The adsorption of methyl orange dye from aqueous solution onto penta-bismuth hepta-oxide nitrate, Bi(5)O(7)NO(3), synthesized by precipitation method, was studied in a batch adsorption system. The effects of operation parameters such as adsorbent dose, initial dye concentration, pH and temperature were investigated. The adsorption equilibrium and mechanism of adsorption was evaluated by Langmuir and Freundlich isotherm and different kinetic models, respectively. The results indicate that adsorption is highly dependent on all operation parameters. At optimum conditions, the adsorption capacity was found to be 18.9 mg/g. The adsorption data fits well with the Langmuir isotherm model indicating monolayer coverage of adsorbate molecules on the surface of Bi(5)O(7)NO(3). The kinetic studies show that the adsorption process is a second-order kinetic reaction. Although intra-particle diffusion limits the rate of adsorption, the multi-linearity plot of intra-particle model shows the importance of both film and intra-particle diffusion as the rate-limiting steps of the dye removal. Thermodynamic parameters show that the adsorption process is endothermic, spontaneous and favourable at high temperature.
Fourier transform infrared (FTIR) spectroscopy studies of poly(vinyl alcohol) (PVA), and chitosan polymer blend doped with ammonium nitrate (NH(4)NO(3)) salt and plasticized with ethylene carbonate (EC) have been performed with emphasis on the shift of the carboxamide, amine and hydroxyl bands. 1% acetic acid solution was used as the solvent. It is observed from the chitosan film spectrum that evidence of polymer-solvent interaction can be observed from the shifting of the carboxamide band at 1660 cm(-1) and the amine band at 1591 cm(-1) to 1650 and 1557 cm(-1) respectively and the shift of the hydroxyl band from 3377 to 3354 cm(-1). The hydroxyl band in the spectrum of PVA powder is observed at 3354 cm(-1) and is observed at 3343 cm(-1) in the spectrum of the PVA film. On addition of NH(4)NO(3) up to 30 wt.%, the carboxamide, amine and hydroxyl bands shifted from 1650, 1557 and 3354 cm(-1) to 1642, 1541 and 3348 cm(-1) indicating that the chitosan has complexed with the salt. In the PVA-NH(4)NO(3) spectrum, the hydroxyl band has shifted from 3343 to 3272 cm(-1) on addition of salt from 10 to 30 wt.%. EC acts as a plasticizing agent since there is no shift in the bands as observed in the spectrum of PVA-chitosan-EC films. The mechanism of ion migration is proposed for the plasticized and unplasticized PVA-chitosan-NH(4)NO(3) systems. In the spectrum of PVA-chitosan-NH(4)NO(3)-EC complex, the doublet CO stretching in EC is observed in the vicinity 1800 and 1700. This indicates that there is some interaction between the salt and EC.
The photo-degradation of nutrients in stormwater in photocatalytic reactor wet detention pond using nano titanium dioxide (TiO2) in concrete was investigated in a scale model as a new stormwater treatment method. Degradation of phosphate and nitrate in the presence of nano-TiO2 under natural ultra violet (UV) from tropical sunlight was monitored for 3 weeks compared with normal ponds. Two types of cement, including ordinary Portland and white cement mixed with TiO2 nano powder, were used as a thin cover to surround the body of the pond. Experiments with and without the catalyst were carried out for comparison and control. Average Anatase diameter of 25 nm and Rutile 100 nm nano particles were applied at three different mixtures of 3, 10 and 30% weight. The amounts of algae available orthophosphate and nitrate, which cause eutrophication in the ponds, were measured during the tests. Results revealed that the utilization of 3% up to 30% weight nano-TiO2 can improve stormwater outflow quality by up to 25% after 48 h and 57% after 3 weeks compared with the control sample in normal conditions with average nutrient (phosphate and nitrate) removal of 4% after 48 h and 10% after 3 weeks.
The study is to identify the extraction of intracellular inulinase (exo- and endoinulinase) and invertase as well as optimization medium composition for maximum productions of intra- and extracellular enzymes from Aspergillus niger ATCC 20611. From two different methods for extraction of intracellular enzymes, ultrasonic method was found more effective. Response surface methodology (RSM) with a five-variable and three-level central composite design (CCD) was employed to optimize the medium composition. The effect of five main reaction parameters including sucrose, yeast extract, NaNO₃, Zn⁺², and Triton X-100 on the production of enzymes was analyzed. A modified quadratic model was fitted to the data with a coefficient of determination (R²) more than 0.90 for all responses. The intra-extracellular inulinase and invertase productions increased in the range from 16 to 8.4 times in the optimized medium (10% (w/v) sucrose, 2.5% (w/v) yeast extract, 2% (w/v) NaNO₃, 1.5 mM (v/v) Zn⁺², and 1% (v/v) Triton X-100) by RSM and from around 1.2 to 1.3 times greater than in the medium optimized by one-factor-at-a-time, respectively. The results of bioprocesses optimization can be useful in the scale-up fermentation and food industry.
Mixotrophic metabolism was evaluated as an option to augment the growth and lipid production of marine microalga Tetraselmis sp. FTC 209. In this study, a five-level three-factor central composite design (CCD) was implemented in order to enrich the W-30 algal growth medium. Response surface methodology (RSM) was employed to model the effect of three medium variables, that is, glucose (organic C source), NaNO3 (primary N source), and yeast extract (supplementary N, amino acids, and vitamins) on biomass concentration, X(max), and lipid yield, P(max)/X(max). RSM capability was also weighed against an artificial neural network (ANN) approach for predicting a composition that would result in maximum lipid productivity, Pr(lipid). A quadratic regression from RSM and a Levenberg-Marquardt trained ANN network composed of 10 hidden neurons eventually produced comparable results, albeit ANN formulation was observed to yield higher values of response outputs. Finalized glucose (24.05 g/L), NaNO3 (4.70 g/L), and yeast extract (0.93 g/L) concentration, affected an increase of X(max) to 12.38 g/L and lipid a accumulation of 195.77 mg/g dcw. This contributed to a lipid productivity of 173.11 mg/L per day in the course of two-week cultivation.
A study was performed to determine the effect of Conway and f/2 media on the growth of microalgae genera. Genera of Chlorella sp., Dunaliella sp., Isochrysis sp., Chaetoceros sp., Pavlova sp. and Tetraselmis sp. were isolated from the South China Sea. During the cultivation period, the density of cells were determined using Syringe Liquid Sampler Particle Measuring System (SLS-PMS) that also generated the population distribution curve based on the size of the cells. The population of the microalgae genera is thought to consist of mother and daughter generations since these microalgae genera reproduce by releasing small non-motile reproductive cells (autospores). It was found that the reproduction of Tetraselmis sp., Dunaliella sp. and Pavlova sp. could be sustained longer in f/2 Medium. Higher cell density was achieved by genus Dunaliella, Chlorella and Isochrysis in Conway Medium. Different genera of microalgae had a preference for different types of cultivation media.
Biofouling is a crucial factor in membrane bioreactor (MBR) applications, particularly for high organic loading operations. This paper reports a study on biofouling in an MBR to establish a relationship between critical flux, Jc, mixed liquor suspended solids (MLSS) (ranging from 5 to 20 g L-1) and volumetric loading rate (6.3 kg COD m-3 h-1) of palm oil mill effluent (POME). A lab-scale 100 L hybrid MBR consisting of anaerobic, anoxic, and aerobic reactors was used with flat sheet microfiltration (MF) submerged in the aerobic compartment. The food-to-microorganism (F/M) ratio was maintained at 0.18 kg COD kg-1 MLSSd-1. The biofouling tendency of the membrane was obtained based on the flux against the transmembrane pressure (TMP) behaviour. The critical flux is sensitive to the MLSS. At the MLSS 20 g L-1 the critical flux is about four times lower than that for the MLSS concentration of 5 g L-1. The results showed high removal efficiency of denitrification and nitrification up to 97% at the MLSS concentration 20 g L-1. The results show that the operation has to compromise between a high and a low MLSS concentration. The former will favour a higher removal rate, while the latter will favour a higher critical flux.
A modified hydrophilic penta-bismuth hepta-oxide nitrate (Bi5O7NO3) surface was synthesized via a precipitation method using TiO2 and Ag as modified agents. The synthesized product was characterized by different analytical techniques. The removal efficiency was evaluated using mono- and di-sulphonated azo dyes as model pollutants. Different kinetic, isotherm and diffusion models were chosen to describe the adsorption process. X-ray photoelectron spectroscopy (XPS) results revealed no noticeable differences in the chemical states of modified adsorbent when compared to pure Bi5O7NO3; however, the presence of hydrophilic centres such as TiO2 and Ag developed positively charged surface groups and improved its adsorption performance to a wide range of azo dyes. Dyes removal was found to be a function of adsorbent dosage, initial dye concentration, solution pH and temperature. The reduction of Langmuir 1,2-mixed order kinetics to the second or first-order kinetics could be successfully used to describe the adsorption of dyes onto the modified adsorbent. Mass transfer can be described by intra-particle diffusion at a certain stage, but it was not the rate limiting step that controlled the adsorption process. Homogenous behavior of adsorbent surface can be explored by applying Langmuir isotherm to fit the adsorption data.
This paper presents the findings of a study on solidification/stabilization (S/S) of lead-contaminated soil using ordinary Portland cement (OPC) and rice husk ash (RHA). The effects of varying lead concentrations (in the form of nitrates) in soil samples on the physical properties of their stabilized forms, namely unconfined compressive strength (UCS), setting times of early mixtures and changes in crystalline phases as well as chemical properties such as leachability of lead, pH and alkalinity of leachates are studied. Results have indicated that usage of OPC with RHA as an overall binder system for S/S of lead-contaminated soils is more favorable in reducing the leachability of lead from the treated samples than a binder system with standalone OPC. On the other hand, partial replacement of OPC with RHA in the binder system has reduced the UCS of solidified samples.
In this study, zinc oxide (ZnO) nanorod arrays were synthesized using a simple hydrothermal reaction on ZnO seeds/n-silicon substrate. Several parameters were studied, including the heat-treatment temperature to produce ZnO seeds, zinc nitrate concentration, pH of hydrothermal reaction solution, and hydrothermal reaction time. The optimum heat-treatment temperature to produce uniform nanosized ZnO seeds was 400°C. The nanorod dimensions depended on the hydrothermal reaction parameters. The optimum hydrothermal reaction parameters to produce blunt tip-like nanorods (770 nm long and 80 nm in top diameter) were 0.1 M zinc nitrate, pH 7, and 4 h of growth duration. Phase analysis studies showed that all ZnO nanorods exhibited a strong (002) peak. Thus, the ZnO nanorods grew in a c-axis preferred orientation. A strong ultraviolet (UV) emission peak was observed for ZnO nanorods grown under optimized parameters with a low, deep-level emission peak, which indicated high optical property and crystallinity of the nanorods. The produced ZnO nanorods were also tested for their UV-sensing properties. All samples responded to UV light but with different sensing characteristics. Such different responses could be attributed to the high surface-to-volume ratio of the nanorods that correlated with the final ZnO nanorods morphology formed at different synthesis parameters. The sample grown using optimum synthesis parameters showed the highest responsivity of 0.024 A/W for UV light at 375 nm under a 3 V bias.
A two-stage anoxic transformation process, involving growth of biomass utilizing two types of different electron acceptors, namely nitrate and nitrite, has been observed. The present water quality modules established for sewer processes cannot account for the two-stage process. This paper outlines the development of a model concept that enables the two-stage anoxic transformation process to be simulated. The proposed model is formulated in a matrix form that is similar to the Activated Sludge Models and Sewer Process Model matrices. The model was successfully applied to simulate changes in nitrate and nitrite concentrations during anoxic transformations in the bulkwater phase of municipal wastewater.
A facile thermal-treatment route was successfully used to synthesize ZnO nanosheets. Morphological, structural, and optical properties of obtained nanoparticles at different calcination temperatures were studied using various techniques. The FTIR, XRD, EDX, SEM and TEM images confirmed the formation of ZnO nanosheets through calcination in the temperature between 500 to 650 °C. The SEM images showed a morphological structure of ZnO nanosheets, which inclined to crumble at higher calcination temperatures. The XRD and FTIR spectra revealed that the samples were amorphous at 30 °C but transformed into a crystalline structure during calcination process. The average particle size and degree of crystallinity increased with increasing calcination temperature. The estimated average particle sizes from TEM images were about 23 and 38 nm for the lowest and highest calcination temperature i.e. 500 and 650 °C, respectively. The optical properties were determined by UV-Vis reflection spectrophotometer and showed a decrease in the band gap with increasing calcination temperature.
Fatty acid methyl esters (FAME) were produced from palm oil using eggshell modified with magnesium and potassium nitrates to form a composite, low-cost heterogeneous catalyst for transesterification. The catalyst, prepared by the combination of impregnation/co-precipitation was calcined at 830 °C for 4 h. Transesterification was conducted at a constant temperature of 65 °C in a batch reactor. Design of experiment (DOE) was used to optimize the reaction parameters, and the conditions that gave highest yield of FAME (85.8%) was 5.35 wt.% catalyst loading at 4.5 h with 16:1 methanol/oil molar ratio. The results revealed that eggshell, a solid waste, can be utilized as low-cost catalyst after modification with magnesium and potassium nitrates for biodiesel production.
Putrajaya Wetlands in Malaysia, a 200ha constructed wetland system consisting of 24 cells, was created in 1997-1998 to treat surface runoff caused by development and agricultural activities from an upstream catchment before entering Putrajaya Lake (400ha). It was designed for stormwater treatment, flood control and amenity use. The water quality improvement performance of a section of the wetland cells is described. The nutrient removal performance was 82.11% for total nitrogen, 70.73% for nitrate-nitrogen and 84.32% for phosphate, respectively, along six wetland cells from Upper North UN6 to UN1 from April to December 2004. Nutrient removal in pilot scale tank systems, simulating a constructed wetland and planted with examples of common species at Putrajaya, the Common Reed Phragmites karka and Tube Sedge Lepironia articulata, and the capacity of these species to retain nutrients in above and below-ground plant biomass and substrate is reported. The uptake of nutrients by the Common Reed and Tube Sedge from the pilot tank system was 42.1% TKN; 28.9% P and 17.4% TKN; 26.1% P, respectively. The nutrient uptake efficiency of the Common Reed was higher in above-ground than in below-ground tissue. The results have implications for plant species selection in the design of constructed wetlands in Malaysia and for optimizing the performance of these systems.
Rice straw/magnetic nanocomposites (RS/Fe3O4-NCs) were prepared via co-precipitation method for removal of Pb(II) and Cu(II) from aqueous solutions. Response surface methodology (RSM) was utilized to find the optimum conditions for removal of ions. The effects of three independent variables including initial ion concentration, removal time, and adsorbent dosage were investigated on the maximum adsorption of Pb (II) and Cu (II). The optimum conditions for the adsorption of Pb(II) and Cu(II) were obtained (100 and 60 mg/L) of initial ion concentration, (41.96 and 59.35 s) of removal time and 0.13 g of adsorbent for both ions, respectively. The maximum removal efficiencies of Pb(II) and Cu(II) were obtained 96.25% and 75.54%, respectively. In the equilibrium isotherm study, the adsorption data fitted well with the Langmuir isotherm model. The adsorption kinetics was best depicted by the pseudo-second order model. Desorption experiments showed adsorbent can be reused successfully for three adsorption-desorption cycles.
The study was conducted to determine thiocyanate (SCN-) and hypothiocyanite (OSCN-) concentrations in resting (RWS) and stimulated whole saliva (SWS) and stimulated parotid saliva (SPS) of 20 healthy young adults aged 21-29 y. Samples of saliva were collected at 12:30, immediately before lunch. Resting saliva was collected by expectoration, and stimulated saliva was collected during the uniform chewing of paraffin wax. Parotid secretion was collected using a modified Carlsson-Crittenden cup (Carlsson et al., Am, J. Physiol., 26, 169-177, 1910). SCN- concentration was determined by the ferric nitrate method (Betts et al., J. Am. Chem. Soc., 75, 5721-5727, 1953) whilst OSCN- was assayed using 2-mercaptoethanol as a reducing agent (Pruitt et al., Caries Res., 16, 315-323, 1982). In RWS, SWS and SPS, the mean SCN- concentrations (in mM) were 1.48 +/- 0.59(S.D.), 0.90 +/- 0.56(S.D.) and 1.24 +/- 0.65(S.D.) whilst the mean OSCN- concentrations (in microM) were 31.21 +/- 13.54(S.D.), 24.90 +/- 12.61 and 30.19 +/- 23.35(S.D.) in the respective salivas. The presence of OSCN- in the secretion collected from the parotid gland supported previous findings by Tenovuo and Pruitt (Tenovuo et al., J. Oral Path, ol. 13, 573-584, 1984), who suggested an endogenous glandular (eukaryotic) source of hydrogen peroxide (H2O2), since parotid saliva from healthy glands is devoid of bacteria and leukocytes.
Recent environmental problems and societal concerns associated with the disposal of petroleum based plastics throughout the world have triggered renewed efforts to develop new biodegradable products compatible with our environment. This article describes the preparation, characterization and biodegradation study of poly(lactic acid)/layered double hydroxide (PLA/LDH) nanocomposites from PLA and stearate-Zn(3)Al LDH. A solution casting method was used to prepare PLA/stearate-Zn(3)Al LDH nanocomposites. The anionic clay Zn(3)Al LDH was firstly prepared by co-precipitation method from a nitrate salt solution at pH 7.0 and then modified by stearate anions through an ion exchange reaction. This modification increased the basal spacing of the synthetic clay from 8.83 Å to 40.10 Å. The morphology and properties of the prepared PLA/stearate-Zn(3)Al LDH nanocomposites were studied by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), thermogravimetric analysis (TGA), tensile tests as well as biodegradation studies. From the XRD analysis and TEM observation, the stearate-Zn(3)Al LDH lost its ordered stacking-structure and was greatly exfoliated in the PLA matrix. Tensile test results of PLA/stearate-Zn(3)Al LDH nanocomposites showed that the presence of around 1.0-3.0 wt % of the stearate-Zn(3)Al LDH in the PLA drastically improved its elongation at break. The biodegradation studies demonstrated a significant biodegradation rate improvement of PLA in the presence of stearate-Zn(3)Al LDH nanolayers. This effect can be caused by the catalytic role of the stearate groups in the biodegradation mechanism leading to much faster disintegration of nanocomposites than pure PLA.
The delivery of a full plasmid, encoding the green fluorescent protein gene into African monkey kidney (Vero3) cells, was successfully achieved using nanobiocomposites based on layered double hydroxides. This demonstrated the potential of using the system as an alternative DNA delivery vector. Intercalation of the circular plasmid DNA, pEGFP-N2, into Mg/Al-NO(3)(-) layered double hydroxides (LDH) was accomplished through anion exchange routes to form the nanobiocomposite material. The host was previously synthesized at the Mg(2+) to Al(3+) molar ratio R(i) = 2 and subsequently intercalated with plasmid DNA. Size expansion of the interlamellae host from 8.8 A in LDH to 42 A was observed in the resulting nanobiocomposite, indicating stable hybridization of the plasmid DNA. The powder x-ray diffraction (PXRD) results, supplemented with Fourier-transform infrared (FTIR) spectroscopy, compositional and electrophoresis studies confirmed the encapsulation episode of the biomaterial. In order to elucidate the use of this resulting nanobiocomposite as a delivery vector, an MTT assay was performed to determine any cytotoxic effects of the host towards cells. The intercalated pEGFP-N2 anion was later successfully recovered through acidification with HNO(3) after treatment with DNA-degrading enzymes, thus also showing the ability of the LDH host to protect the intercalated biomaterial from degradation. Cell transfection studies on Vero3 cells were then performed, where cells transfected with the nanobiocomposite exhibited fluorescence as early as 12 h post-treatment compared to naked delivery of the plasmid itself.
Tuberculosis is a lethal epidemic, difficult to control disease, claiming thousands of lives every year. We have developed a nanodelivery formulation based on para-aminosalicylic acid (PAS) and zinc layered hydroxide using zinc nitrate salt as a precursor. The developed formulation has a fourfold higher efficacy of PAS against mycobacterium tuberculosis with a minimum inhibitory concentration (MIC) found to be at 1.40 μg/mL compared to the free drug PAS with a MIC of 5.0 μg/mL. The newly developed formulation was also found active against Gram-positive bacteria, Gram-negative bacteria, and Candida albicans. The formulation was also found to be biocompatible with human normal lung cells MRC-5 and mouse fibroblast cells-3T3. The in vitro release of PAS from the formulation was found to be sustained in a human body simulated phosphate buffer saline (PBS) solution at pH values of 7.4 and 4.8. Most importantly the nanocomposite prepared using zinc nitrate salt was advantageous in terms of yield and free from toxic zinc oxide contamination and had higher biocompatibility compared to one prepared using a zinc oxide precursor. In summary, these promising in vitro results are highly encouraging for the continued investigation of para-aminosalicylic acid and zinc layered hydroxide nanocomposites in vivo and eventual preclinical studies.
The intercalation of perindopril erbumine into Zn/Al-NO(3)-layered double hydroxide resulted in the formation of a host-guest type of material. By virtue of the ion-exchange properties of layered double hydroxide, perindopril erbumine was released in a sustained manner. Therefore, this intercalated material can be used as a controlled-release formulation.