The interaction of crythrosine B (ErB), a commonly used dye for coloring foods and drinks, with bovine scrum albumin (BSA) was investigated both in the absence and presence of bilirubin (BR) using absorption and absorption difference spectroscopy. ErB binding to BSA was reflected from a significant red shift of 11 nm in the absorption maximum of ErB (527 nm) with the change in absorbance at lamdamax. Analysis of absorption difference spectroscopic titration results of BSA with increasing concentrations of ErB3 using Benesi-Hildebrand equation gave the association constant, K as 6.9 x 10(4) M(-1). BR displacing action of ErB was revealed by a significant blue shift in the absorption maximum, accompanied by a decrease in absorbance difference at lamdamax in the difference spectrum of BR-BSA complex upon addition of increasing concentrations of ErB. This was further substantiated by fluorescence spectroscopy, as addition of increasing concentrations of ErB to BR-BSA complex caused a significant decrease in fluoresccnce at 510 nm. The results suggest that ErB binds to a site in the vicinity of BR binding site on BSA. Therefore, intake of ErB may increase the risk of hyperbilirubinemia in the healthy subjects.
The photocatalytically driven removal of eco-persistent 4-chlorophenol from water using ZnO is reported here. Kinetic dependence of transformation rate on operating variables such as initial 4-chlorophenol concentration and photocatalyst doses was investigated. A complete degradation of 4-chlorophenol at 50 mg L(-1) levels was realised in 3h. Analytical profiles on 4-chlorophenol transformation were consistent with the best-line fit of the pseudo zero-order kinetics. The addition of small amounts of inorganic anions as SO(4)(2-), HPO(4)(-), S(2)O(8)(2-) and Cl(-) revealed two anion types: active site blockers and rate enhancers. Fortunately, Cl(-) and SO(4)(2-) commonly encountered in contaminated waters enhanced the rate of 4-chlorophenol degradation. The reaction intermediates and route to 4-chlorophenol mineralisation were elucidated by combined RP-HPLC and GC-MS methods. In addition to previously reported pathway products of 4-chlorophenol photo-oxidation catechol was detected. A radical mechanism involving o-hydroxylation is proposed to account for the formation of catechol.
Acephate is poorly sorbed to soil, thus the risk of leaching to the aquatic environment is high if it is not quickly degraded. The effect of soil moisture, temperature, microbial activity and application rate on acephate degradation has been studied in three Malaysian soils to examine and identify critical variables determining its degradation and mineralization kinetics. First-order kinetics could be used to describe degradation in all cases (r(2)>0.91). Acephate degraded faster in air-dry (t((1/2)) 9-11 d) and field capacity (t((1/2)) 10-16d) soils than in the wet soils (t((1/2)) 32-77 d). The activation energy of degradation was in the range 17-28 kJ mol(-1) and significantly higher for the soil with higher pH and lower clay and iron oxide contents. Soil sterilization caused a 3- to 10-fold decrease in degradation rates compared to non-sterile soils (t((1/2)) 53-116 d) demonstrating that acephate degradation is mainly governed by microbial processes. At 5-fold increase in application rates (25 microg g(-1)), half-life increased slightly (t((1/2)) 13-19 d) or was unaffected. Half-life from acephate mineralization was similar to those from degradation but much longer at the 5-fold increase in acephate application rates (t((1/2)) 41-96 d) demonstrating that degradation of metabolites is rate limiting. Thus, application of acephate should be restricted or avoided during wet seasons with heavy rainfall and flooded soil as in paddy cultivation. Sandy soils with low microbial activity are more prone to acephate leaching than clay soils rich in humic matter.
In this work, activated carbon was prepared from banana stalks (BSAC) waste to remove the insecticide carbofuran from aqueous solutions. The effects of contact time, initial carbofuran concentration, solution pH and temperature (30, 40 and 50 degrees C) were investigated. Adsorption isotherm, kinetics and thermodynamics of carbofuran on BSAC were studied. Equilibrium data were fitted to the Langmuir, Freundlich and Temkin isotherm models and the data best represented by the Langmuir isotherm. Thermodynamic parameters such as standard enthalpy (DeltaH(o)), standard entropy (DeltaS(o)) and standard free energy (DeltaG(o)) were evaluated. Regeneration efficiency of spent BSAC was studied using ethanol as a solvent. The efficiency was found to be in the range of 96.97-97.35%. The results indicated that the BSAC has good regeneration and reusability characteristics and can be used as alternative to present commercial activated carbon.
The removal of ammonium from aqueous solutions using zeolite NaY prepared from a local agricultural waste, rice husk ash waste was investigated and a naturally occurring zeolite mordenite in powdered and granulated forms was used as comparison. Zeolite NaY and mordenite were well characterized by powder X-ray diffraction (XRD), energy dispersive X-ray (EDX) analysis and the total cation exchange capacity (CEC). CEC of the zeolites were measured as 3.15, 1.46 and 1.34 meq g(-1) for zeolite Y, powdered mordenite and granular mordenite, respectively. Adsorption kinetics and equilibrium data for the removal of NH(4)(+) ions were examined by fitting the experimental data to various models. Kinetic studies showed that the adsorption followed a pseudo-second-order reaction. The equilibrium pattern fits well with the Langmuir isotherm compared to the other isotherms. The monolayer adsorption capacity for zeolite Y (42.37 mg/g) was found to be higher than that powdered mordenite (15.13 mg/g) and granular mordenite (14.56 mg/g). Thus, it can be concluded that the low cost and economical rice husk ash-synthesized zeolite NaY could be a better sorbent for ammonium removal due to its rapid adsorption rate and higher adsorption capacity compared to natural mordenite.
This study was undertaken in order to understand the factors affecting the degradation of an insect repellent, N,N-diethyl-m-toluamide (DEET) by ozonation. Kinetic studies on DEET degradation were carried out under different operating conditions, such as varied ozone doses, pH values of solution, initial concentrations of DEET, and solution temperatures. The degradation of DEET by ozonation follows the pseudo-first-order kinetic model. The rate of DEET degradation increased exponentially with temperature in the range studied (20-50 degrees C) and in proportion with the dosage of ozone applied. The ozonation of DEET under different pH conditions in the presence of phosphate buffer occurred in two stages. During the first stage, the rate constant, k(obs), increased with increasing pH, whereas in the second stage, the rate constant, k(obs2), increased from pH 2.3 up to 9.9, however, it decreased when the pH value exceeded 9.9. In the case where buffers were not employed, the k(obs) were found to increase exponentially with pH from 2.5 to 9.2 and the ozonation was observed to occur in one stage. The rate of degradation decreased exponentially with the initial concentration of DEET. GC/MS analysis of the by-products from DEET degradation were identified to be N,N-diethyl-formamide, N,N-diethyl-4-methylpent-2-enamide, 4-methylhex-2-enedioic acid, N-ethyl-m-toluamide, N,N-diethyl-o-toluamide, N-acetyl-N-ethyl-m-toluamide, N-acetyl-N-ethyl-m-toluamide 2-(diethylamino)-1-m-tolylethanone and 2-(diethylcarbamoyl)-4-methylhex-2-enedioic acid. These by-products resulted from ozonation of the aliphatic chain as well as the aromatic ring of DEET during the degradation process.
This study investigated the electrochemical oxidation of stabilized leachate from Pulau Burung semi-aerobic sanitary landfill by conducting laboratory experiments with sodium sulfate Na(2)SO(4) (as electrolyte) and graphite carbon electrodes. The control parameters were influent COD, current density and reaction time, while the responses were BOD removal, COD removal, BOD:COD ratio, color and pH. Na(2)SO(4) concentration was 1 g/L. Experiments were conducted based on a three-level factorial design and response surface methodology (RSM) was used to analyze the results. The optimum conditions were obtained as 1414 mg/L influent COD concentration, 79.9 mA/cm(2) current density and 4 h reaction time. This resulted in 70% BOD removal, 68% COD removal, 84% color removal, 0.04 BOD/COD ratio and 9.1 pH. Electrochemical treatment using graphite carbon electrode was found to be effective in BOD, COD and color removal but was not effective in increasing the BOD/COD ratio or enhancing biodegradability of the leachate. The color intensity of the treated samples increased at low influent COD and high current density due to corrosion of electrode material.
Oxidation of sulfide in aqueous solution by hydrogen peroxide was investigated in the presence of hydrated ferric oxide catalyst. The ferric oxide catalyst was synthesized by sol gel technique from ferric chloride and ammonia. The synthesized catalyst was characterized by Fourier transform infrared spectroscopy, X-Ray diffraction analysis, scanning electrom microscope and energy dispersive X-ray analysis. The catalyst was quite effective in oxidizing the sulfide by hydrogen peroxide. The effects of sulfide concentration, catalyst loading, H2O2 dosing and temperature on the kinetics of sulfide oxidation were investigated. Kinetic equations and activation energies for the catalytic oxidation reaction were calculated based on the experimental results.
Chitosan-tripolyphosphate (CTPP) beads were synthesized, characterized and were used for the adsorption of Pb(II) and Cu(II) ions from aqueous solution. The effects of initial pH, agitation period, adsorbent dosage, different initial concentrations of heavy metal ions and temperature were studied. The experimental data were correlated with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The maximum adsorption capacities of Pb(II) and Cu(II) ions in a single metal system based on the Langmuir isotherm model were 57.33 and 26.06 mg/g, respectively. However, the beads showed higher selectivity towards Cu(II) over Pb(II) ions in the binary metal system. Various thermodynamic parameters such as enthalpy (DeltaH degrees), Gibbs free energy (DeltaG degrees) and entropy (DeltaS degrees) changes were computed and the results showed that the adsorption of both heavy metal ions onto CTPP beads was spontaneous and endothermic in nature. The kinetic data were evaluated based on the pseudo-first and -second order kinetic and intraparticle diffusion models. Infrared spectra were used to elucidate the mechanism of Pb(II) and Cu(II) ions adsorption onto CTPP beads.
Decolorization of reactive azo dye, reactive black 5 (RB5), was conducted using Fe(III) immobilized on Montmorillonite K10 (MK10) as a catalyst in the presence of H(2)O(2) using Fenton-like oxidation process. The effect of different parameters such as iron ions loading on supported catalyst, catalyst dosage, initial pH of dye solution, initial concentration of H(2)O(2) and dye and reaction temperature on the decolorization efficiency of the process were studied. The results indicated that by using 12 mM of H(2)O(2) and 3.50 g L(-1) of the 0.11 wt.% Fe(III) oxide on MK10 catalyst at pH of 2.5, 99% of decolorization efficiency was achieved within 150 min in a batch process.
The decolorization of Acid Red 1 (AR1) in aqueous solution was investigated by Fenton-like process. The effect of different reaction parameters such as different iron ions loading on rice husk ash (RHA), dosage of catalyst, initial pH, the initial hydrogen peroxide concentration ([H(2)O(2)](o)), the initial concentration of AR1 ([AR1](o)) and the reaction temperature on the decolorization of AR1 was studied. The optimal reacting conditions were found to be 0.070 wt.% of iron (III) oxide loading on RHA, dosage of catalyst=5.0 g L(-1), initial pH=2.0, [H(2)O(2)](o)=8 mM, [AR1](o)=50 mg L(-1) at temperature 30 degrees C. Under optimal condition, 96% decolorization efficiency of AR1 was achieved within 120 min of reaction.
The objective of this study is to evaluate the performance of sequencing batch biofilm reactors (SBBRs) and sequencing batch reactor (SBR) in the simultaneous removal of p-nitrophenol (PNP) and ammoniacal nitrogen. SBBRs involved the use of polyurethane sponge cubes and polyethylene rings, respectively, as carrier materials. The results demonstrate that complete removal of PNP was achievable for the SBR and SBBRs up to the PNP concentration of 350 mg/l (loading rate of 0.368 kg/m3 d). At this loading rate, the average ammoniacal nitrogen removal efficiency for the SBR and SBBR (with polyethylene rings) was reduced to 86% and 96%, respectively. However, the SBBR (with polyurethane sponge cubes) still managed to achieve an almost 100% ammoniacal nitrogen removal. Based on the results, the performance of the SBBRs was better than that of SBR in PNP and ammoniacal nitrogen removal. The results of the gas chromatography mass spectroscopy, high-performance liquid chromatography and ultraviolet-visible analyses indicate that complete mineralization of PNP was achieved in all of the reactors.
Biological kinetic (bio-kinetic) study of the anaerobic stabilization pond treatment of palm oil mill effluent (POME) was carried out in a laboratory anaerobic bench scale reactor (ABSR). The reactor was operated at different feed flow-rates of 0.63, 0.76, 0.95, 1.27, 1.9 and 3.8l of raw POME for a day. Chemical oxygen demand (COD) as influent substrates was selected for bio-kinetic study. The investigation showed that the growth yield (Y(G)), specific biomass decay (b), maximum specific biomass growth rate (mu(max)), saturation constant (K(s)) and critical retention time (Theta(c)) were in the range of 0.990 g VSS/g COD(removed) day, 0.024 day(-1), 0.524 day(-1), 203.433 g COD l(-1) and 1.908 day, respectively.
The effects of polyethyleneimine (PEI) impregnation on the Pb(2+) adsorption kinetics of palm shell-activated carbon and pH profile of bulk solution were investigated. Adsorption data were fitted to four established adsorption kinetics models, namely, pseudo-first-order, pseudo-second-order, Elovich equation and intraparticle diffusion. It was found that PEI impregnation at 16.68 and 29.82 wt% PEI/AC increased the Pb(2+) uptake rate while the opposite was observed for PEI impregnation at 4.76 and 8.41 wt% PEI/AC. The increased uptake rates were due to higher concentration of PEI molecules on the surface of clogged pores as well as varying pore volumes. The adsorption kinetics data fitted the pseudo-second-order model better than the pseudo-first-order model, implying chemisorption was the rate-controlling step. The bulk solution pH generally showed an increasing trend from the use of virgin to PEI-impregnated activated carbon.
In this work, the adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) on activated carbon derived from date stones (DSAC) was studied with respect to pH and initial 2,4-D concentration. The experimental data were analyzed by the Freundlich isotherm, the Langmuir isotherm, and the Temkin isotherm. Equilibrium data fitted well with the Langmuir model with maximum adsorption capacity of 238.10 mg/g. Pseudo-first and pseudo-second-order kinetics models were tested with the experimental data, and pseudo-first-order kinetics was the best for the adsorption of 2,4-D by DSAC with coefficients of correlation R(2)>or=0.986 for all initial 2,4-D concentrations studied. The results indicated that the DSAC is very effective for the adsorption of 2,4-D from aqueous solutions.
In this work, the adsorption of malachite green (MG) on rattan sawdust (RSD) was studied at 30 degrees C. The results indicated that RSD can be used as a low-cost adsorbent for the removal of MG dye from aqueous solutions. Equilibrium data were analyzed by two isotherms, namely the Freundlich isotherm and the Langmuir isotherm. The best fit to the data was obtained with the Langmuir isotherm. The monolayer adsorption capacity of RSD was found to be 62.71 mg/g. The adsorption kinetics can be predicted by the pseudo-first-order model. The mechanism of adsorption was also studied. It was found that for a short time period the rate of adsorption is controlled by film diffusion. However, at longer adsorption times, pore-diffusion controls the rate of adsorption. The amount adsorbed on the outer surface was estimated from the time where film-diffusion stops controlling the adsorption rate.
Ethanol and aqueous extracts of the different parts of Piper sarmentosum were analysed by HPLC for marker compounds to standardise these extracts. The standardised extracts were investigated for antioxidant activity (beta-carotene linoleate model and DPPH model), anti-TB activity (microplate tetrazolium assay), and estimation of total phenolic and amide contents. The extracts of the different parts exhibited different antioxidant activity, phenolic and amide contents (p < 0.01). The ethanol extracts exhibited better antioxidant activity as compared to the aqueous extracts. The leaf ethanol extract was further investigated for dose response relationship and its EC(50) was found to be 38 microg mL(-1). All the extracts have exhibited anti-TB activity with MIC/MBC 12.5 microg mL(-1). The leaf methanol extract was fractionated and the ethyl acetate fraction exhibited anti-TB activity with MIC/MBC 3.12 microg mL(-1) while MIC/MBC of isoniazid (INH) was found to be 0.5 microg mL(-1). A positive correlation was found between antioxidant activity and total polyphenols, flavonoids and amides, in the beta-carotene linoleate model (p = 0.05) and in the DPPH model (p = 0.01). The analytical method was found to have linearity >0.9922, coefficient of variance <5% and accuracy 95.5 +/- 5 to 96.9 +/- 5. This plant possesses promising antioxidant as well as anti-TB properties.
The aim of the present work was to investigate the feasibility of grass waste (GW) for methylene blue (MB) adsorption. The adsorption of MB on GW material was studied as a function of GW dose (0.05-1.20 g), solution pH 3-10, contact time and initial concentration (70-380 mg/L). The influence of these parameters on the adsorption capacity was studied using the batch process. The experimental data were analyzed by the Langmuir and Freundlich isotherms. The adsorption isotherm was found to follow the Langmuir model. The monolayer adsorption capacity was found to be 457.640 mg/g. The kinetic data were fitted to the pseudo-first-order and pseudo-second-order models, and were found to follow closely the pseudo-second-order kinetic model. The results revealed that GW adsorbent is potentially low-cost adsorbent for adsorption of MB.
The adsorption characteristics of 2,4,6-trichlorophenol (TCP) on activated carbon prepared from oil palm empty fruit bunch (EFB) were evaluated. The effects of TCP initial concentration, agitation time, solution pH and temperature on TCP adsorption were investigated. TCP adsorption uptake was found to increase with increase in initial concentration, agitation time and solution temperature whereas adsorption of TCP was more favourable at acidic pH. The adsorption equilibrium data were best represented by the Freundlich and Redlich-Peterson isotherms. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The mechanism of the adsorption process was determined from the intraparticle diffusion model. Boyd plot revealed that the adsorption of TCP on the activated carbon was mainly governed by particle diffusion. Thermodynamic parameters such as standard enthalpy (DeltaH degrees ), standard entropy (DeltaS degrees ), standard free energy (DeltaG degrees ) and activation energy were determined. The regeneration efficiency of the spent activated carbon was high, with TCP desorption of 99.6%.
The liquid-phase adsorption of phenol onto coconut shell-based activated carbon, CS850A was investigated for its equilibrium studies and kinetic modeling. Coconut shell was converted into high quality activated carbon through physiochemical activation at 850 degrees C under the influence of CO(2) flow. Beforehand, the coconut shell was carbonized at 700 degrees C and the resulted char was impregnated with KOH at 1:1 weight ratio. In order to evaluate the performance of CS850A, a series of batch adsorption experiments were conducted with initial phenol concentrations ranging from 100 to 500 mg l(-1), adsorbent loading of 0.2g and the adsorption process was maintained at 30+/-1 degrees C. The adsorption isotherms were in conformation to both Langmuir and Freundlich isotherm models. Chemical reaction was found to be a rate-controlling parameter to this phenol-CS850A batch adsorption system due to strong agreement with the pseudo-second-order kinetic model. Adsorption capacity for CS850A was found to be 205.8 mg g(-1).