Kinetic characterization and modeling simplification of an anaerobic sulfate reducing batch process

BACKGROUND: A series of kinetic experiments for a sulfate reducing process was carried out in a batch laboratory reactor that allowed simplification of a model initially proposed for this system enabling establishment of the kinetic parameters. RESULTS: It was found that an incomplete oxidation of lactate is the most significant bio‐reaction occurring in the reactor; this fact led to model simplifications that allowed determination of the kinetic parameters. Sulfide and pH inhibition can be described using one inhibition term within the model equation, given the fact that sulfide inhibition is not present in the system. Kinetic parameters were obtained, yielding a maximum specific rate (µ_max/Y) of 2.17 ± 0.08 mg sulfate mg^?1 VSS min^?1. A zero‐order kinetics with respect to sulfate and a Monod affinity constant of 142.7 ± 64.9 mg L^?1 for the lactate were found. CONCLUSIONS: The final model for the process can be described by a single Monod term involving the lactate. This model resulted from the lack of sulfide inhibition in the system and the predominance of the partial lactate oxidation to acetate reaction over the complete lactate and acetate oxidation. Copyright © 2010 Society of Chemical Industry     

Pre‐treatment and utilization of raw glycerol from sunflower oil biodiesel for growth and 1,3‐propanediol production by Clostridium butyricum

BACKGROUND: The objective of the present work is to report an efficient pre‐treatment process for sunflower oil biodiesel raw glycerol (SOB‐RG) and its fermentation to 1,3‐propanediol. RESULTS: The growth inhibition percentages of Clostridium butyricum DSM 5431 on grade A (pH 4.0) and grade B (pH 5.0) phosphoric acid‐treated SOB‐RG were similar to those of pure glycerol at 20 g glycerol L^?1; i.e., 18.5 ± 0.707% to 20.5 ± 0.7% inhibition. In grade A, growth inhibition was reduced from 85.25 ± 0.35% to 32 ± 1.4% (a 53.25% reduction) at 40 g glycerol L^?1 by washing grade A raw glycerol twice with n‐hexanol (grade A‐2). The kinetic parameters for product formation and substrate consumption in anaerobic batch cultures gave almost similar values at 20 g glycerol L^?1, while at 50 g glycerol L^?1 volumetric productivity (Q_p) and specific rate of 1,3‐propanediol formation (q_p) were improved from 1.13 to 1.85 g L^?1 h^?1 and 1.60 to 2.65 g g^?1 h^?1, respectively, by employing grade A‐2 raw glycerol, while the yields were similar (0.5–0.52 g g^?1). CONCLUSION: The results are important as the pre‐treatment of SOB‐RG is necessary to develop bioprocess technologies for conversion of SOB‐RG to 1,3‐propanediol. Copyright © 2008 Society of Chemical Industry     

Time‐dependent dosing of Fe2+ for improved lipopeptide production by marine Bacillus megaterium

BACKGROUND: Lipopeptide production is strongly influenced by trace metals. The availability of free Fe²⁺ in the media throughout the process of fermentation was found to be very critical. Since free Fe²⁺ was reported to be sequestered by the lipopeptide as it was produced, intermittent feeding of Fe²⁺ was strategized and optimized for enhanced lipopeptide production by marine Bacillus megaterium in glucose mineral salts medium (GMSM). RESULTS: Studies with the single‐dose Fe²⁺ (0.48 mmol L^?1) supplementation after 8 h of fermentation resulted in lipopeptide concentration of 3.3 ± 0.1 g L^?1. Lipopeptide production was further enhanced to 4.2 ± 0.15 g L^?1 by adopting a multi‐dose Fe²⁺ feeding strategy. The maximum product yield (Y_P/S) of 0.24 ± 0.02 g g^?1 with specific product formation rate (q_p) of 0.124 ± 0.01 g g^?1 h^?1 was achieved when 0.48 mmol L^?1 Fe²⁺ was fed intermittently at different times as per the designed strategy. CONCLUSION: Lipopeptide concentration was improved 4.7‐fold by single‐dosing and 5.8‐fold by multiple dosing of Fe²⁺, when compared with GMSM without Fe²⁺ supplementation. Copyright © 2012 Society of Chemical Industry     

The interaction of hydrogen sulfide with lead- and barium–cadmium–zinc-stabilized poly(vinyl chloride)

Poly(vinyl chloride) polymers stabilized with tribasic lead sulfate discolor upon exposure to hydrogen sulfide gas as a result of lead sulfide formation. The discoloration occurs for samples in both cord and sheet forms and is shown to be a function of total H₂S exposure, reaching a limiting value that is determined by the amount of lead stabilizer used in the polymer formulation. The permeation and diffusion constants for H₂S through PVC stabilized with tribasic lead sulfate and with a liquid Ba–Cd–Zn formulation are found to be P_Pb = (6.0 ± 0.2) × 10^?9, P_BaCdZn = (5.2 ± 0.2) × 10^?9 (both in cm³ gas?cm film/cm² area?sec?cm Hg), D_Pb = (1.3 ± 0.2) × 10^?7 cm²/sec, and D_BaCdZn = (6.4 ± 0.6) × 10^?8 cm²/sec, all measured at 21°C. The stabilizing efficiencies of the formulations were assessed by HCl evolution measurements, which show that exposure to H₂S decreases the initial polymer stability for both Pb-stabilized and Ba–Ca–Zn-stabilized formulations. Protection of stabilized PVC formulations from diffusing hydrogen sulfide is thus advisable for long-term stability as well as for color integrity.     

Removal of sulfur inorganic compounds by a biofilm of sulfate reducing and sulfide oxidizing bacteria in a down‐flow fluidized bed reactor

BACKGROUND: Biological sulfate removal is a process based on the biological sulfur cycle that consists of two steps: (1) production of sulfide by sulfate reduction; and (2) biological or physico‐chemical sulfide oxidation to elemental sulfur (S⁰). The objective of this work was to transform soluble sulfur (sulfate) into insoluble sulfur (elemental sulfur) coupling sulfate reduction and sulfide oxidation in one reactor. To accomplish this, a 2.3 L down‐flow fluidized bed reactor was used. Lactate was supplied as electron donor, sulfate and oxygen (air) were the electron acceptors. RESULTS: After 55 days of batch operation a biofilm with sulfate reducing and sulfide oxidizing activities was developed over a plastic support. Continuous operation for 90 days at a down‐flow superficial velocity of 7.7 m h^?1 and 30 °C, showed that sulfate reduction amounted to 72–77% and carbon removal to 20–31%. Under low aeration rates (2.3 L d^?1) 50% of the sulfate was transformed to elemental sulfur, when aeration increased to 5.4 L d^?1 elemental sulfur recovery was only 30% and sulfide in the effluent amounted to 27% of the sulfur fed. CONCLUSION: It was possible to obtain elemental sulfur through a coupled anaerobic/aerobic process in one reactor using lactate, sulfate and oxygen (air) as substrates. The development of a biofilm with sulfate reducing and sulfide oxidizing activities was the key of the process. Copyright © 2007 Society of Chemical Industry     

Bio‐oxidation of ferrous ions by Acidithioobacillus ferrooxidans in a monolithic bioreactor

BACKGROUND: The bio‐oxidation of ferrous iron is a potential industrial process in the regeneration of ferric iron and the removal of H₂S in combustible gases. Bio‐oxidation of ferrous iron may be an alternative method of producing ferric sulfate, which is a reagent used for removal of H₂S from biogas, tail gas and in the pulp and paper industry. For practical use of this process, this study evaluated the optimal pH and initial ferric concentration. pH control looks like a key factor as it acts both on growth rate and on solubility of materials in the system. RESULTS: Process variables such as pH and amount of initial ferrous ions on oxidation by A. ferrooxidans and the effects of process variables dilution rate, initial concentrations of ferrous on oxidation of ferrous sulfate in the packed bed bioreactor were investigated. The optimum range of pH for the maximum growth of cells and effective bio‐oxidation of ferrous sulfate varied from 1.4 to 1.8. The maximum bio‐oxidation rate achieved was 0.3 g L^?1 h^?1 in a culture initially containing 19.5 g L^?1 Fe²⁺ in the batch system. A maximum Fe²⁺ oxidation rate of 6.7 g L^?1 h^?1 was achieved at the dilution rate of 2 h^?1, while no obvious precipitate was detected in the bioreactor. All experiments were carried out in shake flasks at 30 °C. CONCLUSION: The monolithic particles investigated in this study were found to be very suitable material for A. ferrooxidans immobilization for ferrous oxidation mainly because of its advantages over other commonly used substrates. In the monolithic bioreactor, the bio‐oxidation rate was 6.7 g L^?1 h^?1 and 7 g L^?1 h^?1 for 3.5 g L^?1 and 6 g L^?1 of initial ferrous concentration, respectively. For higher initial concentrations 16 g L^?1 and 21.3 g L^?1, bio‐oxidation rate were 0.9 g L^?1 h^?1 and 0.55 g L^?1 h^?1, respectively. Copyright © 2008 Society of Chemical Industry     

Kinetics and thermodynamics of glucoamylase inhibition by lactate during fermentable sugar production from food waste

BACKGROUND: Glucoamylase hydrolysis is a key step in the bioconversion of food waste with complicated composition. This work investigated the effect of lactate on glucoamylase from Aspergillus niger UV‐60, and inhibition mechanisms of glucoamylase by lactate during food waste hydrolysis. RESULTS: For 125 min hydrolysis of food waste (10%, dry basis), reducing sugars produced in the absence of lactate were 15%, 26% and 56% more than those produced in the presence of 24 g L^?1 lactate at 60, 50 and 40 °C, respectively. Kinetic study showed that the type of glucoamylase inhibition by lactate was competitive, and K_m (Michaelis‐Menten constent), V_max (maximum initial velocity), K_I (inhibition constant) were 103.2 g L^?1, 5.0 g L^?1 min^?1, 100.6 g L^?1, respectively, for food waste hydrolysis at 60 °C and pH 4.6. Lactate also accelerated glucoamylase denaturation significantly. Activation energy of denaturation without inhibitor was 61% greater than that of denaturation with inhibitor (24 g L^?1 lactate). Half‐lives (t_1/2) without inhibitor were 7.6, 2.7, 2.6, 1.7 and 1.2 times longer than those with inhibitor at temperature 40, 45, 50, 55 and 60 °C, respectively. CONCLUSION: These results are helpful to process optimization of saccharification and bioconversion of food waste. Copyright © 2010 Society of Chemical Industry     

Synthesis and in vitro biological evaluation as antitumour drug carriers of folate‐targeted N‐isopropylacrylamide‐based nanohydrogels

Copolymeric nanohydrogels based on N‐isopropylacrylamide, N‐(pyridin‐4‐ylmethyl)acrylamide and tert‐butyl‐2‐acrylamidoethyl carbamate, synthesized by microemulsion polymerization, were characterized using Fourier transform infrared spectroscopy and their size (38–52 nm) determined using quasielastic light scattering. Folic acid was covalently attached to the nanohydrogels (1.40 ± 0.07 mmol g^?1). Tamoxifen (6.7 ± 0.2–7.3 ± 1.2 µg TMX mg^?1 nanohydrogel), a hydrophobic anticancer drug, and 5‐fluorouracil (7.7 ± 0.7–10.14 ± 1.75 µg 5‐FU mg^?1 nanohydrogel), a hydrophilic anticancer drug, were loaded into the nanohydrogels. Maximum in vitro TMX release (77–84% of loaded drug) depended on interactions of the drug with hydrophobic clusters of the nanogels; however, no nanogel/5‐FU interactions allowed total release of the loaded drug. The cytotoxicity of unloaded nanohydrogels in MCF7, T47D and HeLa cells was low. Cell uptake of nanogels without bound folic acid took place in the three cell types by unspecific internalization in a time‐dependent process. Cell uptake increased for folic acid‐targeted nanohydrogels in T47D and HeLa cells, which have folate receptors. The administration of 10 and 30 µmol L^?1 TMX by TMX‐loaded nanogels and 10 µmol L^?1 5‐FU by 5‐FU‐loaded nanogels was effective on the three cell types, and the best results were obtained for folic acid‐targeted nanohydrogels. Copyright © 2012 Society of Chemical Industry     

Strain isolation and optimization of process parameters for bioconversion of glycerol to lactic acid

BACKGROUND: The crude glycerol from biodiesel production represents an abundant and inexpensive source which can be used as raw material for lactic acid production. The first aim of this investigation was to select a strain suitable for producing lactic acid from glycerol with a high concentration and productivity. The second aim was to obtain the optimum fermentation conditions, as a basis for large‐scale lactate production in the future. RESULTS: Eight bacterial strains, which could aerobically convert glycerol to lactic acid, were screened from soil samples. One of the strains, AC‐521, which synthesized lactic acid with a higher concentration, was identified based on its 16S rDNA sequences and physiological characteristics. These results indicated that this strain was a member of Escherichia coli. The optimal fermentation conditions for Escherichia coli AC‐521 were 42 °C, pH 6.5, 0.85 min^?1 (K_La). CONCLUSION: Escherichia coli AC‐521 suitable for producing lactic acid from glycerol with high concentration and productivity was identified. After 88 h of fed‐batch fermentation, both the lactic acid concentration and glycerol consumption reached maximum, giving 85.8 g L^?1 of lactic acid with a productivity of 0.97 g L^?1 h^?1 and a yield of 0.9 mol mol^?1 glycerol. Copyright © 2009 Society of Chemical Industry     

pH和碱度对同步厌氧生物脱氮除硫工艺性能的影响

采用UASB反应器研究了pH和碱度对同步厌氧生物脱氮除硫工艺性能的影响。控制进水pH在7.5～8.0之间,反应器的最大容积硫化物和硝酸盐去除速率分别为2.96 kg·(m³·d)^-1和0.47 kg·(m³·d)^-1（分别以硫元素、氮元素计）,反应过程产碱及残留硫化物,均会导致反应液pH值过高（9.11±0.38）,引发高负荷时工艺失稳。控制反应液pH在7.0±0.1范围,容积硫化物和硝酸盐去除速率分别可达4.78 kg·(m³·d)^-1和0.99 kg·(m³·d)^-1,容积效能高于控制进水pH时的相应值。要维持反应所需的中性条件,碱度宜控制在（454.1±40.5）mg ·L^-1（以CaCO₃计）。反应过程中的碱度变化（增量）可以指示反应器内主导反应的类型及其反应进度。单质硫型生物脱氮除硫反应（硫氮比为5∶2）和硫酸盐型生物脱氮除硫反应（硫氮比为5∶8）的硫化物去除量与碱度减少量之比分别为2.27和2.00,混合型生物脱氮除硫反应（硫氮比为5∶5）的硫化物去除量与碱度减少量之比为5.00。     

Decolorization of Direct Blue GLL with enhanced lignin peroxidase enzyme production in Comamonas sp UVS

BACKGROUND: The present work aims to study the production of lignin peroxidase (LiP) enzyme by Comamonas sp UVS using various media, and lignocellulosic waste materials, and its effect on decolorization of Direct Blue GLL (DBGLL). RESULTS: Yeast extract medium was found to be more effective for the production of LiP and also for the decolorization of DBGLL. The bagasse powder along with yeast extract induced LiP activity. Comamonas sp UVS decolorized DBGLL dye (50 mg L^?1) within 13 h at static condition in YE broth. It could degrade up to 300 mg L^?1 of dye within 55 h. The maximum rate (Vmax) of decolorization was 12.41 ± 0.55 mg dye g cell^?1 h^?1 with the Michaelis constant (Km) value as 6.20 ± 0.27 mg L^?1. The biodegradation was monitored by UV‐Vis, GC‐MS and HPLC. CONCLUSION: The use of agricultural by‐products for the activity enhancement of the ligninolytic enzymes is a cost effective process. It also resolves the problem of the disposal of agro‐residues. This system can be applied for the degradation of different recalcitrant compounds. Copyright © 2008 Society of Chemical Industry     

Removal of high concentrations of H2S from simulated natural gas by Acidithiobacillus ferrooxidans immobilized on polyurethane foam

A chemo‐biochemical process for desulfurization of simulated natural gas containing hydrogen sulfide (H₂S) was investigated. The results showed that using polyurethane foam as a support for immobilization of Acidithiobacillus ferrooxidans obtained good biological oxidation performance and the maximum oxidation rate of ferrous iron was 4.12 kg m^?3 h^?1. Moreover, a semi‐empirical formula was set up for calculating theoretical ferrous oxidation rate as a function of influent Fe²⁺ and Fe²⁺ concentration in the bioreactor. The integrated chemical and biological process achieved removal efficiencies of about 80% when treating high concentrations of H₂S (15 000 ± 100 ppmv). © 2012 Society of Chemical Industry     

Optimization of the culture conditions for production of glutamate decarboxylase by Streptococcus salivarius ssp. thermophilus

The culture conditions for glutamate decarboxylase (GAD) production under submerged fermentation by Streptococcus salivarius ssp. thermophilus were investigated. The results indicated the optimum culture medium was composed as follows: 15.0 g L^?1 of peptone, 12.5 g L^?1 of beef extract, 12.5 g L^?1 of sucrose, 1.03 g L^?1 of dipotassium hydrogen phosphate, 5 g L^?1 of sodium acetate, 2 g L^?1 of ammonium dibasic citrate, 2.12 g L^?1 of calcium chloride, 1 g L^?1 of Tween 80, and initial pH 6.79. The optimum culture temperature and time were 37 °C and 12 h, respectively. Under these conditions, GAD production was 257.46 ± 5.12 U, which was about 1.45‐fold that of Man–Rogosa–Sharpe broth. Copyright © 2008 Society of Chemical Industry     

Production of organic solvent tolerant lipase by Staphylococcus caseolyticus EX17 using raw glycerol as substrate

BACKGROUND: In this work we used Plackett–Burman statistical design and central composite design in order to optimize culture conditions for lipase production by Staphylococcus caseolyticus strain EX17 growing on raw glycerol, which was obtained as a by‐product of the enzymatic synthesis of biodiesel. The stability of lipase was verified over several organic solvents, such as methanol, ethanol and n‐hexane. RESULTS: Optimal culture conditions for lipase production were found to be 36 °C, initial pH 8.12, glycerol 30 g L^?1, olive oil 3.0 g L^?1, and soybean oil 2.5 g L^?1, with 145.8 U L^?1 of enzyme activity. When commercial glycerol was substituted by the raw glycerol from biodiesel synthesis, lipolytic activity was 127.3 U L^?1. Experimental validation of enzyme production matched values predicted by the mathematical model, which was 138.3 U L^?1. Stability tests showed that lipase from S. caseolyticus EX17 was stable in methanol, ethanol, and n‐hexane. CONCLUSIONS: Results obtained in this work suggest that raw glycerol can be used for lipase production by S. caseolyticus EX17 and that this enzyme has a potential application in the synthesis of biodiesel. Copyright © 2008 Society of Chemical Industry     

Purification and enzymatic properties of the extracellular and constitutive chitosanase produced by Bacillus subtilis RKY3

BACKGROUND: Purification and enzymatic properties of a chitosanase from Bacillus subtilis RKY3 have been investigated to produce a chitooligosaccharide. The enzyme reported was extracellular and constitutive, which was purified by two sequential steps including ammonium sulfate precipitation and ion exchange chromatography. RESULTS: Sodium dodecyl sulfate‐polyacrylamide gel electrophoresis of the purified chitosanase revealed one single band corresponding to a molecular weight of around 24 kDa. The highest chitosanase activity was found to be at pH 6.0 and at 60 °C. Although the mercaptide forming agents such as Hg²⁺ (10 mmol L^?1) and p‐hydroxymercuribenzoic acid (1 mmol L^?1, 10 mmol L^?1) significantly or totally inhibited the enzyme activity, its activity was enhanced by the presence of 10 mmol L^?1 Mn²⁺. The enzyme showed activity for hydrolysis of soluble chitosan and glycol chitosan, but colloidal chitin, carboxymethyl cellulose, crystalline cellulose, and soluble starch were not hydrolyzed. The analysis of chitosan hydrolysis by thin‐layer chromatography and viscosity variation revealed that the purified enzyme should be endosplitting‐type chitosanase. CONCLUSION: The chitosanase produced by Bacillus subtilis RKY3 was a novel chitosanlytic enzyme with relatively low molecular weight, which is a versatile enzyme for chitosan hydrolysis because it could hydrolyze soluble chitosan into a biofunctional oligosaccharide at a high level. Copyright © 2011 Society of Chemical Industry     

2,4,6‐Trichlorophenol and phenol removal in methanogenic and partially‐aerated methanogenic conditions in a fluidized bed bioreactor

A fluidized bed bioreactor (FBBR) was operated for more than 575 days to remove 2,4,6‐trichlorophenol (TCP) and phenol (Phe) from a synthetic toxic wastewater containing 80 mg L^?1 of TCP and 20 mg L^?1 of Phe under two regimes: Methanogenic (M) and Partially‐Aerated Methanogenic (PAM). The mesophilic, laboratory‐scale FBBR consisted of a glass column (3 L capacity) loaded with 1 L of 1 mm diameter granular activated carbon colonized by an anaerobic consortium. Sucrose (1 g COD L^?1) was used as co‐substrate in the two conditions. The hydraulic residence time was kept constant at 1 day. Both conditions showed similar TCP and Phe removal (99.9 + %); nevertheless, in the Methanogenic regime, the accumulation of 4‐chlorophenol (4CP) up to 16 mg L^?1 and phenol up to 4 mg L^?1 was observed, whereas in PAM conditions 4CP and other intermediates were not detected. The specific methanogenic activity of biomass decreased from 1.01 ± 0.14 in M conditions to 0.19 ± 0.06 mmolCH₄ h^?1 gTKN^?1 in PAM conditions whereas the specific oxygen uptake rate increased from 0.039 ± 0.008 in M conditions to 0.054 ± 0.012 mmolO₂ h^?1 gTKN^?1, which suggested the co‐existence of both methanogenic archaea and aerobic bacteria in the undefined consortium. The advantage of the PAM condition over the M regime is that it provides for the thorough removal of less‐substituted chlorophenols produced by the reductive dehalogenation of TCP rather than the removal of the parent compound itself. Copyright © 2005 Society of Chemical Industry     

Anaerobic biodegradation of phenol in sulfide‐rich media

In the refinery industry, the washing processes of middle‐distillates using caustic solutions generate phenol‐ and sulfide‐containing waste streams. The spent caustic liquors generated contain phenols at concentrations higher than 60 g dm^?3(638.3 mmol dm^?3). For sulfur compounds, the average sulfide concentration was 48 g dm^?3(1500 mmol dm^?3) in these streams. The goal of this study was to evaluate the specific impact of phenol and sulfide concentrations towards the phenol‐biodegradation activity of a phenol‐acclimated anaerobic granular sludge. An inhibition model was used to calculate the phenol and sulfide inhibitory concentrations that completely stopped the phenol‐biodegradation activity (IC100). A maximum phenol‐biodegradation activity of 83 µmol g^?1 VSS h^?1 was assessed and the IC100 values were 21.8 mmol dm^?3 and 13.4 mmol dm^?3 for phenol and sulfide respectively. The limitation of the phenol biodegradation flow by phenol inhibition seemed to be related to the more important sensitivity of phenol‐degrading bacteria. The up‐flow anaerobic sludge bed reactor operating in a non‐phenol‐dependent inhibition condition did not present any sensitivity to sulfide concentrations below 9.6 mmol dm^?3. At this residual concentration, the pH and bisulfide ions' concentration might be responsible for the general collapsing of the reactor activity. Copyright © 2004 Society of Chemical Industry     

Sorption Potential of Styrene‐Divinylbenzene Copolymer Beads for the Decontamination of Lead from Aqueous Media

Abstract

The decontamination of lead ions from aqueous media has been investigated using styrene‐divinylbenzene copolymer beads (St‐DVB) as an adsorbent. Various physico‐chemical parameters such as selection of appropriate electrolyte, contact time, amount of adsorbent, concentration of adsorbate, effect of foreign ions, and temperature were optimized to simulate the best conditions which can be used to decontaminate lead from aqueous media using St‐DVB beads as an adsorbent. The atomic absorption spectrometric technique was used to determine the distribution of lead. Maximum adsorption was observed at 0.001 mol L^?1 acid solutions (HNO₃, HCl, H₂SO₄ and HClO₄) using 0.2 g of adsorbent for 4.83×10^?5 mol L^?1 lead concentration in two minutes equilibration time. The adsorption data followed the Freundlich, Langmuir, and Dubinin‐Radushkevich (D‐R) isotherms over the lead concentration range of 1.207×10^?3 to 2.413×10^?2 mol L^?1. The characteristic Freundlich constants i.e. 1/n=0.164±0.012 and A=2.345×10^?3±4.480×10^?5 mol g^?1 have been computed for the sorption system. Langmuir isotherm gave a saturated capacity of 0.971±0.011 mmol g^?1, which suggests monolayer coverage of the surface. The sorption mean free energy from D‐R isotherm was found to be 18.26±0.75 kJ mol^?1 indicating chemisorption involving chemical bonding for the adsorption process. The uptake of lead increases with the rise in temperature. Thermodynamic parameters i.e. ΔG, ΔH, and ΔS have also been calculated for the system. The sorption process was found to be exothermic. The developed procedure was successfully applied for the removal of lead ions from real battery wastewater samples.     

Synthesis,solution properties and scale‐inhibiting behaviour of a diallylammonium/sulfur dioxide cyclocopolymer bearing phospho‐ and sulfopropyl pendents

Zwitterion (Z) monomer 3‐[diallyl{3‐(diethoxyphosphoryl)propyl}ammonio]propane‐1‐sulfonate underwent cyclocopolymerization with sulfur dioxide to give a new alternating copolymer poly(Z‐alt‐SO₂) in excellent yield (ca 90%). The polyzwitterion (±) (PZ) (i.e. poly(Z‐alt‐SO₂), bearing a diethylphosphonate as well as a sulfonate functionality in each repeat unit, upon ester hydrolysis gave its corresponding pH‐responsive polyzwitterionic acid (±) (PZA). The pH‐induced equilibrations (+) cationic polyelectrolyte ? (±) PZA ? polyzwitterion/anion (± ?) (PZAN) ? polyzwitterion/dianion (± =) (PZDAN) permitted us to examine the effects of charge types and their densities on the interesting solubility and viscosity behaviours. The apparent protonation constants of the basic functionalities &tbond;N^±PO₃^2? in (± =) PZDAN and &tbond;N^±PO₃H^1? in (± ?) PZAN in salt‐free water and 0.1 mol L^?1 NaCl were determined using potentiometric titrations. (±) PZA at a meagre concentration of 20 ppm was found to be an effective antiscalant to inhibit the precipitation of CaSO₄ from its supersaturated solution: after 500 and 800 min, the respective scale inhibitions of 86 and 98% indicated its potential use as an effective antiscalant in reverse osmosis plant. © 2014 Society of Chemical Industry     

Electrochemical biosensor for detection of formaldehyde in rain water

BACKGROUD: This study describes the construction of an electrochemical formaldehyde biosensor based on poly(glycidyl methacrylate‐co‐3‐methylthienyl methacrylate)/formaldehyde dehydrogenase/polypyrrole [poly(GMA‐co‐MTM)/FDH/PPy] composite film electrode. Formaldehyde dehydrogenase (FDH) was chemically immobilized via the epoxy groups of the glycidyl methacrylate (GMA) side chain of the polymer. Formaldehyde measurements were conducted in 0.1 mol L^?1, pH 8 phosphate buffer solution (PBS) including 0.1 mol L^?1 KCl, 0.5 mmol L^?1 of NAD⁺ (cofactor of the enzyme) and 1 mmol L^?1 of 1,2‐napthoquinone‐4‐sulfonic acid sodium salt (NQS) as mediator with an applied potential of ? 0.23 V (vs. Ag/AgCl, 3 mol L^?1 NaCl). Analytical parameters of the biosensor were calculated and discussed. The biosensor was tested in rain water samples. RESULTS: Sensitivity was found to be 15 000 per mmol L^?1 (500 nA ppm^?1) in a linear range between 0.1 ppm and 3 ppm (3.3–100 µmol L^?1). A minimum detectable concentration of 4.5 ppb (0.15 µmol L^?1) (S/N = 3) with a relative standard deviation (RSD) of 0.73% (n = 5) was obtained from the biosensor. Response time of the biosensor was very short, reaching 99% of its maximum response in about 4 s. The biosensor was also tested for formaldehyde measurements in rain water samples. Formaldehyde concentrations in samples were calculated using the proposed biosensor with recovery values ranged between 92.2 and 97.7% in comparison with the colorimetric Nash method. CONCLUSION: The poly(GMA‐co‐MTM)/FDH/PPy) electrode showed excellent measurement sensitivity in comparison with other formaldehyde biosensor studies. Strong chemical bonding between the enzyme and the copolymer was created via the epoxy groups of the composite film. The proposed biosensor could be used successfully in rain waters without a pretreatment step. © 2012 Society of Chemical Industry