Salt stress altered anaerobic microbial community and carbon metabolism characteristics: The trade-off between methanogenesis and chain elongation.

Discharge of saline organic wastewater is increasing worldwide, yet how salt stress disrupts the microbial community's structure and metabolism in bioreactors has not been systematically investigated. The non-adapted anaerobic granular sludge was inoculated into wastewater with varying salt concentration (ranging from 0% to 5%) to examine the effects of salt stress on the structure and function of the anaerobic microbial community. Result indicated that salt stress had a significant impact on the metabolic function and community structure of the anaerobic granular sludge. Specifically, we observed a notable reduction in methane production in response to all salt stress treatments (r = -0.97, p < 0.01), while an unexpected increase in butyrate production (r = 0.91, p < 0.01) under moderate salt stress (1-3%) with ethanol and acetate as carbon sources. In addition, analysis of microbiome structures and networks demonstrated that as the degree of salt stress increased, the networks exhibited lower connectance and increased compartmentalization. The abundance of interaction partners (methanogenic archaea and syntrophic bacteria) decreased under salt stress. In contrast, the abundance of chain elongation bacteria, specifically Clostridium kluyveri, increased under moderate salt stress (1-3%). As a consequence, the microbial carbon metabolism patterns shifted from cooperative mode (methanogenesis) to independent mode (carbon chain elongation) under moderate salt stress. This study provides evidence that salt stress altered the anaerobic microbial community and carbon metabolism characteristics, and suggests potential guidance for steering the microbiota to promote resource conversion in saline organic wastewater treatment.

Highly Effective Anti-Organic Fouling Performance of a Modified PVDF Membrane Using a Triple-Component Copolymer of P(Stx-co-MAAy)-g-fPEGz as the Additive.

In this study, a triple-component copolymer of P(Stx-co-MAAy)-g-fPEGz containing hydrophobic (styrene, St), hydrophilic (methacrylic acid, MAA), and oleophobic (perfluoroalkyl polyethylene glycol, fPEG) segments was synthesized and used as an additive polymer to prepare modified PVDF membrane for enhanced anti-fouling performance. Two compositions of St:MAA at 4:1 and 1:1 for the additive and two blending ratios of the additive:PVDF at 1:9 and 3:7 for the modified membranes were specifically examined. The results showed that the presence of the copolymer additive greatly affected the morphology and performance of the modified PVDF membranes. Especially, in a lower ratio of St to MAA (e.g., St:MAA at 1:1 versus 4:1), the additive polymer and therefore the modified PVDF membrane exhibited both better hydrophilic as well as oleophobic surface property. The prepared membrane can achieve a water contact angle at as low as 48.80° and display an underwater oil contact angle at as high as 160°. Adsorption experiments showed that BSA adsorption (in the concentration range of 0.8 to 2 g/L) on the modified PVDF membrane can be reduced by as much as 93%. From the filtration of BSA solution, HA solution, and oil/water emulsion, it was confirmed that the obtained membrane showed excellent resistance to these organic foulants that are often considered challenging in membrane water treatment. The performance displayed slow flux decay during filtration and high flux recovery after simple water cleaning. The developed membrane can therefore have a good potential to be used in such applications as water and wastewater treatment where protein and other organic pollutants (including oils) may cause severe fouling problems to conventional polymeric membranes.

Anticorrosion Performance of PVDF Membranes Modified by Blending PTFE Nanoemulsion and Prepared through Usual Non-Solvent-Induced Phase Inversion Method.

In this study, PVDF/PTFE composite membranes were prepared by adding a PTFE nanoemulsion to a PVDF solution and casting it through the conventional non-solvent-induced phase separation method. The objective was to explore the effectiveness of using a simple and economical method to modify PVDF membranes with PTFE to enhance their anticorrosion performance, especially under highly acidic or alkaline conditions. PTFE nanoparticles (of around 200 nm in size) in nanoemulsion form were blended with PVDF at a mass ratio of PTFE:PVDF in the range of 0-0.3:1. The obtained membranes were examined to determine the effect of the added PTFE nanoparticles on the structure of the modified PVDF membranes as well as on their mechanical strength and surface characteristics. The membranes were then immersed in various concentrations of acidic or alkaline solutions for varied durations ranging from a few days up to as long as 180 days (6 months). The impacts of by the corrosive solutions on the tensile strength, surface roughness, and water flux of the membranes with different exposure times were quantified. The results showed that although a certain extent of change may occur with extended immersion times, greatly enhanced anticorrosion performance was obtained with the prepared PVDF/PTFE membranes compared with the unmodified PVDF membrane. For example, after being immersed in 5 mol-H+··L-1 H2SO4, HCl, and HNO3 solutions for 6 months, the tensile strength at breaking point remained at up to 69.70, 74.07, and 71.38%, respectively, of the initial strength for the PVDF/PTFE (M30) membrane. This was in contrast to values of only 55.77, 70.43, and 61.78% for the unmodified PVDF membrane (M0). Although the water flux and surface roughness showed a change trends to the tensile strength, the PVDF/PTFE (M30) membrane had much higher stability than the PVDF (M0) membrane. In a continuous filtration experiment containing H2SO4 at 0.01 mol-H+·L-1 for 336 h (14 days), the PVDF/PTFE membrane showed a maximum flux change of less than 30%. This was in comparison with a change of up to 50% for the PVDF membrane. However, the PVDF/PTFE membranes did not seem to have a greatly enhanced anticorrosion performance in the alkaline solution environment tested.

Removal of Mercury (II) by EDTA-Functionalized Magnetic CoFe2O4@SiO2 Nanomaterial with Core-Shell Structure.

In order to reduce the difficulty and risk of operation, decrease the preparation time and improve the adsorption performance of magnetic nano-silicon adsorbent with core-shell structure, a carboxylated CoFe2O4@SiO2 was prepared by EDTA-functionalized method using a safe, mild and simple hydrothermal method. The results show that the prepared material of CoFe2O4@SiO2-EDTA has a maximum adsorption capacity of 103.3 mg/g for mercury ions (Hg(II)) at pH = 7. The adsorption process of Hg(II) is a chemical reaction involving chelation and single-layer adsorption, and follows the pseudo-second-order kinetic and Langmuir adsorption isotherm models. Moreover, the removal of Hg(II) is a spontaneous and exothermic reaction. The material characterization, before and after adsorption, shows that CoFe2O4@SiO2-EDTA has excellent recyclability, hydrothermal stability and fully biodegradable properties. To summarize, it is a potential adsorption material for removing heavy metals from aqueous solutions in practical applications.

A Mild and Facile Synthesis of Amino Functionalized CoFe2O4@SiO2 for Hg(II) Removal.

To avoid the dangerous operational conditions, shorten the preparation time, and improve the adsorption performance of amino-functionalized nanomagnetic materials with a core⁻shell structure, a magnetic nanocomposite of CoFe2O4@SiO2 was successfully functionalized with amino group (-NH2) through a mild and facile hydrothermal method without the use of any toxic or harmful solvents at a relatively low temperature. The preparation time of the key steps of amino functionalization was shortened from 30 h to about 10 h. The core-shell structure and successful grafting were confirmed by various means. The amino-functionalized CoFe2O4@SiO2 was used for the removal mercury (Hg(II)), a heavy metal, and exhibited excellent magnetic properties and a high Langmuir adsorption capacity of 149.3 mg Hg(II)/g. The adsorption of Hg(II) onto CoFe2O4@SiO2⁻NH2 followed the pseudo-second-order kinetic equation and Langmuir model. The thermodynamic data showed that the Hg(II) adsorption process was achieved through spontaneous exothermic and monolayer adsorption with electrostatic adsorption and chemisorption. In addition, the as-prepared CoFe2O4@SiO2⁻NH2 nanoparticles had a good reusable value, good application performance and stability, and can provide a mild and facile way to remove heavy metals from aqueous solution.

Separation of Biologically Active Compounds by Membrane Operations.

BACKGROUND: Bioactive compounds from various natural sources have been attracting more and more attention, owing to their broad diversity of functionalities and availabilities. However, many of the bioactive compounds often exist at an extremely low concentration in a mixture so that massive harvesting is needed to obtain sufficient amounts for their practical usage. Thus, effective fractionation or separation technologies are essential for the screening and production of the bioactive compound products. The applicatons of conventional processes such as extraction, distillation and lyophilisation, etc. may be tedious, have high energy consumption or cause denature or degradation of the bioactive compounds. Membrane separation processes operate at ambient temperature, without the need for heating and therefore with less energy consumption. The "cold" separation technology also prevents the possible degradation of the bioactive compounds. The separation process is mainly physical and both fractions (permeate and retentate) of the membrane processes may be recovered. Thus, using membrane separation technology is a promising approach to concentrate and separate bioactive compounds. METHODS: A comprehensive survey of membrane operations used for the separation of bioactive compounds is conducted. The available and established membrane separation processes are introduced and reviewed. RESULTS: The most frequently used membrane processes are the pressure driven ones, including microfiltration (MF), ultrafiltration (UF) and nanofiltration (NF). They are applied either individually as a single sieve or in combination as an integrated membrane array to meet the different requirements in the separation of bioactive compounds. Other new membrane processes with multiple functions have also been developed and employed for the separation or fractionation of bioactive compounds. The hybrid electrodialysis (ED)-UF membrane process, for example has been used to provide a solution for the separation of biomolecules with similar molecular weights but different surface electrical properties. In contrast, the affinity membrane technology is shown to have the advantages of increasing the separation efficiency at low operational pressures through selectively adsorbing bioactive compounds during the filtration process. CONCLUSION: Individual membranes or membrane arrays are effectively used to separate bioactive compounds or achieve multiple fractionation of them with different molecule weights or sizes. Pressure driven membrane processes are highly efficient and widely used. Membrane fouling, especially irreversible organic and biological fouling, is the inevitable problem. Multifunctional membranes and affinity membranes provide the possibility of effectively separating bioactive compounds that are similar in sizes but different in other physical and chemical properties. Surface modification methods are of great potential to increase membrane separation efficiency as well as reduce the problem of membrane fouling. Developing membranes and optimizing the operational parameters specifically for the applications of separation of various bioactive compounds should be taken as an important part of ongoing or future membrane research in this field.

Formic acid enhanced effective degradation of methyl orange dye in aqueous solutions under UV-Vis irradiation.

Developing efficient technologies to treat recalcitrant organic dye wastewater has long been of great research and practical interest. In this study, a small molecule, formic acid (FA), was applied as a process enhancer for the degradation of methyl orange (MO) dye as a model recalcitrant organic pollutant in aqueous solutions under the condition of UV-Vis light irradiation and air aeration at the ambient temperature of 25 °C. It was found that the decolouration of the dye solutions can be rapidly achieved, reducing the time, for example, from around 17.6 h without FA to mostly about less than 2 h with the presence of FA. The mineralization rate of MO dye reached as high as 81.8% in 1.5 h in the case of initial MO dye concentration at 25 mg L(-1), which is in contrast to nearly no mineralization of the MO dye for a similar system without the FA added. The study revealed that the generation of the H2O2 species in the system was enhanced and the produced OH radicals effectively contributed to the degradation of the MO dye. Process parameters such as the initial concentration of MO dye, FA dosage and solution pH were all found to have some effect on the degradation efficiency under the same condition of UV-Vis light irradiation and air aeration. The MO dye degradation performance was found to follow a first-order reaction rate to the MO dye concentration in most cases and there existed a positive correlation between the reaction rate constant and the initial FA concentration. Compared to the traditional H2O2/UV-Vis oxidation system, the use of FA as a process-enhancing agent can have the advantages of low cost, easy availability, and safe to use. The study hence demonstrates a promising approach to use a readily available small molecule of FA to enhance the degradation of recalcitrant organic pollutants, such as MO dye, especially for their pre-treatment.

Immobilization of silver in polypropylene membrane for anti-biofouling performance.

In this study, a method was developed to immobilize silver onto polypropylene (PP) membrane surfaces for improved anti-biofouling performance. A commercial PP membrane was first grafted with the thiol functional groups, and then silver ions were immobilized onto the PP membrane surface through coordinating with the thiol groups. The immobilized silver was found to be very stable, with only ~1.1% of the immobilized silver being leached out during a leaching test. The surface of the modified membrane (PPS-Ag) was examined with ATR-FTIR and XPS analysis, which verified the successful grafting of the thiol groups and the coordination of silver ions on the membrane surface. The surface properties of the membrane were also characterized by SEM, AFM and water contact angle measurements. The PPS-Ag membrane was found to have a smoother and more hydrophilic surface than the PP membrane. Both Gram-negative bacteria, Escherichia coli, and Gram-positive bacteria, Staphylococcus aureus, were used to evaluate the antibacterial and anti-biofouling performance of the PPS-Ag membrane. From disk diffusion experiments, the PPS-Ag membrane exhibited the capability of inhibiting the growth of both the Gram-negative and Gram-positive bacteria tested. The anti-biofouling performance of the membrane was assessed by immersion in a mixed suspension of E. coli and S. aureus and filtration tests. The PPS-Ag membrane showed a stable and significantly enhanced anti-biofouling performance as compared with the PP membrane. The results in this study demonstrate that biofouling of a PP membrane can be sufficiently overcome through immobilizing silver onto the membrane surface.

Extended study of DETA-functionalized PGMA adsorbent in the selective adsorption behaviors and mechanisms for heavy metal ions of Cu, Co, Ni, Zn, and Cd.

In this paper, the adsorption selectivity and mechanism of diethylenetriamine (DETA)-functionalized PGMA adsorbent (denoted as P-DETA) toward a number of heavy metal ions, including Cu, Co, Ni, Zn, and Cd ions, were experimentally and analytically examined. Experimental results showed a selective adsorption sequence, based on the adsorption affinity, of Cu>Co>Ni>Zn>Cd ions on P-DETA. X-ray absorption fine structure (XAFS) analysis was used to reveal the adsorption coordination geometry, bond length, and coordination number of each type of metal ion with the DETA group. The analysis indicated that Cu, Ni, and Zn ions formed tetrahedral geometry (fourfold coordination) when adsorbed, while Co ion showed an octahedral geometry (sixfold coordination). However, the coordination geometry for Cd could not be obtained in the analysis due to the lack of reference information. The analysis from EXAFS further confirmed that the ratio of DETA ligand to the adsorbed metal ion was probably 1 for Cu, Ni, or Zn ions, while that ratio was 2 for Co ion. From the stability constant (in the log K form) for a metal ion-DETA ligand coordination (denoted as ML(n), where M indicates a heavy metal ion, and L(n) indicates n numbers of ligands involved), a relationship of log K (CuL)>log K (CoL(2))>log K (NiL)>log K (ZnL)>log K (CdL) is suggested. This sequence is in good correlation with the experimentally derived adsorption selective sequence of Cu>Co>Ni>Zn>Cd ions, indicating that the coordination geometry played an important role in the determination of the adsorption selectivity for heavy metal ions by the polyamine-functionalized adsorbent of P-DETA.

A novel electrolyte-responsive membrane with tunable permeation selectivity for protein purification.

A novel electrolyte-responsive membrane, RC-g-PSBMA, was successfully prepared from regenerated cellulose (RC) membrane through surface-initiated atom transfer radical polymerization (ATRP) of a zwitterionic monomer, sulfobetaine methacrylate (SBMA). Different degrees of polymerization for the grafted SBMA polymers (i.e., PSBMA) on the RC membrane were easily obtained by adjusting the ATRP reaction conditions. The electrolyte-responsive behavior of RC-g-PSBMA was first evaluated through the permeation experiments with sodium chloride (NaCl) solutions of different concentrations. It was found that the permeability of RC-g-PSBMA showed a clear dependence on NaCl concentration in the solutions. To further examine the potential of RC-g-PSBMA for protein purification, bovine serum album (BSA) was chosen as a model protein and polystyrene nanoparticles (NPs) of different sizes were used as representative impurities in the solutions. The rejection rates of BSA and NPs by RC-g-PSBMA were examined with the solutions containing BSA and NPs at different NaCl concentrations. The results showed that the rejection rates of BSA were at a very low level regardless of the concentration of NaCl in the solutions, indicating that the membrane allowed BSA to permeate. However, the rejection rates of NPs of different sizes by RC-g-PSBMA changed remarkably with the concentration of NaCl in the solutions. The study has demonstrated the possibility to separate BSA from NPs of different sizes by using the same membrane but simply altering the concentration of NaCl in the solutions. Membranes with such properties will have a great potential for protein purification as well as for many other separation applications.

Achieving highly effective non-biofouling performance for polypropylene membranes modified by UV-induced surface graft polymerization of two oppositely charged monomers.

A major problem in membrane technology for applications such as wastewater treatment or desalination is often the loss of membrane permeability due to biofouling initiated from protein adsorption and biofilm formation on the membrane surface. In this study, we developed a relatively simple and yet versatile approach to prepare polypropylene (PP) membrane with highly effective non-biofouling performance. Copolymer brushes were grafted to the surface of PP membrane through UV-induced polymerization of two oppositely charged monomers, i.e., [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TM) and 3-sulfopropyl methacrylate potassium salt (SA), with varying TM:SA molar ratios. Surface analysis with scanning electron microscope (SEM) clearly showed the grafted copolymer brushes on the membrane surfaces and that with X-ray photoelectron spectroscope (XPS) revealed a similar TM:SA ratio of the grafted copolymer brushes to that of the monomer solution used for the polymerization. Water contact angle measurements indicated that the hydrophilicity of the membrane surfaces was remarkably improved by the grafting of the TM/SA copolymer brushes, with the lowest water contact angle of 27 degrees being achieved at the TM:SA ratio of around 1:1. Experiments for antiprotein adsorption with bovine serum album (BSA) and lysozyme (LYZ) and antibiofilm formation with Escherichia coli (E. coli) demonstrated a great dependence of the membrane performance on the TM:SA ratios of the grafted copolymer brushes. It was found that the characteristics of the surface charges of the membrane surfaces played a very important role in the non-biofouling performance, and the membrane surface with balanced positive and negative charges showed the best non-biofouling performance for the proteins and bacteria tested in this study.

Functionalization of adsorbent with different aliphatic polyamines for heavy metal ion removal: characteristics and performance.

This paper examines the characteristics of poly(glycidyl methacrylate) (PGMA) beads functionalized with different aliphatic polyamines as adsorbents and their performance in copper ion adsorption. The four aliphatic polyamines evaluated include ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA). Various analytical tools, including elemental analysis, BET, and XAFS (XANES+EXAFS), were used to characterize the adsorbents in terms of their immobilized amine contents, polyamine densities, and their coordination structures for the adsorption of a typical heavy metal ion, Cu(2+). It was found that the immobilized polyamine densities followed the order of EDA>DETA>TETA>TEPA, but the immobilized amine contents followed the opposite order of TEPA>TETA>DETA>EDA. XAFS analysis for the adsorbents after copper ion adsorption revealed that the average coordination number of copper ion with the nitrogen atoms (in the range between 3 and 4) followed the order of DETA

Biodegradation of acetonitrile by adapted biofilm in a membrane-aerated biofilm reactor.

A membrane-aerated biofilm reactor (MABR) was developed to degrade acetonitrile (ACN) in aqueous solutions. The reactor was seeded with an adapted activated sludge consortium as the inoculum and operated under step increases in ACN loading rate through increasing ACN concentrations in the influent. Initially, the MABR started at a moderate selection pressure, with a hydraulic retention time of 16 h, a recirculation rate of 8 cm/s and a starting ACN concentration of 250 mg/l to boost the growth of the biofilm mass on the membrane and to avoid its loss by hydraulic washout. The step increase in the influent ACN concentration was implemented once ACN concentration in the effluent showed almost complete removal in each stage. The specific ACN degradation rate achieved the highest at the loading rate of 101.1 mg ACN/g-VSS h (VSS, volatile suspended solids) and then declined with the further increases in the influent ACN concentration, attributed to the substrate inhibition effect. The adapted membrane-aerated biofilm was capable of completely removing ACN at the removal capacity of up to 21.1 g ACN/m(2) day, and generated negligible amount of suspended sludge in the effluent. Batch incubation experiments also demonstrated that the ACN-degrading biofilm can degrade other organonitriles, such as acrylonitrile and benzonitrile as well. Denaturing gradient gel electrophoresis studies showed that the ACN-degrading biofilms contained a stable microbial population with a low diversity of sequence of community 16S rRNA gene fragments. Specific oxygen utilization rates were found to increase with the increases in the biofilm thickness, suggesting that the biofilm formation process can enhance the metabolic degradation efficiency towards ACN in the MABR. The study contributes to a better understanding in microbial adaptation in a MABR for biodegradation of ACN. It also highlights the potential benefits in using MABRs for biodegradation of organonitrile contaminants in industrial wastewater.

Membrane aerated biofilm reactors: a brief current review.

Membrane aerated biofilm reactors (MABRs) represent a relatively new biotreatment technology. In a MABR, biofilm is grown on a gas-permeable membrane (often a hollow fiber membrane). Soluble organic compounds in the liquid are supplied to the biofilm from the biofilm-liquid interface whereas oxygen supply to the biofilm is from the biofilm-membrane interface (by oxygen diffusing through the membrane). MABRs can achieve bubble-less aeration and high oxygen utilization efficiency (up to 100%) and the biofilm can be stratified into aerobic/anoxic/anaerobic zones to simultaneously achieve removal of carbonaceous organic pollutants as well as nitrification and denitrification (if needed) in a single biofilm. This article briefly reviews the MABR process, including the characteristics, membrane materials, modular design, operation parameters and the potential applications, from relevant recent patents and literature.

Distribution and composition of extracellular polymeric substances in membrane-aerated biofilm.

Extracellular polymeric substances (EPS) are one of the main components of the biofilm and perform important functions in the biofilm system. In this study, two membrane-aerated biofilms (MABs) were developed for the thin and thick biofilms under different surface loading rates (SLRs). Supplies of oxygen and substrates in the MAB were from two opposite directions. This counter diffusion of nutrients resulted in a different growth environment, in contrast to conventional biofilms receiving both oxygen and substrates from the same side. The compositions, distributions and physicochemical properties (solubility and bindability) of EPS in the MABs of different thicknesses under different SLRs were studied. The effect of dissolved oxygen (DO) concentration within the MAB on EPS properties and distribution was investigated. Experimental results showed the different biofilm thicknesses produced substantially different profiles of EPS composition and distribution. Soluble proteins were more dominant than soluble polysaccharides in the inner aerobic layer of the biofilms; in contrast, bound proteins were greater than bound polysaccharides in the outer anoxic or anaerobic layer of the biofilms. The biofilm-EPS matrix consisted mainly of bound EPS. Bound EPS exhibited a hump-shaped profile with the highest content occurring in an intermediate region in the thin MAB and relatively more uniformly in the one half of the biofilm close to the membrane side and then declined towards the biofilm-liquid interface in the thick MAB. The profiles of soluble EPS presented a similar declining trend from the membrane towards the outer region in both thin and thick MABs. The study suggested that not only EPS composition but also EPS distribution and properties (solubility and bindability) played a crucial role in controlling the cohesiveness and maintaining the structural stability and stratification of the MABs.

Membrane-aerated biofilm reactor for the treatment of acetonitrile wastewater.

A membrane-aerated biofilm reactor (MABR) was studied for the treatment of wastewater containing acetonitrile, a typical organonitrile compound. The MABR used hydrophobic hollow fiber membranes as the diffusers for bubbleless aeration as well as the carriers for biofilm growth. The objectives were to prevent the stripping-loss of acetonitrile during aeration and to achieve acetonitrile biodegradation plus nitrogen removal simultaneously in a single biolfilm on the membranes. In the MABR, oxygen and substrates were supplied to the biofilm from opposite sides, in contrast to those from the same side in conventional biofilm bioreactors. Operational factors, including surface loading rate and upflow fluid velocity in the bioreactor, on the effect of acetonitrile biodegradation performance were examined. The profiles of dissolved oxygen concentration and microbial activities and populations in the biofilm were investigated. Experimental results showed that, with the adapted microorganisms, removal of acetonitrile at approximately 98.6 and 83.3%, in terms of total organic carbon and total nitrogen, were achieved at a surface loading rate (in terms of membrane surface) of up to 11.29 g acetonitrile/ m2 x d with an upflow fluid velocity of 12 cm/s and a hydraulic retention time of 30 h. The biofilm on the membranes developed an average thickness of about 1.6 mm in the steady state and consisted of oxic/anoxic/anaerobic zones that provided different functions for acetonitrile degradation, nitrification, and denitrification. The acetonitrile-degrading bacteria in the MABR appeared to secrete more extracellular polymeric substances that enhanced the attachment and development of the biofilm on the membranes. The study demonstrated the potential of using the MABR for the treatment of organonitrile wastewater.

Selective removal of copper and lead ions by diethylenetriamine-functionalized adsorbent: behaviors and mechanisms.

The selective removal of copper and lead ions from aqueous solutions by diethylenetriamine (DETA)-functionalized polymeric adsorbent was investigated. The adsorbent was prepared by amination of the micro-beads synthesized from glycidyl methacrylate and trimethylolpropane trimethacrylate co-polymerization (denoted as P-DETA). In the single metal species system (only copper or lead ions present), P-DETA was found to adsorb copper ions or lead ions significantly (with a slightly higher adsorption uptake capacity for lead ions than copper ions). However, P-DETA displayed an excellent selectivity in the adsorption of copper ions over lead ions in the binary metal species system (with both copper and lead ions present). It was also found that initially (or previously) adsorbed lead ions on P-DETA were displaced, even completely, by subsequently adsorbed copper ions from the solution but the case was not vice versa. The greater electronegativity of copper ions than lead ions was identified as the major factor that caused P-DETA to selectively adsorb copper ions over lead ions during competitive adsorption in the binary metal species system. It was speculated that the displacement of already adsorbed lead ions on P-DETA by subsequently adsorbed copper ions was through an adjacent attachment and repulsion mechanism. P-DETA has been shown to have the potential to be used as an effective adsorbent for the removal as well as selective recovery of heavy metal ions in water or wastewater treatment.

Biodegradation of organonitriles by adapted activated sludge consortium with acetonitrile-degrading microorganisms.

A microbial process for the degradation of three types of structurally distinct organonitriles (i.e., saturated and unsaturated aliphatic nitrile and aromatic nitrile) was studied. Microorganisms were enriched from the activated sludge of a pharmaceutical wastewater treatment plant and adapted through providing acetonitrile as the sole carbon and nitrogen source for their growth. The adapted mixed culture was then examined for their capability of degrading acetonitrile, acrylonitrile and benzonitrile under various operational conditions. The performance of biodegradation and the metabolic intermediate- and end-products in the process were monitored. The results show that an average removal rate of 0.083 g acetonitrile g(-1)-VSS h(-1), 0.0074 g acrylonitrile g(-1)-VSS h(-1) or 0.0029 g benzonitrile g(-1)-VSS h(-1) was achieved in the batch bioreactor under the common operational condition of 25 degrees C and pH 7. The biodegradation of acetonitrile and acrylonitrile showed a two-step pathway, with the generation of acetamide followed by acetic acid and ammonia for acetonitrile or acrylamide followed by acrylic acid and ammonia for acrylonitrile. However, the biodegradation of benzonitrile appeared to have only one step, with the direct production of benzoic acid and ammonia, but without benzamide being detected in the process. The results suggest that, depending on the substrates, the adapted mixed culture can develop very different degradation pathways, such as nitrile hydratase plus amidase for acetonitrile or acrylonitrile and nitrilase for benzonitrile. Therefore, the adapted mixed culture has a great potential and flexibility for actual applications in biodegradation of various organonitrile compounds.

Diethylenetriamine-grafted poly(glycidyl methacrylate) adsorbent for effective copper ion adsorption.

Amine-functionalized adsorbents have attracted increasing interest in recent years for heavy metal removal. In this study, diethylenetriamine (DETA) was successfully grafted (through a relatively simple solution reaction) onto poly(glycidyl methacrylate) (PGMA) microgranules to obtain an adsorbent (PGMA-DETA) with a very high content of amine groups and the PGMA-DETA adsorbent was examined for copper ion removal in a series of batch adsorption experiments. It was found that the PGMA-DETA adsorbent achieved excellent adsorption performance in copper ion removal and the adsorption was most effective at pH>3 in the pH range of 1-5 examined. X-ray photoelectron spectroscopy (XPS) revealed that there were different types of amine sites on the surfaces of the PGMA-DETA adsorbent but copper ion adsorption was mainly through forming surface complexes with the neutral amine groups on the adsorbent, resulting in better adsorption performance at a higher solution pH value. The adsorption isotherm data best obeyed the Langmuir-Freundlich model and the adsorption capacity reached 1.5 mmol/g in the case of pH 5 studied. The adsorption process was fast (with adsorption equilibrium time less than 1-4 h) and closely followed the pseudo-second-order kinetic model. Desorption of copper ions from the PGMA-DETA adsorbent was most effectively achieved in a 0.1 M dilute nitric acid solution, with 80% of the desorption being completed within the first 1 min. Consecutive adsorption-desorption experiments showed that the PGMA-DETA adsorbent can be reused almost without any loss in the adsorption capacity.

Enhanced and selective adsorption of mercury ions on chitosan beads grafted with polyacrylamide via surface-initiated atom transfer radical polymerization.

Enhanced and selective removal of mercury ions was achieved with chitosan beads grafted with polyacrylamide (chitosan-g-polyacrylamide) via surface-initiated atom transfer radical polymerization (ATRP). The chitosan-g-polyacrylamide beads were found to have significantly greater adsorption capacities and faster adsorption kinetics for mercury ions than the chitosan beads. At pH 4 and with initial mercury concentrations of 10-200 mg/L, the chitosan-g-polyacrylamide beads can achieve a maximum adsorption capacity of up to 322.6 mg/g (in comparison with 181.8 mg/g for the chitosan beads) and displayed a short adsorption equilibrium time of less than 60 min (compared to more than 15 h for the chitosan beads). Coadsorption experiments with both mercury and lead ions showed that the chitosan-g-polyacrylamide beads had excellent selectivity in the adsorption of mercury ions over lead ions at pH < 6, in contrast to the chitosan beads, which did not show clear selectivity for either of the two metal species. Mechanism study suggested that the enhanced mercury adsorption was due to the many amide groups grafted onto the surfaces of the beads, and the selectivity in mercury adsorption can be attributed to the ability of mercury ions to form covalent bonds with the amide. It was found that adsorbed mercury ions on the chitosan-g-polyacrylamide beads can be effectively desorbed in a perchloric acid solution, and the regenerated beads can be reused almost without any loss of adsorption capacity.