Personal Research Database

? Al Hawari, A. (2004), Biosorption of lead, copper, cadmium and nickel by anaerobic biomass. Ph.D. Thesis, Concordia University, Canada.

Full Text: Thesis\Al Hawari, A.pdf

Abstract: This study will introduce anaerobic granules as a novel type of biosorbent for the removal of lead, copper, cadmium, and nickel from aqueous solutions. The work investigated the equilibrium, batch dynamics and continuous column operation for the biosorption process. Binding capacity experiments using viable biomass revealed a higher value than those for nonviable biomass. Binding capacity experiments using non-viable biomass treated with Ca revealed a high value of metals uptake. The solution initial value affected metal sorption. Time dependency experiments for the metal ions uptake showed that adsorption equilibrium was reached almost 30 minutes after metal addition. It was found that the qmax for Pb²⁺, Cu²⁺, Cd²⁺ and Ni²⁺, were 2.46, 1.74, 1.06 and 0.88 meq/g respectively. The data pertaining to the sorption dependence upon metal ion concentration fitted the Langmiur isotherm model. The kinetics of sorption of Pb²⁺, Cu²⁺, Cd²⁺ and Ni²⁺ were modelled using a pseudo-second order rate equation. Column adsorption studies were performed for Pb²⁺, Cu²⁺, Cd²⁺, and Ni²⁺. The removal of Pb²⁺, Cu²⁺, Cd²⁺, and Ni²⁺ ions from the bed was accompanied by the elution of Ca²⁺ ions from the packed-bed. Ion exchange was identified to be the dominant mechanism for the biosorption of nickel by the anaerobic biomass. For copper and cadmium 77% and 82% of the total amount adsorbed was attributed to ion exchange respectively. 18% and 15% of the total amount adsorbed of copper and cadmium was attributed to the extent of a complexation process competing with the ion exchange one respectively. For the case of Pb ions it was found out that ion exchange was attributed to be almost 50% of the total uptake mechanism. 30% of the total uptake mechanism was attributed to precipitation mechanism. The remaining 20% was attributed to a complexation process competing with the ion exchange and precipitation. The affinity order of anaerobic biomass for the four metals under study has been established as: Pb > Cu > Ni > Cd. The selectivity of the biomass for Pb over the other three metals was well exhibited by the results obtained using the flow-through column.

? Atatürk, M.K. (2004), Investigation of adsorbability of Basic Blue 41 dye by anaerobic and activated sludge biomass. Ms.C. Thesis, Cukurova University, Adana, Turkey.

Full Text: Ataturk, MK

In this study, the adsorption of Basic Blue 41 (BB41) dye onto live activated sludge and anaerobic sludge was investigated. The results showed that both sludge were good adsorbents for BB41 dye, however, it was found that the adsorption capacity of activated sludge (Q_max = 437,0 mg/g) was higher than that of anaerobic sludge (Qmax = 232,6 mg/g). The adsorption isotherms of both adsorbents were described by Freundlich isotherm (activated sludge, R = 0,957, K_f = 11,06, n = 1,285) (anaerobic sludge, R = 0,998, K_f = 3,806, n = 1,209) better than Langmuir isotherm. Kinetics of both adsorption processes was best described by pseudo-second order model. The pseudo isotherms of both adsorption processes were also studied with the help of pseudo second order constants and it was concluded that the real isotherms described the anaerobic sludge/BB41 process better than the pseudo isotherms, but pseudo Freundlich isotherm (R = 0,9714) described the activated sludge/BB41 process better than the real isotherms. The thermodynamic calculations showed that Gibbs free energies of both processes (activated sludge, G = -5,44 kJ/mol, anaerobic sludge, G = -5,33 kJ/mol) have negative values indicating the spontaneous nature of the processes.

Keywords: Biosorption, Kinetics, Pseudo Isotherm, Thermodynamics

? Chen, C.Y. (2004), Characteristics differences of humic acids from lake sediments and uncultivated meountain soils and their sorption of toluene. Ms.C. Thesis, Chaoyang University of Technology, Taiwan

Full Text: Thesis\Chen CY.pdf

? Chao, A.C. (2004), The fabrication of tyrosinase on chitosan using in chemical engineering process. Ph.D. Thesis, National Central University, Taoyuan, Taiwan.

Full Text: Thesis\Chao AC.pdf

Abstract: In this study chitosan was modified to posses carboxyl group via the enzymatical grafting reaction of tyrosinase, or was used to immobilize tyrosinase. The purpose of this thesis was to find applications of these fabricated chitosans using in chemical process. In chapter three, 3,4-dihydroxybenzoic acid, 3,4- dihydroxyphenylacetic acid, and hydrocaffeic acid were used individually as substrates of tyrosinase to graft onto chitosan. The grafting amounts of these phenol derivatives onto chitosan were examined and the modified chitosan were used in experiments on uptake of the cationic dyes crystal violet and bismarck brown Y by a batch adsorption technique. In chapter four, tyrosinase was used to convert phenol to polyquinone, then polyquinone was removed by chitosan beads and tyrosinase was adsorbed by those carboxylly modified chitosan beads. The thermodynamic and kinetic models of tyrosinase adsorbed by modified chitosan were investigated. In chapter five, Chitosan was activated with glutaraldehyde, epichlorohydrin and ethylene glycol diglycidyl ether respectively in order to immobilize tyrosinase for the production of L-dopa from L-tyrosine. The effects of coupling agents and amine capping agents on the operation stability of immobilized tyrosinase were studied. A practical route to immobilize tyrosinase on chitosan for producing L-dopa from L-tyrosine was found. Finally in chapter six, chitosan was used to prepared tyrosinase-based biosensor on glassy carbon electrode for detecting the concentration of phenols. The effect of immobilizing methods, including chitosan gel mixed with enzyme, sandwich entrapped enzyme between two pieces of chitosan films, and covalently bonded enzyme on chitosan films, upon the apparent response of biosensor were studied. A highly stable biosensor was fabricated.

? Courseault, C.R. (2004), A text mining framework linking technical intelligence from publication databases to strategic technology decisions. Ph.D. Thesis, Georgia Institute of Technology.

Full Text: 2004\Courseault, CR.pdf

Abstract: This research developed a comprehensive methodology to quickly monitor key technical intelligence areas, provided a method that cleanses and consolidates information into an understandable, concise picture of topics of interest, thus bridging issues of managing technology and text mining. This research evaluated and altered some existing analysis methods, and developed an overall framework for answering technical intelligence questions. A six-step approach worked through the various stages of the Intelligence and Text Data Mining Processes to address issues that hindered the use of Text Data Mining in the Intelligence Cycle and the actual use of that intelligence in making technology decisions. A questionnaire given to 34 respondents from four different industries identified the information most important to decision-makers as well as clusters of common interests. A bibliometric/text mining tool applied to journal publication databases, profiled technology trends and presented that information in the context of the stated needs from the questionnaire. In addition to identifying the information that is important to decision-makers, this research improved the methods for analyzing information. An algorithm was developed that removed common non-technical terms and delivered at least an 89% precision rate in identifying synonymous terms. Such identifications are important to improving accuracy when mining free text, thus enabling the provision of the more specific information desired by the decision-makers. This level of precision was consistent across five different technology areas in clustering, while portraying the broad relationships as well.

? Fang, Y.C. (2004), Scientific research impact and data mining applications in hydrogeology. Ph.D. Thesis, Ohio State University.

Full Text: 2004\Fang, YC.pdf

Abstract: This dissertation focuses on the use of citation data to evaluate the impactfulness of research in hydrogeology. This study not only explores research impact, but also applies one of the most useful information technologies: data mining techniques on textual data and a practical hydrogeological problem. Following the Schwartz, Fang and Ibaraki (2002) paper in Ground Water, I examined the citation data from ISI in order to check the stability of the bibliometric data and validation of use of this information. I looked at the citation growth patterns of highly-cited papers from the 80s and used that pattern to predict the citation growth for the highly-cited papers in the next decade. This exercise ensures me the use of citation data and gives us an overview of evolution of science in hydrogeology. ‘Innovation’ of the research is another important key to create its impact besides research topics. Water Resources Research papers from 1991 are selected to compare with papers before and follow-on. The most highly cited papers in 1991 appear to be unique in that there are relatively few papers like them that were published previously. Moreover, these papers were sufficiently influential to produce a relatively large number of similar follow-on papers. However, the citation pattern of some classic papers shows that the activities and impact of follow-on papers gradually decline with time. The results of this study reinforce the importance of being a pioneer in a research strand, strategically shifting research strands, adopting strategies that can facilitate really major research shifts. Applications of data mining techniques on two types of data show the advantage of information technology. I evaluated two general strategies and several variants thereof on the one type of database: textual data. The first strategy is based on Naive Bayes, a popular text classification algorithm. The second strategy is based on Principle Direction Divisive Partitioning, an unsupervised document clustering algorithm. While the performance of both approaches is quite good, some of the new variants that I examined including one, which involves a combination of these two approaches yield even better results. The other type of database is digital photo images. Statistics information (texture) of digital images (in grayscale) and spatial information along with measured hydraulic conductivities for some area in the outcrop are important attributes in the database. Self Organizing Maps (SOM) clustering with these attributes is applied to cluster small images extracted from the outcrop along with 122 sampling points and successfully predict the hydraulic conductivities for the whole section of the outcrop.

? Folk, L.C. (2004), A study of the veterinary medical database. Ph.D. Thesis, University of Missouri - Columbia.

Full Text: 2004\Folk, LC.pdf

Abstract: The Veterinary Medical Database (VMDB), originally established by the National Cancer Institute to track cases of veterinary cancer, contains more than six million abstracts of veterinary case records collected over a period of more than forty years. This represents a significant repository of information potentially useful in epidemiologic research and the development of evidence-based standards for veterinary practice. However, the utility of the database is currently diminished by an out-of-date controlled terminology, an antiquated file format, and the absence of a direct user interface. These technical shortcomings constitute an impediment to the effective use of the data already deposited in the database and a barrier to the addition of new records. We analyzed and suggested solutions for each of the VMDB’s three problems. We examined the controlled terminology currently in use and experimentally demonstrated the feasibility of mapping it to an up-to-date nomenclature. We examined the current file format and developed a modern relational alternative designed to facilitate query access to the data. We examined the interface by which users’ query requests currently are fulfilled, experimentally assessed the current users’ query requirements, and proposed modifications to the current interface to enhance its usefulness to its users. Finally, we used bibliometric techniques to assess the extent to which the VMDB has contributed to scientific and public knowledge during its existence. We discovered a small but influential body of published research based upon VMDB data and a surprisingly wide-spread public awareness of the database.

? Huang, F.C. (2004), The effects of soil structure and chemical properties on the adsorption/desorption of volatile organic compounds. Ph.D. Thesis, National Central University, Taoyuan, Taiwan.

Full Text: Thesis\Huang, FC.pdf

Abstract: The effects of soil structure and chemical properties on the adsorption/desorption of volatile organic compounds were evaluated. The migration and the fates of nonionic organic compounds in soils are found to be highly depended on their vapor-phase sorptive behavior. However, it is difficult to explicit the mechanism of adsorption/desorption due to the complexity of environmental medium.

Vapor-phase adsorption/desorption isotherms of water, benzene, hexane, and cyclohexane on dry soil with different soil organic matters, such as Ca-montmorillonite, Ti-montmorillonite, Shamon Mountain Soil and Florida Peat, were gravimetrically measured under 15¢XC, 20¢XC and 25¢XC. The surface area, pore structure, and adsorption/desorption characteristic were analyzed to show the soil structure and chemical properties effect on the adsorption/desorption of VOCs.

After exchanged with metal cations, the porous structure of the soil mineral fraction was significanting changed. The results demonstrate that Ti-montmorillnite possess higher surface area, extensive pore size distribution, and better pore connection. Both the surface area and the pore structure of soil were characterized based on the classical and fractal analyses of the nitrogen adsorption isotherms. The surface fractal dimension D was calculated from their nitrogen isotherms using the fractal version of FHH (Frenkel-Halsay-Hill) equation. The results revealed that a smaller metal cation on the clay may slightly increase D values as a result of the increase in the BET surface area and the decrease in the pore size.

The adsorption capacity of Florida Peat is greater than that of the Shamon Mountain Soil for the sorption of water and benzene, owing to the Florida Peat contains aromatic groups. Conversely, the mineral fraction was significant for aliphatic compounds, and the soil organic matter was quite significant for aromatic compounds. The steric structure of molecular effect on VOCs adsorption for soil, following the order Gthe plane form-benzene Öthe chain form-hexane Öthe chair form-cyclohexane.

The experimental data were examined by the four sorption kinetic model Gthe pseudo-first order equation, the pseudo-second order equation, the intraparticle diffusion model and the Elovich rate equation. According to the sum of the errors squared (SSE), it showed that the intraparticle diffusion model fitted the data well, and the Elovich rate equation fitted the Florida Peat data well at relatively high pressure.

Keywords: Montmorillnite, Adsorption/Desorption, Isotherm, Peat

? Chang, Y.C. (2004), Preparation and applications of chitosan-coated multifunctional magnetic nano-carrier. Ph.D. Thesis, National Cheng Kung University, Tainan, Taiwan.

Full Text: Chang, YC

Abstract: This dissertation concerns the preparation of chitosan-coated multifunctional iron oxide magnetic nanoparticles and their uses as the magnetic nano-adsorbent, the magnetically manipulated catalyst carrier, and the magnetic targeting carrier for drugs.

The chitosan-coated iron oxide nanoparticles were prepared by the carboxymethylation of chitosan and the followed covalently binding on the surface of iron oxide nanoparticles via carbodiimide activation. Transmission electron microscopy (TEM) micrograph and dynamic light scattering (DLS) measurement showed that the chitosan-coated iron oxide nanoparticles were monodisperse with a mean core diameter of 13.5 nm and a mean hydrodynamic diameter of 17.1 nm. X-ray diffraction (XRD) patterns indicated the iron oxide nanoparticles were pure Fe₃O₄ with a spinel structure, and the binding of chitosan did not result in the phase change. In addition, the magnetic measurement revealed that they were superparamagnetic with a saturation magnetization of 63.2 emu/g, a remanent magnetization of 0.83 emu/g, a coercivity of 8.3 Oe, and a squareness of 0.013. The covalently binding of chitosan onto the surface of iron oxide nanoparticles was demonstrated by FTIR analysis and the measurement of zeta potential. The weight percentage of chitosan bound onto Fe₃O₄ nanoparticles was about 4.92 wt%, and the isoelectric point of the product was 5.95.

For the study on the use of the chitosan-coated iron oxide nanoparticles as a novel magnetic nano-adsorbent, its capability for the adsorption of metal cations, metal anions, and acid dyes from the aqueous solutions via chelating and/or anion exchange mechanism was examined. The results showed the adsorption capacity was quite high and the time required to reach the equilibrium was significantly shorter than those for the micro-sized adsorbents due to the high specific surface area and the absence of pore diffusion resistance. Moreover, the adsorption of Cu²⁺ ions, AuCl₄^- ions, and acid dyes AO12 and AG25 all obeyed the Langmuir equation, and the adsorption kinetics of AuCl₄^- ions and acid dyes revealed both the adsorption processes obeyed the pseudo-second-order kinetic model. Thus, the chitosan-coated iron oxide nanoparticles as a magnetic nano-adsorbent not only could be magnetically manipulated but also possessed the advantages of fast adsorption and high adsorption capacity. They are expected to be efficiently applied in separation processes.

The study on the use of the chitosan-coated iron oxide nanoparticles as a novel magnetically manipulated catalyst carrier, Cu²⁺ ions were adsorbed and their ability for the catalytic hydrolysis of bis(4-nitrophenyl) phosphate (BNPP) was examined. In addition, AuCl₄^- ions were adsorbed and reduced into Au nanoparticles. Their ability for the catalytic reduction of aromatic nitro compounds was investigated. The results showed both the Cu²⁺ ions and Au nanoparticles, adsorbed and supported chitosan-coated magnetic carriers respectively, exhibited high catalytic activities. Also, high catalytic activities retained after being reused and magnetically recovery several times, revealing the catalyst carrier had high stability. So, the chitosan-coated iron oxide nanoparticles could be used as a good catalyst carrier which could be magnetically manipulated and applied in catalytic reaction processes.

For the study on the use of the chitosan-coated iron oxide nanoparticles as a novel magnetic targeting carrier for drugs, the anti-cancer drug epirubicin was adsorbed and the in vitro anti-cancer efficacy of the conjugate was evaluated. The adsorption study indicated that the conjugate was stable at pH 3-7 and 25-40˚C and a high epirubicin loading could be achieved. The desorption kinetics showed that about 80% epirubicin released from the chitosan-coated magnetic carrier after 150 and 300 min in serum and 0.03 M phosphate buffer, respectively. In vitro cytotoxicity evaluation revealed that the epirubicin-loaded magnetic conjugate was able to exhibit comparable efficacy as free epirubicin did alone. Because of the combined functions of magnetic targeting Bdrug therapy, and MRI diagnosis, the chitosan-coated iron oxide nanoparticles will be quite useful in the field of biomedicine.

? Chao, A.C. (2004), The fabrication of tyrosinase on chitosan using in chemical engineering process. Ph.D. Thesis, National Central University, Taoyuan, Taiwan.

Full Text: Thesis\Chao, AC.pdf

Abstract: In this study chitosan was modified to posses carboxyl group via the enzymatical grafting reaction of tyrosinase, or was used to immobilize tyrosinase. The purpose of this thesis was to find applications of these fabricated chitosans using in chemical process. In chapter three, 3,4-dihydroxybenzoic acid, 3,4-dihydroxyphenylacetic acid, and hydrocaffeic acid were used individually as substrates of tyrosinase to graft onto chitosan. The grafting amounts of these phenol derivatives onto chitosan were examined and the modified chitosan were used in experiments on uptake of the cationic dyes crystal violet and Bismarck brown Y by a batch adsorption technique. In chapter four, tyrosinase was used to convert phenol to polyquinone, then polyquinone was removed by chitosan beads and tyrosinase was adsorbed by those carboxylly modified chitosan beads. The thermodynamic and kinetic models of tyrosinase adsorbed by modified chitosan were investigated. In chapter five, Chitosan was activated with glutaraldehyde, epichlorohydrin and ethylene glycol diglycidyl ether respectively in order to immobilize tyrosinase for the production of L-dopa from L-tyrosine. The effects of coupling agents and amine capping agents on the operation stability of immobilized tyrosinase were studied. A practical route to immobilize tyrosinase on chitosan for producing L-dopa from L-tyrosine was found. Finally in chapter six, chitosan was used to prepared tyrosinase-based biosensor on glassy carbon electrode for detecting the concentration of phenols. The effect of immobilizing methods, including chitosan gel mixed with enzyme, sandwich entrapped enzyme between two pieces of chitosan films, and covalently bonded enzyme on chitosan films, upon the apparent response of biosensor were studied. A highly stable biosensor was fabricated.

? Huang, C.T. (2004), Removal of lead ions from aqueous solution by using tree fern. M.Sc. Thesis, Taipei Medical University, Taiwan.

Full Text: Huang, CT

? Liu, J.Y. (2004), Removal of arsenic from water by chemical modified chitosan. M.Sc. Thesis, National Yunlin University of Science and Technology, Yunlin, Taiwan.

Full Text: Liu, JY

Abstract: The aim of this thesis was to study the removal of arsenic from water by chemical modification chitosan beads. Two types of chitosan beads, including uncrosslinked and crosslinked were prepared. Both beads were modified by impregnation with molybdate solution. A SEM was utilized to observe the surface structure of chitosan beads. An FTIR was used to conform crosslinking reaction. The equilibrium adsoption and kinetic experiments were conducted to gain the optimal pH value of arsenate solution by batch experimental process. The parameters such as the chitosan concentration, crosslinking agent concentration, crosslinking time and pH of solutions, were investigated.

The adsorption capacities of arsenic were 1.95 mgAs(III)g^-1, 5.853 mgAs(V)g^-1 on uncrosslinking chitosan beads. For crosslinking chitosan beads, the adsorption amounts were 0.931mg As(III)g^-1, 5.115mg As(V)g^-1. After chemical modification, the adsorption capacities increase to 2.746 mg As(III)g^-1, 9. 5425 mg As(V)g^-1, and 2.44 mg As(III)g^-1, 7.635mg As(V)g^-1 for uncrosslinking and crosslinking chitosan beads, respectively. The experimental equilibrium data fitted the Langmuir model well. The pseudo second order kinetic model was found to fit the kinetic experimental data. The regeneration process was performed by hydrochloric acid or phosphoric acid to desorb arsenic from chitosan beads. It was found that chitosan beads still have high adsorption capacity after five cycles of adsorption-desorption processes. The experimental results showed the impregnated molybdate chitosan beads were promised to remove arsenic from water.

? Lin, P.H. (2004), Adsorption of fluoride onto commercial activated alumina and novel magnetic fluoride selective nano-adsorbents from aqueous solutions. M.Sc. Thesis, National Taiwan University, Taiwan.

Full Text: Lin, PH

Abstract: The adsorption process applied in the removal of fluoride from aqueous solutions was investigated in this study. Commercial activated alumina (γ-Al₂O₃) and two novel magnetic alumina adsorbents, which were synthesized by precipitation method (MAP) and sol-gel method (MASG), were used as the alumina-type adsorbents. The physicochemical characteristics of three adsorbents and factors affecting the adsorption equilibrium and kinetics were further examined in this study.
The Langmuir and Freundlich isotherms were successfully used to predict the adsorption behavior of fluoride ontoγ-Al₂O₃, MAP, and MASG, in which the monolayer adsorption capacity (qL) of MASG is the highest among three adsorbents. Furthermore, the linear isotherm also well described the adsorption behavior of fluoride onto both novel magnetic nano-adsorbents, MAP and MASG. Therefore, the novel magnetic nano-adsorbents, which were prepared by Fe₃O₄ coated with SiO₂ and sequentially synthesized by means of precipitation and sol-gel methods in this study, can successfully be applied in the removal of fluoride from solutions. Regarding the adsorption kinetics of fluoride from solutions, among the tested kinetics models in this study (e.g. pseudo-first-order equation, pseudo-second-order equation and Elovich rate equation), both the pseudo-second-order equation and Elovich rate equation can well predict the adsorption kinetics of fluoride onto MASG in CFSTR.

The removal of fluoride by commercial Al₂O₃ was also carried out in the fixed-bed adsorber. The optimal operating conditions were the pH value of 4 for the fed fluoride solution, the regeneration agent (NaOH) of 0.01 N, and the neutralization pH of 4 by means of 3.16×10^-4 N HNO₃. Under the optimal conditions, the removal efficiency of fluoride from solutions was not reduced for at least fourteen runs. In addition, the fluoride adsorption capacity increased with decreasing pH of fluoride solution and can be divided into two parts: adsorbed by alumina and by aluminum hydroxide, in which the former might be the major mechanism in the whole adsorption process and the latter mainly influenced the adsorption in the plateau area.

The main composition and pH value of the aged scrubbing solution in the semiconductor manufacturing industries are fluoride of 40 ~ 60 mg/L, and 3.6, respectively. Therefore, on the basis of the data obtained from this study it is deduced that Al₂O₃, MAP and MASG possess high potential as the adsorbents for the application of adsorption process in the defluoridation from aged scrubbing solution.

? Wang, H.C. (2004), Adsorption of fluoride, chloride, bromide, sulfate and nitrate onto commercial and superparamagnetic activated alumina from aqueous solutions. M.Sc. Thesis, National Taiwan University, Taiwan.

Full Text: Wang, HC

Abstract: The main species of the aged scrubbing solution in the semiconductor manufacturing industries are F^-, Cl^-, Br^-, NO₃^- and SO₄^2- with concentrations of about 54, 2.2, 1.5, 10 and 2 mg/L respectively. The pH value of the solution is about 3.6. Therefore, on the basis of the results obtained from Lin (2004), the adsorption process applied in the removal of anions, including F^-, Cl^-, Br^-, NO₃^- and SO₄^2-, from the synthesized aqueous solutions was investigated in this study.

Commercial activated alumina activated using 0.01 N NaOH followed by 3.16×10^-4 N HNO₃ (noted as γ-Al₂O₃-N) or HClO₄ (denoted as γ-Al₂O₃-P) and modified magnetic alumina adsorbent, which was synthesized employing sol-gel method (called as MMASG), were used as the alumina-type adsorbents. The physicochemical characteristics of two adsorbents and factors affecting the adsorption equilibrium and kinetics were further examined in the study.

The Langmuir and Freundlich isotherms were successfully used to predict the adsorption equilibrium behavior of the target anions onto γ-Al₂O₃-N and MMASG. The monolayer equilibrium adsorption capacity (qL) of MMASG is higher than that of γ-Al₂O₃-N. Besides, MMASG which was prepared by Fe₃O₄ coated with SiO₂ and sequentially synthesized by sol-gel method in this study, can properly be applied in the removal of the said anions from solutions.

Regarding the adsorption kinetics of the target anions from solutions, among the kinetic models tested (e.g. pseudo-first-order equation, pseudo-second-order equation and Elovich rate equation), both the pseudo-second-order equation and Elovich rate equation can well predict the adsorption kinetics of the said anions onto γ-Al₂O₃-P and MMASG in a completely stirred tank reactor (CSTR).

The removal of anions by the commercial activated Al₂O₃-P was also carried out in a fixed-bed adsorber. The operating conditions were at pH value of 4 with various inlet concentrations for the fed anionic solutions. In addition, the adsorption patterns of anions can be divided into two types: inner-sphere (‘chemical bond’) adsorption, such as F^- and SO₄^2-, and outer-sphere complex (ion pair) adsorption, such as Cl^-, Br^- and NO₃^-. Besides, Yoon and Nelson equation for breakthrough modeling can well predict the adsorption kinetics of anions ontoγ-Al₂O₃-P in a fixed-bed adsorber.

This study takes into account for the practical data of the aged scrubbing solution in the semiconductor manufacturing industries. The results indicate that γ-Al₂O₃-P and MMASG possess proper potential as the adsorbents for the application of adsorption process in the defluoridation from aged scrubbing solution. As for the weak anions such as Cl^-, Br^- and NO₃^-, the applicabilities of theγ-Al₂O₃-P and MMASG are moderate.

? Chin, Y.C. (2005), Arsenic adsorption using citrate/Fe(III), silicate/Fe(III) synthetic iron oxides. M.Sc. Thesis, National Sun Yat-sen University, Kaohsiung, Taiwan.

Full Text: Chin, YC

Abstract: This study is to probe into the surface characteristics, crystalline identification and inner structural changes of the synthetic iron oxides which are synthesized from pure Fe(III), citrate/Fe(III) and silicate/Fe(III) solutions at different MRs respectively. This study is also to compare the adsorption capabilities of these synthetic iron oxides serving as the adsorptive materials in containing arsenic wastewater through adsorption experiments. By means of the XRD identification analysis, the synthetic iron oxides of pure Fe(III) and silicate/Fe(III) are non-crystal ferrihydrite, but the synthetic iron oxide of citrate/Fe(III) is crystal magnetite with magnetism. By means of IR spectrum analysis and comparison with the IR spectrum of iron mineral, the FTIR spectrum of pure Fe(III) and silicate/Fe(III) synthetic iron oxide are similar to that of ferrihydrite; The FTIR spectrum of citrate/Fe(III) synthetic iron oxide is similar to that of magnetite. The degree of pore volume and surface area for synthetic iron oxides are as follows: silicate/Fe(III) > Fe(III) > citrate/Fe(III). With the citrate/Fe(III) MRs increasing, the pore volume and surface area of synthetic iron oxide will decrease. However, with the silicate/Fe(III) MRs increasing, the pore volume and surface area of synthetic iron oxide do not make great difference. Results of kinetic adsorption experiments show that the synthetic iron oxides of citrate/Fe(Ⅲ) or silicate/Fe(III) at different MRs will adsorb arsenic better at low pH. With the pseudo-first order and the second order kinetic adsorption model to simulate the adsorption experiment data, the results show that the simulation results are consistent with the pseudo-second order kinetic adsorption model. The equilibrium adsorption experiments show that the adsorption capacity of arsenic for synthetic iron oxides is as follows: citrate/Fe(III) > Fe(III) > silicate/Fe(III), and that the adsorption capacity will decrease with the pH increasing.

? Čivilienė, L. (2005), Kinetics and equilibrium adsorption of dye on crabs chitin and chitosan. Ph.D. Thesis, Vilnius Pedagogical University, Vilnius, Lithuania.

Full Text: Civiliene L

Abstract: Chitin, chitosan recovered from fly crabs shells have been investigated by the elemental analysis, potentiometric titraton and FT–IR spectrometry methods. The molecular weght of chitosan was determined by measuring their viscosity.

The adsorption kinetics of reactive dye and equilibrium conditions has been investigated.

The adsorption of reactive dye on chitin and chitosan proceeds according to pseudo – second – order kinetic equation.

Adsorption investigations under equilibrium conditions showed that. Theses results were fitted by both Langmuir and Freudlich models.

? Fiol Santaló, N. (2005), Aprofitament de residus vegetals per a la concentració I separació d’ions metàl lics de solucions aquoses. Ph.D. Thesis, Universitat de Girona, Girona, Span.

Full Text: Thesis\Fiol Santalo, N.pdf, Thesis\Fiol Santalo, N-1.pdf, Thesis\Fiol Santalo, N-2.pdf, Thesis\Fiol Santalo, N-3.pdf, Thesis\Fiol Santalo, N-4.pdf

Abstract: Adsorption with activated carbon is a usual treatment to remove metals from wastewater. In order to reduce the cost of the treatment, several studies have been carried out to evaluate the use of low cost sorbents as an alternative to conventional sorbents used in wastewater treatment. In this work, the use of different vegetable wastes from agricultural or industrial processes has been evaluated as sorbents for metal removal from aqueous solutions. The aim of this work was to study first, the usefulness of olive stones as a sorbent for divalent metals such as Cd(II), Cu(II), Ni(II) and Pb(II) from aqueous solutions and then the use of four vegetable wastes (yohimbe bark, grape stalks, cork and olive stones) for the removal of Cr(VI) from aqueous solutions. The vegetable waste powder was encapsulated in calcium alginate to obtain spherical gel beads that were used in continuous flow process for Cr(VI) removal.

In all sorption experiments, kinetic data were modeled by the pseudo-second order kinetic equation and determine the constants sorption rates. Langmuir and Freundlich model isotherms were use to describe sorption equilibrium data and to obtain the isotherm parameters. In binary mixtures, the extended Langmuir isotherm model was used. The results showed that olive stones are a good sorbent for studied divalent metal. Metal uptake was pH dependent and the presence of salts in solution provokes a decrease in metal uptake. A clear competence between metals to be adsorbed on the waste was observed in metal binary mixtures. Although results obtained in Cr(VI) removal studies show that the four studied wastes can adsorb Cr(VI), grape stalks and yohimbe bark wastes showed the best chromium sorption capacity. X-Ray Photoelectron Spectroscopy analysis on grape stalks and yohimbe chromium loaded samples put into evidence that both Cr(VI) and Cr(III) were sorbed on wastes surface indicating that Cr(VI) sorption process involves a redox reaction.

The gel beads obtained when encapsulating grape stalks in calcium alginate showed a significant increase in Cr(VI) sorption capacity compared to the original grape stalks waste. A diffusion model was used to analyze the experimental data and to determine the diffusion coefficient for Cr(VI) sorption by beads containing different percentage of grape stalks encapsulated in calcium alginate.

Finally, preliminary studies of Cr(VI) removal in continuous flow using the beads containing grape stalks powder gel in laboratory columns have been carried out. The effect of operating parameters such as feed metal concentration, flow rate and bed depth was studied. The mass transfer and diffusion model used to describe column data showed the effect of feed metal concentration and flow rate in both, diffusion and mass transfer coefficients, respectively. The bed depth service time model (BDST) failed in predicting the service time when changing operating parameters due to the complexity of the sorption process. With these preliminary column experiments we established the basis for Cr(VI) sorption by the proposed sorbent in continuous flow process for further development of the process to be used in higher scale columns.

? Lin, H.Y. (2005), Investigation on adsorption of vapor-phase mercury chloride on powdered activated carbon derived from recycled waste. Ph.D. Thesis, National Sun Yat-sen University, Kaohsiung, Taiwan.

Full Text: Thesis\Lin, HY.pdf

Abstract: This study investigated the production of powdered activated carbon derived from carbon black of pyrolyzed waste tires, and their adsorptive capacity on vapor-phase mercury chloride (HgCl₂) using both adsorption column and thermogravimetric adsorption systems. The adsorption isotherms and kinetic models were further simulated in the study. In addition, an innovative compositive impregnation process was developed to increase the sulfur content of powdered activated carbon derived from waste tires.

The activation of carbon black to form powdered activated carbon was performed in a tubular oven. The operating parameters including activation temperatures, activation time, and water feed rates were investigated in this study. Experimental results indicated that the yield of carbon-black derived powdered activated carbon (CBPAC) decreased with the increase of activation temperature, activation time, and water feed rate, while the BET surface area and pore volume decreased. In the comparison of activation time and water feed rate in the activation process, activation time had an important impact on the production of specific surface area than water feed rate. The optimal operating parameters included activation temperature of 900C, activation time of 180min, water feed rate of 0.5 mLH₂O/gC-sec, and water injection behind activation process of 17.5 min.

From the analysis of carbon surface, the carbon contents of powdered carbon black (PCB), CBPAC, commercial powdered activated carbon (CPAC) were 89.5%, 87.6%, and 88%, respectively. The C (1s) peak region of PCB consisted of 49.8% C-C, 38.9% C-O, 10.5% C=O or O-C-O. Similar analysis results showed that the total area of the C (1s) peak region of CBPAC consisted of 57.5% C-C, 26.8% C-O, 8.1% C=O or O-C-O, and 7.6% O-C=O. Similar to CPAC, the C (1s) peak region consisted of 42.6% C-C, 41.8% C-O, and 15.6% O-C=O. Furthermore, the sulfur contents of PCB and CBPAC were both 0.5%. The S (2p) peak region of PCB consisted of 58.9% ZnS (zinc sulfide) and 41.1% S=C=S. For CBPAC, the S (2p) peak region solely contained S=C=S.

The comparison of two sulfur impregnation processes revealed that the innovative compositive impregnation process could simultaneously increased the sulfur content and the BET surface area of powdered activated carbon (PAC), however, the direct impregnation process increased the sulfur content while the BET surface area of PAC decreased linearly. Without the disadvantages of time and energy consumption associated with direct impregnation, the compositive impregnation is an efficient and energy-saving process for producing sulfurized PAC with a high BET surface area and high sulfur content.

Experimental results obtained from the adsorption column tests indicated that the influence of the adsorption depth on the adsorptive capacity of CBPAC did not vary much, while the adsorptive capacity of CBPAC increased with HgCl₂ concentration. Furthermore, the adsorptive capacity of CBPAC on vapor-phase HgCl₂ was less than that of CPAC at the adsorption temperatures of 25~150C and high humidity of 12.3 wt %. The difference of adsorptive capacity for CBPAC and CPAC correlated closely with BET surface area and sulfur content.

Results form the thermogravimetric adsorption analysis indicated that the adsorptive capacity of CBPAC and initial adsorption rate on vapor-phase HgCl₂ increased with HgCl₂ concentration and decreased with adsorption temperature. In the kinetic modeling, the deviation of experimental and simulated values simulated by the pseudo-first-order model was lower than those of pseudo-second-order models. Furthermore, the r (correlation coefficient) of pseudo-first-order and pseudo-second-order models were 0.9745~0.9977 and 0.9217~0.9780, respectively. It suggested that the pseudo-first-order model could simulate the adsorption of HgCl₂ onto CBPAC better than pseudo-second-order model.

? Lin, P.H. (2005), Adsorption of fluoride, chloride, bromide, sulfate and nitrate onto commercial and superparamagnetic activated alumina from aqueous solutions. M.Sc. Thesis, National Taiwan University, Taiwan.

Full Text: Lin, PH

Abstract: The adsorption process applied in the removal of fluoride from aqueous solutions was investigated in this study. Commercial activated alumina (γ-Al₂O₃) and two novel magnetic alumina adsorbents, which were synthesized by precipitation method (MAP) and sol-gel method (MASG), were used as the alumina-type adsorbents. The physicochemical characteristics of three adsorbents and factors affecting the adsorption equilibrium and kinetics were further examined in this study.

The Langmuir and Freundlich isotherms were successfully used to predict the adsorption behavior of fluoride onto γ-Al₂O₃, MAP, and MASG, in which the monolayer adsorption capacity (qL) of MASG is the highest among three adsorbents. Furthermore, the linear isotherm also well described the adsorption behavior of fluoride onto both novel magnetic nano-adsorbents, MAP and MASG. Therefore, the novel magnetic nano-adsorbents, which were prepared by Fe₃O₄ coated with SiO₂ and sequentially synthesized by means of precipitation and sol-gel methods in this study, can successfully be applied in the removal of fluoride from solutions. Regarding the adsorption kinetics of fluoride from solutions, among the tested kinetics models in this study (e.g. pseudo-first-order equation, pseudo-second-order equation and Elovich rate equation), both the pseudo-second-order equation and Elovich rate equation can well predict the adsorption kinetics of fluoride onto MASG in CFSTR.

The removal of fluoride by commercial Al₂O₃ was also carried out in the fixed-bed adsorber. The optimal operating conditions were the pH value of 4 for the fed fluoride solution, the regeneration agent (NaOH) of 0.01 N, and the neutralization pH of 4 by means of 3.16×10^-4 N HNO₃. Under the optimal conditions, the removal efficiency of fluoride from solutions was not reduced for at least fourteen runs. In addition, the fluoride adsorption capacity increased with decreasing pH of fluoride solution and can be divided into two parts: adsorbed by alumina and by aluminum hydroxide, in which the former might be the major mechanism in the whole adsorption process and the latter mainly influenced the adsorption in the plateau area.

The main composition and pH value of the aged scrubbing solution in the semiconductor manufacturing industries are fluoride of 40~ 60 mg/L, and 3.6, respectively. Therefore, on the basis of the data obtained from this study it is deduced that Al₂O₃, MAP and MASG possess high potential as the adsorbents for the application of adsorption process in the defluoridation from aged scrubbing solution.

? Liu, C.W. (2005), Hexavalent chromium removal by zerovalent iron. M.Sc. Thesis, National Taiwan University, Taiwan.

Full Text: Liu CW

Abstract: Chromium is a common pollutant in groundwater in industrial region because it is a raw material which is often used by many industries. Zero valent iron has been widely used in remediation of groundwater pollution. The potential for using zero valent iron to treat chromium pollution in situ has been concerned in recent years. The surface area and the passivity of the passive film on the iron surface are very important factors for chromium removal by zero valent iron. The surface area for nanolized iron is much larger and the passive film for nanolized iron is much thinner than that for commercial powder iron. Therefore, the chromium removal rate in nanolized iron system should be much higher than that in commercial powder iron system. The efficiencies of chromium removal in nanolized iron and commercial powder iron (J. T. Baker) systems were compared in this work.

Three factors, co-existing anions (Cl^-, SO₄^2-, NO₃^-, ClO₄^- and PO₄^3-), initial pH and temperature affected on chromium removal were investigated in commercial powder iron system. The same factors except the temperature were investigated in nanolized iron system. The kinetics of the chromium removal reaction was also examined in this study.

The results show that the existence of chloride and sulfate ions can increase the rate of chromium removal by zero valent iron in commercial powder iron system. Otherwise existence of the phosphate, perchloride and nitrate ions can reduce the rate of chromium removal by zero valent iron in commercial powder iron system. However, in nanolized iron system, the influences of chloride, sulfate, nitrate and perchloride ions on chromium removal rate were very relatively insignificant. But the existence of phosphate ion can still decrease the chromium removal rate.

The chromium removal per unit weight of iron in nonalized iron system was much larger than that in commercial powder iron system. This phenomenon indicates the destruction of passive film is the rate-determining step for chromium removal by zero valent iron in commercial powder iron system but is not in nonalized iron system.

Both the removal rate of chromium decreased when the initial pH of chromium is higher. As chromium involves chloride, the kinetic of chromium removal by commercial powder iron follows pseudo-first-order reaction. But in the nanolized iron system, the kinetic follows pseudo-second-order. The chromium removal rate increased with the increase of temperature.

Keywords: Chromium, Commercial Powder Iron, Nanolized Iron, pH, Kinetic

? Lorenc-Grabowska, E. (2005), Adsorption of organic compounds from aqueous solution on activated carbons. Ph.D. Thesis, Politechnika Wroclawska, Poland.

Full Text: Lorenc-Grabowska, E

Abstract: In this work the influence of porous texture and the surface chemistry of activated carbons (ACs) on the adsorption process of selected organic compounds that represent typical water contaminations was studied. The first part of this work deals with preparation of mesoporous activated carbons and the modification of surface of microporous ACs. The second part describes the adsorption of humic acids, vitamin B₁₂, Congo Red, 2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol and 4-nitrophenol on selected carbons. For efficient removing humic acids, Vitamin B₁₂ and Congo Red, the ACs with developed mesopores structure are required. A number of mesoporous activated carbons were prepared by carbonization and subsequent steam activation of doped flame coal (subA) and gas coal (hvBb). The two different pretreatments such as impregnation with yttrium, cerium and titanium oxide acetyloacetonate and loading of the calcium exchanged coal with iron by ion-exchange process were performed to modify the coals. To obtain materials with different surface properties the commercial activated carbon was modified by different chemical and thermal treatment. The activated carbon was oxidized with 40% HNO₃ and 20% H ₂O₂, treated with HCl and HF. The starting carbon was also heated in the atmosphere of NH₃ (450°C) and N₂ (800°C). The adsorption tests were carried out in static conditions. At first the equilibrium time was estimated for a given adsorptive/ACs system. The kinetics of adsorption process have been analysed by three kinetic model, the pseudo first order model, a pseudo second order model and intraparticle diffusion model. The Langmuir and Freundlich models were applied to analyse adsorption isotherms. For Congo Red, an influence of ionic strength of solution on the extent of adsorption on ACs was studied. An effect of solution pH was studied in the case of humic acid adsorption.

? Lussky, J.P. (2005), Bibliometric patterns in an historical medical index: Using the newly digitized ‘Index Catalogue of the Library of the Surgeon General’s Office, United States Army’. Ph.D. Thesis, Drexel University.

Full Text: Thesis\Lussky, JP.pdf

Abstract: The newly digitized Index Catalogue of the Library of the Surgeon-General’s Office, United States Army (IndexCat) provides powerful opportunities for the application of bibliometric techniques to support research in the history of medicine. It far exceeds any other medical bibliographic tool in its total number of documents indexed, span of decades represented in the publication dates of the indexed documents, international inclusiveness, and breadth of subject indexing. The work presented here will explore the viability of the IndexCat as a dataset for bibliometric research and as an adjunct to contemporary, qualitative research on the history of medicine. A bibliometric analysis of the subject headings and title words within the IndexCat demonstrates that they can be combined to link developing theories of disease causation with developing understandings of specific diseases. Furthermore, these bibliometric patterns compliment and enrich contemporary, historical accounts of the research on specific diseases.

? Ma, J.H. (2005), Evaluation of output of chemical research in china by bibliometric methods. Ph.D. Thesis, Peking University, Bejing, China.

Full Text: Ma, JH

Abstract: Science and technology are playing very important roles in promoting the development of society. More and more people have realized that science and technology have strong relations with economical development, security of country, and international competition. Many countries have put S&T in the priority position and give a great deal of support of human, material and financial resources. However, with the contradiction between the demands of S&T and the limited resources, the evaluation of S&T is inevitable. Reasonable and effective S&T assessment system is very essential in inspiring researchers, building up innovative environment, and promoting the formation of national innovative systems. Bibliometrics is a quantitative method and has been used widely in S&T evaluation. Chemistry is a major scientific field and is chosen as an exploration in assessment of output of scientific field. By combining several methods such as bibliometrics, questionnaire of peer review, comprehensive analysis and comparative analysis, the research is focused on the productivity, international impact or visibility and innovative ability of chemical research in China. The main research is conducted in following aspects: time sequence distribution of journal article in chemistry and international comparison, average impact of journal article in ISI database, dynamic impact in past ten years, the position of Chinese institutions in chemical research, the contribution of Chinese chemists in highly cited papers, patent output in chemistry and metallurgy.The results show that productivity and impact of Chinese chemical research are growing rapidly, but the problems are very severe. Academic institutions and state institutes are key force in producing high quality papers. Chemistry is relatively strong in comparison with other scientific fields in China. Original creativity is very limited. There is a great lack of outstanding or influential chemists in China. The output in chemical patents is far below the main industrial countries and some emerging countries. This should arouse great attention in government and related sectors. Different indicators are used in evaluating different stages of chemical research. For basic research and some applied research, journal article and citation are used as the indicators of output. For applied research, which is one stage of development of R&D, patent indicator is chosen. Journal article and patent indicators covered the whole process of R&D. Bibliometrics and peer review are combined together first time in macro level of evaluation of a research field in China. Questionnaire of chemists can provide some explanation on the evaluation results and avoid some disadvantages of bibliometric methods. The correlation between the expenditure of R&D in China and the number of journal article has been analyzed. Suggestions have been made in S&T resource management and strategic policy-making.

? Morris, S.A. (2005), Unified mathematical treatment of complex cascaded bipartite networks: The case of collections of journal papers. Ph.D. Thesis, Oklahoma State University.

Full Text: 2005\Morris, SA.pdf

Abstract: A mathematical treatment is proposed for analysis of entities and relations among entities in complex networks consisting of cascaded bipartite networks. This treatment is applied to the case of collections of journal papers, in which entities are papers, references, paper authors, reference authors, paper journals, reference journals, institutions, terms, and term definitions. An entity-relationship model is introduced that explicitly shows direct links between entity-types and possible useful indirect relations. From this a matrix formulation and generalized matrix arithmetic are introduced that allow easy expression of relations between entities and calculation of weights of indirect links and co-occurrence links. Occurrence matrices, equivalence matrices, membership matrices and co-occurrence matrices are described. A dynamic model of growth describes recursive relations in occurrence and co-occurrence matrices as papers are added to the paper collection. Graph theoretic matrices are introduced to allow information flow studies of networks of papers linked by their citations. Similarity calculations and similarity fusion are explained. Derivation of feature vectors for pattern recognition techniques is presented. The relation of the proposed mathematical treatment to seriation, clustering, multidimensional scaling, and visualization techniques is discussed. It is shown that most existing bibliometric analysis techniques for dealing with collections of journal papers are easily expressed in terms of the proposed mathematical treatment: co-citation analysis, bibliographic coupling analysis, author co-citation analysis, journal co-citation analysis, Braam-Moed-vanRaan (BMV) co-citation/co-word analysis, latent semantic analysis, hubs and authorities, and multidimensional scaling. This report discusses an extensive software toolkit that was developed for this research for analyzing and visualizing entities and links in a collection of journal papers. Additionally, an extensive case study is presented, analyzing and visualizing 60 years of anthrax research. When dealing with complex networks that consist of cascaded bipartite networks, the treatment presented here provides a general mathematical framework for all aspects of analysis of static network structure and network dynamic growth. As such, it provides a basic paradigm for thinking about and modeling such networks: computing direct and indirect links, expressing and analyzing statistical distributions of network characteristics, describing network growth, deriving feature vectors, clustering, and visualizing network structure and growth.

? Moya de la Calle, M. (2005), Spanish medical literature (‘La Gaceta Medica Catalana’, 1900--1922). Ph.D. Thesis, Universidad de Valladolid, Spain.

Full Text: Moya de la Calle, M

Abstract: I have done a bibliometric research about the Spanish medical literature. For that purpose I have used one of the most important medical publications of that period, La Gaceta Médica Catalana, as a support. I have study the second period of the magazine, from 1900 to its extinction in December of 1921, through the permanent section called Publicaciones recibidas. In this section we can find the editorial novelties in medicine in the period. Likewise, it provides the theoretical basis of my research. A double view on the thesis is presented: on the one hand, a bibliometric study applying the main bibliometric laws; and on the other hand, a historical study with a complete analysis of the situation. I have gone through the historical period in which the publication is framed, in general terms, as well as focusing on the history of Spanish edition. We have also analyzed the magazine, its history, its main events, etc. I contribute a new comparative study with the most relevant medical reviews in those years to evidence the importance of the publication above mentioned. I have gone deep into the identity of the director and founder of the magazine, Rafael Rodriguez Méndez, his life, his career, etc. He was the soul of the magazine until his death and one of the main medical figures at this time. Finally, I have enclosed three appendixes: the first including the bibliographic information about the books, obtained from the research; the second being a summary of Rafael Rodriguez Méndez’s main academic achievements; and the third one containing the articles written by Santiago Ramón y Cajal and published in the magazine.

? Ramos Rodriguez, A.R. (2005), Intellectual structure of entrepreneurship research: A bibliometric study, 1956--2003. Ph.D. Thesis, Universidad de Cadiz, Spain.

Full Text: Thesis\Ramos Rodriguez AR.pdf

Abstract: Entrepreneurship is “a burning” subject for the society, educative institutions and the academic investigation. In individual, generally it is accepted by academic and professional the affirmation of which the scientific discipline of entrepreneurship is a young and emergent field. Nevertheless, little empirical evidence exists that sustains the appreciations made on its origin, evolution, social structure and thematic of investigation. On the contrary, it exists a clear discord between the academic ones on its definition, scope and other numerous aspects. In this sense, he is habitual to find valuations little encouraging because the state of development of the investigation on entrepreneurship is in its pre-theoretical state (Déry and Toulouse, 1996), happens through its stage of adolescence (Grégoire, Déry and Béchard, 2001) and has obtained to a progress limited towards its consolidation like discipline of knowledge (Aldrich and Baker, 1997; Romano and Ratnatunga, 1996; Busenitz et al., 2003). All these appreciations and still more disquieting others cause that entrepreneurship research deserves to be analyzed. For that reason, there is interesting similarity to explore the development of the academic investigation on the entrepreneurship phenomenon with the intention to obtain a general vision of the discipline that studies it and that allows to its suitable valuation and understanding. This generic objective has taken shape with the exposition of a series of questions of investigation related to four concrete aspects: the evolution of the scientific production, the social structure of its authors, the most influential documents and the structure of its knowledge base. In order to approach these questions it has been chosen to use a quantitative approach. In particular, after making a revision of literature on bibliometric methods and another one on investigations that have used to the own discipline of entrepreneurship as study object, a collection of representative works of the investigation in this discipline has been compiled by means of a search by key words and has been analyzed systematically with bibliometric techniques.

? Shih, C.C. (2005), Single- and multi-metal biosorption by an indigenous isolate Enterobacter sp. and recombinant Escherichia coli strains expressing metallothionein. M.Sc. Thesis, National Cheng Kung University, Tainan, Taiwan.

Full Text: Thesis\Shih, CC.pdf

? Wang, H.C. (2005), Adsorption of fluoride, chloride, bromide, sulfate and nitrate onto commercial and superparamagnetic activated alumina from aqueous solutions. M.Sc. Thesis, National Taiwan University, Taiwan.

Full Text: Wang HC

Abstract: The main species of the aged scrubbing solution in the semiconductor manufacturing industries are F^-, Cl^-, Br^-, NO₃^- and SO₄^2- with concentrations of about 54, 2.2, 1.5, 10 and 2 mg/L respectively. The pH value of the solution is about 3.6. Therefore, on the basis of the results obtained from Lin (2004), the adsorption process applied in the removal of anions, including F^-, Cl^-, Br^-, NO₃^- and SO₄^2-, from the synthesized aqueous solutions was investigated in this study.

Commercial activated alumina activated using 0.01 N NaOH followed by 3.16×10^-4 N HNO₃ (noted asγ-Al₂O₃-N) or HClO₄ (denoted as γ-Al₂O₃-P) and modified magnetic alumina adsorbent, which was synthesized employing sol-gel method (called as MMASG), were used as the alumina-type adsorbents. The physicochemical characteristics of two adsorbents and factors affecting the adsorption equilibrium and kinetics were further examined in the study.

The Langmuir and Freundlich isotherms were successfully used to predict the adsorption equilibrium behavior of the target anions onto γ-Al₂O₃-N and MMASG. The monolayer equilibrium adsorption capacity (qL) of MMASG is higher than that of γ-Al₂O₃-N. Besides, MMASG which was prepared by Fe₃O₄ coated with SiO₂ and sequentially synthesized by sol-gel method in this study, can properly be applied in the removal of the said anions from solutions.

Regarding the adsorption kinetics of the target anions from solutions, among the kinetic models tested (e.g. pseudo-first-order equation, pseudo-second-order equation and Elovich rate equation), both the pseudo-second-order equation and Elovich rate equation can well predict the adsorption kinetics of the said anions onto γ-Al₂O₃-P and MMASG in a completely stirred tank reactor (CSTR).

The removal of anions by the commercial activated γ-Al₂O₃-P was also carried out in a fixed-bed adsorber. The operating conditions were at pH value of 4 with various inlet concentrations for the fed anionic solutions. In addition, the adsorption patterns of anions can be divided into two types: inner-sphere (‘chemical bond’) adsorption, such as F^- and SO₄^2-, and outer-sphere complex (ion pair) adsorption, such as Cl^-, Br^- and NO₃^-. Besides, Yoon and Nelson equation for breakthrough modeling can well predict the adsorption kinetics of anions onto γ-Al₂O₃-P in a fixed-bed adsorber.

This study takes into account for the practical data of the aged scrubbing solution in the semiconductor manufacturing industries. The results indicate that γ-Al₂O₃-P and MMASG possess proper potential as the adsorbents for the application of adsorption process in the defluoridation from aged scrubbing solution. As for the weak anions such as Cl^-, Br^- and NO₃^-, the applicabilities of the γ-Al₂O₃-P and MMASG are moderate.

? Yin, X. (2005), Analysis of the traditional Chinese treatment regulation of chloasma from the related essays for 15 years. M.Sc. Thesis, Guangzhou University of Traditional Chinese Medicine, China.

Full Text: Yin, X

Abstract: Background of the study Chloasma is a kind of common skin disease with pigmentation on the face. The young girls and the women at middle age more easily suffer from Chloasma. Chloasma is a chronic disease which have a unprogressive course and affect the patients’ appearance seriously. The etiological factor and pathogenesis of Chloasma are fairly complicated and no substantial progress had been made up to now since middle period of 19 centuries although the relevant research is extensively. For there’s no...

Keywords: Chloasma, Traditional Chinese Treatment, Bibliometrics Analysis

? Chu, Y.C. (2006), The preparation of the amino acid grafted chitosan macroporous membranes and their applications. M.Sc. Thesis, National United University, Taiwan.

Full Text: 2006\Chu YC.pdf

Abstract: In this study, nine compounds (L-Histidine (His), L-Cysteine (Cys), L-Aspartic acid (Asp), L-Tryptophan (Try), L-Glutamic acid (Glu), L-Tyrosine (Tyr), L-3,4-dihydroxyphenyl-alanine (L-DOPA), p-Aminobenzoic acid (BA), p-Aminophenylacetic acid (PA))with bifunctional groups (amino and carboxyl groups) were grafted onto marcroporous chitosan membrane as ligand by the linkage of genipin. The prepared chitosan membranes were aimed to purify tyrosinase from Agaricus bisporus.

FTIR spectrum indicate the amino group of the nine compounds was coupled with the amino group of chitosan via the linkage of genipin. After working at different pH environments, the p-Aminobenzoic acid grafted chitosan exhibited the excellent adsorbing capacity by a 0.1 M PBS buffer as the extracting solution of Agaricus bisporus acetone powder at pH 4. The p-Aminobenzoic acid showed a competitive inhibition with tyrosinase. The analysis of the purified tyrosinase by SDS-PAGE showed only one band on the electrophoresis gel, this identified the selectivity of the BA grafted chitosan toward tyrosinase. The molecule weight of the purified tyrosinase is 111 kD which is almost the same as the molecule weight of the Sigma prepared tyrosinase (119 kD). The maximum adsorption capacity of the BA grafted chitosan toward tyrosinase reached 145 mg/g at 10℃, so this BA grafted chitosan membrane can be served as an affinity membrane on tyrosinase for commercial application.

The thermodynamic data showed the adsorption of tyrosinase by the BA grafted chitosan membrane obeyed Freundlich isotherm. The negative value of the adsorption ΔG and ΔH indicated the adsorption behavior is a spontaneous and exothermic process, and the adsorption capacity will decrease as the operation temperature increase. The negative value of the adsorption ΔS showed the arrangement of the protein molecule was more regulated on the BA grafted chitosan membrane than on the solution state. The kinetic data showed the adsorption of tyrosinase by the BA grafted chitosan membrane can be well expressed by pseudo second order kinetics.

Keywords: Macroporous Chitosan Membrane, Grafting, Ligand, Affinity Membrane, Tyrosinase

? Hsu, G.E. (2006), A study of application of novel adsorbents on the removal of pesticides from water. M.Sc. Thesis, National Taiwan University, Taiwan.

Full Text: Hsu GE

Abstract: Activated carbon (F-400) and novel hypercrosslinked polymer (Macronet MN-100, MN-150, and MN-500) were used as the adsorbents for the removal of pesticide (i.e., methomyl) from the aqueous solution. The physicochemical characteristics of adsorbents, and adsorption behaviors including adsorption kinetics and dynamics were investigated. Furthermore, factors affecting the adsorption equilibrium and kinetics were also examined in this study.

Marcronet resins and activated carbon F-400 possess high specific surface areas and all are microporous due to the high micropore volume. In addition, Marcronet resins are more uniform and homogeneous than activated carbon F-400. The Langmuir and Freundlich isotherms successfully predicted the adsorption equilibrium behaviors of methomyl onto F-400 and Marcronet resins. Furthermore, the monolayer adsorption capacity (qL) of F-400 for methomyl (145 g kg^-1) was higher than that of Marcronet resins. The natural organic matter decreased the adsorption capacity of methomyl onto F-400 and MN-150 because of the competitive adsorption.

Regarding the adsorption kinetics of methomyl on various adsorbents from solutions in completely stirred tank reactor (CSTR), global kinetics (pseudo-first-order, pseudo-second-order, and Elovich rate equations) and traditional kinetics (surface, pore, and branched pore diffusion kinetics) models were investigated in this study. The pseudo-second-order, Elovich rate equations and traditional kinetics models can well predict the adsorption kinetics of methomyl onto F-400 and Marcronet resins.

The adsorption dynamics of methomyl in the fixed bed showed that the adsorption capacity of methomyl on F-400 was the highest among the adsorbents investigated. The parameters obtained from surface diffusion model combined with linear driving force model, and Yoon and Nelson equation can well describe the breakthrough curve of adsorption of methomyl in the adsorber systems. The organic solvent (i.e., methanol) can completely regenerate the exhausted adsorbent without reducing the original adsorption capacity of methomyl.

Keywords: Methomyl, Activated Carbon, Hypercrosslinked Polymer, Adsorption Isotherm, Adsorption Kinetics, Adsorption Dynamics

? Hsu, Y.L. (2006), Adsorption of aqueous copper(II) and Cadmium(II) onto carbon nanotubes. M.Sc. Thesis, National Yunlin University of Science and Technology, Taiwan.

Full Text: Thesis\Hsu YL.pdf

? Huang, L.Y. (2006), Influences of sulfur impregnation on the properties of activated carbons and adsorption of low-concentration mercury in flue gases. M.Sc. Thesis, National Sun Yat-sen University, Kaohsiung, Taiwan.

Full Text: Huang LY

Abstract: Activated carbons derived from two precursors (coal and coconut shell) were used to develop low-concentration (i.e., ppb level) mercury adsorbents with various physical and chemical properties via gas- and liquid-phase sulfur impregnation methods. The goal is to achieve a full-scale production of mercury adsorbents. Results showed that sulfur impregnation altered the physical properties of activated carbons. Sulfur impregnation assembled chemical activation, which created new porous structure as well as sulfur doping. When the impregnation process was scaled-up, gas-phase sulfur impregnation significantly blocked the porous structure, indicating that sulfur impregnation simultaneously causes the pore opening and blocking. Liquid-phase impregnation did not act as activation, the resulting surface area and pore volume thus decreased as the sulfur amount increased, which was more significant in pilot-scale samples. Mercury adsorption capacity was proportional to the sulfur content of resulting samples, however, with an insignificant correlation. This result suggests that other factors, beside sulfur content, controls the adsorption behaviors as well. The pilot-scale carbon products had an adsorption capacity > 1000 g/g. Results also showed that a pseudo-first-order model can successfully simulate the adsorption behaviors of all tested adsorbents, indicating that Hg0 adsorption by tested samples was in a unimolecular reaction form. In addition, the kinetic study also showed that the tested samples with large adsorption capacities typically had poor adsorption kinetics, indicating that the Hg0 adsorption equilibrium and kinetics of sulfur-impregnated activated carbon were not able to be well correlated.

? Ling, C.N. (2006), Destructive adsorption mechanisms for the treatment of dye wastewater by nanoscale magnesium oxide. M.Sc. Thesis, National Sun Yat-sen University, Kaohsiung, Taiwan.

Full Text: Ling, CN

Abstract: This study was to prepare nanoscale MgO using the homogeneous precipitation process and to investigate its destructive adsorption with dye wastewater of reactive black-5 and reactive blue-19. In addition, UV-vis Spectrophotometer, Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry (MALDI-TOF/MS) and Gas Chromatograph/Mass Spectrometer (GC/MS) were used to analyze the intermediates resulting from destructive adsorption. Based on the results obtained, the destructive adsorption mechanisms for the treatment of dye wasterwater by nanoscale MgO were proposed in this study.

In this work, the optimal operating conditions for nanoscale MgO synthesis were determined to be the following: (1) a chemical reaction time of 7 hr, (2) reaction temperature of 125, (3) molar ratio of 9 for urea/MgCl2 6H2O, (4) water addition of 250 mL, (5) mixing intensity of 90 strokes per min, (6) calcination at 450 for 4 hr, (7) reflux time of 24 hr, (8) freeze-drying method, (9) two stage calcinations. Using these operating conditions one is able to prepare 2-D nanoscale MgO of hexagonal platelets with a thickness of 20-30 nm and BET surface area of 120-125 m²/g.

The adsorption model of nanoscale MgO for RB-5 and RB-19 was fitted to the Langmuir equation and their adsorption capacity were 196.08 mg/g and 163.93 mg/g, respectively. Both of them were fitted to the pseudo-second-order kinetic model equation. The optimal operating conditions of nanoscale MgO for destructive adsorption of both dyes were determined to be the following: (1) an initial dye concentration of 1000 mg/L, (2) a nanoscale MgO dose of 15 g/L, (3) a vigorous mixing of 30 min, (4) no need of system pH adjustment. Under such conditions, chemical oxygen demand (COD) and American Dye Manufacturers Institute (ADMI) of RB-5 and RB-19 were lower than the textile effluent standards.

According to the UV-vis spectrophotometer scanning results, the color removal of nanoscale MgO for RB-5 and RB-19 was good. At the same time, the absorbance of their second maximal peaks was decreased and some peaks were observed. Therefore, it proved that the model dyes were destroyed. Experimental results have shown that nanoscale MgO has a better performance of destructive adsorption on RB-5 than that of RB-19. This might be ascribed to the following reasons: (1) a greater molecular weight, (2) a longer molecule structure, (3) more sulfate ethyl sulfone groups for RB-5, and (4) a hard to be destroyed structure of anthraquinone for RB-19.

The destructive adsorption of dye wastewater by nanoscale MgO presumably took place mainly on the surface active sites of nanoscale MgO, including anion/cation vacancies, superoxide anion, edge, corner, isolated OH, lattice bound OH and assiocited-OH groups. According to the results of MALDI-TOF/MS and GC/MS analysis, the relevant reaction mechanism for RB-5 could be divided into three stages: (1) adsorption and water-soluble groups exfoliation stage, (2) chromophor decomposition and decolorization stage, and (3) further degradation stage for light-color intermediates. On the other hand, the relevant reaction mechanism for RB-19 might involve only the adsorption and auxochrome exfoliation stage and chromophor decomposition and decolorization stage.

? Liu, C.T. (2006), A study on the sorption of nickel(II) from water with purified carbon nanotubes. M.Sc. Thesis, National Chung Hsing University, Taiwan.

Full Text: Liu CT

Abstract: Single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT) were purified by sodium hypochlorite solutions and were employed as sorbents to study sorption characteristics of nickel(II) from aqueous solution. The surface properties of purified CNTs such as functional groups, total acidities and negatively charged surface carbon were greatly improved after purification and thus resulted in sorption of more Ni²⁺. The Ni²⁺ removal by CNTs quickly increased with initial solution pH in the range 1–12 and temperatures. The thermodynamic analysis revealed that the Ni²⁺ sorption by CNTs is endothermic and spontaneous. The sorption/desorption study showed that the Ni²⁺ could be easily removed from the CNTs surface by a 0.1 M HNO₃ solution and the sorption capacity was maintained after 10 cycles of sorption/desorption process.

A comparative study on the Ni²⁺ sorption between CNTs and activated carbons was also conducted. The maximum Ni²⁺ sorption capacities of Purified-SWCNT, Purified-MWCNT, Purified-GAC, PAC and GAC calculated by the Langmuir model are 47.85, 38.46, 26.39, 16.29 and 14.53 mg/g, respectively, with an initial Ni²⁺ concentration range 10 - 80 mg/L. The shorter equilibrium time as well as the better sorption capacity as compared to activated carbons suggests that both possess highly potential applications for the removal of Ni²⁺ from aqueous solution.

Keywords: Carbon Nanotubes, Sorption, Purification, Nickel, Thermodynamics, Activated Carbons, Desorption

? Lundber, J. (2006), Bibliometrics as a research assessment tool – impact beyond the impact factor. Ph.D. Thesis, Karoliska Institutet, Sweden.

Full Text: Thesis\Lundber, J.pdf

? Su, F.S. (2006), A study on the adsorption of dissolved organic matters from drinking water by multiwalled carbon nanotubes. M.Sc. Thesis, National Chung Hsing University, Taiwan.

Full Text: Su FS

Abstract: Multi-walled carbon nanotubes (MWCNTs) were thermally treated and employed as adsorbents to study adsorption characteristics of dissolved organic matters (DOMs) and assimilable organic carbon (AOC) from drinking water. The adsorption capacity of DOC and AOC onto MWCNTs increased with the decrease of pH and temperature of the solution but increased with the increase of ionic strength of the solution in the range of 0 - 0.01 M. The maximum adsorbed amounts of DOC and AOC onto heated MWCNTs calculated by the Langmuir model at 25C were 26.138 mg/g and 0.548 mg/g respectively, which were much higher than that onto commercially available granular activated carbon (DOC:14.710 mg/g, AOC:0.341 mg/g). The activity energies for adsorption of DOC and AOC onto MWCNTs indicated the film diffusion is the rate-controlling mechanism in the reaction. According to thermodynamic analysis, the adsorption of DOC and AOC onto MWCNTs is an exothermic and spontaneous process. A comparative study on the adsorption of DOMs among heated MWCNTs and GAC was also conducted. Heated MWCNTs possess superior capacities for adsorption of DOMs and AOC than GAC. The better capacity, much regeneratation times and durability as compared to GAC suggest that heated MWCNTs have highly potential applications for the removal of DOMs and AOC from aqueous solution.

Keywords: Adsorption, Carbon Nanotubes, Dissolved Organic Matter, Assimilable Organic Carbon, Regeneration, Thermal Treatment

? Hua, T.S. (2007), Sorption behavior of zeolite p and its modified forms in the removal of some heavy metals and oxyanions from aqueous media. M.Sc. Thesis, Universiti Teknologi Malaysia, Malaysia.

Full Text: Thesis\Hua TS.pdf

Abstract: Disebabkan oleh ketoksikan dan kekekalan yang wujud, ion-ion logam Me rbahaya seperti plumbum (Pb²⁺), Kadmium (Cd²⁺) and Zink (Zn²⁺) serta oksianion seperti selenit, Se(IV) and selenat, Se(VI) memaparkan sebagai ancaman terhadap alam sekitar dan kesihatan manusia apabila mereka dilepaskan ke dalam sumbersumber air sebagai bahan sisa. Penyelidikan ini merangkumi kerja-kerja sintesis, pencirian dan analisis ke atas pembangunan suatu penjerap tak organik yang murah dan cekap, iaitu zeolit Na-P2 di mana ia disintesis dengan menggunakan abu sekam padi tempatan sebagai bahan mentah. Produk itu dicirikan dengan pelbagai jenis teknik yang canggih dan seterusnya ia dimodifikasi kepada bentuk natrium dan kalsium hampir-homoionik agar dapat mengkaji tabiat penjerapan bagi sampel zeolit yang berbentuk kationik ini terhadap ion-ion logam merbahaya terpilih. Penjerapan ion-ion logam terpilih seperti Pb²⁺, Cd²⁺ and Zn²⁺ telah dibuktikan sebagai proses penukargantian ion melalui kajian penjerapan berkelompok. Kecekapan penyingkiran bagi spesies-spesies zeolit ini telah dikaji melalui beberapa pembolehubah seperti masa, kepekatan, pH and persaingan di antara bahan terjerap. Isoterma penukargantian ion binari telah dibina dengan menggunakan model keseimbangan termodinamik dan tenaga bebas piawai bagi penukargantian juga telah dikira. Susunan kepilihan bagi zeolit Na-P2 adalah Pb²⁺>Cd²⁺>Na⁺>Zn²⁺ manakala bagi garronit tertukarganti kalsium yang dilabel sebagai Homo-Ca, susunan kepilihannya adalah Pb²⁺>Ca²⁺>Cd²⁺>Zn²⁺. Penukargantian komponen multi bagi zeolit Na-P2 juga dikaji. Di samping itu, zeolit Na-P2 asal dimuatkan dengan menggunakan aluminium sulfat selepas penyingkiran silika untuk mengkaji kecekapannya dalam penyingkiran spesies selenit and selenat dalam air. Pembolehubah bagi penjerapan spesies-spesies selenium ke atas zeolit Na-P2- ter muat-aluminium seperti masa, kepekatan dan kekuatan ionik juga telah dikaji. Keputusan menunjukkan zeolite Na-P2-termuat-aluminium (sampel 10Al-P) mempunyai prestasi yang baik berbanding dengan bahan-bahan lain dalam penyingkiran oksianion selenium daripada air. Sebagai kesimpulannya, zeolit Na-P2 dan bentuk-bentuk terubahsuai dapat digunakan sebagai agen penyingkiran logam yang cekap dalam proses penulenan air.

? Yaghi, N.Z.A. (2007), Iron oxide based materials for the removal of copper from drinking water - A study of Freundlich adsorption isotherms, site energy distributions and energy frequency distributions. M.Sc. Thesis, Chalmers University of Technology, Göteborg, Sweden.

Full Text: Thesis\Yaghi NZA.pdf

Abstract: This study describes experiments in which iron oxide coated sand and iron oxide coated LECA were used to study the removal of copper ion in drinking water. Two possible compounds were used to prepare Iron oxide coated with LECA and sand. The isotherm study results showed that the observed data fitted well with the Freundlich model. Isotherm studies were conducted by varying the mass of adsorbents and all experiments were conducted at room temperature, at pH =6.5, initial concentration 100μg/L and with a duration of 17 hours. The results shows that LECA coated with ferric nitrate and LECA coated with ferric chloride seems to have higher removal than other adsorbents, whereas it gives efficiency of removal in the case of LECA nitrate rated from 82% to 98% and in the case of LECA Chloride rated from 80% to 96%. using adsorption isotherms and values of n and Kf (Freundlich constants), the third size of LECA coated with nitrate gave best value of n and Kf, estimated to 0.9997 and 3.4750 respectively and in second rank comes when LECA coated with ferric chloride size five which gave value for n and kf of 0.9998 and 3.8645 respectively. After studying the adsorption isotherm, site energy distribution and energy frequency distribution to all adsorbents using the theory of heterogeneity have been studied. The results shows that the loss occurs preferentially across sites having highest energy frequency distribution with the number of sites in the lowest energy range, as what is happened in uncoated LECA and uncoated sand. The final result and occurrence of the value of site energy distribution and energy frequency distribution showed that LECA coated nitrate is the best adsorbent among the other category and uncoated LECA is the worst.

Keywords: Copper, Drinking Water, Iron Oxide Coated Sand With, Iron Oxide Coated LECA, Ferric Nitrate, Ferric Chloride, Freundlich Isotherm Model, Freundlich Constants, Site Energy Distribution, And Energy Frequency Distribution