Particles and porous tablets based on Fe0/ZSM-5 composites prepared by ball-milling for heavy metals removal: Dissolved Fe2 +, pH, and mechanism

Novel, low-cost Fe~0/ZSM-5-based particles and porous tablets were prepared by a ballmilling method and used for the removal of Pb~(2+) in solution. Solid-phase characterization by scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy(SEMEDS) and transmission electron microscopy(TEM) revealed that the Fe0 microparticles were evenly loaded and tightly immobilized on the surface of ZSM-5 because of the extrusion/welding impact during ball-milling. For different Pb~(2+) concentrations, batch experiments indicated that the removal of Pb~(2+) increased with the decline of dissolved Fe2+and p H value in the solution for particles; opposite results were obtained for the tablets. The differences in the contact between both materials and Pb~(2+) were the main factor controlling Pb~(2+) removal in the solution. Investigation into the effect of initial p H value revealed that high p H reduced the number of electrons released from Fe corrosion. Consequently, low levels of removed Pb~(2+) and dissolved Fe~(2+) were synchronously observed. Also, simulated electroplating wastewater was treated using the prepared particles and porous tablets,and the removal order of Pb~(2+) Cr~(6+) Cu~(2+)≈ Cd~(2+) was observed. The Fe~0/ZSM-5 particles and tablets prepared through ball-milling show potential as materials for treatment of Pb~(2+) and other toxic metals.     

Adsorption of heavy metal ions from aqueous solution by carboxylated cellulose nanocrystals

A novel nanoadsorbent for the removal of heavy metal ions is reported.Cotton was first hydrolyzed to obtain cellulose nanocrystals(CNCs).CNCs were then chemically modified with succinic anhydride to obtain SCNCs.The sodic nanoadsorbent(NaSCNCs) was further prepared by treatment of SCNCs with saturated NaHCO 3 aqueous solution.Batch experiments were carried out with SCNCs and NaSCNCs for the removal of Pb 2+ and Cd 2+.The effects of contact time,pH,initial adsorption concentration,coexisting ions and the regeneration performance were investigated.Kinetic studies showed that the adsorption equilibrium time of Pb 2+ and Cd 2+ was reached within 150 min on SCNCs and 5 min on NaSCNCs.The adsorption capacities of Pb 2+ and Cd 2+ on SCNCs and NaSCNCs increased with increasing pH.The adsorption isotherm was well fitted by the Langmuir model.The maximum adsorption capacities of SCNCs and NaSCNCs for Pb 2+ and Cd 2+ were 367.6 mg/g,259.7 mg/g and 465.1 mg/g,344.8 mg/g,respectively.SCNCs and NaSCNCs showed high selectivity and interference resistance from coexisting ions for the adsorption of Pb 2+.NaSCNCs could be efficiently regenerated with a mild saturated NaCl solution with no loss of capacity after two recycles.The adsorption mechanisms of SCNCs and NaSCNCs were discussed.     

Effect of wet flue gas desulfurization (WFGD) on fine particle (PM2.5) emission from coal-fired boilers

In this study, the characteristics of fine particles before and after wet flue gas desulfurization(WFGD) in three coal-fired heating boilers in northern China were investigated by using a dilution-based emission sampling experimental system. The influences of the WFGD process on the mass and number concentrations as well as the chemical composition of fine particles were analyzed. The removal efficiency of desulfurization processes on particulate matter mass was 30.06%–56.25% for the three study units. The WFGD had a great influence on the size distributions of particle mass concentration and number concentration. A significant increase in the number and mass concentration of particles in the size range of 0.094–0.946 μm was observed. The watersoluble ion content accounted for a very large proportion of PM_(2.5) mass, and its proportion in PM_(2.5) increased from 28.39%–41.08% to 48.96%–61.21% after the WFGD process for the three units. The desulfurizing process also drastically increased the proportion of cation component(Ca~(2+) for unit A, Mg~(2+) for unit B, and Na+for unit C) and the proportion of SO_4~(2-) in PM_(2.5), and it increased the CE/AE values of PM_(2.5) from 0.82–0.98 to 0.93–1.27 for the three study units.     

Simultaneous adsorption of lead and cadmium on MnO2-loaded resin

MnO2-loaded D301 weak basic anion exchange resin has been used as adsorbent to simultaneously remove lead and cadmium ions from aqueous solution. The e ects of adsorbent dosage, solution pH and the coexistent ions on the adsorption were investigated. Experimental results showed that with the adsorbent dosage more than 0.6 g/L, both Pb2+ and Cd2+ were simultaneously removed at pH range 5–6. Except for HPO4 2??, the high concentration coexistent ions such as Na+, K+, Cl??, NO3??, SO4 2?? and HCO3??, showed no significant e ect on the removal e ciency of both Pb2+ and Cd2+ under the experimental conditions. The coexistence of Mg2+, Ca2+ caused the reduction of Cd2+ removal, but not for Pb2+. The adsorption equilibrium for Pb2+ and Cd2+ could be excellently described by the Langmuir isotherm model with R2 > 0.99. The maximum adsorption capacity was calculated as 80.64 mg/g for Pb2+ and 21.45 mg/g for Cd2+. The adsorption processes followed the pseudo first-order kinetics model. MnO2-loaded D301 resin has been shown to have a potential to be used as an e ective adsorbent for simultaneous removal of lead and cadmium ions from aqueous solution.     

Kinetics of phenol and m-cresol biodegradation by an indigenous mixed microbial culture isolated from a sewage treatment plant

An acclimatized mixed microbial culture, predominantly Pseudomonas sp., was enriched from a sewage treatment plant, and its potential to simultaneously degrade mixtures of phenol and m-cresol was investigated during its growth in batch shake flasks. A 22 full factorial design with the two substrates at two di erent levels and di erent initial concentration ranges (low and high), was employed to carry out the biodegradation experiments. The substrates phenol and m-cresol were completely utilized within 21 h when present at low concentrations of 100 mg/L for each, and at high concentration of 600 mg/L for each, a maximum time of 187 h was observed for their removal. The biodegradation results also showed that the presence of phenol in low concentration range (100–300 mg/L) did not inhibit m-cresol biodegradation. Whereas the presence of m-cresol inhibited phenol biodegradation by the culture. Moreover, irrespective of the concentrations used, phenol was degraded preferentially and earlier than m-cresol. A sum kinetics model was used to describe the variation in the substrate specific degradation rates, which gave a high coe cient of determination value (R2 > 0.98) at the low concentration range of the substrates. From the estimated interaction parameter values obtained from this model, the inhibitory e ect of phenol on m-cresol degradation by the culture was found to be more pronounced compared to that of m-cresol on phenol. This study showed a good potential of the indigenous mixed culture in degrading mixed substrate of phenolics.     

Removal of nitric oxide from simulated flue gas via denitrification in a hollow-fiber membrane bioreactor

A hollow-fiber membrane bioreactor(HMBR) was studied for its ability to treat nitric oxide(NO) from simulated flue gas. The HMBR was operated for 9 months and showed a maximum elimination capacity of 702 mg NO/(m2·day) with a removal efciency of 86%(gas residence time of 30 sec, inlet NO concentration of 2680 mg/m3, pH 8). Varying operation parameters were tested to determine the stability and response of the HMBR. Both the inlet NO concentration and gas residence time influenced the removal of NO in the HMBR. NO elimination capacity increased with an increase in inlet NO concentration or a shortening of gas residence time. Higher removal efciency of NO was obtained at a longer gas residence time or a lower inlet NO concentration. Microbial communities of the HMBR were sensitive to the variation in pH value and alkalescence corresponding to an optimum pH value of 8. In addition, NO elimination capacity and removal efciency were inversely proportional to the inlet oxygen concentration. Sulfur dioxide had no great influence on elimination capacity and removal efciency of NO. Product analysis was performed to study N2O and N2 production and confirmed that the majority of the microorganisms were denitrifying bacteria in the HMBR. Compared to other bioreactors treating NO, this study showed that the denitrifying HMBR was a good option for the removal of NO.     

Simultaneous pyridine biodegradation and nitrogen removal in an aerobic granular system

Simultaneous pyridine biodegradation and nitrogen removal were successfully achieved in a sequencing batch reactor(SBR) based on aerobic granules. In a typical SBR cycle, nitritation occurred obviously after the majority of pyridine was removed, while denitrification occurred at early stage of the cycle when oxygen consumption was aggravated. The effect of several key operation parameters, i.e., air flow rate, influent NH_4~+-N concentration,influent p H and pyridine concentration, on nitritation, pyridine degradation and total nitrogen(TN) removal, was systematically investigated. The results indicated that high air flow rate had a positive effect on both pyridine degradation and nitritation but a negative impact of overhigh air flow rate. With the increase of NH_4~+ dosage, both nitritation and TN removal could be severely inhibited. Slightly alkaline condition, i.e., pH 7.0–8.0, was beneficial for both pyridine degradation and nitritation. High pyridine dosage often resulted in the delay of both pyridine degradation and nitritation. Besides, extracellular polymeric substances production was affected by air flow rate, NH_4~+ dosage, pyridine dosage and p H.In addition, high-throughput sequencing analysis demonstrated that Bdellovibrio and Paracoccus were the dominant species in the aerobic granulation system. Coexistence of pyridine degrader, nitrification related species, denitrification related species, polymeric substances producer and self-aggregation related species was also confirmed by highthroughput sequencing.     

An insight into the removal of fluoroquinolones in activated sludge process: Sorption and biodegradation characteristics

The detailed sorption steps and biodegradation characteristics of fluoroquinolones(FQs)including ciprofloxacin, enrofloxacin, lomefloxacin, norfloxacin, and ofloxacin were investigated through batch experiments. The results indicate that FQs at a total concentration of 500 μg/L caused little inhibition of sludge bioactivity. Sorption was the primary removal pathway of FQs in the activated sludge process, followed by biodegradation, while hydrolysis and volatilization were negligible. FQ sorption on activated sludge was a reversible process governed by surface reaction. Henry and Freundlich models could describe the FQ sorption isotherms well in the concentration range of 100–300 μg/L. Thermodynamic parameters revealed that FQ sorption on activated sludge is spontaneous, exothermic, and enthalpy-driven. Hydrophobicity-independent mechanisms determined the FQ sorption affinity with activated sludge. The zwitterion of FQs had the strongest sorption affinity, followed by cation and anion, and aerobic condition facilitated FQ sorption. FQs were slowly biodegradable, with long half-lives( 100 hr). FQ biodegradation was enhanced with increasing temperature and under aerobic condition,and thus was possibly achieved through co-metabolism during nitrification. This study provides an insight into the removal kinetics and mechanism of FQs in the activated sludge process, but also helps assess the environmental risks of FQs resulting from sludge disposal.     

Biosorption mechanisms involved in immobilization of soil Pb by Bacillus subtilis DBM in a multimetal-contaminated soil

Mechanisms of soil Pb immobilization by Bacillus subtilis DBM, a bacterial strain isolated from a heavy-metal-contaminated soil, were investigated. Adsorption and desorption experiments with living bacterial cells as well as dead cells revealed that both extracellular adsorption and intracellular accumulation were involved in the Pb2＋removal from the liquid phase. Of the sequestered Pb（II）, 8.5% was held by physical entrapment within the cell wall, 43.3% was held by ion-exchange, 9.7% was complexed with cell surface functional groups or precipitated on the cell surface, and 38.5% was intracellularly accumulated.Complexation of Pb2＋with carboxyl, hydroxyl, carbonyl, amido, and phosphate groups was demonstrated by Fourier transform infrared spectroscopic analysis. Precipitates of Pb5（PO4）3OH, Pb5（PO4）3Cl and Pb10（PO4）6（OH）2that formed on the cell surface during the biosorption process were identified by X-ray diffraction analysis. Transmission electron microscopy–energy dispersive spectroscopic analysis confirmed the presence of the Pb（II）precipitates and that Pb（II） could be sequestered both extracellularly and intracellularly.Incubation with B. subtilis DBM significantly decreased the amount of the weak-acid-soluble Pb fraction in a heavy-metal-contaminated soil, resulting in a reduction in Pb bioavailability, but increased the amount of its organic-matter-bound fraction by 71%. The ability of B.subtilis DBM to reduce the bioavailability of soil Pb makes it potentially useful for bacteria-assisted phytostabilization of multi-heavy-metal-contaminated soil.     

Stimulation impact of electric currents on heterotrophic denitrifying microbial viability and denitrification performance in high concentration nitrate-contaminated wastewater

Electric current stimulation has been shown to have a positive influence on heterotrophic denitrifying microbial viability and has the potential to improve wastewater denitrification performance. This study investigated the effects of varying current densities on microbial activity and NO_3~- removal efficiency under heterotrophic conditions.NO_3~-removal rate was highest at an applied current density of 400 mA/m~2. However, the optimum removal efficiency of total inorganic nitrogen(TIN; 99%) was achieved when the current density was fixed at 200 m A/m~2. Accumulation of NH_4~+-N and NO_2~--N byproducts were also minimized at this current density. The activity of heterotrophic denitrifying microorganisms was much higher at both 200 and 400 mA/m~2. Moreover, the average adenosine-5′-triphosphate(ATP)content(an indicator of cell metabolism) at a current density of 1600 mA/m~2 was lower than that under no current, indicating heterotrophic denitrifying microbial activity can be inhibited at high current densities. Hence, direct electrical stimulation on the activity of heterotrophic denitrifying microorganisms in the developed system should be lower than 1600 mA/m~2. This study improves the understanding of electric current influence on heterotrophic denitrifying microorganisms and promotes the intelligent application of direct electrical stimulation on wastewater treatment processes.     

Influence of biosurfactant on the diesel oil remediation in soil-water system

There were six high diesel oil degrading bacteria strains isolated from the oil contaminated soil that collected from Linzi City. The strain YI was able to produce biosurfactant rhanmolipid when cultivated on diesel oil as carbon source. The critical micelle concentrations （CMC） of rhanmolipid in water and in the soil were measured respectively according to the correlation between the surface tension of the medium and the added rhamnolipid concentration. The results showed that the CMC of rhanmolipid in water was 65 mg/L, and was 185 mg/L in soil. The tests on diesel oil biodegradation were conducted with the addition of different concentrations of rhamnolipid in water and in soil respectively. When 0.01% rhanmolipid was added to water, the diesel oil degradation was enhanced. On the contrary, when the same concentration of rhanmolipid was added to the soil, the degradation of diesel oil was inhibited. The results suggested that the rhamnolipid could enhance the diesel oil biodegradation, indicating that the concentration of rhamnolipid was higher than the corresponding CMC in the medium. Kinetics parameters for the diesel oil biodegradation parameters such as biodegradation constant （λ）, coefficient of correlation （r） and half life （t1/2） in both tests were numerically analyzed in this paper, indicating that the moderate concentration of rhamnolipid in the medium could not only enhance the extent of diesel oil biodegradation but also shorten the time for oil remediation.     

Effects of Cd2+ and Pb2+ on the substrate biofilms in the integrated vertical-flow constructed wetland

The effects of single Cd~(2+)and Pb~(2+),and combined Cd~(2+)and Pb~(2+)on dehydrogenase activity and polysaccharide content of the substrate biofilms in the integrated vertical-flow constructed wetland(IVCW)were studied.Dehydrogenase activities decreased linearly with the increasing concentrations of Cd~(2+)and Pb~(2+)at different times(6,24,72,and 120 h).The activities at both 6 and 24 h were significantly higher than that at 72 and 120 h in the case of single and combined treatments.The single Cd~(2+)...     

Reduction of nitrobenzene by the catalyzed Fe/Cu process

The polarization behavior of the couple Fe/Cu in 100 mg/L nitrobenzene aqueous solution was studied using Evans coupling diagrams.The results indicated that the iron corrosion was limited by both anodic and cathodic half-cell reactions under the neutral conditions,and cathodically controlled under the alkaline conditions.Batch experiments were performed to study the effect of solution pH,reaction duration,concentration,type of electrolyte,and dissolved oxygen(DO)on the reduction of nitrobenzene by the ca...     

Synthesis of malachite@clay nanocomposite for rapid scavenging of cationic and anionic dyes from synthetic wastewater

Synthesis of malachite@clay nanocomposite was successfully carried out for the removal of cationic (Methylene Blue, MB) and anionic dyes (Congo Red, CR) from synthetic wastewater. Nanocomposite was characterized by TEM, SEM, FT-IR, EDS analysis and zeta potential. TEM analysis indicated that the particle diameter of nanocomposite was in the range of 14 to 23 nm. Various important parameters viz. contact time, concentration of dyes, nanocomposite dosage, temperature and solution pH were optimized to achieve maximum adsorption capacity. In the case of MB, removal decreased from 99.82% to 93.67% while for CR, removal decreased from 88.55% to 75.69% on increasing dye concentration from 100 to 450 mg/L. pH study confirmed the higher removal of CR in acidic range while MB removal was higher in alkaline range. Kinetic study revealed the applicability of pseudo-second-order model for the adsorption of both dyes. Negative values of ΔG⁰ for both systems suggested the feasibility of dye removal and support for spontaneous adsorption of CR and MB on nanocomposite. Nanocomposite showed 277.77 and 238.09 mg/g Langmuir adsorption capacity for MB and CR respectively. Desorption of dyes from the dye loaded nanocomposite was easily carried out with acetone. The results indicate that the prepared malachite@clay nanocomposite is an efficient adsorbent with high adsorption capacity for the aforementioned dyes.     

Removal of Pb(II) from aqueous solution by hydrous manganese dioxide: Adsorption behavior and mechanism

Hydrous manganese dioxide (HMO) synthesized by redox of potassium permanganate and hydrogen peroxide was used as an adsorbent for Pb(Ⅱ) removal.The specific surface area,pore volume and BJH pore diameter of the HMO were 79.31m2/g,0.07cm3/g and 3.38 nm,respectively.The adsorption equilibrium at 298K could be well described by the Langmuir isotherm equation with q max value of 352.55mg/g.The negative values of G and the positive values of H and S indicated the adsorption process was spontaneous and endothermic.The pseudo second-order equation could best fit the adsorption data.The value of the calculated activation energy for Pb(Ⅱ) adsorption onto the HMO was 38.23 kJ/mol.The uptake of Pb(Ⅱ) by HMO was correlated with increasing surface hydroxyl group content and the main adsorbed speciation was PbOH+.The final chemical state of Pb(Ⅱ) on the surface of HMO was similar to PbO.HMO was a promising candidate for Pb(Ⅱ) removal from aqueous solution.     

Toluene removal characteristics by a superimposed wire-plate dielectric barrier discharge plasma reactor

A superimposed wire-plate dielectric barrier discharge reactor was used to remove toluene in this study. The effects of oxygen content, gas flow rate, gas initial concentration and with/without catalyst on toluene decomposition were investigated. It was found that an optimal toluene removal was achieved when the oxygen content was about 5%. Under this condition, the highest toluene removal efficiency of 80.8% was achieved when the gas concentration was 80 mg/m^3. The toluene removal efficiency decreased with the increase of the gas flow rate and the initial concentration of toluene. In addition, the ozone concentration decreased with the increase of the initial concentration of toluene. It suggested that combining DBD （dielectric barrier discharge） with Co3O4/Al2O3/foam nickel catalyst in-situ could improve the toluene removal efficiency and suppress ozone formation. Products analysis showed that the main products were CO and CO2 when oxygen was more than 5%.     

Performance study and kinetic modeling of hybrid bioreactor for treatment of bi-substrate mixture of phenol-m-cresol in wastewater: Process optimization with response surface methodology

Performance of a hybrid reactor comprising of trickling filter(TF) and aeration tank(AT) unit was studied for biological treatment of wastewater containing mixture of phenol and m-cresol,using mixed microbial culture.The reactor was operated with hydraulic loading rates(HLR) and phenolics loading rates(PLR) between 0.222-1.078m3/(m2·day) and 0.900-3.456kg/(m3·day),respectively.The efficiency of substrate removal varied between 71%-100% for the range of HLR and PLR studied.The fixed film unit showed better substrate removal efficiency than the aeration tank and was more resistant to substrate inhibition.The kinetic parameters related to both units of the reactor were evaluated and their variation with HLR and PLR were monitored.It revealed the presence of substrate inhibition at high PLR both in TF and AT unit.The biofilm model established the substrate concentration profile within the film by solving differential equation of substrate mass transfer using boundary problem solver tool ’bvp4c’ of MATLAB 7.1 software.Response surface methodology was used to design and optimize the biodegradation process using Design Expert 8 software,where phenol and m-cresol concentrations,residence time were chosen as input variables and percentage of removal was the response.The design of experiment showed that a quadratic model could be fitted best for the present experimental study.Significant interaction of the residence time with the substrate concentrations was observed.The optimized condition for operating the reactor as predicted by the model was 230mg/L of phenol,190mg/L of m-cresol with residence time of 24.82 hr to achieve 99.92% substrate removal.     

Influence of temperature on performance of anaerobic digestion of municipal solid waste

The influence of temperature on the performance of anaerobic reactors for treating the organic fraction of municipal sohd waste （OFMSW） was studied. Batch digestion of OFMSW was carded out for 32 d at different temperature （25℃, 35℃, 45℃ and 55℃） conditions for total solid concentrations （TS） 17% with the ratio of total organic carbon to nitrogen （C/N） being, 25：1 respectively, while keeping other parameters constant such as inoculum, start-up pH, reactor volume （2 L） and so on. Temperature can influence the methanogenic bacteria activity, accordingly inhibiting the OFMSW biodegradation and stabilization efficiency. Anaerobic reactors excelled at TS reduction, total volatile solid reduction, chemical oxygen demand reduction, increasing cumulative biogas production, whose rate was at temperature （35℃ and 55℃） conditions. Methane concentration in the biogas was above 65% in four reactors. In addition, the fluctuation of temperatures resulted in the biogas production variation. The data obtained indicated that temperature had a significant influence on anaerobic process.     

Pb（II） biosorption using chitosan and chitosan derivatives beads： Equilibrium, ion exchange and mechanism studies

The study examined the adsorption of Pb(II) ions from aqueous solution onto chitosan, chitosan-GLA and chitosan-alginate beads. Several important parameters influencing the adsorption of Pb(II) ions such as initial pH, adsorbent dosage and di erent initial concentration of Pb(II) ions were evaluated. The mechanism involved during the adsorption process was explored based on ion exchange study and using spectroscopic techniques. The adsorption capacities obtained based on non–linear Langmuir isotherm for chitosan, chitosan-GLA and chitosan-alginate beads in single metal system were 34.98, 14.24 and 60.27 mg/g, respectively. However, the adsorption capacity of Pb(II) ions were reduced in the binary metal system due to the competitive adsorption between Pb(II) and Cu(II) ions. Based on the ion exchange study, the release of Ca2+, Mg2+, K+ and Na+ ions played an important role in the adsorption of Pb(II) ions by all three adsorbents but only at lower concentrations of Pb(II) ions. Infrared spectra showed that the binding between Pb(II) ions and the adsorbents involved mostly the nitrogen and oxygen atoms. All three adsorbents showed satisfactory adsorption capacities and can be considered as an e cient adsorbent for the removal of Pb(II) ions from aqueous solutions.     

Biodegradation of mixture of VOC's in a biofilter

Volatile organic compounds(VOC‘s) in air have become major concern in recent years. Biodegradation of a mixture of ethanol and methanol vapor was evaluated in a laboratory biofilter with a bed of compost and polystyrene particles using an acclimated mixed culture. The continuous performance of the biofilter was studied with different proportion of ethanol and methanol at different initial concentration and flow rates. The result showed significant removal for both ethanol and methanol, which were composition dependent.The presence of either compound in the mixture inhibited the biodegradation of the other.