Effect of ozone on the performance of a hybrid ceramic membrane-biological activated carbon process

Two hybrid processes including ozonation-ceramic membrane-biological activated carbon （BAC） （Process A） and ceramic membrane-BAC （Process B） were compared to treat polluted raw water. The performance of hybrid processes was evaluated with the removal efficiencies of turbidity, ammonia and organic matter. The results indicated that more than 99% of particle count was removed by both hybrid processes and ozonation had no significant effect on its removal. BAC filtration greatly improved the removal of ammonia. Increasing the dissolved oxygen to 30.0 mg/L could lead to a removal of ammonia with concentrations as high as 7.80 mg/L and 8.69 mg/L for Processes A and B, respectively. The average removal efficiencies of total organic carbon and ultraviolet absorbance at 254 nm （UV254, a parameter indicating organic matter with aromatic structure） were 49% and 52% for Process A, 51% and 48% for Process B, respectively. Some organic matter was oxidized by ozone and this resulted in reduced membrane fouling and increased membrane flux by 25%-30%. However, pre-ozonation altered the components of the raw water and affected the microorganisms in the BAC, which may impact the removals of organic matter and nitrite negatively.     

Phosphorus release from phosphate rock and iron phosphate by low-molecular-weight organic acids

Low-molecular-weight(LMW) organic acids widely exist in soils, particularly in the rhizosphere. A series of batch experiments were carded out to investigate the phosphorus release from rock phosphate and iron phosphate by low-molecular-weight organic acids.Results showed that citdc acid had the highest capacity to solubilize P from both rock and iron phosphate. P solubUization from rock phosphate and iron phosphate resulted in net proton consumption. P release from rock phosphate was positively correlated with the pκa values. P release from iron phosphate was positively correlated with Fe-organic acid stability constants except for aromatic acids, but was not correlated with pκa. Increase in the concentrations of organic acids enhanced P solubilization from both rock and iron phosphate almost linearly. Addition of phenolic compounds further increased the P release from iron phosphate. Initial solution pH had much more substantial effect on P release from rock phosphate than from iron phosphate.     

Combination of biodiesel-ethanol-diesel fuel blend and SCR catalyst assembly to reduce emissions from a heavy-duty diesel engine

In this study, the efforts to reduce NOx and particulate matter （PM） emissions from a diesel engine using both ethanol-selective catalytic reduction （SCR） of NOx over an Ag/Al2O3 catalyst and a biodiesel-ethanol-diesel fuel blend （BE-diesel） on an engine bench test are discussed. Compared with diesel fuel, use of BE-diesel increased PM emissions by 14% due to the increase in the soluble organic fraction （SOF） of PM, but it greatly reduced the Bosch smoke number by 60%-80% according to the results from 13-mode test of European Stationary Cycle （ESC） test. The SCR catalyst was effective in NOx reduction by ethanol, and the NOx conversion was approximately 73%. Total hydrocarbons （THC） and CO emissions increased significantly during the SCR of NOx process. Two diesel oxidation catalyst （DOC） assemblies were used after Ag/Al2O3 converter to remove CO and HC. Different oxidation catalyst showed opposite effect on PM emission. The PM composition analysis revealed that the net effect of oxidation catalyst on total PM was an integrative effect on SOF reduction and sulfate formation of PM. The engine bench test results indicated that the combination of BE-diesel and a SCR catalyst assembly could provide benefits for NOx and PM emissions control even without using diesel particle filters （DPFs）.     

Effect of alkalinity on nitrite accumulation in treatment of coal chemical industry wastewater using moving bed biofilm reactor

Nitrogen removal via nitrite （the nitrite pathway） is more suitable for carbon-limited industrial wastewater. Partial nitrification to nitrite is the primary step to achieve nitrogen removal via nitrite. The effect of alkalinity on nitrite accumulation in a continuous process was investigated by progressively increasing the alkalinity dosage ratio （amount of alkalinity to ammonia ratio, mol/mol）. There is a close relationship among alkalinity, pH and the state of matter present in aqueous solution. When alkalinity was insufficient （compared to the theoretical alkalinity amount）, ammonia removal efficiency increased first and then decreased at each alkalinity dosage ratio, with an abrupt removal efficiency peak. Generally, ammonia removal efficiency rose with increasing alkalinity dosage ratio. Ammonia removal efficiency reached to 88% from 23% when alkalinity addition was sufficient. Nitrite accumulation could be achieved by inhibiting nitrite oxidizing bacteria （NOB） by free ammonia （FA） in the early period and free nitrous acid in the later period of nitrification when alkalinity was not adequate. Only FA worked to inhibit the activity of NOB when alkalinity addition was sufficient.     

Ultrafiltration with in-line coagulation for the removal of natural humic acid and membrane fouling mechanism

Experimental and theoretical analysis were made on the natural humic acid removal and the membrane fouling of ultrafiltration （UF） with in-line coagulation. The results showed dissolved organic carbon （DOC） and UV254 removals by the UF with in-line coagulation at pH 7 were increased from 28% to 53% and 40% to 78% in comparison with direct UF treatment respectively. At the same time, the analysis of high performance liquid chromatography showed that UF with coagulation had significant improvement of removal of humic acid with molecular weights less than 6000 Da in particular. Compared to direct UF, the in-line coagulation UF also kept more constant permeate flux and very slight increase oftransmembrane pressure during a filtration circle. Two typical membrane fouling models were used by inducing two coefficients Kc and Kp corresponding to cake filtration model and pore narrowing model respectively. It was found that membrane fouling by pore-narrowing effect was effectively alleviated and that by cake-filtration was much decreased by in-line coagulation. Under the condition of coagulation prior to ultrafiltration at pH 7, the cake layer formed on the membrane surface became thicker, but the membrane filtration resistance was lower than that at pH 5 with the extension of operation time.     

Debromination of decabromodiphenyl ether by organo-montmorillonite-supported nanoscale zero-valent iron：Preparation, characterization and influence factors

An organo-montmorillonite-supported nanoscale zero-valent iron material(M-NZVI) was synthesized to degrade decabromodiphenyl ether(BDE-209). The results showed that nanoscale zero-valent iron had good dispersion on organo-montmorillonite and was present as a core-shell structure with a particle size range of nanoscale iron between 30–90 nm, characterized by XRD, SEM, TEM, XRF, ICP-AES, and XPS. The results of the degradation of BDE-209 by M-NZVI showed that the efficiency of M-NZVI in removing BDE-209 was much higher than that of NZVI. The efficiency of M-NZVI in removing BDE-209 decreased as the pH and the initial dissolved oxygen content of the reaction solution increased, but increased as the proportion of water in the reaction solution increased.     

Characteristics of high-sulfate wastewater treatment by two-phase anaerobic digestion process with Jet-loop anaerobic fluidized bed

A new anaerobic reactor, Jet-loop anaerobic fluidized bed （JLAFB）, was designed for treating high-sulfate wastewater. The treatment characteristics, including the effect of influent COD/SO42 ratio and alkalinity and sulfide inhibition in reactors, were discussed for a JLAFB and a general anaerobic fiuidized bed （AFB） reactor used as sulfate-reducing phase and methane-producing phase, respectively, in two-phase anaerobic digestion process. The formation of granules in the two reactors was also examined. The results indicated that COD and sulfate removal had different demand of influent COD/SO4^2- ratios. When total COD removal was up to 85%, the ratio was only required up to 1.2, whereas, total sulfate removal up to 95% required it exceeding 3.0. The alkalinity in the two reactors increased linearly with the growth of influent alkalinity. Moreover, the change of influent alkalinity had no significant effect on pH and volatile fatty acids （VFA） in the two reactors. Influent alkalinity kept at 400-500 mg/L could meet the requirement of the treating process. The JLAFB reactor had great advantage in avoiding sulfide and free-H2S accumulation and toxicity inhibition on microorganisms. When sulfate loading rate was up to 8. 1 kg/（m^3.d）, the sulfide and free-H2S concentrations in JLAFB reactor were 58.6 and 49.7 mg/L, respectively. Furthermore, the granules, with offwhite color, ellipse shape and diameters of 1.0-3.0 mm, could be developed in JLAFB reactor. In granules, different groups of bacteria were distributed in different layers, and some inorganic metal compounds such as Fe, Ca, Mg etc. were found.     

A porous biochar supported nanoscale zero-valent iron material highly efficient for the simultaneous remediation of cadmium and lead contaminated soil

Risk associated with heavy metals in soil has been received widespread attention.In this study,a porous biochar supported nanoscale zero-valent iron（BC-nZVI） was applied to immobilize cadmium（Cd） and lead（Pb） in clayey soil.Experiment results indicated that the immobilization of Cd or Pb by BC-nZVI process was better than that of BC or nZVI process,and about 80% of heavy metals immobilization was obtained in BC-nZVI process.Addition of BC-nZVI could increase soil pH and organic matter（SOM）.Cd or...     

Effects of Cu2+ and humic acids on degradation and fate of TBBPA in pure culture of Pseudomonas sp. strain CDT

Soil contamination with tetrabromobisphenol A(TBBPA) has caused great concerns;however, the presence of heavy metals and soil organic matter on the biodegradation of TBBPA is still unclear. We isolated Pseudomonas sp. strain CDT, a TBBPA-degrading bacterium, from activated sludge and incubated it with ~(14)C-labeled TBBPA for 87 days in the absence and presence of Cu~(2+)and humic acids(HA). TBBPA was degraded to organic-solvent extractable(59.4% ± 2.2%) and non-extractable(25.1% ± 1.3%) metabolites,mineralized to CO_2(4.8% ± 0.8%), and assimilated into cells(10.6% ± 0.9%) at the end of incubation. When Cu~(2+)was present, the transformation of extractable metabolites into non-extractable metabolites and mineralization were inhibited, possibly due to the toxicity of Cu~(2+)to cells. HA significantly inhibited both dissipation and mineralization of TBBPA and altered the fate of TBBPA in the culture by formation of HA-bound residues that amounted to 22.1% ± 3.7% of the transformed TBBPA. The inhibition from HA was attributed to adsorption of TBBPA and formation of bound residues with HA via reaction of reactive metabolites with HA molecules, which decreased bioavailability of TBBPA and metabolites in the culture. When Cu~(2+)and HA were both present, Cu~(2+)significantly promoted the HA inhibition on TBBPA dissipation but not on metabolite degradation. The results provide insights into individual and interactive effects of Cu~(2+)and soil organic matter on the biotransformation of TBBPA and indicate that soil organic matter plays an essential role in determining the fate of organic pollutants in soil and mitigating heavy metal toxicity.     

Nanoscale zero-valent iron/magnetite carbon composites for highly efficient immobilization of U(VI)

Nanoscale zerovalent iron/magnetic carbon (NZVI/MC) composites were successfully synthesized by simply calcining yellow pine and iron precursors. NZVI/MC pyrolyzed at 800°C (NZVI/MC800) had a higher percentage of NZVI and displayed better resistance to aggregation and oxidation of NZVI than samples prepared at other temperatures. The NZVI/MC800 material was applied for the elimination of U(VI) from aqueous solutions. The results suggested that the NZVI/MC800 displayed excellent adsorption capacity (203.94?mg/g) toward U(VI). The significant adsorption capacity and fast adsorption kinetics were attributed to the presence of well-dispersed NZVI, which could quickly reduce U(VI) into U(IV), trapping the guest U(IV) in the porous biocarbon matrix. The removal of U(VI) on the NZVI/MC samples was strongly affected by solution pH. The NZVI/MC samples also displayed outstanding reusability for U(VI) removal after multiple cycles. These findings indicate that NZVI/MC has great potential for remediation of wastewater containing U(VI).     

Assessing the effects of surface-bound humic acid on the phototoxicity of anatase and rutile TiO2 nanoparticles in vitro

In this study,the cytotoxicity of two different crystal phases of TiO₂ nanoparticles,with surface modification by humic acid（HA）,to Escherichia coli,was assessed.The physicochemical properties of TiO₂ nanoparticles were thoroughly characterized.Three different initial concentrations,namely 50,100,and 200 ppm,of HA were used for synthesis of HA coated TiO₂ nanoparticles（denoted as A/RHA50,A/RHA100,and A/RHA200,respectively）.Results indicate that rutile（LC50（concentration that causes 50%mortality compared the control group）=6.5）was more toxic than anatase（LC₅0=278.8）under simulated sunlight（SSL）irradiation,possibly due to an extremely narrow band gap.It is noted that HA coating increased the toxicity of anatase,but decreased that of rutile.Additionally,AHA50 and RHA50had the biggest differences compared to uncoated anatase and rutile with LC₅0of 201.9 and21.6,respectively.We then investigated the formation of reactive oxygen species（ROS）by TiO₂ nanoparticles in terms of hydroxyl radicals（OH）and superoxide anions（O₂^-）.Data suggested that O₂^- was the main ROS that accounted for the higher toxicity of rutile upon SSL irradiation.We also observed that HA coating decreased the generation of OH and O₂^- on rutile,but increased O₂^- formation on anatase.Results from TEM analysis also indicated that HA coated rutile tended to be attached to the surface of E.coli more than anatase.     

Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: A review

The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals(·OH)from reactions between recyclable solid catalysts and H_2O_2 at acidic or even circumneutral pH.Hence,it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology.Due to the complex reaction system,the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating,and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies.Iron-based materials usually possess high catalytic activity,low cost,negligible toxicity and easy recovery,and are a superior type of heterogeneous Fenton catalysts.Therefore,this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials..OH,hydroperoxyl radicals/superoxide anions(HO_2./O_2~-.)and high-valent iron are the three main types of reactive oxygen species(ROS),with different oxidation reactivity and selectivity.Based on the mechanisms of ROS generation,the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron,the heterogeneous catalysis mechanism,and the heterogeneous reaction-induced homogeneous mechanism.Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed.Finally,related future research directions are also suggested.     

Assessing the effect of different natural dissolved organic matters on the cytotoxicity of titanium dioxide nanoparticles with bacteria

Titanium dioxide nanoparticles(TiO_2 NPs) are among the most widely manufactured nanomaterials on a global scale. However, prudent and vigilant surveillance, incumbent upon the scientific community with the advent of new technologies, has revealed potentially undesirable effects of TiO_2 NPs on biological systems and the natural environment during their application and discharge. Such effects are likely best evaluated by first assessing the fate of the TiO_2 NPs in natural environments. In this study, the effects of terrestrial humic acid(HA) and tannic acid(TA), two major members of the collective:dissolved organic matter(DOM), on the cytotoxicity of TiO_2 NPs to Escherichia coli were investigated in the presence and absence of natural sunlight. Qualitative(transmission electron microscopy(TEM)) and quantitative(LC50) analyses were employed in this study. In addition, the production of reactive oxygen species(ROS) in the form of UOH was further assessed—as HA or TA increased the production of ROS decreased. The inhibition of bacterial viability in the light treatment groups, with respective treatment organics at concentrations of 10 ppm, was less in TA than in terrestrial HA. SAS was used to analyze the treatment effect of individual factors of light irradiation, DOM, and concentration of TiO_2 NPs.     

Quantum chemical investigation on photodegradation mechanisms of sulfamethoxypyridazine with dissolved inorganic matter and hydroxyl radical

Sulfamethoxypyridazine(SMP) is one of the commonly used sulfonamide antibiotics(SAs).SAs are mainly studied to undergo triplet-sensitized photodegradation in water under natural sunlight with other coexisting aquatic environmental organic pollutants.In this work,SMP was selected as a representative of SAs.We studied the mechanisms of triplet-sensitized photodegradation of SMP and the influence of selected dissolved inorganic matter,i.e.,anions(Br~-,Cl~-,and NO~-_3) and cations ions(Ca~(2+),Mg~(2+),and Zn~(2+)) on SMP photodegradation mechanism by quantum chemical methods.In addition,the degradation mechanisms of SMP by hydroxyl radical(OH·) were also investigated.The creation of SO_2 extrusion product was accessed with two different energy pathways(pathway-1 and pathway-2) by following two steps(step-I and step-II) in the tripletsensitized photodegradation of SMP.Due to low activation energy,the pathway-1 was considered as the main pathway to obtain SO_2 extrusion product.Step-II of pathway-1 was measured to be the rate-limiting step(RLS) of SMP photodegradation mechanism and the effect of the selected anions and cations was estimated for this step.All selected anions and cations promoted photodegradation of SMP by dropping the activation energy of pathway-1.The estimated low activation energies of different degradation pathways of SMP with OH·radical indicate that OH·radical is a very powerful oxidizing agent for SMP degradation via attack through benzene derivative and pyridazine derivative ring.