Biomedical subjects

Teik-Thye Lim

Publications and source records attributed to Teik-Thye Lim.

12 recordsLinked to original sources

PubMed2007

Kinetic and mechanistic examinations of reductive transformation pathways of brominated methanes with nano-scale Fe and Ni/Fe particles.

In this study, carbon tetrabromide (CTB), bromoform (BF) and dibromomethane (DBM) were the target compounds investigated for their reduction kinetics and pathways with nano-scale Fe and Ni/Fe particles synthesized in laboratory. The BET surface areas of these nano-scale particles were around two orders of magnitude higher than that of the commercial micro-scale Fe particles. Batch reduction experiments were carried out with a metal loading of 2.5gl(-1) for the nano-scale particles, and 125gl(-1) for the commercial micro-scale Fe. The nano-scale Ni/Fe was the most reactive for reductive dehalogenation of the brominated methanes. The rates of bromide ion liberated during the reduction of the brominated methanes were usually higher than the disappearance rates of the parent compounds, indicating occurrence of concerted debromination mechanism. Analysis of the reduction kinetics showed that CTB and BF were mainly reduced through hydrogenolysis reaction, while over 76% of DBM was reduced through concerted reductive debromination to methane. Addition of Ni to Fe increased the specific reduction rates of the target compounds and reactive intermediates, but only marginally changed the distribution of their end products. Through comprehensive kinetic and mechanistic examinations of the reduction dehalogenation of various brominated methanes, a scheme summarizing their overall reduction pathways with the nano-scale Fe and Ni/Fe is proposed.

Hydrocarbons, Brominated↗

PubMed2006

Iron-mediated reduction rates and pathways of halogenated methanes with nanoscale Pd/Fe: analysis of linear free energy relationship.

The influence of halogen substitution in chlorinated methanes and brominated methanes on their abiotic reductive dehalogenation with nanoscale Pd/Fe bimetallic particles was investigated in this study. The 0.2% and 1.0% Pd/Fe particles, with particle sizes of less than 100nm, were synthesized in the laboratory. Reduction of the halogenated methanes with the Pd/Fe particles followed pseudo-first-order kinetics. The Pd/Fe bimetallic particles demonstrated at least an order of magnitude higher in reactivity compared to the unpalladized Fe particles of similar particle size. Comparing the 0.2% Pd/Fe and the 1.0% Pd/Fe particles, the latter exhibited higher reduction rates of various halogenated methanes. On the other hand, the reduction rates of chlorinated methanes were consistently lower than those of their brominated counterparts. The compounds with higher number of halogen substitutions were more readily reduced than the lightly halogenated ones. Coupled hydrogenolysis-elimination processes were the important mechanism for complete dehalogenation of the chlorinated and brominated methanes. From the kinetic examination of their transformation rates and mechanistic insight into the associated pathways, an attempt to analyze linear free energy relationship between the observed kinetics and the associated thermodynamic constants was performed. The observed reaction rate constants were analyzed for their correlations with one-electron potential (E(1)), two-electron potential (E(2)), bond dissociation energy (BDE) and the lowest unoccupied molecular orbital (LUMO) energy (E(LUMO)). LUMO energy appeared to be the best descriptor for the kinetic prediction, while E(1) and E(2) might be more suitable for mechanistic analysis.

Environmental Pollutants↗

PubMed2006

Evaluation of kapok (Ceiba pentandra (L.) Gaertn.) as a natural hollow hydrophobic-oleophilic fibrous sorbent for oil spill cleanup.

Oil sorption capacity and hydrophobic-oleophilic characteristics of an agricultural product, kapok (Ceiba pentandra), was thoroughly examined. The kapok fiber has a hollow structure with large lumen. Its performance was compared with that of a polypropylene (PP), a widely used commercial oil sorbent for oil spill cleanup. The oils investigated were diesel, hydraulic oil (AWS46), and engine oil (HD40). Reusability of the kapok after application to various oils was also evaluated. Both loose (at its natural state) and densely packed kapok assemblies were examined. Sorption capacities of the packed kapok assemblies were very much dependent on their packing densities. At 0.02gcm(-3), its oil sorption capacities were 36, 43 and 45gg(-1) for diesel, ASW46 and HD40, respectively. The values decreased to 7.9, 8.1 and 8.6gg(-1) at 0.09gcm(-3). Its sorption capacities for the three oils were significantly higher than those of PP. When the oil-saturated kapok assemblies were allowed to drain, they exhibited high oil retention ability, with less than 8% of the absorbed diesel and HD40, and 12% of the absorbed AWS46 lost even after 1h of dripping. When applied on oil-over-water baths, the kapok exhibited high selectivity for the oils over the water; almost all oils spilled could be removed with the kapok, leaving an invisible oil slick on water. After the 4th cycle of reuse, the reused kapok assembly only lost 30% of its virgin sorption capacity if packed at 0.02gcm(-3), and the loss in sorption capacity was much less at higher packing densities. The hydrophobic-oleophilic characteristics of the kapok fiber could be attributed to its waxy surface, while its large lumen contributed to its excellent oil absorbency and retention capacity.

Absorption↗

PubMed2006

Reductive dechlorination of 1,2,4-trichlorobenzene with palladized nanoscale Fe(zero-valent) particles supported on chitosan and silica.

In this study, nanoscale Pd-Fe particles, with diameters less than 100 nm, were synthesized and dispersed over the chitosan and silica supports. Three different Pd-Fe particles were synthesized, namely 0.1% Pd-Fe, 0.5% Pd-Fe and 1.0% Pd-Fe. SEM images confirmed that the Pd-Fe particles were dispersed over the surface of the supports while SEM-EDX confirmed evenly distribution of Pd over Fe(zero-valent). alpha-Fe(zero-valent) crystallites were identified by means of XRD and observed in TEM. Reductive dechlorinations of 1,2,4-trichlorobenzene (1,2,4-TCB) with the nanoscale Pd-Fe/chitosan and Pd-Fe/silica were carried out in the batch experiment system. Disappearance of the parent species and formation of the reaction intermediates and end product were monitored at discrete times. The results show that the nano-scale Pd-Fe particles were able to completely dechlorinate the chlorinated benzenes within a very short timescale. Complete dechlorinations of 1,2,4-TCB to benzene were achieved within 60 min with the 1.0% Pd-Fe/chitosan and within 100 min with the 1.0% Pd-Fe/silica. Reaction rates were observed to increase with increasing Pd content of the Pd-Fe/support. The reactions apparently followed pseudo-first-order kinetics with respect to the 1,2,4-TCB transformation. A kinetic model is constructed to fit the experimental results for the reactions, enabling identification of the major and minor dechlorination pathways of 1,2,4-TCB. The model suggests that the 1,2,4-TCB transformation mainly followed the primary pathway of direct reductive dechlorination to benzene and secondary pathway of sequential hydrogenolysis to 1,2-dichlorobenzene (1,2-DCB) and then chlorobenzene (CB) or benzene.

Chitosan↗

PubMed2006

In situ oil/water separation using hydrophobic-oleophilic fibrous wall: a lab-scale feasibility study for groundwater cleanup.

Kapok, a natural plant fiber, possesses excellent hydrophobic-oleophilic characteristics. Its innovative use as hydrophobic-oleophilic wall that allows permeation of oil but not water into an oil recovery well is proposed. Its performance was investigated through laboratory experiments, in which diesel was used as the experimental oil. A two-dimensional hydraulic flume was setup to physically model the oil/water separation by the kapok wall. The influences of packing density, kapok wall thickness and oil thickness on the oil recovery rate were examined. The oil permeability of the packed kapok decreased from 0.0165 cm2 at 34 g/L packing density to 0.0038 cm2 at 70 g/L packing density. The kapok wall exhibited complete rejection of water while allowed oil to permeate through. The excellent oil/water separation by the kapok wall was due to surface interaction between the kapok fibers and the oil, which resulted in spontaneous penetration and permeation of the oil through the kapok wall. The oil recovery rate increased with thickness of the oil layer in the feed stream. When the oil thickness exceeded 60 mm, a constant flux of 3.8-5.0, 3.2-3.3 and 2.5-2.7 L/(m2 min) could be achieved by the kapok wall of 55-, 75- and 95-mm thick, respectively, under the natural pressure gradient. The kapok wall could be reused for several wetting/drying cycles, and only lost 27% of its initial oil permeability.

Ceiba↗

PubMed2006

Assessment of the use of spent copper slag for land reclamation.

The shortage of waste landfill space for waste disposal and the high demand for fill materials for land reclamation projects in Singapore have prompted a study on the feasibility of using spent copper slag as fill material in land reclamation. The physical and geotechnical properties of the spent copper slag were first assessed by laboratory tests, including hydraulic conductivity and shear strength tests. The physical and geotechnical properties were compared with those of conventional fill materials such as sands. The potential environmental impacts associated with the use of the spent copper slag for land reclamation were also evaluated by conducting laboratory tests including pH and Eh measurements, batch-leaching tests, acid neutralization capacity determination, and monitoring of long-term dissolution of the material. The spent copper slag was slightly alkaline, with pH 8.4 at a solid : water ratio of 1 : 1. The batch-leaching test results show that the concentrations of the regulated heavy metals leached from the material at pH 5.0 were significantly lower than the maximum concentrations for their toxicity limits referred by US EPA's Toxicity Characteristic Leaching Procedure (TCLP). It was also found that the material is unlikely to cause significant change in the redox condition of the subsurface environment over a long-term period. In terms of physical and geotechnical properties, the spent copper slag is a good fill material. In general, the spent copper slag is suitable to be used as a fill material for land reclamation.

Conservation of Natural Resources↗

PubMed2005

Pathways and kinetics of carbon tetrachloride and chloroform reductions by nano-scale Fe and Fe/Ni particles: comparison with commercial micro-scale Fe and Zn.

Groundwater and wastewater contaminated with chlorinated organic compounds (COCs) can be treated with zero-valent metals. The practicality of this treatment method depends on the reduction rates of the target compounds and their byproducts. In this study, nano-scale Fe and Fe/Ni particles were synthesized so that they could be used to rapidly degrade carbon tetrachloride (CT) and chloroform (CF). Their BET surface areas were around two orders higher than those of commercial micro-scale Fe and Zn particles. Batch reduction experiments carried out with a metal loading of 2.5 gl(-1) showed that complete reduction of CT by the nano-scale Fe/Ni and Fe particles could be achieved within 20 min and 60 min, respectively. With the commercial micro-scale Fe and Zn particles applied at 125 gl(-1), complete CT reduction could only be achieved after 4h and 1.5h, respectively. Reductions of CT and CF with the nano-scale particles followed pseudo-first-order kinetics, and the specific reaction rate constants with the nano-scale Fe/Ni particles were 2-8 times higher than those of the nano-scale Fe particles. CT was degraded through hydrogenolysis to CF, and subsequently via both complete reduction pathway to methane and hydrogenolysis pathway to dichloromethane (DCM). Significantly more methane was generated with the use of the nano-scale Fe/Ni particles than with the nano-scale Fe particles. While the commercial Zn particles were more reactive than the commercial Fe particles, they failed to transform CT directly into methane, causing accumulation of DCM in the aqueous phase.

Carbon Tetrachloride↗

PubMed2005

Selenium extractability from a contaminated fine soil fraction: implication on soil cleanup.

Two batches of fine soil fraction of an acidic soil were deliberately contaminated with selenite (Se(IV)) and selenate (Se(VI)), respectively, and aged for more than 220 days. Speciation analysis using continuous flow-through hydride generation atomic absorption spectrometry (HGAAS) indicated that the species were predominant in their respective aged soils. A selective sequential extraction scheme was employed to fractionate the Se retained in the soils into six fractions of varying retentions. Abilities of various chemical reagents in extracting the Se in the two soil batches were then evaluated. The reagents investigated were sodium salts such as sodium chloride (NaCl), sodium sulfate (Na2SO4), sodium carbonate (Na2CO3), and sodium phosphate (Na3PO4), and two oxidants, namely, hydrogen peroxide (H2O2) and potassium permanganate (KMnO4). It was found that NaCl, Na2SO4, and Na2CO3 could only extract the exchangeable fraction of Se, while Na3PO4 could extract the exchangeable and strongly-bound fractions. Selenate was extracted more than Se(IV) by the salts. The kinetics of Se(IV) extraction by Na3PO4 could be best described by the Elovich model, while the Ritchie second-order model was the most appropriate to describe Se(VI) extraction. Efficiencies of the oxidants in Se(IV) extraction highly depended on their applied dosages. Both H2O2 and KMnO4 were able to extract greater than 93% of total Se, and therefore were significantly more effective than the salts in Se(IV) extraction.

Chemical Fractionation↗

PubMed2005

Process evaluation for optimization of EDTA use and recovery for heavy metal removal from a contaminated soil.

This study aimed to establish an optimized, closed loop application of ethylenediaminetetraacetic acid (EDTA) in heavy metal removals from a contaminated soil through integrating EDTA recovery/regeneration and metal precipitation processes in the treatment train. Three divalent heavy metals were investigated, namely, Pb, Cd, and Ni. The extractability of the metals by EDTA followed the decreasing order of CdPb>>Ni. The first part of this study was to search for the optimal use of the fresh EDTA in removing these heavy metals from the contaminated soil. The second part of this study was devoted to the recovery/regeneration of the spent EDTA which followed the sequential processes involving (1) complex destabilization by adding ferric ion (Fe(III)) to liberate Pb, Cd, and Ni, (2) precipitation of the liberated Pb, Cd, and Ni in phosphate (PO4(3-)) forms, and (3) precipitation of the excess Fe(III) which eventually produced free EDTA for reuse. The process variables were dosages of Fe(III) and PO4(3-), pH and reaction times. Laborious trial experiments would be needed in searching for the optimum conditions for the above processes. To expedite this exercise, a geochemical equilibrium model, MINTEQA2, was used to find the thermodynamically favorable conditions for recoveries of both EDTA and heavy metals. This was then followed by experimental examination of the process kinetics to observe for the optimal reaction time for each thermodynamically favorable process. This study revealed that 2 h of reaction time each for the complex destabilization reaction and the metal phosphate precipitation reaction was sufficient to achieve equilibrium. With the optimized process condition identified in this study, a total of 95%, 89% and 90% of the extracted Pb, Cd and Ni, respectively, could be precipitated from the spent EDTA solution, with 84% EDTA recovery. The reused EDTA maintained more than 90% of its preceding extraction power in each cycle of reuse.

Chelating Agents↗

PubMed2004

Geochemistry of inorganic arsenic and selenium in a tropical soil: effect of reaction time, pH, and competitive anions on arsenic and selenium adsorption.

Factors that can affect As and Se adsorption by soils influence the bioavailability and mobility of these elements in the subsurface. This research attempted to compare the adsorption capacities of As(III), As(V), Se(IV), and Se(VI) on a tropical soil commonly found in Singapore in a single-species system. The effect of reaction time, pH, and competitive anions at different concentrations on the adsorption of both As and Se species were investigated. The As and Se adsorption isotherm were also obtained under different background electrolytes. The batch adsorption experiments showed that the sequence of the As and Se adsorption capacities in the soil was As(V) > Se(IV) > As(III) > Se(VI). The adsorption kinetics could be best described by the Elovich equation. The adsorption of As(V), Se(IV), and Se(VI) appeared to be influenced by the variable pH-dependent charges developed on the soil particle surfaces. Phosphate had more profound effect than SO4(2-) on As and Se adsorption in the soil. The competition between PO4(3-) and As or Se oxyanions on adsorption sites was presumably due to the formation of surface complexes and the surface accumulation or precipitation involving PO4(3-). The thermodynamic adsorption data for As(V) and Se(IV) adsorption followed the Langmuir equation, while the As(III) and Se(VI) adsorption data appeared to be best-represented by the Freundlich equation.

Adsorption↗

PubMedDate not supplied

Contamination time effect on lead and cadmium fractionation in a tropical coastal clay.

The capability of a tropical coastal clay to immobilize lead (Pb) and cadmium (Cd) was investigated in laboratory batch sorption tests conducted under acidic, neutral, and slightly alkaline conditions. The contact time was extended to 65 d. The distribution of Pb and Cd among various sorbed phases was examined using a sequential extraction technique. The sorbed phases were fractionated into the exchangeable, carbonate, reducible, organic, and residual fractions. There were only small changes in the total Pb and Cd sorption beyond a 1-d sorption period. The metal fractionation results show that the amount of Pb and Cd in various fractions changed with sorption time, and the changes were pH-dependent. These changes could be attributed to mineral dissolution and transformation or redistribution of the sorbed phases. Transformation of the sorbed phases resulted in increasing Pb and Cd retention in the more persistent fractions with time, at the expense of reductions in the loosely bound fractions. Nevertheless, Pb and Cd fractionation in the solid phase appeared to reach equilibrium within the 65-d sorption period. These Pb and Cd fractionation results reflect the effect of contamination time on the heavy metal lability and bioavailability in the subsurface environment.

Adsorption↗

PubMedDate not supplied

Significance of aqueous cation composition on heavy metal mobility in a natural clay.

Heavy metal mobility in soils is influenced by various soil variables and environmental factors, including the composition of the soil-aqueous phase. This study used the sequential extraction technique to study how major cations could affect heavy metal sorption and speciation in a natural clay. The sorption of Zn, Pb, and Cd by the soil in the presence of Na+ and Ca2+ and the resulting metal speciation in the sorbed phases were examined. Sorption experiments were performed at pH levels of 3 to 8. Sorptions occurring in both single and multiple heavy metal systems were investigated. The results show that Na+ and Ca2+ significantly inhibited Zn, Pb, and Cd sorption in the acidic pH range only. The reduction in the exchangeable sorption was responsible for a large part of the reduction in the total Zn, Pb, and Cd sorption in the presence of Na+ and Ca2+. Specific adsorptions of heavy metals in other fractions of sorbed phases were only marginally affected by the composition of cations. The reduction in the exchangeable sorption increased with increasing concentration of Na+ and Ca2+. In the presence of a major cation, the competitive adsorption among the heavy metals seemed to have only a minor effect on individual heavy metal sorption.

Adsorption↗