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.
The gene for the catalytic domain of thermostable endo-β-1,3-glucanase (laminarinase) LamA was cloned from Thermotoga maritima MSB8 and heterologously expressed in a bioengineered Synechococcus sp. PCC 7002. The mutant strain was cultured in a photobioreactor to assess biomass yield, recombinant laminarinase activity, and CO2 uptake. The maximum enzyme activity was observed at a pH of 8.0 and a temperature of 70°C. At a CO2 concentration of 5%, we obtained a maximum specific growth rate of 0.083 h–1, a biomass productivity of 0.42 g?L–1?d–1, a biomass concentration of 3.697 g?L–1, and a specific enzyme activity of the mutant strain of 4.325 U?mg–1 dry mass. All parameters decreased as CO2 concentration increased from 5% to 10% and further to 15% CO2, except enzyme activity, which increased from 5% to 10% CO2. However, the mutant culture still grew at 15% CO2 concentration, as reflected by the biomass productivity (0.26 g?L–1?d–1), biomass concentration (2.416 g?L–1), and specific enzyme activity (3.247 U?mg–1 dry mass).
Effect of different carbon sources on purification performance and change of microbial community structure in a novel A2N-MBR process were investigated. The results showed that when fed with acetate, propionate or acetate and propionate mixed (1:1) as carbon sources, the effluent COD, NH4+-N, TN and TP were lower than 30, 5, 15 and 0.5 mg?L–1, respectively. However, taken glucose as carbon source, the TP concentration of effluent reached 2.6 mg?L–1. Process analysis found that the amount of anaerobic phosphorus release would be the key factor to determine the above effectiveness. The acetate was beneficial to the growth of Candidatus Accumulibacter associated with biological phosphorus removal, which was the main cause of high efficiency phosphorus removal in this system. In addition, it could eliminate the Candidatus Competibacter associated with glycogen-accumulating organisms and guarantee high efficiency phosphorus uptake of phosphorus accumulating organisms in the system with acetate as carbon source.
Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) and microelectrode technology were employed to evaluate the Nitrous oxide (N2O) production in biological aerated filters (BAFs) under varied dissolved oxygen (DO) concentrations during treating wastewater under laboratory scale. The average yield of gasous N2O showed more than 4-fold increase when the DO levels were reduced from 6.0 to 2.0 mg?L–1, indicating that low DO may drive N2O generation. PCR-DGGE results revealed that Nitratifractor salsuginis were dominant and may be responsible for N2O emission from the BAFs system. While at a low DO concentration (2.0 mg?L–1), Flavobacterium urocaniciphilum might play a role. When DO concentration was the limiting factor (reduced from 6.0 to 2.0 mg?L–1) for nitrification, it reduced NO2--N oxidation as well as the total nitrification. The data from this study contribute to explain how N2O production changes in response to DO concentration, and may be helpful for reduction of N2O through regulation of DO levels.
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.
In this study, a new water treatment system that couples (photo-) electrochemical catalysis (PEC or EC) in a microbial fuel cell (MFC) was configured using a stainless-steel (SS) cathode coated with Fe0/TiO2. We examined the destruction of methylene blue (MB) and tetracycline. Fe0/TiO2 was prepared using a chemical reduction-deposition method and coated onto an SS wire mesh (500 mesh) using a sol technique. The anode generates electricity using microbes (bio-anode). Connected via wire and ohmic resistance, the system requires a short reaction time and operates at a low cost by effectively removing 94% MB (initial concentration 20 mg?L–1) and 83% TOC/TOC0 under visible light illumination (50 W; 1.99 mW?cm–2 for 120 min, MFC-PEC). The removal was similar even without light irradiation (MFC-EC). The EEo of the MFC-PEC system was approximately 0.675 kWh?m–3?order–1, whereas that of the MFC-EC system was zero. The system was able to remove 70% COD in tetracycline solution (initial tetracycline concentration 100 mg?L–1) after 120 min of visible light illumination; without light, the removal was 15% lower. The destruction of MB and tetracycline in both traditional photocatalysis and photoelectrocatalysis systems was notably low. The electron spinresonance spectroscopy (ESR) study demonstrated that ?OH was formed under visible light, and ?O2– was formed without light. The bio-electricity-activated O2 and ROS (reactive oxidizing species) generation by Fe0/TiO2 effectively degraded the pollutants. This cathodic degradation improved the electricity generation by accepting and consuming more electrons from the bio-anode.
Denitrifying biofilter (DNBF) is widely used for advanced nitrogen removal in the reclaimed wastewater treatment plants (RWWTPs). Manual control of DNBF easily led to unstable process performance and high cost. Consequently, there is a need to automatic control of two decisive operational processes, carbon dosage and backwash, in DNBF. In this study, online control of DNBF was investigated in the pilot-scale DNBF (600 m3·d–1), and then applied in the full-scale DNBF (10 × 104 m3·d–1). A novel simple online control strategy for carbon dosage with the effluent nitrate as the sole control parameter was designed and tested in the pilot-scale DNBF. Backwash operation was optimized based on the backwash control strategy using turbidity as control parameter. Using the integrated control strategy, in the pilot-scale DNBF, highly efficient nitrate removal with effluent TN lower than 3 mg·L–1 was achieved and DNBF was not clogged any more. The online control strategy for carbon dosage was successfully applied in a RWWTP. Using the online control strategy, the effluent nitrate concentration was controlled relatively stable and carbon dosage was saved for 18%.
We designed photoelectrochemical cells to achieve efficient oxidation of rhodamine B (RhB) without the need for photocatalyst or supporting electrolyte. RhB, the metal anode/cathode, and O2 formed an energy-relay structure, enabling the efficient formation of O2– species under ultraviolet illumination. In a single-compartment cell (S cell) containing a titanium (Ti) anode, Ti cathode, and 10 mg·mL–1 RhB in water, the zero-order rate constant of the photoelectrochemical oxidation (kPEC) of RhB was 0.049 mg·L–1·min–1, while those of the photochemical and electrochemical oxidations of RhB were nearly zero. kPEC remained almost the same when 0.5 mol·L–1 Na2SO4 was included in the reactive solution, regardless of the increase in the photocurrent of the S cell. The kPEC of the illuminated anode compartment in the two-compartment cell, including a Ti anode, Ti cathode, and 10 mg·mL–1 RhB in water, was higher than that of the S cell. These results support a simple, eco-friendly, and energysaving method to realize the efficient degradation of RhB.
Nutrients and water play an important role in microalgae cultivation. Using wastewater as a culture medium is a promising alternative to recycle nutrients and water, and for further developing microalgae-based products. In the present study, two species of microalgae, Chlorella sp. (high ammonia nitrogen tolerance) and Spirulina platensis (S. platensis, high growth rate), were cultured by using poultry wastewater through a two-stage cultivation system for algal biomass production. Ultrafiltration (UF) or centrifuge was used to harvest Chlorella sp. from the first cultivation stage and to recycle culture medium for S. platensis growth in the second cultivation stage. Results showed the two-stage cultivation system produced high microalgae biomass including 0.39 g·L–1Chlorella sp. and 3.45 g·L–1S. platensis in the first-stage and second-stage, respectively. In addition, the removal efficiencies of NH4+ reached 19% and almost 100% in the first and the second stage, respectively. Total phosphorus (TP) removal reached 17% and 83%, and total organic carbon (TOC) removal reached 55% and 72% in the first and the second stage, respectively. UF and centrifuge can recycle 96.8% and 100% water, respectively. This study provides a new method for the combined of pure microalgae cultivation and wastewater treatment with culture medium recycling.
Chromium oxide and manganese oxide promoted ZrO2-CeO2 catalysts were prepared by a homogeneous precipitation method for the selective catalytic reduction of NOx with NH3. A series of characterization including X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), Brunauer–Emmett–Teller (BET) surface area analysis, H2 temperatureprogrammed reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS) were used to evaluate the influence of the physicochemical properties on NH3-SCR activity. Cr-Zr-Ce and Mn-Zr-Ce catalysts are much more active than ZrO2-CeO2 binary oxide for the low temperature NH3-SCR, mainly because of the high specific surface area, more surface oxygen species, improved reducibility derived from synergistic effect among different elements. Mn-Zr-Ce catalyst exhibited high tolerance to SO2 and H2O. Cr-Zr-Ce mixed oxide exhibited>80% NOx conversion at a wide temperature window of 100°C–300°C. In situ DRIFT studies showed that the addition of Cr is beneficial to the formation of Bronsted acid sites and prevents the formation of stable nitrate species because of the presence of Cr6 +. The present mixed oxide can be a candidate for the low temperature abatement of NOx.
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.
Cadmium (Cd) and lead (Pb) in water and soil could be adsorbed by biochar produced from corn straw. Biochar pyrolyzed under 400°C for 2 h could reach the ideal removal efficiencies (99.24%and 98.62% for Cd and Pb, respectively) from water with the biochar dosage of 20 g·L–1 and initial concentration of 20 mg·L–1. The pH value of 4–7 was the optimal range for adsorption reaction. The adsorption mechanism was discussed on the basis of a range of characterizations, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and Raman analysis; it was concluded as surface complexation with active sorption sites (-OH, -COO-), coordination with π electrons (C = C, C = O) and precipitation with inorganic anions (OH-, CO32–, SO42–) for both Cd and Pb. The sorption isotherms fit Langmuir model better than Freundlich model, and the saturated sorption capacities for Cd and Pb were 38.91 mg·g-1 and 28.99 mg·g–1, respectively. When mixed with soil, biochar could effectively increase alkalinity and reduce bioavailability of heavy metals. Thus, biochar derived from corn straw would be a green material for both removal of heavy metals and amelioration of soil.
Because the efficiency of biological nutrient removal is always limited by the deficient carbon source for the low carbon/nitrogen (C/N) ratio in real domestic sewage, the denitrifying phosphorus removal (DNPR) was developed as a simple and efficient method to remove nitrogen and phosphorous. In addition, this method has the advantage of saving aeration energy while reducing the sludge production. In this context, a pre-denitrification anaerobic/anoxic/post-aeration + nitrification sequence batch reactor (pre-A2NSBR) system, which could also reduce high ammonia effluent concentration in the traditional two-sludge DNPR process, is proposed in this work. The pre-A2NSBR process was mainly composed of a DNPR SBR and a nitrifying SBR, operating as alternating anaerobic/anoxic/post-aeration + nitrification sequence. Herein, the long-term performance of different nitrate recycling ratios (0–300%) and C/N ratios (2.5–8.8), carbon source type, and functional microbial community were studied. The results showed that the removal efficiency of total inorganic nitrogen (TIN, including NH4+-N, NO2– -N, and NO3– -N) gradually increased with the nitrate recycling ratios, and the system reached the highest DNPR efficiency of 94.45% at the nitrate recycling ratio of 300%. The optimum C/N ratio was around 3.9–7.3 with a nitrogen and phosphorus removal efficiency of 80.15% and 93.57%, respectively. The acetate was proved to be a high-quality carbon source for DNPR process. The results of fluorescence in situ hybridization (FISH) analysis indicated that nitrifiers and phosphorus accumulating organisms (PAOs) were accumulated with a proportion of 19.41% and 26.48%, respectively.
The toxic and recalcitrant polychlorinated biphenyls (PCBs) adversely affect human and biota by bioaccumulation and biomagnification through food chain. In this study, an anaerobic microcosm was developed to extensively dechlorinate hexa- and hepta-CBs in Aroclor 1260. After 4 months of incubation in defined mineral salts medium amended PCBs (70 mmol·L–1) and lactate (10 mmol·L–1), the culture dechlorinated hexa-CBs from 40.2% to 8.7% and hepta-CBs 33.6% to 11.6%, with dechlorination efficiencies of 78.3% and 65.5%, respectively (all in moL ratio). This dechlorination process led to tetra-CBs (46.4%) as the predominant dechlorination products, followed by penta-(22.1%) and tri-CBs (5.4%). The number of meta chlorines per biphenyl decreased from 2.50 to 1.41. Results of quantitative real-time PCR show that Dehalococcoides cells increased from 2.39 ×105±0.5 × 105 to 4.99 × 107±0.32 × 107 copies mL–1 after 120 days of incubation, suggesting that Dehalococcoides play a major role in reductive dechlorination of PCBs. This study could prove the feasibility of anaerobic reductive culture enrichment for the dehalogenation of highly chlorinated PCBs, which is prior to be applied for in situ bioremediation of notorious halogenated compounds.
In the present study, a novel approach was used to control zero valent iron aggregation and separation problems by fixing zero valent iron (ZVI) on bentonite-fly ash pellets. For this purpose, porous low cost bentonite-fly ash (BFA) pellets with size of 2.00 cm in length and 0.35 cm in diameter were prepared and fixed with ZVI to manufacture zero valent iron bentonite-fly ash (ZVI-BFA) pellets. Importantly, unlike powdered adsorbents, ZVI-BFA can easily be separated from final effluents when exhausted without any disintegration. The performance of the developed novel adsorbent was investigated for the removal of Pb2+ and Cd2+ from aqueous media. At 100 mg·L–1 and 1 g adsorbent, a maximum of 89.5% of Cd2+ and 95.6% of Pb2+ was removed by ZVI-BFA as compared to 56% and 95% removal by BFA. At 200 mg·L–1, Cd2+ and Pb2+ removal by ZVI-BFA was 56% and 99.8% respectively as compared to only 28% and 96% by BFA. Further, the removal kinetics was best fitted for pseudo-second order model. The study provides the basis for improving the removal capacity of porous materials by iron fixation while taking separation ability into consideration.
Sulfamethoxazole (SMX) and trimethoprim (TMP) are two critical sulfonamide antibiotics with enhanced persistency that are commonly found in wastewater treatment plants. Recently, more scholars have showed interests in how SMX and TMP antibiotics are biodegraded, which is seldom reported previously. Novel artificial composite soil treatment systems were designed to allow biodegradation to effectively remove adsorbed SMX and TMP from the surface of clay ceramsites. A synergy between sorption and biodegradation improves the removal of SMX and TMP. One highly efficient SMX and TMP degrading bacteria strain, Bacillus subtilis, was isolated from column reactors. In the removal process, this bacteria degrade SMX and TMP to NH4+, and then further convert NH4+ to NO3– in a continuous process. Microbial adaptation time was longer for SMX degradation than for TMP, and SMX was also able to be degraded in aerobic conditions. Importantly, the artificial composite soil treatment system is suitable for application in practical engineering.
The Ti-modified sepiolite (Ti-Sep)-supported Mn-Cu mixed oxide (yMn5Cu/Ti-Sep) catalysts were synthesized using the co-precipitation method. The materials were characterized by the X-ray diffraction scanning electron microscope, N2 adsorption-desorption, H2-TPR, O2-TPD, and XPS techniques, and their catalytic activities for CO oxidation were evaluated. It was found that the catalytic activities of yMn5Cu/Ti-Sep were higher than those of 5Cu/Ti-Sep and 30Mn/Ti-Sep, and the Mn/Cu molar ratio had a distinct influence on catalytic activity of the sample. Among the yMn5Cu/Ti- Sep samples, the 30Mn5Cu/Ti-Sep catalyst showed the best activity (which also outperformed the 30Mn5Cu/Sep catalyst), giving the highest reaction rate of 0.875 × 10–3 mmol·g–1·s–1 and the lowest T50% and T100% of 56°C and 86°C, respectively. Moreover, the 30Mn5Cu/Ti-Sep possessed the best low-temperature reducibility, the lowest O2 desorption temperature, and the highest surface Mn3+/Mn4+ atomic ratio. It is concluded that factors, such as the strong interaction between the copper or manganese oxides and the Ti-Sep support, good low-temperature reducibility, and good mobility of chemisorbed oxygen species, were responsible for the excellent catalytic activity of 30Mn5Cu/Ti-Sep.
Ambient PM2.5 samples were collected at four sites in Xiamen, including Gulangyu (GLY), Hongwen (HW), Huli (HL) and Jimei (JM) during January, April, July and October 2013. Local source samples were obtained from coal burning power plants, industries, motor vehicles, biomass burning, fugitive dust, and sea salt for the source apportionment studies. The highest value of PM2.5 mass concentration and species related to human activities (SO42–, NO3–, Pb, Ni, V, Cu, Cd, organic carbon (OC) and elemental carbon (EC)) were found in the ambient samples from HL, and the highest and lowest loadings of PM2.5 and its components occurred in winter and summer, respectively. The reconstructed mass balance indicated that ambient PM2.5 consisted of 24% OM (organic matter), 23% sulfate, 14% nitrate, 9% ammonium, 9% geological material, 6% sea salt, 5% EC and 10% others. For the source profiles, the dominant components were OC for coal burning, motor vehicle, biomass burning and sea salt; SO42– for industry; and crustal elements for fugitive dust. Source contributions were calculated using a chemical mass balance (CMB) model based on ambient PM2.5 concentrations and the source profiles. GLY was characterized by high contributions from secondary sulfate and cooking, while HL and JM were most strongly affected by motor vehicle emissions, and biomass burning and fugitive dust, respectively. The CMB results indicated that PM2.5 from Xiamen is composed of 27.4% secondary inorganic components, 20.8% motor vehicle emissions, 11.7% fugitive dust, 9.9% sea salt, 9.3% coal burning, 5.0% biomass burning, 3.1% industry and 6.8% others.
Eutrophication with a large number of Microcystis aeruginosa commonly occurs worldwide, thereby threatening the aquatic ecosystem and human health. In this study, four kinds of algicides were tested to explore their influence on cell density and chlorophyll-a of M. aeruginosa. Results showed that aluminum silicate agent, which inhibited more than 90% cell growth compared with the control group, demonstrated the strongest inhibition effect immediately on M. aeruginosa growth. Furthermore, the production and release of microcystin (MC)-LR were investigated. Aluminum silicate, CuSO4, and Emma-11 were more effective than pyrogallic acid in disrupting the cells of M. aeruginosa, thereby increasing the extracellular MC-LR concentration. Aluminum silicate caused the highest extracellular MC-LR concentration of more than 45 mg·L–1. Biotoxicity was also detected to evaluate the environmental risks of MC-LR release, which were related to the usages of different algicides. Extracellular MC-LR concentration mostly increased when the biotoxicity of algae solution increased. The experiments were also designed to reveal the effects of physical conditions in riverways, such as natural sunlight, aeration and benthal sludge, on MC-LR degradation. These findings indicated that UV rays in sunlight, which can achieve a MC-LR removal efficiency of more than 15%, played an important role in MC-LR degradation. Among all the physical pathways of MC-LR removal, benthal sludge adsorption presented the optimal efficiency at 20%.
Transport of engineered antibiotic resistance plasmids in porous media has been reported to potentially cause significant spreading of antibiotic resistance in the environment. In this work, transport of an indigenous resistance plasmid pK5 in porous media was investigated through packed column experiments. At identical ionic strengths in CaCl2 solutions, the breakthroughs of pK5 from soil columns were very close to those from quartz sand columns, indicating that transport of pK5 in quartz sand and soil was similar. A similarity in transport behavior was also found between pK5 and an engineered plasmid pBR322 that has approximately the same number of base pairs as pK5. The influence of surfactants, a major group of constituents in soil solutions, was examined using an engineered plasmid pcDNA3.1(+)/myc-His A. The impact of an anionic surfactant, sodium dodecyl sulfate (SDS), was negligible at concentrations up to 200 mg·L–1. Cetyltrimethyl ammonium bromide (CTAB), a cationic surfactant, was found to significantly enhance plasmid adsorption at high concentrations. However, at environmentally relevant concentrations (<1 mg·L–1), the effect of this surfactant was also minimal. The negligible impact of surfactants and the similarity between the transport of engineered and indigenous plasmids indicate that under environmentally relevant conditions, indigenous plasmids in soil also have the potential to transport over long distances and lead to the spreading of antibiotic resistance.
