An innovative approach using soybean residues for the production of bioflocculants through solid-state fermentation was carried out in 4.5 L near-to-adiabatic bioreactors at pilot-scale level. An added inoculum of the strain Bacillus subtilis UPMB13 was tested in comparison with control reactors without any inoculation after the thermophilic phase of the fermentation. The flocculating performances of the extracted bioflocculants were tested on kaolin suspensions, and crude bioflocculants were obtained from 20 g of fermented substrate through ethanol precipitation. The production of bioflocculants was observed to be higher during the death phase of microbial growth. The bioflocculants were observed to be granular in nature and consisted of hydroxyl, carboxyl and methoxyl groups that aid in their flocculating performance. The results show the vast potential of the idea of using wastes to produce bioactive materials that can replace the current dependence on chemicals, for future prospect in water treatment applications.
The ability of Pycnoporus sanguineus to adsorb heavy metals from aqueous solution was investigated in fixed-bed column studies. The experiments were conducted to study the effect of important design parameters such as column bed height, flow rate and initial concentration of solution. The breakthrough profiles were obtained in these studies. A mathematical model based on external mass transfer and pore diffusion was used for the prediction of mass transfer coefficient and effective diffusivity of metals in macro-fungi bed. Experimental breakthrough profiles were compared with the simulated breakthrough profiles obtained from the mathematical model. Bed Depth Service Time (BDST) model was used to analyse the experimental data and evaluated the performance of biosorption column. The BDST model parameters needed for the design of biosorption columns were evaluated for lead, copper and cadmium removal in the column. The columns were regenerated by eluting the metal ions using 0.1 M hydrochloric acid solution after the adsorption studies. The columns were subjected to repeated cycles of adsorption of same metal ions and desorption to evaluate the removal efficiency after adsorption-desorption.
This work was aimed to evaluate the feasibility of castor bean residue based activated carbons prepared through metals chloride activation. The activated carbons were characterized for textural properties and surface chemistry, and the adsorption data of rhodamine B were established to investigate the removal performance. Zinc chloride-activated carbon with specific surface area of 395 m(2)/g displayed a higher adsorption capacity of 175 mg/g. Magnesium chloride and iron(III) chloride are less toxic and promising agents for composite chemical activation. The adsorption data obeyed Langmuir isotherm and pseudo-second-order kinetics model. The rate-limiting step in the adsorption of rhodamine B is film diffusion. The positive values of enthalpy and entropy indicate that the adsorption is endothermic and spontaneous at high temperature.
Acinetobacter haemolyticus, a Gram-negative aerobic locally isolated bacterium, immobilized on wood-husk showed the ability to detoxify Cr(VI) to Cr(III). Wood-husk, a natural cellulose-based support material, packed in an upward-flow column was used as support material for bacterial attachment. Around 97% of the Cr(VI) in wastewater containing 15 mg L(-1) of Cr(VI) was reduced at a flow rate of 8.0 mL min(-1). The wastewater containing Cr(VI) was added with liquid pineapple wastewater as nutrient source for the bacteria. Electron microscopic examinations of the wood-husk after 42 days of column operation showed gradual colonization of the wood-husk by bacterial biofilm. The use of 0.1% (v/v) formaldehyde as a disinfecting agent inhibited growth of bacteria present in the final wastewater discharge. This finding is important in view of the ethical code regarding possible introduction of exogenous bacterial species into the environment.
Possible application of a locally isolated environmental isolate, Acinetobacter haemolyticus to remediate Cr(VI) contamination in water system was demonstrated. Cr(VI) reduction by A. haemolyticus seems to favour the lower concentrations (10-30 mg/L). However, incomplete Cr(VI) reduction occurred at 70-100 mg/L Cr(VI). Initial specific reduction rate increased with Cr(VI) concentrations. Cr(VI) reduction was not affected by 1 or 10 mM sodium azide (metabolic inhibitor), 10 mM of PO(4)3-, SO4(2-), SO(3)2-, NO3- or 30 mg/L of Pb(II), Zn(II), Cd(II) ions. However, heat treatment caused significant dropped in Cr(VI) reduction to less than 20% only. A. haemolyticus cells loses its shape and size after exposure to 10 and 50 mg Cr(VI)/L as revealed from TEM examination. The presence of electron-dense particles in the cytoplasmic region of the bacteria suggested deposition of chromium in the cells.
In this study of coagulation operation, a comparison was made between the optimum jar test values for pH, coagulant and coagulant aid obtained from traditional methods (an adjusted one-factor-at-a-time (OFAT) method) and with central composite design (the standard design of response surface methodology (RSM)). Alum (coagulant) and polymer (coagulant aid) were used to treat a water source with very low pH and high aluminium concentration at Sri-Gading water treatment plant (WTP) Malaysia. The optimum conditions for these factors were chosen when the final turbidity, pH after coagulation and residual aluminium were within 0-5 NTU, 6.5-7.5 and 0-0.20 mg/l respectively. Traditional and RSM jar tests were conducted to find their respective optimum coagulation conditions. It was observed that the optimum dose for alum obtained through the traditional method was 12 mg/l, while the value for polymer was set constant at 0.020 mg/l. Through RSM optimization, the optimum dose for alum was 7 mg/l and for polymer was 0.004 mg/l. Optimum pH for the coagulation operation obtained through traditional methods and RSM was 7.6. The final turbidity, pH after coagulation and residual aluminium recorded were all within acceptable limits. The RSM method was demonstrated to be an appropriate approach for the optimization and was validated by a further test.
In this paper, the newly explored TiO(2)-Chitosan/Glass was suggested as a promising alternative material to conventional means of wastewater treatment. Characterization of TiO(2)-Chitosan/Glass photocatalyst was studied with SEM-EDX, XRD, and Fourier transform infrared spectroscopy (FTIR) analysis. The combination effect of photodegradation-adsorption process for the removal of methyl orange (MO), an acid dye of the monoazo series occur promisingly when four layers of TiO(2)-Chitosan/Glass photocatalyst was used for MO removal. Approximately, 87.0% of total MO removal was achieved. The reactive -NH(2), -OH, and metal oxide contents in the prepared photocatalyst responsible for the photodegradation-adsorption effect were confirmed by FTIR study. Similarly, MO removal behavior was well supported by SEM-EDX and XRD analysis. Significant dependence of MO removal on the TiO(2)-Chitosan loading can be explained in terms of relationship between quantum yield of photocatalytic reactions and photocatalyst structure/activity. Hence, the research work done thus far suggests a new method, having both the advantages of photodegradation-adsorption process in the abatement of various wastewater pollutants.
Mixed dye consists of six commercial dyes and textile effluents from cotton dyeing process were treated by electrochemical-assisted photodegradation under halogen lamp illumination. Two types of effluents were collected which are samples before and after undergone pre-treatment at the factory wastewater treatment plant. The photodegradation process was studied by evaluating the changes in concentration employing UV-vis spectrophotometer (UV-vis) and total organic carbon (TOC) analysis. The photoelectrochemical degradation of mixed dye was found to follow the Langmuir Hinshelwood pseudo-first order kinetic while pseudo-second order kinetic model for effluents by using TOC analyses. The chemical oxygen demand (COD) and biochemical oxygen demand (BOD) values of mixed dye and raw effluents were reported. Photoelectrochemical characteristic of pollutants was studied using the cyclic voltammetry technique. Raw effluent was found to exhibit stronger reduction behaviour at cathodic bias potential but slightly less photoresponse at anodic bias than mixed dye.
Electrochemical-assisted photodegradation of methyl orange has been investigated using TiO2 thin films. The films were prepared by sol-gel dip-coating method. Several operational parameters to achieve optimum efficiency of this electrochemical-assisted photodegradation system have been tested. Photoelectrochemical degradation was studied using different light sources and light intensity. The light sources chosen ranged from ultraviolet to visible light. The effect of agitation of the solution at different speeds has also been studied. Slight improvement of photodegradation rate was observed by applying higher agitation speed. Investigation on the electrode after repeated usages show the electrode can be reused up to 20 times with percentage of deficiency less than 15%. The study on the effect of solution temperature indicated that the activation energy of the methyl orange degradation is 18.63 kJ mol(-1).
A greener method based on cloud point extraction was developed for removing phenol species including 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and 4-nitrophenol (4-NP) in water samples by using the UV-Vis spectrophotometric method. The non-ionic surfactant DC193C was chosen as an extraction solvent due to its low water content in a surfactant rich phase and it is well-known as an environmentally-friendly solvent. The parameters affecting the extraction efficiency such as pH, temperature and incubation time, concentration of surfactant and salt, amount of surfactant and water content were evaluated and optimized. The proposed method was successfully applied for removing phenol species in real water samples.
The effects of Mecoprop (RS)-MCPP were investigated in an anaerobic membrane bioreactor (AnMBr) fed with synthetic wastewater containing stepwise increases in Mecoprop concentration, 5-200 mg L(-1) over 240 days. Effects were observed in terms of soluble chemical oxygen demand (COD) removal efficiency, volatile fatty acid (VFA) production, and methane yield. Soluble COD removal efficiency was stable at Mecoprop concentrations below 200 (±3) mg L(-1), with an average of 98 (±0.7)% removal. However, at 200 (±3) mg L(-1) Mecoprop, the COD removal efficiency decreased gradually to 94 (±1.5)%. At 5 mg L(-1) Mecoprop, acetic and propionic acid concentrations increased by 60% and 160%, respectively. In contrast, when Mecoprop was increased to 200 (±3) mg L(-1), the formation and degradation of acetate was unaffected by the higher Mecoprop concentration, acetate remaining below 35 mg L(-1). Increases in the Mecoprop specific utilization rate were observed as Mecoprop was increased stepwise between 5 and 200 mg L(-1).
Nitrification of mature sanitary landfill leachate with high-strength of N-NH(4) + (1080-2350 mg L(-1)) was performed in a 10 L continuous nitrification activated sludge reactor. The nitrification system was acclimatized with synthetic leachate during feed batch operation to avoid substrate inhibition before being fed with actual mature leachate. Successful nitrification was achieved with an approximately complete ammonium removal (99%) and 96% of N-NH(4) + conversion to N-NO(-) (3) . The maximum volumetric and specific nitrification rates obtained were 2.56 kg N-NH(4) (+) m(-3) day(-1) and 0.23 g N-NH(4) ( +) g(-1) volatile suspended solid (VSS) day(-1), respectively, at hydraulic retention time (HRT) of 12.7 h and solid retention time of 50 days. Incomplete nitrification was encountered when operating at a higher nitrogen loading rate of 3.14 kg N-NH(4) (+) m(-3) day(-1). The substrate overloading and nitrifiers competition with heterotrophs were believed to trigger the incomplete nitrification. Fluorescence in situ hybridization (FISH) results supported the syntrophic association between the ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria. FISH results also revealed the heterotrophs as the dominant and disintegration of some AOB cell aggregates into single cells which further supported the incomplete nitrification phenomenon.
Zeolites P in sodium (NaP) and potassium (KP) forms were used as adsorbents for the removal of calcium (Ca2+) and zinc (Zn2+) cations from aqueous solutions. Zeolite KP was prepared by ion exchange of K+ with Na+ which neutralizes the negative charge of the zeolite P framework structure. The ion exchange capacity of K+ on zeolite NaP was determined through the Freundlich isotherm equilibrium study. Characterization of zeolite KP was determined using infrared spectroscopy and X-ray diffraction (XRD) techniques. From the characterization, the structure of zeolite KP was found to remain stable after the ion exchange process. Zeolites KP and NaP were used for the removal of Ca and Zn from solution. The amount of Ca2+ and Zn2+ in aqueous solution before and after the adsorption by zeolites was analysed using the flame atomic absorption spectroscopy method. The removal of Ca2+ and Zn2+ followed the Freundlich isotherm rather than the Langmuir isotherm model. This result also revealed that zeolite KP adsorbs Ca2+ and Zn2+ more than zeolite NaP and proved that modification of zeolite NaP with potassium leads to an increase in the adsorption efficiency of the zeolite. Therefore, the zeolites NaP and KP can be used for water softening (Ca removal) and reducing water pollution/toxicity (Zn removal).
Pristine chitosan beads were modified with sulfur (S)-containing functional groups to produce thiolated chitosan beads (ETB), thereby increasing S donor ligands and crosslinks. The effect of temperature, heating time, carbon disulfide (CS2)/chitosan ratio, and pH on total S content of ETB was examined using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The total S content of ETB increased with increasing CS2/chitosan ratio and decreased with decreasing pH and increasing temperature (>60 °C) and heating time (at 60 °C). Spectroscopic analyses revealed the presence of thiol (-SH)/thione, disulfide (-S-S-), and sulfonate groups in ETB. The thiolation mechanism involves decomposition of dithiocarbamate groups, thereby forming thiourea crosslinks and trithiocarbonate, resulting in -SH oxidation to produce -S-S- crosslinks. The partially formed ETB crosslinks contribute to its acid stability and are thermodynamically feasible in adsorbing Cd and Cu. The S-containing functional groups added to chitinous wastes act as sorbents for metal remediation from acidic environments.
Palm shell activated carbon was modified via surface impregnation with polyethyleneimine (PEI) to enhance removal of Cu(2+) from aqueous solution in this study. The effect of PEI modification on batch adsorption of Cu(2+) as well as the equilibrium behavior of adsorption of metal ions on activated carbon were investigated. PEI modification clearly increased the Cu(2+) adsorption capacities by 68% and 75.86% for initial solution pH of 3 and 5 respectively. The adsorption data of Cu(2+) on both virgin and PEI-modified AC for both initial solution pH of 3 and 5 fitted the Langmuir and Redlich-Peterson isotherms considerably better than the Freundlich isotherm.
Phytoremediation is an environmentally friendly and sustainable alternative for treatment of nitrogen-enriched wastewaters. In this study, Ta-khian (Hopea odorata) and Lagos mahogany (Khaya ivorensis), two tropical timber plants, were investigated for their performances in treatment of urea manufacturing factory effluent with high nitrogen (N) content. Plant seedlings received four concentrations of N (190, 240, 290 and 340 mg/L N) in laboratory-scale constructed wetlands every 4 days for a duration of 8 weeks. The solution volumes supplied to each container, amount of N recovered by plants and plant growth characteristics were measured throughout the experiment. Results showed that Ta-khian plants were highly effective at reducing N concentration and volume of water. A maximum of 63.05% N recovery was obtained by Ta-khian plants grown in 290 mg/L N, which was assimilated in the chlorophyll molecule structure and shoot biomass. Significant positive correlations have been shown between N recovery percentages and plant growth parameters. Ta-Khian plants can be applied as suitable phytoremediators for mitigating N pollution in water sources.
Oily wastewater, especially water-oil emulsion has become serious environmental issue and received global attention. Chemical demulsifiers are widely used to treat oil-water emulsion, but the toxicity, non-recyclable and non-environmental friendly characteristic of chemical demulsifiers had limited their practical application in oil-water separation. Therefore, it is imperative to develop an efficient, simple, eco-friendly and recyclable demulsifiers for breaking up the emulsions from the oily wastewater. In this study, a magnetic demulsifier, magnetite-reduced graphene oxide (M-rGO) nanocomposites were proposed as a recyclable demulsifier to break up the surfactant stabilized crude oil-in-water (O/W) emulsion. M-rGO nanocomposites were prepared via in situ chemical synthesis by using only one type Fe salt and GO solid as precursor at room temperature. The prepared composites were fully characterized by various techniques. The effect of demulsifier dosage and pH of emulsion on demulsification efficiency (ED) has been studied in detailed. The demulsification mechanism was also proposed in this study. Results showed that M-rGO nanocomposites were able to demulsify crude O/W emulsion. The ED reaches 99.48% when 0.050 wt.% of M-rGO nanocomposites were added to crude O/W emulsion (pH = 4). Besides, M-rGO nanocomposites can be recycled up to 7 cycles without showing a significant change in terms of ED. Thus, M-rGO nanocomposite is a promising demulsifier for surfactant stabilized crude O/W emulsion.
The potential use of non-viable biomass of a Gram negative bacterium i.e. Acinetobacter haemolyticus to remove Cr(III) species from aqueous environment was investigated. Highest Cr(III) removal of 198.80 mg g(-1) was obtained at pH 5, biomass dosage of 15 mg cell dry weight, initial Cr(III) of 100 mg L(-1) and 30 min of contact time. The Langmuir and Freundlich models fit the experimental data (R(2)>0.95) while the kinetic data was best described using the pseudo second-order kinetic model (R(2)>0.99). Cr(III) was successfully recovered from the bacterial biomass using either 1M of CH(3)COOH, HNO(3) or H(2)SO(4) with 90% recovery. TEM and FTIR suggested the involvement of amine, carboxyl, hydroxyl and phosphate groups during the biosorption of Cr(III) onto the cell surface of A. haemolyticus. A. haemolyticus was also capable to remove 79.87 mg g(-1) Cr(III) (around 22.75%) from raw leather tanning wastewater. This study demonstrates the potential of using A. haemolyticus as biosorbent to remove Cr(III) from both synthetic and industrial wastewater.
Bio-hydrogen production from wastewater using sludge as inoculum is a sustainable approach for energy production. This study investigated the influence of initial pH and temperature on bio-hydrogen production from dairy wastewater using pretreated landfill leachate sludge (LLS) as an inoculum. The maximum yield of 113.2 ± 2.9 mmol H2/g chemical oxygen demand (COD) (12.8 ± 0.3 mmol H2/g carbohydrates) was obtained at initial pH 6 and 37 °C. The main products of volatile fatty acids were acetate and butyrate with the ratio of acetate:butyrate was 0.4. At optimum condition, Gibb's free energy was estimated at -40 kJ/mol, whereas the activation enthalpy and entropy were 65 kJ/mol and 0.128 kJ/mol/l, respectively. These thermodynamic quantities suggest that bio-hydrogen production from dairy wastewater using pretreated LLS as inoculum was effective and efficient. In addition, genomic and bioinformatics analyses were performed in this study.
A novel preparation method of magnetized palm shell waste-based powdered activated carbon (MPPAC, avg. size 112 μm) was developed. The prepared MPPAC was assessed by several physicochemical analyses, and batch tests were performed for ibuprofen (IBP) removal. Field emission scanning electron microscopy (FESEM) and N2 gas isotherms revealed that magnetite and maghemite were homogeneous and deposited mostly on the surface of PPAC without a significant clogging effect on the micropores. Isotherm results showed that 3.8% Fe (w/w) impregnated PPAC [MPPAC-Fe(3.8%)] had about 2.2-fold higher maximum sorption capacity (157.3 mg g-1) and a 2.5-fold higher sorption density (0.23 mg m-2) than pristine PPAC. Both Fourier-transform infrared spectroscopy (FTIR) and isotherm data indicated that the high sorption capacity and density of IBP by MPPAC was primarily attributable to donor-acceptor complexes with the C = O group and dispersive π-π interactions with the carbon surface. Based on kinetic and repeated adsorption tests, pore diffusion was the rate-limiting step, and MPPAC-Fe(3.8%) had about 1.9~2.8- and 9.1~15.8-fold higher rate constants than MPPAC-Fe(8.6%) and palm shell-waste granular activated carbon (PGAC, avg. size 621 μm), respectively. MPPAC showed almost eight fold greater re-adsorption capacity than PPAC due to a thermal catalytic effect of magnetite/maghemite.