Abstract: Spent catalysts are considered as hazardous residues of major concern, mainly due to the simultaneous presence of several metals in elevated concentrations. Although hydrometallurgical, pyrometallurgical and chelating agent methods are available to remove and recover some metals contained in spent catalysts; these procedures generate potentially hazardous wastes and the emission of harmful gases. Thus, biotechnological treatments are currently gaining importance to avoid the negative impacts of chemical technologies. To this end, diverse microorganisms have been used to assess the removal of metals from spent catalysts, comprising bacteria, archaea and fungi, whose resistance and metal uptake capabilities differ depending on the microorganism tested. Acidophilic sulfur oxidizing bacteria have been used to investigate the biotreatment and extraction of valuable metals from spent catalysts, namely Acidithiobacillus thiooxidans and Acidithiobacillus ferroxidans, as they present the ability to produce leaching agents such as sulfuric acid and sulfur oxidation intermediates. In the present work, the ability of A. thiooxidans DSM 26636 for the bioleaching of metals contained in five different spent catalysts was assessed by growing the culture in modified Starkey mineral medium (with elemental sulfur at 1%, w/v), and 1% (w/v) pulp density of each residue for up to 21 days at 30 °C and 150 rpm. Sulfur-oxidizing activity was periodically evaluated by determining sulfate concentration in the supernatants according to the NMX-k-436-1977 method. The production of sulfuric acid was assessed in the supernatants as well, by a titration procedure using NaOH 0.5 M with bromothymol blue as acid-base indicator, and by measuring pH using a digital potentiometer. On the other hand, Inductively Coupled Plasma - Optical Emission Spectrometry was used to analyze metal removal from the five different spent catalysts by A. thiooxidans DSM 26636. Results obtained show that, as could be expected, sulfuric acid production is directly related to the diminish of pH, and also to highest metal removal efficiencies. It was observed that Al and Fe are recurrently removed from refinery spent catalysts regardless of their origin and previous usage, although these removals may vary from 9.5 ± 2.2 to 439 ± 3.9 mg/kg for Al, and from 7.13 ± 0.31 to 368.4 ± 47.8 mg/kg for Fe, depending on the spent catalyst proven. Besides, bioleaching of metals like Mg, Ni, and Si was also obtained from automotive spent catalysts, which removals were of up to 66 ± 2.2, 6.2±0.07, and 100±2.4, respectively. Hence, the data presented here exhibit the potential of A. thiooxidans DSM 26636 for the simultaneous bioleaching of metals contained in spent catalysts from diverse provenance.
Abstract: Rice bran protein hydrolysates (RBPH) were prepared from defatted rice bran of two different Thai rice cultivars (Plai-Ngahm-Prachinburi; PNP and Khao Dok Mali 105; KDM105) using an enzymatic method. This research aimed to optimize enzyme-assisted protein extraction. In addition, the functional properties of RBPH and their stabilities to environmental stresses including pH (3 to 8), ionic strength (0 mM to 500 mM) and the thermal treatment (30 °C to 90 °C) were investigated. Results showed that enzymatic process for protein extraction of defatted rice bran was as follows: enzyme concentration 0.075 g/ 5 g of protein, extraction temperature 50 °C and extraction time 4 h. The obtained protein hydrolysate powders had a degree of hydrolysis (%) of 21.05% in PNP and 19.92% in KDM105. The solubility of protein hydrolysates at pH 4-6 was ranged from 27.28-38.57% and 27.60-43.00% in PNP and KDM105, respectively. In general, antioxidant activities indicated by total phenolic content, FRAP, ferrous ion-chelating (FIC), and 2,2’-azino-bis-3-ethylbenzthiazoline-6-sulphonic acid (ABTS) of KDM105 had higher than PNP. In terms of functional properties, the emulsifying activity index (EAI) was was 8.78 m²/g protein in KDM105, whereas PNP was 5.05 m²/g protein. The foaming capacity at 5 minutes (%) was 47.33 and 52.98 in PNP and KDM105, respectively. Glutamine, Alanine, Valine, and Leucine are the major amino acid in protein hydrolysates where the total amino acid of KDM105 gave higher than PNP. Furthermore, we investigated environmental stresses on the stability of 5% oil in water emulsion (5% oil, 10 mM citrate buffer) stabilized by RBPH (3.5%). The droplet diameter of emulsion stabilized by KDM105 was smaller (d < 250 nm) than produced by PNP. For environmental stresses, RBPH stabilized emulsions were stable at pH around 3 and 5-6, at high salt (< 400 mM, pH 7) and at temperatures range between 30-50°C.
Abstract: Iron nanoparticles were used to cleanup effluents. This paper involves synthesis of iron nanoparticles chemically by sodium borohydride reduction of ammonium ferrous sulfate solution (FAS). Iron oxide nanoparticles have lesser efficiency of adsorption than Zero Valent Iron nanoparticles (nZVI). Glucosamine acts as a stabilizing agent and chelating agent to prevent Iron nanoparticles from oxidation. nZVI particles were characterized using Scanning Electron Microscopy (SEM). Thus, the synthesized nZVI was subjected to entrapment in biopolymer, viz. barium (Ba)-alginate beads. The beads were characterized using SEM. Batch dye degradation studies were conducted using Reactive black Water soluble Nontoxic Natural substances (WNN) dye which is one of the most hazardous dyes used in textile industries. Effect of contact time, effect of pH, initial dye concentration, adsorbent dosage, isotherm and kinetic studies were carried out.
Abstract: Magnetic spinel ferrites are materials that possess size, magnetic properties and heating ability adequate for their potential use in biomedical applications. The Mn0.5Ga0.5Fe2O4 magnetic nanoparticles (MNPs) were synthesized by sol-gel method using citric acid as chelating agent of metallic precursors. The synthesized samples were identified by X-Ray Diffraction (XRD) as an inverse spinel structure with no secondary phases. Saturation magnetization (Ms) of crystalline powders was 45.9 emu/g, which was higher than those corresponding to GaFe2O4 (14.2 emu/g) and MnFe2O4 (40.2 emu/g) synthesized under similar conditions, while the coercivity field (Hc) was 27.9 Oe. The average particle size was 18 ± 7 nm. The heating ability of the MNPs was enough to increase the surrounding temperature up to 43.5 °C in 7 min when a quantity of 4.5 mg of MNPs per mL of liquid medium was tested. Cytotoxic effect (hemolysis assay) of MNPs was determined and the results showed hemolytic values below 1% in all tested cases. According to the results obtained, these synthesized nanoparticles can be potentially used as thermoseeds for hyperthermia therapy.
Abstract: Natural dyes, extracted from black carrot and bramble, were utilized as photosensitizers to prepare dye-sensitized solar cells (DSSCs). Spectrophotometric studies of the natural dyes in solution and on a titanium dioxide substrate were carried out in order to assess changes in the status of the dyes. The results show that the bathochromic shift is seen on the photo-electrode substrate. The chemical binding of the natural dyes at the surface photo-electrode were increased by the chelating effect of the Ti(IV) ions. The cyclic voltammetry results showed that all extracts are suitable to be performed in DSSCs. Finally, photochemical performance and stability of DSSCs based on natural dyes were studied. The DSSCs sensitized by black carrot extract have been reported to achieve up to Jsc=1.17 mAcm-2, Voc= 0.55 V, FF= 0.52, η=0.34%, whereas Bramble extract can obtain up to Jsc=2.24 mAcm-2, Voc= 0.54 V, FF= 0.57, η=0.71%. The power conversion efficiency was obtained from the mixed dyes in DSSCs. The power conversion efficiency of dye-sensitized solar cells using mixed Black carrot and Bramble dye is the average of the their efficiency in single DSSCs.
Abstract: The contamination of significant quantities of soils and sediments with uranium and other actinide elements as a result of nuclear activity poses many environmental risks. The electrokinetic process is one of the most promising remediation techniques for sludge, sediment, and saturated or unsaturated soils contaminated with heavy metals and radionuclides. However, secondary waste is a major concern for soil contaminated with nuclides. To minimize the generation of secondary wastes, this study used the anion and cation exchange membranes to improve the performance of the experimental apparatus. Remediation experiments of uranium-contaminated soil were performed with different agents. The results show that using acetic acid and EDTA as chelating agents clearly enhances the migration ability of the uranium. The ion exchange membranes (IEMs) used in the experiments not only reduce secondary wastes, but also, keep the soil pH stable.
Abstract: Aqueous ethanol and aqueous acetone extracts of
Moringa oleifera (outer pericarp of immature fruit and flower) and
Sesbania grandiflora white variety (flower and leaf) were examined
for radical scavenging capacities and antioxidant activities. Ethanol
extract of S. grandiflora (flower and leaf) and acetone extract of M.
oleifera (outer pericarp of immature fruit and flower) contained
relatively higher levels of total dietary phenolics than the other
extracts. The antioxidant potential of the extracts were assessed by
employing different in vitro assays such as reducing power assay,
DPPH˙, ABTS˙+ and ˙OH radical scavenging capacities,
antihemolytic assay by hydrogen peroxide induced method and metal
chelating ability. Though all the extracts exhibited dose dependent
reducing power activity, acetone extract of all the samples were
found to have more hydrogen donating ability in DPPH˙ (2.3% -
65.03%) and hydroxyl radical scavenging systems (21.6% - 77.4%)
than the ethanol extracts. The potential of multiple antioxidant
activity was evident as it possessed antihemolytic activity (43.2 % to
68.0 %) and metal ion chelating potency (45.16 - 104.26 mg EDTA/g
sample). The result indicate that acetone extract of M. oleifera (OPIF
and flower) and S. grandiflora (flower and leaf) endowed with
polyphenols, could be utilized as natural antioxidants/nutraceuticals.
Abstract: Hot aqueous and methanol extracts of the two selected
herbal medicines such are Vellarugu chooranam (V.C) and
Amukkirai Chooranam (A.C) were examined for total phenolic and
flavonoid contents and in vitro antioxidant activity using four
different methods. The total phenolic and flavonoid contents in
methanol extract of V.C were found to be higher (44.41±1.26mg
GAE/g; 174.44±9.32mg QE/g) than in the methanol extract of A.C
(20.56±0.67mg GAE/g; 7.21±0.85mg QE/g). Hot methanol and
aqueous extracts of both medicines showed low antioxidant activity
in DPPH, ABTS, and FRAP methods and Iron chelating activity not
found at highest possible concentration. V.C contains higher
concentrations of total phenolic and flavonoid contents than A.C and
can also exert greater antioxidant activity than A.C, although the
activities demonstrated were lower than the positive control Trolox.
The in vitro antioxidant activity was not related with the total
phenolic and flavonoid contents of the methanol and aqueous extracts
of both herbal medicines (A.C and V.C).
Abstract: The powders of Ba(Ce1-xZrx)0.90Y0.1O3-δ (BCZY) with 0.2 ≤ x ≤ 0.6 have been prepared by a modified sol-gel method. Triethylenetetramine (TETA) was employed as chelating agent. Phase formation of calcined powders at 1100oC and sintered pellets at 1400oC of BCZY were examined by an X-ray diffractrometer (XRD). XRD results showed the calcined powder and sintered pellet formed a single perovskite phase over the entire range of x values. As the amount of zirconium substitution (x values) increase, the main peaks are shifted to the higher 2theta values which suggest a complete substitution of zirconium into cerium sites. All the obtained calcined powders and sintered pellets possess cubic structure (Pm-3m) at all x values.
Abstract: A novel new vanadium (IV) complexes incorporating the chelating diamido cyclopentadienyl {ArN(CH2)3NAr)}2-((ηn-Cp)Cp)} (Ar = 2,6-Pri2C6H3)(Cp = C5H5 and n = 1,2,3,4 and 5) have been studied with calculation of the properties of species involved in various of cyclopentadienyl reaction. These were carried out under investigation of density functional theory (DFT) calculation, and comparing together. Other methods, explicitly including electron correlation, are necessary for more accurate calculations; MB3LYP (Becke) (Lee–Yang–Parr) level of theory often being used to obtain more exact results. These complexes were estimated of electronic energy for molecular system, because it accounts for all electron correlation interactions.
The optimised of [V(ArN(CH2)3NAr)2Cl(η5-Cp)] (Ar = 2,6-Pri2C6H3 and Cp= C5H5) was found to be thermally more stable than others of vanadium cyclopentadienyl. In the meantime the complex [V(ArN(CH2)3NAr)2Cl(η1-Cp)] (Ar = 2,6-Pri2C6H3 and Cp= C5H5) which is showed a low thermal stability in case of the just one carbon of cyclopentadienyl can be insertion with vanadium metal centre. By using Dewar-Chatt-Duncanson model, as a basis of the molecular orbital (MO) analysis and showed the highest occupied molecular orbital (HOMO) and lowest occupied molecular orbital LUMO.
Abstract: Polystyrene (PS) was extracted from Styrofoam (expanded polystyrene foam) waste, so called white pollutant. The PS was functionalized with N,N- Bis(2-aminobenzylidene)benzene-1,2-diamine (ABA) ligand through an azo spacer. The resin was characterized by FT-IR spectroscopy and elemental analysis. The PS-N=N-ABA resin was used for the enrichment and speciation of Cr(III)/Cr(VI) ions and total Cr determination in aqueous samples by flame atomic absorption spectrometry (FAAS). The separation of Cr(III)/Cr(VI) ions was achieved at pH 2. The recovery of Cr(VI) ions was achieved ≥ 95.0% at optimum parameters: pH 2; resin amount 300mg; flow rates 2.0mL min-1 of solution and 2.0mL min-1 of eluent (2.0mol L-1 HNO3). Total Cr was determined by oxidation of Cr(III) to Cr(VI) ions using H2O2. The limit of detection (LOD) and quantification (LOQ) of Cr(VI) were found to be 0.40 and 1.20μg L-1, respectively with preconcentration factor of 250. Total saturation and breakthrough capacitates of the resin for Cr(IV) ions were found to be 0.181 and 0.531mmol g-1, respectively. The proposed method was successfully applied for the preconcentration/speciation of Cr(III)/Cr(VI) ions and determination of total Cr in industrial effluents.
Abstract: Extraction of Fe(III) from aqueous solution using Trin-
butyl Phosphate (TBP) as carrier needs a highly acidic medium
(>6N) as it favours formation of chelating complex FeCl3.TBP.
Similarly, stripping of Iron(III) from loaded organic solvents requires
neutral pH or alkaline medium to dissociate the same complex. It is
observed that TBP co-extracts acids along with metal, which causes
reversal of driving force of extraction and iron(III) is re-extracted
back from the strip phase into the feed phase during Liquid Emulsion
Membrane (LEM) pertraction. Therefore, rate of extraction of
different mineral acids (HCl, HNO3, H2SO4) using TBP with and
without presence of metal Fe(III) was examined. It is revealed that in
presence of metal acid extraction is enhanced. Determination of mass
transfer coefficient of both acid and metal extraction was performed
by using Bulk Liquid Membrane (BLM). The average mass transfer
coefficient was obtained by fitting the derived model equation with
experimentally obtained data. The mass transfer coefficient of the
mineral acid extraction is in the order of kHNO3 = 3.3x10-6m/s > kHCl =
6.05x10-7m/s > kH2SO4 = 1.85x10-7m/s. The distribution equilibria of
the above mentioned acids between aqueous feed solution and a
solution of tri-n-butyl-phosphate (TBP) in organic solvents have been
investigated. The stoichiometry of acid extraction reveals the
formation of TBP.2HCl, HNO3.2TBP, and TBP.H2SO4 complexes.
Moreover, extraction of Iron(III) by TBP in HCl aqueous solution
forms complex FeCl3.TBP.2HCl while in HNO3 medium forms
complex 3FeCl3.TBP.2HNO3
Abstract: The antioxidant capability of beverage blends made from cocoa, zobo and ginger with standard antioxidant assay procedures was investigated. The DPPH (2,2-diphenyl-1- picrylhydrazyl) scavenging capacity ranged from 21.2-25.8% in comparison with GSH of 37.1%. The ferric reducing ability was highest in the zobo drink and lowest in ginger. The superoxide scavenging capacity was also highest in the zobo drink followed by the drink with alkalized cocoa. The metal chelating power decreased as the level of zobo in the blends decreases. The chelating power of zobo and ginger were significantly lower than the natural and alkalized cocoa. The 100% zobo drink inhibited linoleic acid till the fifth day while natural and alkalized cocoa as well as the blend with 50% alkalized cocoa inhibited linoleic acid greatly till the sixth day. The finding describes the potential health benefit of the phytochemical antioxidants of cocoa:zobo:ginger beverage blends.
Abstract: One of the most challenges for hard surface cleaning product is to get rid of soap scum, a filmy sticky layer in the bathroom. The deposits of soap scum can be removed by using a proper surfactant solution with chelating agent. Unfortunately, the conventional chelating agent, ethylenediamine tetraacetic acid (EDTA), has low biodegradability, which can be tolerance in water resources and harmful to aquatic animal and microorganism. In this study, two biodegradable chelating agents, ethylenediamine disuccinic acid (EDDS) and glutamic acid diacetic acid (GLDA) were introduced as a replacement of EDTA. The result shows that using GLDA with amphoteric surfactant gave the highest equilibrium solubility of soap scum.
Abstract: This work focuses on the remediation of polycyclic
aromatic hydrocarbons (PAHs)-contaminated soil via Fenton
treatment coupled with novel chelating agent (CA). The feasibility of
chelated modified Fenton (MF) treatment to promote PAH oxidation
in artificially contaminated soils was investigated in laboratory scale
batch experiments at natural pH. The effects of adding inorganic and
organic CA are discussed. Experiments using different iron catalyst
to CA ratios were conducted, resulting in hydrogen peroxide: soil:
iron: CA weight ratios that varied from 0.049: 1: 0.072: 0.008 to
0.049: 1: 0.072: 0.067. The results revealed that (1) inorganic CA
could provide much higher PAH removal efficiency and (2) most of
the proposed CAs were more efficient than commonly utilised CAs
even at mild ratio. This work highlights the potential of novel
chelating agents in maintaining a suitable environment throughout
the Fenton treatment, particularly in soils with high buffer capacity.
Abstract: In this study, Li4SiO4 powder was successfully
synthesized via sol gel method followed by drying at 150oC. Lithium
oxide, Li2O and silicon oxide, SiO2 were used as the starting
materials with citric acid as the chelating agent. The obtained powder
was then sintered at various temperatures. Crystallographic phase
analysis, morphology and ionic conductivity were investigated
systematically employing X-ray diffraction, Fourier Transform
Infrared, Scanning Electron Microscopy and AC impedance
spectroscopy. XRD result showed the formation of pure monoclinic
Li4SiO4 crystal structure with lattice parameters a = 5.140 Å, b =
6.094 Å, c = 5.293 Å, β = 90o in the sample sintered at 750oC. This
observation was confirmed by FTIR analysis. The bulk conductivity
of this sample at room temperature was 3.35 × 10-6 S cm-1 and the
highest bulk conductivity of 1.16 × 10-4 S cm-1 was obtained at
100°C. The results indicated that, the Li4SiO4 compound has
potential to be used as host for LISICON structured solid electrolyte
for low temperature application.
Abstract: The performance of modified Fenton (MF) treatment
to promote PAH oxidation in artificially contaminated soil was
investigated in packed soil column with a hydrogen peroxide (H2O2)
delivery system simulating in situ injection. Soil samples were spiked
with phenanthrene (low molecular weight PAH) and fluoranthene
(high molecular weight PAH) to an initial concentration of 500
mg/kg dried soil each. The effectiveness of process parameters
H2O2/soil, iron/soil, chelating agent/soil weight ratios and reaction
time were studied using a 24 three level factorial design experiments.
Statistically significant quadratic models were developed using
Response Surface Methodology (RSM) for degrading PAHs from the
soil samples. Optimum operating condition was achieved at mild
range of H2O2/soil, iron/soil and chelating agent/soil weight ratios,
indicating cost efficient method for treating highly contaminated
lands.
Abstract: The fluorescent pseudomonad strain R81 is a root
colonizing rhizobacteria which promotes the growth of many plants
by various mechanisms. Its broth containing siderophore (ironchelating
compound) and 2,4- diacetyl phloroglucinol (DAPG) is
used for preparing bioinoculant formulations for agronomical
applications. Glycerol was found to be the best carbon source for
improved biomass production. Splitting of nitrogen source to NH4Cl
and urea had a stabilizing effect on pH during batch cultivation. Ltryptophan
at 0.5 % in the medium increased the siderophore
production to 850 mg/l. During batch cultivation of the strain in a
bioreactor, a maximum of 4 g/l of dry cell mass, 1.8 g/l of
siderophore and 20 mg/l of DAPG was achieved when glycerol was
15 g/l and C/N ratio was maintained at 12.5. In case of intermittent
feeding of fresh medium during fed-batch cultivation, the dry cell
mass was increased to 25 g/l with improved production of DAPG to
70 mg/l.
Abstract: A new chelating resin is prepared by coupling
Amberlite XAD-4 with 1-amino-2-naphthole through an azo spacer.
The resulting sorbent has been characterized by FT-IR, elemental
analysis and thermogravimetric analysis (TGA) and studied for
preconcentrating of Cu (II) using flame atomic absorption
spectrometry (FAAS) for metal monitoring. The optimum pH value
for sorption of the copper ions was 6.5. The resin was subjected to
evaluation through batch binding of mentioned metal ion.
Quantitative desorption occurs instantaneously with 0.5 M HNO3.
The sorption capacity was found 4.8 mmol.g-1 of resin for Cu (II) in
the aqueous solution. The chelating resin can be reused for 10 cycles
of sorption-desorption without any significant change in sorption
capacity. A recovery of 99% was obtained the metal ions with 0.5 M
HNO3 as eluting agent. The method was applied for metal ions
determination from industrial waste water sample.
Abstract: The present paper discusses the selection of process
parameters for obtaining optimal nanocrystallites size in the CuOZrO2
catalyst. There are some parameters changing the inorganic
structure which have an influence on the role of hydrolysis and
condensation reaction. A statistical design test method is
implemented in order to optimize the experimental conditions of
CuO-ZrO2 nanoparticles preparation. This method is applied for the
experiments and L16 orthogonal array standard. The crystallites size
is considered as an index. This index will be used for the analysis in
the condition where the parameters vary. The effect of pH, H2O/
precursor molar ratio (R), time and temperature of calcination,
chelating agent and alcohol volume are particularity investigated
among all other parameters. In accordance with the results of
Taguchi, it is found that temperature has the greatest impact on the
particle size. The pH and H2O/ precursor molar ratio have low
influences as compared with temperature. The alcohol volume as
well as the time has almost no effect as compared with all other
parameters. Temperature also has an influence on the morphology
and amorphous structure of zirconia. The optimal conditions are
determined by using Taguchi method. The nanocatalyst is studied by
DTA-TG, XRD, EDS, SEM and TEM. The results of this research
indicate that it is possible to vary the structure, morphology and
properties of the sol-gel by controlling the above-mentioned
parameters.