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Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) are efficient processes to degrade organic pollutants in water. In this paper, the influence of different reaction parameters in WAO, such as temperature, oxygen pressure, pH, stirring speed are analyzed in detail. Homogenous and heterogeneous catalysts including carbon materials, transitional metal oxides and noble metals are extensively discussed in CWAO. Three different kinds of the reactor in the CWAO (autocla [Detail] ...
There is a rapidly emerging and potentially huge market for the remediation of contaminated groundwater in China. The Chinese government published a Water Action Plan in April 2015, a Soil Action Plan in May 2016, and a draft Soil Pollution Prevention and Control Law in June 2017. All of these new policies and regulations put pressures on local governments and contaminated site owners, obliging them to conduct site investigation and to cleanup contaminated groundwater. The Chinese population in northern regions heavily depend on groundwater, with nearly 70% of water supply coming from aquifer sources in the Beijing-Tianjin-Hebei region. However, poor groundwater quality due to natural geochemical background and anthropogeic pollution is a serious concern, with poor or very poor quality water observed in nearly 80% of groundwater monitoring wells in 17 northern provinces. Shallow groundwater in many areas has been contaminated by toxic pollutants such as heavy metals and chlorinated organic compounds. There is an urgent need to better understand the situation and to conduct groundwater remediation at contaminated sites. The Chinese government is investing heavily in the research and development for groundwater remediation, which is expected to greatly add to the quality and quantity of groundwater remediation projects in the near future.
Fe-BEA with zirconia binder has higher SCR activity in high temperature. Alumina enhances the low-temperature activity for greater NO oxidation and storage. The SCR activity of Fe-BEA/Al decreases in high temperature.
Fe-BEA catalysts are active for the NH3-SCR of NO. For industrial application, a binder should be added to the Fe-BEA catalysts to make them tightly adhere to the monoliths. The addition of alumina and zirconia as binders to the Fe-BEA led to a different effect on NO conversion. The catalytic activity of the mixed samples was evaluated by the temperature programmed procedure in a flow-reactor system, and the mechanism was analyzed via SEM, BET, XRD and XPS. It was found that larger iron particles were formed by the migration of parent iron particles in the Fe-BEA catalyst with alumina. This led to the increase of Fe3+ magnitude and iron cluster, enhancing the abilities of NO oxidation and storage. Accordingly, the SCR activity increased slightly in low temperature but decreased sharply in high temperature. For the Fe-BEA with zirconia sample, NO oxidation and storage abilities decreased due to the less iron clusters. The increase of Fe3+ magnitude resulted in higher catalytic oxidation ability, which gave rise to little change in the SCR activity compared with the Fe-BEA.
Peak of surface runoff was lagged and clipped by BRU with turf grass and B. Sinica. Lag of peak and extent of clipping was influenced flow regime of inflow and plants grown. TN, TP and COD were removed by filtration of the media and bio-degradation of reservoir layer. Infiltration rate and storage depth could be transferred key parameters for engineering design.
A bioretention unit (BRU) or cell is a green infrastructure practice that is widely used as a low impact development (LID) technique for urban stormwater management. Bioretention is considered a good fit for use in China’s sponge city construction projects. However, studies on bioretention design, which incorporates site-specific environmental and social-economic conditions in China are still very much needed. In this study, an experimental BRU, consisted of two cells planted with Turf grass and Buxus sinica,was tested with eighteen synthesized storm events. Three levels (high, median, low) of flows and concentrations of pollutants (TN, TP and COD) were fed to the BRU and the performance of which was examined. The results showed that the BRU not only delayed and lowered the peak flows but also removed TN, TP and COD in various ways and to different extents. Under the high, medium and low inflow rate conditions, the outflow peaks were delayed for at least 13 minutes and lowered at least 52%. The two cells stored a maximum of 231 mm and 265 mm for turf grass and Buxus sinica, respectively. For both cells the total depth available for storage was 1,220 mm, including a maximum 110 mm deep ponding area. The largest infiltrate rate was 206 mm/h for both cells with different plants. For the eighteen events, TP and COD were removed at least 60% and 42% by mean concentration, and 65% and 49% by total load, respectively. In the reservoir layer, the efficiency ratio of removal of TN, TP and COD were 52%, 8% and 38%, respectively, within 5 days after runoff events stopped. Furthermore, the engineering implication of the hydrological and water quality performances in sponge city construction projects is discussed.
Performance of CMAQ-Hg is better using Model-driven BCs than default BC. Model-VAT provides a better user experience to convert Model-driven BCs. Model-VAT is designed to efficiently access and analyze the results of multi-models.
Atmospheric models are essential tools to study the behavior of air pollutants. To interpret the complicated atmospheric model simulations, a new-generation Model Visualization and Analysis Tool (Model-VAT) has been developed for scientists to analyze the model data and visualize the simulation results. The Model-VAT incorporates analytic functions of conventional tools and enhanced capabilities in flexibly accessing, analyzing, and comparing simulated results from multi-scale models with different map projections and grid resolutions. The performance of the Model-VAT is demonstrated by a case study of investigating the influence of boundary conditions (BCs) on the ambient Hg formation and transport simulated by the CMAQ model over the Pearl River Delta (PRD) region. The alternative BC options are taken from (1) default time-independent profiles, (2) outputs from a CMAQ simulation of a larger nesting domain, and (3) concentration files from GEOS-Chem (re-gridded and re-projected using the Model-VAT). The three BC inputs and simulated ambient concentrations and deposition were compared using the Model-VAT. The results show that the model simulations based on the static BCs (default profile) underestimates the Hg concentrations by ~6.5%, dry depositions by ~9.4%, and wet depositions by ~43.2% compared to those of the model-derived (e.g. GEOS-Chem or nesting CMAQ) BCs. This study highlights the importance of model nesting approach and demonstrates that the innovative functions of Model-VAT enhances the efficiency of analyzing and comparing the model results from various atmospheric model simulations.
PM2.5 in Chengdu showed clear seasonal and diurnal variation. 5, 5, 5 and 3 mean clusters are generated in spring, summer, autumn, and winter. Short-distance air masses are important pathways in Chengdu. Emissions within the Sichuan Basin contribute significantly to PM2.5 pollution. Long-range transport from Southern Xinjiang is a dust invasion path to Chengdu.
Seasonal pattern of transport pathways and potential sources of PM2.5 in Chengdu during 2012–2013 were investigated based on hourly PM2.5 data, backward trajectories, clustering analysis, potential source contribution function (PSCF), and concentration-weighted trajectory (CWT) method. The annual hourly mean PM2.5 concentration in Chengdu was 97.4 mg·m–3. 5, 5, 5 and 3 mean clusters were generated in four seasons, respectively. Short-distance air masses, which travelled within the Sichuan Basin with no specific source direction and relatively high PM2.5 loadings (>80 mg·m–3) appeared as important pathways in all seasons. These short pathways indicated that emissions from both local and surrounding regions of Chengdu contributed significantly to PM2.5 pollution. The cities in southern Chengdu were major potential sources with PSCF>0.6 and CWT>90 mg·m–3. The northeastern pathway prevailed throughout the year with higher frequency in autumn and winter and lower frequency in spring and summer. In spring, long-range transport from southern Xinjiang was a representative dust invasion path to Chengdu, and the CWT values along the path were 30-60 mg·m–3. Long-range transport was also observed in autumn from southeastern Xinjiang along a northwesterly pathway, and in winter from the Tibetan Plateau along a westerly pathway. In summer, the potential source regions of Chengdu were smaller than those in other seasons, and no long-range transport pathway was observed. Results of PSCF and CWT indicated that regions in Qinghai and Tibet contributed to PM2.5 pollution in Chengdu as well, and their CWT values increased to above 30 mg·m-3 in winter.
Nitrobenzene degraded rapidly and was removed completely in native sediments. Indigenous microorganisms in native sediments are abundant. Proteobacteria and Firmicutes might play important roles in nitrobenzene removal. P. australis could provide a more suitable environment for Thauera.
The feasibility of using Phragmites australis-JS45 system in removing nitrobenzene from sediments was conducted. However, it was observed that nitrobenzene degraded rapidly and was removed completely within 20 days in native sediments, raising the possibility that indigenous microorganisms may play important roles in nitrobenzene degradation. Consequently, this study aimed to verify this possibility and investigate the potential nitrobenzene degraders among indigenous microorganisms in sediments. The abundance of inoculated strain JS45 and indigenous bacteria in sediments was quantified using real-time polymerase chain reaction. Furthermore, community structure of the indigenous bacteria was analyzed through high throughput sequencing based on Illumina MiSeq platform. The results showed that indigenous bacteria in native sediments were abundant, approximately 1014 CFU/g dry weight, which is about six orders of magnitude higher than that in fertile soils. In addition, the levels of indigenous Proteobacteria (Acinetobacter, Comamonadaceae_uncultured, Pseudomonas, and Thauera) and Firmicutes (Clostridium, Sporacetigenium, Fusibacter, Youngiibacter, and Trichococcus) increased significantly during nitrobenzene removal. Their quantities sharply decreased after nitrobenzene was removed completely, except for Pseudomonas and Thauera. Based on the results, it can be concluded that indigenous microorganisms including Proteobacteria and Firmicutes can have great potential for removing nitrobenzene from sediments. Although P. australis - JS45 system was set up in an attempt to eliminate nitrobenzene from sediments, and the system did not meet the expectation. The findings still provide valuable information on enhancing nitrobenzene removal by optimizing the sediment conditions for better growth of indigenous Proteobacteria and Firmicutes.
N2O release varies in response to enzyme-catalyzed nitrogen imbalances. The enzymology involved in N2O production and consumption are introduced. The pathways of N2O production and consumption are summarized. Key factors affecting N2O release and enzymatic mechanisms are summarized/revealed. Enzymatic strategies are proposed to mitigate N2O emissions.
Nitrous oxide (N2O), a potent greenhouse gas, is emitted during nitrogen removal in wastewater treatment, significantly contributing to greenhouse effect. Nitrogen removal generally involves nitrification and denitrification catalyzed by specific enzymes. N2O production and consumption vary considerably in response to specific enzyme-catalyzed nitrogen imbalances, but the mechanisms are not yet completely understood. Studying the regulation of related enzymes’ activity is essential to minimize N2O emissions during wastewater treatment. This paper aims to review the poorly understood related enzymes that most commonly involved in producing and consuming N2O in terms of their nature, structure and catalytic mechanisms. The pathways of N2O emission during wastewater treatment are briefly introduced. The key environmental factors influencing N2O emission through regulatory enzymes are summarized and the enzyme-based mechanisms are revealed. Several enzyme-based techniques for mitigating N2O emissions directly or indirectly are proposed. Finally, areas for further research on N2O release during wastewater treatment are discussed.
Electrochemical removal is promising in nitrate elimination from wastewater. Influencing factors of nitrate electrochemical removal are critically reviewed. Electroreduction pathways of nitrate undergo electron transfer and hydrogenation. Electrocoagulation pathways of nitrate undergo coagulation, reduction, flotation. Electrodialysis pathways of nitrate undergo dialysis, reduction and oxidation.
A number of recent studies have demonstrated that electrochemical technologies, including electroreduction (ER), electrocoagulation (EC), and electrodialysis (ED), are effective in nitrate elimination in wastewater due to their high reactivity. To obtain the maximal elimination efficiency and current efficiency, many researchers have conducted experiments to investigate the optimal conditions (i.e., potential, current density, pH value, plate distance, initial nitrate concentration, electrolyte, and other factors) for nitrate elimination. The mechanism of ER, EC and ED for nitrate removal has been fully elucidated. The ER mechanism of nitrate undergoes electron transfer and hydrogenation reduction. The EC pathways of nitrate removal include reduction, coagulation and flotation. The ED pathways of nitrate include redox reaction and dialysis. Although the electrochemical technology can remove nitrate from wastewater efficiently, many problems (such as relatively low selectivity toward nitrogen, sludge production and brine generation) still hinder electrochemical treatment implementation. This paper critically presents an overview of the current state-of-the-art of electrochemical denitrification to enhance the removal efficiency and overcome the shortages, and will significantly improve the understanding of the detailed processes and mechanisms of nitrate removal by electrochemical treatment and provide useful information to scientific research and actual practice.
Fe2O3-CeO2-Bi2O3/γ-Al2O3, an environmental friendly material, was investigated. The catalyst exhibited good catalytic performance in the CWAO of cationic red GTL. The apparent activation energy for the reaction was 79 kJ·mol−1. HO2· and O2·− appeared as the main reactive species in the reaction.
The Fe2O3-CeO2-Bi2O3/γ-Al2O3 catalyst, a novel environmental-friendly material, was used to investigate the catalytic wet air oxidation (CWAO) of cationic red GTL under mild operating conditions in a batch reactor. The catalyst was prepared by wet impregnation, and characterized by special surface area (BET measurement), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Fe2O3-CeO2-Bi2O3/γ-Al2O3 catalyst exhibited good catalytic activity and stability in the CWAO under atmosphere pressure. The effect of the reaction conditions (catalyst loading, degradation temperature, solution concentration and initial solution pH value) was studied. The result showed that the decolorization efficiency of cationic red GTL was improved with increasing the initial solution pH value and the degradation temperature. The apparent activation energy for the reaction was 79 kJ·mol−1. Hydroperoxy radicals (HO2·) and superoxide radicals (O2−·) appeared as the main reactive species upon the CWAO of cationic red GTL.
The applicability of FeVO4 extended the optimum pH range for heterogeneous Fenton process towards neutral conditions. The datas for the removal of OG in FeVO4 systems conform to the Langmuir–Hinshelwood model. The irradiation of FeVO4 by visible light significantly increases the degradation rate of OG due to the enhanced rates of the iron and vanadium cycles.
In this study, FeVO4 was prepared and used as Fenton-like catalyst to degrade orange G (OG) dye. The removal of OG in an aqueous solution containing 0.5 g·L-1 FeVO4 and 15 mmol·L-1 hydrogen peroxide at pH 7.0 reached 93.2%. Similar rates were achieved at pH 5.7 (k = 0.0471 min-1), pH 7.0 (k = 0.0438 min-1), and pH 7.7 (k = 0.0434 min-1). The FeVO4 catalyst successfully overcomes the problem faced in the heterogeneous Fenton process, i.e., the narrow working pH range. The data for the removal of OG in FeVO4 systems containing H2O2 conform to the Langmuir–Hinshelwood model (R2 = 0.9988), indicating that adsorption and surface reaction are the two basic mechanisms for OG removal in the FeVO4–H2O2 system. Furthermore, the irradiation of FeVO4 by visible light significantly increases the degradation rate of OG, which is attributed to the enhanced rates of the iron cycles and vanadium cycles.
SPAC significantly enhanced the efficacy of catalytic ozonation. Large external surface reduced the diffusion resistance. Surface reaction was dominant for SPAC-based catalytic ozonation. Simple ball milling brought favorable material characteristics for catalysis.
In this study, super-fine powdered activated carbon (SPAC) has been proposed and investigated as a novel catalyst for the catalytic ozonation of oxalate for the first time. SPAC was prepared from commercial granular activated carbon (GAC) by ball milling. SPAC exhibited high external surface area with a far greater member of meso- and macropores (563% increase in volume). The catalytic performances of activated carbons (ACs) of 8 sizes were compared and the rate constant for pseudo first-order total organic carbon removal increased from 0.012 min-1 to 0.568 min-1 (47-fold increase) with the decrease in size of AC from 20 to 40 mesh (863 mm) to SPAC (~1.0 mm). Furthermore, the diffusion resistance of SPAC decreased 17-fold compared with GAC. The ratio of oxalate degradation by surface reaction increased by 57%. The rate of transformation of ozone to radicals by SPAC was 330 times that of GAC. The results suggest that a series of changes stimulated by ball milling, including a larger ratio of external surface area, less diffusion resistance, significant surface reaction and potential oxidized surface all contributed to enhancing catalytic ozonation performance. This study demonstrated that SPAC is a simple and effective catalyst for enhancing catalytic ozonation efficacy.
The adsorption behavior of DB BN on microwave catalyst MgFe2O4-SiC was investigated and the effects of concentration, temperature and pH on the adsorption process were discussed in this study. The microwave-induced catalytic degradation rate of DB BN decreased even more than ten percent after the adsorption equilibrium were attained. The degradation intermediate products of DB BN were identified and analyzed by GC-MS and LC-MS. The proposed degradation pathways of direct black BN (DB BN) were described by combining with the microwave-induced catalytic reaction mechanism of MgFe2O4-SiC.
The novel microwave catalyst MgFe2O4-SiC was synthesized via sol-gel method, to remove azo dye Direct Black BN (DB BN) through adsorption and microwave-induced catalytic reaction. Microwave-induced catalytic degradation of DB BN, including adsorption behavior and its influencing factors of DB BN on MgFe2O4-SiC were investigated. According to the obtained results, it indicated that the pseudo-second-order kinetics model was suitable for the adsorption of DB BN onto MgFe2O4-SiC. Besides, the consequence of adsorption isotherm depicted that the adsorption of DB BN was in accordance with the Langmuir isotherm, which verified that the singer layer adsorption of MgFe2O4-SiC was dominant than the multi-layer one. The excellent adsorption capacities of MgFe2O4-SiC were kept in the range of initial pH from 3 to 7. In addition, it could be concluded that the degradation rate of DB BN decreased over ten percent after the adsorption equilibrium had been attained, and the results from the result of comparative experiments manifested that the adsorption process was not conducive to the process of microwave-induced catalytic degradation. The degradation intermediates and products of DB BN were identified and determined by GC-MS and LC-MS. Furthermore, combined with the catalytic mechanism of MgFe2O4-SiC, the proposed degradation pathways of DB BN were the involution of microwave-induced ·OH and holes in this catalytic system the breakage of azo bond, hydroxyl substitution, hydroxyl addition, nitration reaction, deamination reaction, desorbate reaction, dehydroxy group and ring-opening reaction.
Deposition Au nanoparticles on both TiO2 and RGO to fabricate Au/TiO2/RGO. Au/TiO2/RGO displayed a high H2O2 and •OH production in photocatalytic process. RGO is a good collector to transfer electrons from TiO2 to Au.
A new type of Au/TiO2/reduced graphene oxide (RGO) nanocomposite was fabricated by the hydrothermal synthesis of TiO2 on graphene oxide followed by the photodeposition of Au nanoparticles. Transmission electron microscopy images showed that Au nanoparticles were loaded onto the surface of both TiO2 and RGO. Au/TiO2/RGO had a better photocatalytic activity than Au/TiO2 for the degradation of phenol. Electrochemical measurements indicated that Au/TiO2/RGO had an improved charge transfer capability. Meanwhile, chemiluminescent analysis and electron spin resonance spectroscopy revealed that Au/TiO2/RGO displayed high production of hydrogen peroxide and hydroxyl radicals in the photocatalytic process. This high photocatalytic performance was achieved via the addition of RGO in Au/TiO2/RGO, where RGO served not only as a catalyst support to provide more sites for the deposition of Au nanoparticles but also as a collector to accept electrons from TiO2 to effectively reduce photogenerated charge recombination.
• Catalytic reduction technology for water treatment was reviewed. • Hydrodehalogenation for wastewater treatment was covered. • Hydrogenation of nitrate for groundwater remediation was introduced. • Combination of water splitting with catalytic reduction was illustrated.
Treating water contaminants via heterogeneously catalyzed reduction reaction is a subject of growing interest due to its good activity and superior selectivity compared to conventional technology, yielding products that are non-toxic or substantially less toxic. This article reviews the application of catalytic reduction as a progressive approach to treat different types of contaminants in water, which covers hydrodehalogenation for wastewater treatment and hydrogenation of nitrate/nitrite for groundwater remediation. For hydrodehalogenation, an overview of the existing treatment technologies is provided with an assessment of the advantages of catalytic reduction over the conventional methodologies. Catalyst design for feasible catalytic reactions is considered with a critical analysis of the pertinent literature. For hydrogenation, hydrogenation of nitrate/nitrite contaminants in water is mainly focused. Several important nitrate reduction catalysts are discussed relating to their preparation method and catalytic performance. In addition, novel approach of catalytic reduction using in situ synthesized H2 evolved from water splitting reaction is illustrated. Finally, the challenges and perspective for the extensive application of catalytic reduction technology in water treatment are discussed. This review provides key information to our community to apply catalytic reduction approach for water treatment.
Tunisian clay has been successfully pillared with Al and Fe by microwave irradiation. Microwave method reduces considerably the synthesis time and the water consumption. AlFe-pillared clays are highly stable in the severe operating conditions of CWAO. Oxidation takes place through a heterogeneous mechanism. Microwave pillared-clays are good candidate for CWAO industrial water treatment.
Microwave irradiation has been used to prepare Al, Fe-pillared clays from a natural Tunisian smectite from the El Hicha deposit (province of Gabes). Chemical analysis, XRD spectra and surface properties evidenced the success of pillaring process. The obtained solids present higher surface area and pore volume than conventionally prepared Al-Fe pillared clays. The main advantages of the microwave methodology are the considerable reduction of the synthesis time and the consumption of water. The microwave-derived Al-Fe pillared clays have been tested for catalytic wet air oxidation (CWAO) of phenol in a stirred tank at 160°C and 20 bar of pure oxygen pressure. These materials are efficient for CWAO of phenol and are highly stable despite the severe operating conditions (acidic media, high pressure, high temperature). The catalyst deactivation was also significantly hindered when compared to conventionally prepared clays. Al-Fe pillared clays prepared by microwave methodology are promising as catalysts for CWAO industrial water treatment.
Different reaction parameters are emphasized in the WAO process. Homogenous catalysts and heterogeneous catalysts are extensively discussed. Mechanism and kinetic of WAO are elaborated. Three kinds of the reactors for CWAO are compared. Integration of CWAO with biological degradation is discussed.
Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) are efficient processes to degrade organic pollutants in water. In this paper, we especially reviewed the WAO and CWAO processes for phenolic compounds degradation. It provides a comprehensive introduction to the CWAO processes that could be beneficial to the scientists entering this field of research. The influence of different reaction parameters, such as temperature, oxygen pressure, pH, stirring speed are analyzed in detail; Homogenous catalysts and heterogeneous catalysts including carbon materials, transitional metal oxides and noble metals are extensively discussed, among which Cu based catalysts and Ru catalysts were shown to be the most active. Three different kinds of the reactor implemented for the CWAO (autoclave, packed bed and membrane reactors) are illustrated and compared. To enhance the degradation efficiency and reduce the cost of the CWAO process, biological degradation can be combined to develop an integrated technology.
