thermal-induced experiments, the temperature was set at 40 °C, 60 °C, and 80 °C at acid strengths of 0.04-18.4 M. Photo-induced experiments were conducted at pH 0.5, 7.0, and 13.0 under a light intensity of (150 ± 10) × 100 µW/cm2. The degradation first-order rate constant (k1, h-1) as a function of [H+] was modeled by considering equilibrium of nondissociated (F(CF2)nCOOH, HX) and dissociated (F(CF2)nCOO-, X-) species of PFCAs (HX ⇌ X- + H+, pKa = -0.1). Species-specific rate constants, k1HX, reasonably described the trend of thermal and photo decay of PFCAs, where k1HX increased with acidity of solution and the carbon chain length of PFCAs. Mechanism of degradation of PFCAs (e.g. perfluorooctanoic acid (PFOA)) involved homolytic breakage of CC bond between alkyl and carboxyl groups, which produced radicals and subsequently decarboxylation to perfluoroheptene-1. Density functional theory (DFT) calculations supported the mechanism. The calculations indicated that a breaking of CC bond is more feasible with nondissociated HX than dissociated X- species of PFCAs and also with increase in chain length. The potential of a combination of thermal- and photo-induced processes under acidic conditions to enhance degradation of PFOA in water is presented.

Solid surface-mediated photochemical transformation of decabromodiphenyl ether (BDE-209) in aqueous solution.

Polybrominated diphenyl ethers (PBDEs) are brominated flame retardants which have received considerable attention due to their global distribution, bioaccumulation potential, environmental persistence, and possible toxic effects. In this work, the photodegradation of decabromodiphenyl ether (BDE-209) in aqueous system was investigated by preloading it on the surface of various solid matrices. After 6 h of Xe lamp irradiation, almost complete degradation of BDE-209 was observed on silica gel (SG), with much slower degradation occurring in other adsorbents. The degradation of BDE-209 on SG sample followed pseudo-first-order kinetics, and the observed reaction rate constant was decreased by lowering pH, adding humic acid and increasing the initial BDE-209 concentration. In addition to direct photolysis, BDE-209 could be oxidized by hydroxyl radicals generated from SG, as confirmed by the electron paramagnetic resonance (EPR) technology. Product analysis showed that BDE-209 was mainly decomposed into lower brominated PBDEs, polybrominated dibenzofurans (PBDFs), hydroxylated PBDEs (OH-PBDEs), hydroxylated PBDFs (OH-PBDFs), bromophenols and bromide ions. Thus, consecutive debromination, intramolecular elimination of HBr, hydroxyl addition and the cleavage of ether bond were proposed as the degradation pathways. This study may help understanding the photochemical transformation of solid surface adsorbed BDE-209 in natural surface waters, which is important to evaluate the environmental fate of PBDEs.

The toxic effect and bioaccumulation in aquatic oligochaete Limnodrilus hoffmeisteri after combined exposure to cadmium and perfluorooctane sulfonate at different pH values.

Cadmium (Cd) and Perfluorooctane sulfonate (PFOS) have been detected in aquatic environment. In this study, we investigated the acute effect, bioaccumulation and oxidative stress status in the aquatic oligocheate Limnodrilus hoffmeisteri after exposure to Cd and PFOS at different pH values. In the studied pH range, acute Cd toxicity was significantly enhanced with pH increasing from 6.2 to 8.0, and the 48h-EC50 of Cd was (significantly) decreased in the presence of PFOS. Bioaccumulation analysis results show that the accumulated Cd/PFOS in single exposure group increased with increasing exposure concentrations, and co-exposure makes internal Cd concentration significantly lowered for Cd(0.1) group at pH 8.0. Significant changes in superoxide dismutase activity, glutathione level and malondialdehyde content were observed in single and combined treatments. Based on IBR value, single Cd and PFOS exposure caused largest damage to the antioxidant defense system at pH 8.0 and pH 6.2, respectively, while the harmful effects of joint exposure were always the "compromise" between single Cd and PFOS exposure. This work could provide useful information for the risk assessment of co-exposure to perfluorinated compounds and heavy metals in natural environment.

Experimental and theoretical insights into the photochemical decomposition of environmentally persistent perfluorocarboxylic acids.

Decomposition of perfluorocarboxylic acids (PFCAs) is of great significance due to their global distribution, persistence and toxicity to organisms. In this study, the photodegradation of a series of PFCAs (∼C2C12) in water by a medium-pressure mercury lamp was experimentally and theoretically examined. We found that photolysis of PFCAs all follow pseudo-first-order kinetics with the rate constant (kapp) increasing with carbon chain lengths, except for trifluoroacetic acid (TFA) which cannot be degraded by the polychromatic irradiation. Product analysis showed that the PFCAs were mainly decomposed into shorter carbon chain length PFCAs in a stepwise manner, with the accumulation of TFA and fluoride ions as the end products. Moreover, a small amount of perfluoroolefins (CnF2n) was determined as gas-phase products. Wiberg bond order calculations confirmed the cleavage of the CC bond between carboxylic carbon and the adjacent carbon as the first reaction step, and density functional theory-based calculations revealed that kapp value is correlated with some molecular structural parameters. In the case of mixture irradiation, the evolution profiles of individual PFCAs were different from that in single-component systems, due to the dynamic balance between production and degradation. This work reveals the main molecular descriptors controlling the degradation rate of different PFCAs species, and improves the general understanding on the photodegradation mechanisms, which will provide useful information for future researches.

Evaluation of single and joint toxicity of perfluorooctane sulfonate and zinc to Limnodrilus hoffmeisteri: Acute toxicity, bioaccumulation and oxidative stress.

Perfluorooctane sulfonate (PFOS) and zinc have been detected in aquatic environment widely. In order to study the combined effects of PFOS and Zn, a series of experiments was conducted to explore the acute mortality, bioaccumulation and antioxidant status of Limnodrilus hoffmeisteri. The acute toxicity was evaluated by calculating 24h-EC50 values, and it was observed that 24h-EC50 values in single and joint treatments decreased with decreasing pH value or increasing exposure concentration. Toxic unit analysis suggested that the combined effects of the PFOS+Zn binary mixture were mostly simple addition, with 8 groups showing synergism and only one group showing antagonism. The analysis of internal Zn and PFOS concentration showed that the possible interaction between Zn and PFOS can affect the bioaccumulation of the two chemicals in L. hoffmeisteri. In addition, oxidative stress status was assessed by measuring oxidation-related biochemical parameters such as superoxide dismutase, glutathione peroxidase and malondialdehyde, and the integrated biomarker response index was estimated to rank the toxicity order. Exposures to Zn and PFOS were found to evoke some changes in the antioxidant defense system, and a strong self-adaptive ability was noticed for L. hoffmeisteri after 10 d exposure.

Effect of different carbon nanotubes on cadmium toxicity to Daphnia magna: The role of catalyst impurities and adsorption capacity.

Experiments were conducted to investigate the effect of four different carbon nanotubes single- and multi-walled carbon nanotubes (SWCNTs and MWCNTs) and hydroxylated and carboxylated multi-walled carbon nanotubes (OH-MWCNTs and COOH-MWCNTs) on Cd toxicity to the aquatic organism Daphnia magna. The acute toxicity results indicated that all CNTs could enhance the toxicity of Cd to D. magna. Furthermore, the filtrate toxicity and adsorption tests showed that the toxicity-increasing effect of SWCNTs and MWCNTs in the overall system was mainly caused by catalysts impurities from the pristine CNTs, whereas the greater adsorption of Cd onto OH-MWCNTs (30.52 mg/g) and COOH-MWCNTs (24.93 mg/g) was the key factor contributing to the enhanced toxicity. This result raised a concern that the metal catalyst impurities, adsorption capacities, and accumulation of waterborne CNTs were responsible for the toxicity of Cd to aquatic organism.

Toxicity and bioaccumulation of copper in Limnodrilus hoffmeisteri under different pH values: Impacts of perfluorooctane sulfonate.

Aquatic oligochaete Limnodrilus hoffmeisteri (L. hoffmeisteri) has been commonly used as a lethal and/or sub-lethal toxicological model organism in ecological risk assessments in contaminated water environments. In this study, experiments were conducted to investigate the potential toxic effects of copper (Cu(II)) with or without perfluorooctane sulfonate (PFOS) under different pH values (6.0, 7.0 and 8.0) on LC50, bioaccumulation, and oxidative stress biomarkers in L. hoffmeisteri after 3 and 7 days. The LC50 values of Cu(II) decreased with the increasing pH and the addition of PFOS. After each exposure, increasing bioaccumulation of Cu(II) in L. hoffmeisteri was observed in the combined exposure treatments, whereas the bioaccumulation of PFOS decreased. Moreover, the activity of superoxide dismutase, the level of glutathione, and the content of malondialdehyde were significantly altered after these exposures, possibly indicating that the bioaccumulation of Cu(II) and PFOS caused adverse effects on antioxidant defenses of L. hoffmeisteri. The integrated biomarker response index, indicates that the combined effect was proposed as synergism, which is coincided with the results of toxic unit. Moreover, this work showed that aquatic environment may become more livable when water conditions changed from acidic to near-neutral or alkaline.