Advanced oxidation processes may transform unknown PFAS in groundwater into known products.

Per- and polyfluoroalkyl substances (PFAS) are a group of fluorinated organic contaminants classified as persistent in the aquatic environment. Early studies using targeted analysis approaches to evaluate the degradation of PFAS by advanced oxidation processes (AOP) in real water matrices may have been misinterpreted due to the presence of undetected or unknown PFAS in these matrices. The aims of the present study were to (1) screen selected commercially available AOPs (UV, UV + H2O2, O3/H2O2) and UV photocatalysis in a pilot system using commercially used and novel photocatalysts (TiO2, boron nitride [BN]) for removing PFAS contaminants and (2) evaluate their role on the conversion of non-detected/unknown to known PFAS compounds in real groundwater used as drinking water supplies. Results indicated that, while AOPs have the potential to achieve removal of the EPA method 533 target PFAS compounds (PFDA [100%], PFNA [100%], PFOA [85-94%], PFOS [25-100%], PFHxS [3-100%], PFPeS [100%], PFBS [100%]), AOPs transformed non-detected/unknown longer-chain PFAS compounds to detectable shorter-chain ones under very high-dose AOP operating conditions, leading to an increase in ∑PFAS concentration ranging from 95% to 340%. As emerging PFAS treatment processes transition from lab-scale investigations of target PFAS to pilot testing of real water matrices, studies will need to consider impact of the presence of non-target long-chain PFAS to transform into targeted PFAS compounds. A promising approach to address the potential risks and unforeseen consequences could involve an increased reliance on adsorbable organic fluorine (AOF) analysis before and after advanced oxidation process (AOP) treatment.

Carbon nitride nanotubes anchored with Cu(I) triggers peracetic acid activation with visible light for removal of antibiotic contaminants: Probing mechanisms of non-radical pathways and identifying active sites.

The peracetic acid (PAA)-activation process has attracted much attention in wastewater treatment. However, the low electron efficiency at the interface between heterogeneous catalysts and PAA has affected its practical application. For this study, we developed a carbon nitride hollow-nanotube catalysts with dispersed Cu(I) sites (Cu(I)-TCN) for the photocatalytic activation of PAA for antibiotics degradation. The obtained Cu(I)-TCN catalyst demonstrated an enhanced capacity for visible light harvesting along with increased charge transfer rates. Specifically, the developed Cu(I)-TCN/visible light/PAA system was able to completely remove antibiotics within 20 min, with a kinetic constant that was 25 times higher than a Cu(I)-TCN/visible light system, and 83 times higher than Cu(I)-TCN/PAA systems. Scavenging experiment and electron paramagnetic resonance (EPR) indicated that singlet oxygen was dominant reactive specie for sulfisoxazole (SIZ) removal. Besides, electrochemical tests and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy verified that the electron transfer efficiency of PAA activation was promoted due to the formation of inner-sphere interactions between PAA and Cu(I)-TCN, resulting in the quick removal of antibiotics. Further, after exposure to visible light, the Cu(I)-TCN excited photogenerated electrons which supplemented the electrons consumed in the reaction and drove the valence cycle of Cu ions. Overall, this research offered novel insights into the non-radical pathway for heterogeneous visible light-driven advanced oxidation processes and their potential for practical wastewater remediation.

Improving organic matter and nutrients removal and minimizing sludge production in landfill leachate pre-treatment by Fenton process through a comprehensive response surface methodology approach.

Landfill leachate (LL) represents a very complex effluent difficult to treat and to manage which usually requires a chemical pre-treatment. In this study, response surface methodology (RSM) was used to identify the optimum operating conditions of the Fenton process as a pre-treatment of LL in order to reduce the high organic content and simultaneously optimize the BOD5:TN:TP ratio. The dosages of Fenton process reagents, namely Fe2+ and H2O2, were used as variables for the implementation of RSM. Chemical oxygen demand (COD), five-days biochemical oxygen demand (BOD5), total nitrogen (TN), total phosphorus (TP) removals (and simultaneously BOD5:TN:TP ratio), sludge-to-iron ratio (SIR) and organic removal-to-sludge ratio (ORSR) were selected as target responses. This approach considered the SIR and ORSR parameters which are a useful tool for assessing sludge formation during the process along with organic matter removal. The variables (H2O2 and Fe2+ concentrations) significantly affected the responses, as the role of oxidation mechanism is dominant with respect to coagulation one. The pH for the process was fixed to 2.8 while the treatment time was set to 2 h. The optimum operational conditions obtained by perturbation and 3D surface plot, were found to be 4262 mg/L and 5104 mg/L for Fe2+ and H2O2, respectively (H2O2/Fe2+ molar ratio = 2) with COD, BOD5, TN and TP removals of 70%, 67%, 84% and 96% respectively, while SIR and ORSR final values were 1.15 L/mol and 33.79 g/L respectively, in accordance with models-predicted values. Moreover, the initial unbalanced BOD5:TN:TP ratio (9:1:1) was significantly improved (100:6:1), making the effluent suitable for a subsequent biological treatment. The investigated approach allowed to optimize the removal of organic load and nutrients as well as to minimize the sludge formation in Fenton process, providing a useful tool for the operation and management of LL pre-treatment.

Modifications to microplastics by potassium ferrate(VI): impacts on sorption and sinking capability in water treatment.

Pre-treatment (oxidation) may induce potential modifications to microplastics (MPs), further affecting their behaviors and removal efficiency in drinking water treatment plants. Herein, potassium ferrate(VI) oxidation was tested as a pre-treatment for MPs with four polymer types and three sizes each. Surface oxidation occurred with morphology destruction and oxidized bond generation, which were prosperous under low acid conditions (pH 3). As pH increased, the generation and attachment of nascent state ferric oxides (FexOx) gradually became dominant, making MP-FexOx complexes. These FexOx were identified as Fe(III) compounds, including Fe2O3 and FeOOH, firmly attaching to the MP surface. Using ciprofloxacin as the targeted organic contaminant, the presence of FexOx enhanced MP sorption dramatically, e.g., the kinetic constant Kf of ciprofloxacin raised from 0.206 (6.5 µm polystyrene) to 1.062 L g-1 (polystyrene-FexOx) after oxidation at pH 6. The sinking performance of MPs was enhanced, especially for small MPs (< 10 µm), which could be attributed to the increasing density and hydrophilicity. For instance, the sinking ratio of 6.5 µm polystyrene increased by 70% after pH 6 oxidation. In general, ferrate pre-oxidation possesses multiple enhanced removals of MPs and organic contaminants through adsorption and sinking, reducing the potential risk of MPs.

The Zebrafish (Danio rerio) Embryo Model as a Tool to Assess Drinking Water Treatment Efficacy for Freshwater Impacted by Crude Oil Spill.

Traditional approaches toward evaluating oil spill mitigation effectiveness in drinking water supplies using analytical chemistry can overlook residual hydrocarbons and treatment byproducts of unknown toxicity. Zebrafish (Danio rerio) were used to address this limitation by evaluating the reduction in toxicity to fish exposed to laboratory solutions of dissolved crude oil constituents treated with 3 mg/L ozone (O3 ) with or without a peroxone-based advanced oxidation process using 0.5 M H2 O2 /M O3 or 1 M H2 O2 /M O3 . Crude oil water mixtures (OWMs) were generated using three mixing protocols-orbital (OWM-Orb), rapid (OWM-Rap), and impeller (OWM-Imp) and contained dissolved total aromatic concentrations of 106-1019 µg/L. In a first experiment, embryos were exposed at 24 h post fertilization (hpf) to OWM-Orb or OWM-Rap diluted to 25%-50% of full-strength samples and in a second experiment, to untreated or treated OWM-Imp mixtures at 50% dilutions. Toxicity profiles included body length, pericardial area, and swim bladder inflation, and these varied depending on the OWM preparation, with OWM-Rap resulting in the most toxicity, followed by OWM-Imp and then OWM-Orb. Zebrafish exposed to a 50% dilution of OWM-Imp resulted in 6% shorter body length, 83% increased pericardial area, and no swim bladder inflation, but exposure to a 50% dilution of OWM-Imp treated with O3 alone or with 0.5 M H2 O2 /M O3 resulted in normal zebrafish development and average total aromatic destruction of 54%-57%. Additional aromatic removal occurred with O3 + 1 M H2 O2 /M O3 but without further attenuation of toxicity to zebrafish. This study demonstrates using zebrafish as an additional evaluation component for modeling the effectiveness of freshwater oil spill treatment methods. Environ Toxicol Chem 2022;41:2822-2834. © 2022 SETAC.

FeCl3-activated biochar catalyst for heterogeneous Fenton oxidation of antibiotic sulfamethoxazole in water.

One-step FeCl3-mediated pyrolysis/activation was developed for preparation of bermudagrass (BG)-derived FeCl3-activated biochars (FA-BCs) from bermudagrass (BG) as a heterogenous Fenton catalyst for heterogeneous Fenton oxidation of sulfamethoxazole (SMX) in water. The FA-BC prepared at the FeCl3 to BG mass ratio of 2 (FA-BC) exhibited higher adsorption and Fenton oxidation of SMX than other mass ratios of the FeCl3 to BG. FA-BC presented the great surface area (835 m2/g) and high SMX adsorption capacity (195 mg SMX/g BC), which was higher than various BCs in the previous studies. Additionally, the surface of FA-BC was attached with Fe2O3, Fe0, and Fe3O4 after the FeCl3 activation. Under the optimal conditions for Fenton reaction (SMX concentration, 100 mg/L; loading of FA-BC, 0.1 g/L; dose of H2O2, 200 mg/L; temperature, 20 °C; pH 3; reaction time, 12 h), SMX and COD removal efficiencies reached 99.94% and 65.19%, respectively. Increasing reaction temperature from 20 to 50 °C significantly improved the SMX oxidation rate from 0.46 to 1.04 h-1. The HO· radicals were proved to play a major role during the Fenton oxidation of SMX. In addition, the SMX solution treated by Fenton oxidation showed much less toxicity than the initial SMX solution. Additionally, the reusability tests of FA-BC indicated that 89.58% removal efficiency for SMX was still achieved after 3 cycles of Fenton oxidation under the optimal conditions. Furthermore, FA-BC can also efficiently remove SMX from the dairy wastewater. Therefore, FA-BC showed a high potential to eliminate aqueous SMX through adsorption and heterogeneous Fenton oxidation.

Enhanced UV Direct Photolysis and UV/H2O2 for Oxidation of Triclosan and Ibuprofen in Synthetic Effluent: an Experimental Study.

This study aimed to evaluate the implementation of an advanced oxidation system based on UV radiation and UV/H2O2 for degradation of TCS and IBU in synthetic effluent. The assays occurred in a 2-L reactor, protected from external light and equipped with a UV lamp (λ = 254 nm). The effect of contaminant concentration, fractions of chemical species present, and mineralization were evaluated. In the UV/ H2O2 system, different concentrations of H2O2 were studied for oxidation of the contaminants. The kinetic experiments took place between 75 and 270 min of UV irradiation. The results showed > 99% oxidation of TCS in the direct photolysis system at pH 9.4 after 12 min. The degradation of IBU in the UV/H2O2 system, when 10 mg L-1 of H2O2 was used, was 97.39% oxidation. We obtained k' values of 0.189 min-1 for TCS when its highest oxidation occurred and k' values of 0.0219 min-1 for IBU. The system was not able to completely mineralize the contaminants, presenting high values of TOC and COD after treatment, thus suggesting the occurrence of phototransformation. Supplementary Information: The online version contains supplementary material available at 10.1007/s11270-022-05583-z.

A new spent coffee grounds based biochar - Persulfate catalytic system for enhancement of urea removal in reclaimed water for ultrapure water production.

The demand for ultrapure water (UPW) in the semiconductor industry has increased in recent years, while the idea to use reclaimed water instead of tap water for UPW production has also attracted more attention. However, since urea concentration in reclaimed water is higher than that in tap water, UPW production has not been efficient. To resolve this problem, this study aims to develop a new spent coffee grounds based biochar (SCG-BC)/persulfate catalytic system as a pretreatment unit. The objective is to enhance urea removal from reclaimed water so that UPW production is more effective. In this study, the biochar used was prepared from spent coffee grounds with detailed characterization. Results strongly suggested that the urea removed by SCG-BC/persulfate catalytic system was very encouraging (up to 73%). The best possible dosages for SCG-BC and persulfate for urea removal were 0.2 and 2.0 g L-1, respectively. Furthermore, this system could remove urea effectively in a wide range of pH (3-10). Moreover, the characterizations of SCG-BC (graphite C, defective edges and functional groups, i.e. -OH, CO, carboxyl C-O) helped to activate persulfate in the catalytic process. OH• and SO4• - were all involved in this process, while the SO4• - was the main radical for urea degradation.

Treatment of real wastewater by photoelectrochemical methods: An overview.

An inadequate and inefficient performance ability of conventional methods to remove persistent organic pollutants urges the need of alternative or complementary advanced wastewater treatments methods to ensure the safer reuse of reclaimed water. Photoelectrochemical methods are emerging as promising options among other advanced oxidation processes because of the higher treatment efficiency achieved due to the synergistic effects of combined photochemical and electrolysis reactions. Synergistic effects of integrated photochemical, electrochemical and photoelectrochemical processes not only increase the hydroxyl radical production; an enhancement on the mineralization ability through various side reactions is also achieved. In this review, fundamental reaction mechanisms of different photoelectrochemical methods including photoelectrocatalysis, photo/solar electro-Fenton, photo anodic oxidation, photoelectroperoxone and photocatalytic fuel cell are discussed. Various integrated photochemical, electrochemical and photoelectrochemical processes and their synergistic effects are elaborated. Different reactor configurations along with the positioning of electrodes, photocatalysts and light source of the individual/combined photoelectrochemical treatment systems are discussed. Modified photoanode and cathode materials used in the photoelectrochemical reactors and their performance ability is presented. Photoelectrochemical treatment of real wastewater such as landfill leachate, oil mill, pharmaceutical, textile, and tannery wastewater are reviewed. Hydrogen production efficiency in the photoelectrochemical process is further elaborated. Cost and energy involved in these processes are briefed, but the applicability of photocatalytic fuel cells to reduce the electrical dependence is also summarised. Finally, the use of photoelectrochemical approaches as an alternative for treating soil washing effluents is currently discussed.

Dielectric barrier discharge plasma with photocatalysts as a hybrid emerging technology for degradation of synthetic organic compounds in aqueous environments: A critical review.

Dielectric barrier discharge (DBD) plasma has been recently used for removal of synthetic organic compounds (SOCs) from aqueous environments. The removal of SOCs by alone DBD is significantly limited by its high electricity needs and inefficient mineralization, which affects the further application of DBD for SOCs. The combined application of DBD with other technologies and the addition of a supplementary substance for energy-saving were proposed to resolve these problems. The addition of catalysts is considered to be a promising and innovative approach to increase the energy yield of DBD, improve the environment friendly of DBD, develop the variety of goal SOCs, and improve the removal efficiency of DBD system. Despite the increasing use of the coupling form of DBD and catalysts, as catalytic dielectric barrier discharge (CDBD), but it still requires a comprehensive review to summarize the last studies and highlight the future perspectives in this area. Therefore, this work is the first literature review aimed to critically assess the latest developments of catalysts coupling with DBD employed in aqueous environments. Moreover, performance evaluation, energy yield, toxicity, eco-friendly, and future perspectives of the CDBD systems for SOCs removal were discussed and overviewed. The results showed that the coupling of catalysts with DBD presents synergistic effects and had excellent removal performance for aqueous SOCs. Overall, it can be concluded that the essential principles of environmental and economic sustainability have been addressed for the removal of persistent pollutants from aqueous environments in the CDBD systems.

Are iron chelates suitable to perform photo-Fenton at neutral pH for secondary effluent treatment?

There have been concerns about which iron chelate is most suitable for application in the photo-Fenton process as well as the fate of these chelates after application. In this study, five chelating agents, i.e. citric acid (CA), oxalic acid (OA), ethylenediamine disuccinic acid (EDDS), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), representing the most used iron chelates were assessed for suitability of application in homogeneous photo-Fenton-like process at pH of 7. The efficiency of the iron chelates were assessed in the disinfection of secondary effluent. The results for the disinfection and bacteria regrowth followed the order EDTA>OA>NTA>CA>OA. All the iron chelates were observed to have increased the COD of the effluent with EDDS having the highest COD contribution. The ability of the chelates to remove aromaticity was measured by the UV254 measurement. The efficiency of the chelates to remove aromaticity decreased in the order CA>EDDS>NTA>CA>OA. To determine the fate of the chelates, toxicity tests were conducted on the chelates before and after irradiation and the results revealed a decrease in toxicity after photoirradiation, implying the chelates were degraded and the products/intermediates produced were of less toxicity as compared to the parent compounds.

Evaluation of hospital laundry effluents treated by advanced oxidation processes and their cytotoxic effects on Allium cepa L.

Hospital laundries are responsible for a significant part of the amount of wastewater that is generated in hospitals. Hospital laundry wastewater represents a complex mixture of chemicals that arouse concerns about possible environmental risks. The objective of the present study was to evaluate the cytotoxicity of different laundry effluents from the Regional University Hospital of Maringá, Paraná, Brazil, on Allium cepa L. meristematic root cells. The effluents were characterised as rinsing, wetting, prewashing, washing, softening, wastewater (the effluent generated at the end of the washing process), the wastewater that was treated by physicochemical (PC) processes and the wastewater that was treated by advanced oxidation processes (PC + UV, PC + H2O2 and PC + UV/H2O2). The mitotic indexes were calculated by scoring 5000 cells per group and the statistical analyses were performed by one-way ANOVA, followed by Tukey's post-test (α = 0.05). Results showed that the rinsing, wetting, prewashing and wastewater laundry effluents were cytotoxic at 24 h of exposure, significantly reducing the mitotic index. Despite the slight cytotoxicity of the PC + UV/H2O2 treatment, physicochemical and advanced oxidation processes efficiently reduced the critical parameters of wastewater, such as the biochemical and chemical oxygen demands, to tolerable levels of effluent discharge. It is essential to perform constant monitoring of these effluents in order to reduce the possible occurrence of environmental impacts.

AOPs-based remediation of petroleum hydrocarbons-contaminated soils: Efficiency, influencing factors and environmental impacts.

Petroleum hydrocarbons are a class of anthropogenic compounds including alkanes, aromatic hydrocarbons, resins, asphaltenes and other organic matters, and soil pollution caused by petroleum hydrocarbons has drawn increasing interest in recent years. Multiple advanced oxidation processes (AOPs) are emerging to remediate petroleum hydrocarbons-contaminated soils, while very few studies have focused on the features of AOPs applied in soils. This review aims to provide an updated overview of the state of the science about the efficiency, influencing factors and environmental implications of AOPs. The key findings from this review include: 1) cyclodextrin and its derivatives can be used to synthesize targeting reagents; 2) soil organic matter (SOM), glucose and cement can activate persulfate; 3) SOM affects redox circumstance in soil and could be further developed for enhancing the catalysis effect of transition metals; 4) non-thermal plasma and wet oxidation are promising methods of AOPs to remove petroleum hydrocarbons from soil; 5) the occurrence, fate, and transformation of intermediates during the degradation of petroleum hydrocarbons in soil should be considered more. Overall, this review reveals an urgent need to develop the cost-effective remedial strategies for petroleum hydrocarbons contaminated soils, and to advance our knowledge on the generation, transport and propagation of radicals in soils.

Environmentally friendly synthesized and magnetically recoverable designed ferrite photo-catalysts for wastewater treatment applications.

Fenton processes are promising wastewater treatment alternatives for bio-recalcitrant compounds. Three different methods (i.e., reverse microemulsion, sol-gel, and combustion) were designed to synthesize environmentally friendly ferrites as magnetically recoverable catalysts to be applied for the decomposition of two pharmaceuticals (ciprofloxacin and carbamazepine) that are frequently detected in water bodies. The catalysts were used in a heterogeneous solar photo-Fenton treatment to save the cost of applying high-energy UV radiation sources, and was performed under a slightly basic pH to avoid metal leaching and adding salts for pH adjustment. All the developed catalysts resulted in the effective treatment of ciprofloxacin and carbamazepine in both synthetic and real domestic wastewater. In particular, the sol-gel synthesized ferrite was more magnetic and more suitable for reuse. The degradation pathways of both compounds were elucidated for this treatment. The degradation of ciprofloxacin involved attacks to the quinolone and piperazine rings. The degradation pathway of carbamazepine involved the formation of hydroxyl carbamazepine and dihydroxy carbamazepine before yielding acridine by hydrogen abstraction, decarboxylation, and amine cleavage, which would be further oxidized.

Phenanthrene degradation using Fe(III)-EDDS photoactivation under simulated solar light: A model for soil washing effluent treatment.

In this work, for the first time, the nonionic surfactant polyoxyethylene-(20)-sorbitan monooleate (Tween 80, C64H124O26) aided soil washing effluent was treated by enhanced activation of persulfate (PS) using Fe(III)-EDDS (EDDS: ethylenediamine-N, N-disuccinic acid) complexes under simulated solar light irradiation. The performance of this system was followed via the production and reactivity of radical species (SO4-, HO, Cl2-) and degradation of phenanthrene (PHE) used as a model pollutant in soils. Different physico-chemical parameters such as the concentration of reactive species and pH were investigated through the PHE degradation efficiency. The second-order rate constants of the reactions for generated radicals with PHE and Tween 80 in solution were identified through competitive reaction experiments under steady-state conditions and application of nanosecond laser flash photolysis (LFP) as well. A kinetic approach was applied to assess the selectivity and reactivity of photo-generated radicals in aqueous medium in order to explain the observed degradation trends. This work proposes an innovative technology of management of soil washing solutions using Fe(III)-EDDS complexes and solar light for the activation of persulfate.

Unsubstituted metallophthalocyanine catalysts for the removal of endocrine disrupting compounds using H2O2 as oxidant.

Advanced oxidation processes have become increasingly important to treat non-biodegradable compounds entering environmental waters. In recent decades, water-soluble metallophthalocyanines have been shown to catalyse H2O2-containing oxidation reactions through the production of unique reactive species, nucleophilic metal-peroxo complexes. Few reports in the literature have examined water insoluble metallophthalocyanines (MPc). The oxidative catalytic activity of water insoluble manganese- and iron-phthalocyanine (MnPc, FePc) at pH 7 has been shown through the decolourisation of methylene blue and removal of bisphenol A. These studies expand on this previous study, exploring the catalytic activity of a range of metallophthalocyanines catalysts under both acidic and neutral conditions. FePc, while only active under neutral conditions, was the best performing catalyst. This activity was significantly improved upon by the addition of acetonitrile as a co-solvent, as well as increasing the ratio of H2O2 to catalyst. MnPc was catalytically active at both pH 3 and 7. FePc and MnPc catalysts showed the ability to remove bisphenol A in the presence of dam water. Reaction rates were reduced for bisphenol A removal with FePc as a catalyst but were unchanged in the presence of MnPc. The removal of 17ß-estradiol, estrone, and coumestrol was successfully demonstrated, with greater than 96% removal of all tested EDC's achieved. This is the first reported study showing the removal of the phytoestrogen, coumestrol. Even though considerably lower concentrations of costly catalysts and oxidation reagents were used in our work, the removal extent of EDC's by the MPc-catalysed oxidation reactions achieved here compares favourably with literature.

Effective method of treatment of effluents from production of bitumens under basic pH conditions using hydrodynamic cavitation aided by external oxidants.

Utilization of cavitation in advanced oxidation processes (AOPs) is a promising trend in research on treatment of industrial effluents. The paper presents the results of investigations on the use of hydrodynamic cavitation aided by additional oxidation processes (O3/H2O2/Peroxone) to reduce the total pollution load in the effluent from the production of bitumens. A detailed analysis of changes in content of volatile organic compounds (VOCs) for all processes studied was also performed. The studies revealed that the most effective treatment process involves hydrodynamic cavitation aided by ozonation (40% COD reduction and 50% BOD reduction). The other processes investigated (hydrodynamic cavitation+H2O2, hydrodynamic cavitation+Peroxone and hydrodynamic cavitation alone) ensure reduction of COD by 20, 25 and 13% and reduction of BOD by 49, 32 and 18%, respectively. The results of this research revealed that most of the VOCs studied are effectively degraded. The formation of byproducts is one of the aspects that must be considered in evaluation of the AOPs studied. This work confirmed that furfural is one of the byproducts whose concentration increased during treatment by hydrodynamic cavitation alone as well as hydrodynamic cavitation aided by H2O2 as an external oxidant and it should be controlled during treatment processes.

Role of sulfate, chloride, and nitrate anions on the degradation of fluoroquinolone antibiotics by photoelectro-Fenton.

Taking ciprofloxacin (CIP) as a fluoroquinolone antibiotic model, this work explores the role of common anions (sulfate, nitrate, and chloride) during the application of photoelectro-Fenton (PEF) at natural pH to degrade this type of compound in water. The system was composed of an IrO2 anode, Ti, or gas diffusion electrode (GDE) as cathode, Fe2+, and UV (254 nm). To determine the implications of these anions, the degradation pathway and efficiency of the PEF sub-processes (UV photolysis, anodic oxidation, and electro-Fenton at natural pH) were studied in the individual presence of the anions. The results highlight that degradation routes and kinetics are strongly dependent on electrolytes. When chloride and nitrate ions were present, indirect electro-chemical oxidation was identified by electro-generated HOCl and nitrogenated oxidative species, respectively. Additionally, direct photolysis and direct oxidation at the anode surface were identified as degradation routes. As a consequence of the different pathways, six primary CIP by-products were identified. Therefore, a scheme was proposed representing the pathways involved in the degradation of CIP when submitted to PEF in water with chloride, nitrate, and sulfate ions, showing the complexity of this process. Promoted by individual and synergistic actions of this process, the PEF system leads to a complete elimination of CIP with total removal of antibiotic activity against Staphylococcus aureus and Escherichia coli, and significant mineralization. Finally, the role of the anions was tested in seawater containing CIP, in which the positive contributions of the anions were partially suppressed by its OH radical scavenger action. The findings are of interest for the understanding of the degradation of antibiotics via the PEF process in different matrices containing sulfate, nitrate, and chloride ions.

Trend and current practices of palm oil mill effluent polishing: Application of advanced oxidation processes and their future perspectives.

Palm oil processing is a multi-stage operation which generates large amount of effluent. On average, palm oil mill effluent (POME) may contain up to 51, 000 mg/L COD, 25,000 mg/L BOD, 40,000 TS and 6000 mg/L oil and grease. Due to its potential to cause environmental pollution, palm oil mills are required to treat the effluent prior to discharge. Biological treatments using open ponding system are widely used for POME treatment. Although these processes are capable of reducing the pollutant concentrations, they require long hydraulic retention time and large space, with the effluent frequently failing to satisfy the discharge regulation. Due to more stringent environmental regulations, research interest has recently shifted to the development of polishing technologies for the biologically-treated POME. Various technologies such as advanced oxidation processes, membrane technology, adsorption and coagulation have been investigated. Among these, advanced oxidation processes have shown potentials as polishing technologies for POME. This paper offers an overview on the POME polishing technologies, with particularly emphasis on advanced oxidation processes and their prospects for large scale applications. Although there are some challenges in large scale applications of these technologies, this review offers some perspectives that could help in overcoming these challenges.

Non-thermal plasma treatment of Radix aconiti wastewater generated by traditional Chinese medicine processing.

The wastewater effluent from Radix aconiti processing, an important step in the production processes of traditional Chinese medicine (TCM), is a type of toxic wastewater and difficult to treat. Plasma oxidation methods have emerged as feasible techniques for effective decomposition of toxic organic pollutants. This study examined the performance of a plasma reactor operated in a dielectric barrier discharge (DBD) to degrade the effluent from R. aconiti processing. The effects of treatment time, discharge voltage, initial pH value and the feeding gas for the reactor on the degradation of this TCM wastewater were investigated. A bacterium bioluminescence assay was adopted in this study to test the toxicity of the TCM wastewater after non-thermal plasma treatment. The degradation ratio of the main toxic component was 87.77% after 60min treatment with oxygen used as feed gas and it was 99.59% when the initial pH value was 8.0. High discharge voltage and alkaline solution environment were beneficial for improving the degradation ratio. The treatment process was found to be capable of reducing the toxicity of the wastewater to a low level or even render it non-toxic. These experimental results suggested that the DBD plasma method may be a competitive technology for primary decomposition of biologically undegradable toxic organic pollutants in TCM wastewater.