Magnetic and transport properties of LaMnO3+δ, La1-xCaxMnO3, La1-xCaxMn1-yFeyO3 and La1-xSrxMn1-yFeyO3

Interest to hole-doped mixed-valence manganite perovskites is connected to the ‘colossal’ magnetoresistance. This effect or huge drop of the resistivity, ρ, in external magnetic field, B, attains usually the maximum value near the ferromagnetic Curie temperature, TC. In this thesis are investigated conductivity mechanisms and magnetic properties of the manganite perovskite compounds LaMnO3+, La1-xCaxMnO3, La1-xCaxMn1-yFeyO3 and La1- xSrxMn1-yFeyO3. When the present work was started the key role of the phase separation and its influence on the properties of the colossal magnetoresistive materials were not clear. Our main results are based on temperature dependencies of the magnetoresistance and magnetothermopower, investigated in the temperature interval of 4.2 - 300 K in magnetic fields up to 10 T. The magnetization was studied in the same temperature range in weak (up to 0.1 T) magnetic fields. LaMnO3+δ is the parent compound for preparation of the hole-doped CMR materials. The dependences of such parameters as the Curie temperature, TC, the Coulomb gap, Δ, the rigid gap, γ, and the localization radius, a, on pressure, p, are observed in LaMnO3+δ. It has been established that the dependences above can be interpreted by increase of the electron bandwidth and decrease of the polaron potential well when p is increased. Generally, pressure stimulates delocalization of the electrons in LaMnO3+δ. Doping of LaMnO3 with Ca, leading to La1-xCaxMnO3, changes the Mn3+/Mn4+ ratio significantly and brings an additional disorder to the crystal lattice. Phase separation in a form of mixture of the ferromagnetic and the spin glass phases was observed and investigated in La1- xCaxMnO3 at x between 0 and 0.4. Influence of the replacement of Mn by Fe is studied in La0.7Ca0.3Mn1−yFeyO3 and La0.7Sr0.3Mn1−yFeyO3. Asymmetry of the soft Coulomb gap and of the rigid gap in the density of localized states, small shift of the centre of the gaps with respect to the Fermi level and cubic asymmetry of the density of states are obtained in La0.7Ca0.3Mn1−yFeyO3. Damping of TC with y is connected to breaking of the double-exchange interaction by doping with Fe, whereas the irreversibility and the critical behavior of the magnetic susceptibility are determined by the phase separation and the frustrated magnetic state of La0.7Sr0.3Mn1−yFeyO3.

Potential impact of the global climate changes on the spatial distribution of areas of risk for the occurrence of eucalyptus rust in Brazil

Rust, caused by Puccinia psidii, is one of the most important diseases affecting eucalyptus in Brazil. This pathogen causes disease in mini-clonal garden and in young plants in the field, especially in leaves and juvenile shoots. Favorable climate conditions for infection by this pathogen in eucalyptus include temperature between 18 and 25 ºC, together with at least 6-hour leaf wetness periods, for 5 to 7 consecutive days. Considering the interaction between the environment and the pathogen, this study aimed to evaluate the potential impact of global climate changes on the spatial distribution of areas of risk for the occurrence of eucalyptus rust in Brazil. Thus, monthly maps of the areas of risk for the occurrence of this disease were elaborated, considering the current climate conditions, based on a historic series between 1961 and 1990, and the future scenarios A2 and B2, predicted by IPCC. The climate conditions were classified into three categories, according to the potential risk for the disease occurrence, considering temperature (T) and air relative humidity (RH): i) high risk (18 < T < 25 ºC and RH > 90%); ii) medium risk (18 < T < 25 ºC and RH < 90%; T< 18 or T > 25 ºC and RH > 90%); and iii) low risk (T < 18 or T > 25 ºC and RH < 90%). Data about the future climate scenarios were supplied by GCM Change Fields. In this study, the simulation model Hadley Centers for Climate Prediction and Research (HadCm3) was adopted, using the software Idrisi 32. The obtained results led to the conclusion that there will be a reduction in the area favorable to eucalyptus rust occurrence, and such a reduction will be gradual for the decades of 2020, 2050 and 2080 but more marked in scenario A2 than in B2. However, it is important to point out that extensive areas will still be favorable to the disease development, especially in the coldest months of the year, i.e., June and July. Therefore, the zoning of areas and periods of higher occurrence risk, considering the global climate changes, becomes important knowledge for the elaboration of predicting models and an alert for the integrated management of this disease.

Root colonization and interaction among growth promoting rhizobacteria isolates and eucalypts species

This work aimed to evaluate root colonization and interaction among isolates of rhizobacteria and eucalypt species. The method used to evaluate "in vitro" root colonization was able to indicate if the effect was benefic or deleterious allowing to pre-select isolates as potential growth promoter. There was interaction among isolates of rhizobacteria and Eucalyptus species for seed germinating and seedling growth. MF2 (Pseudomonas sp.) was the best rhizobacteria isolate for growth promotion of E. cloeziana e E. grandis. S1 (Bacillus subtilis) was the most effective for E. globulus, and Ca (Pseudomonas fulva), MF2 (Pseudomonas sp.), CIIb (Stenotrophomonas maltophilia) and S2 (B. subtilis) were the most promising isolates for the E. urophylla.

Ion selective electrodes for determination of low and ultra low concentrations of lead (II) in natural waters

Att övervaka förekomsten av giftiga komponenter i naturliga vattendrag är nödvändigt för människans välmående. Eftersom halten av föroreningar i naturens ekosystem bör hållas möjligast låg, pågår en ständig jakt efter kemiska analysmetoder med allt lägre detektionsgränser. I dagens läge görs miljöanalyser med dyr och sofistikerad instrumentering som kräver mycket underhåll. Jonselektiva elektroder har flera goda egenskaper som t.ex. bärbarhet, låg energiförbrukning, och dessutom är de relativt kostnadseffektiva. Att använda jonselektiva elektroder vid miljöanalyser är möjligt om deras känslighetsområde kan utvidgas genom att sänka deras detektionsgränser. För att sänka detektionsgränsen för Pb(II)-selektiva elektroder undersöktes olika typer av jonselektiva membran som baserades på polyakrylat-kopolymerer, PVC och PbS/Ag2S. Fast-fas elektroder med membran av PbS/Ag2S är i allmänhet enklare och mer robusta än konventionella elektroder vid spårämnesanalys av joniska föroreningar. Fast-fas elektrodernas detektionsgräns sänktes i detta arbete med en nyutvecklad galvanostatisk polariseringsmetod och de kunde sedan framgångsrikt användas för kvantitativa bestämningar av bly(II)-halter i miljöprov som hade samlats in i den finska skärgården nära tidigare industriområden. Analysresultaten som erhölls med jonselektiva elektroder bekräftades med andra analytiska metoder. Att sänka detektionsgränsen m.hj.a. den nyutvecklade polariseringsmetoden möjliggör bestämning av låga och ultra-låga blyhalter som inte kunde nås med klassisk potentiometri. Den verkliga fördelen med att använda dessa blyselektiva elektroder är möjligheten att utföra mätningar i obehandlade miljöprov trots närvaron av fasta partiklar vilket inte är möjligt att göra med andra analysmetoder. Jag väntar mig att den nyutvecklade polariseringsmetoden kommer att sätta en trend i spårämnesanalys med jonselektiva elektroder.

Electroactive ion exchange membranes based on conducting polymers

Ion exchange membranes are indispensable for the separation of ionic species. They can discriminate between anions and cations depending on the type of fixed ionic group present in the membrane. These conventional ion exchange membranes (CIX) have exceptional ionic conductivity, which is advantageous in various electromembrane separation processes such as electrodialysis, electrodeionisation and electrochemical ion exchange. The main disadvantage of CIX membranes is their high electrical resistance owing to the fact that the membranes are electronically non conductive. An alternative can be electroactive ion exchange membranes, which are ionically and electronically conducting. Polypyrrole (PPy) is a type of electroactive ion exchange material as well as a commonly known conducting polymer. When PPy membranes are repeatedly reduced and oxidised, ions are pumped through the membrane. The main aim of this thesis was to develop electroactive cation transport membranes based on PPy for the selective transport of divalent cations. Membranes developed composed of PPy films deposited on commercially available support materials. To carry out this study, cation exchange membranes based on PPy doped with immobile anions were prepared. Two types of dopant anions known to interact with divalent metal ions were considered, namely 4-sulphonic calix[6]arene (C6S) and carboxylated multiwalled carbon nanotubes (CNT). The transport of ions across membranes containing PPy doped with polystyrene sulphonate (PSS) and PPy doped with para-toluene sulphonate (pTS) was also studied in order to understand the nature of ion transport and permeability across PPy(CNT) and PPy(C6S) membranes. In the course of these studies, membrane characterisation was performed using electrochemical quartz crystal microbalance (EQCM) and scanning electron microscopy (SEM). Permeability of the membranes towards divalent cations was explored using a two compartment transport cell. EQCM results demonstrated that the ion exchange behaviour of polypyrrole is dependent on a number of factors including the type of dopant anion present, the type of ions present in the surrounding medium, the scan rate used during the experiment and the previous history of the polymer film. The morphology of PPy films was found to change when the dopant anion was varied and even when the thickness of the film was altered in some cases. In nearly all cases the permeability of the membranes towards metal ions followed the order K+ > Ca2+ > Mn2+. The one exception was PPy(C6S), for which the permeability followed the order Ca2+ ≥ K+ > Mn2+ > Co2+ > Cr3+. The above permeability sequences show a strong dependence on the size of the metal ions with metal ions having the smallest hydrated radii exhibiting the highest flux. Another factor that affected the permeability towards metal ions was the thickness of the PPy films. Films with the least thickness showed higher metal ion fluxes. Electrochemical control over ion transport across PPy(CNT) membrane was obtained when films composed of the latter were deposited on track-etched Nucleopore® membranes as support material. In contrast, the flux of ions across the same film was concentration gradient dependent when the polymer was deposited on polyvinylidene difluoride membranes as support material. However, electrochemical control over metal ion transport was achieved with a bilayer type of PPy film consisting of PPy(pTS)/PPy(CNT), irrespective of the type of support material. In the course of studying macroscopic charge balance during transport experiments performed using a two compartment transport cell, it was observed that PPy films were non-permselective. A clear correlation between the change in pH in the receiving solution and the ions transported across the membrane was observed. A decrease in solution pH was detected when the polymer membrane acted primarily as an anion exchanger, while an increase in pH occurred when it functioned as a cation exchanger. When there was an approximately equal flux of anions and cations across the polymer membrane, the pH in the receiving solution was in the range 6 - 8. These observations suggest that macroscopic charge balance during the transport of cations and anions across polypyrrole membranes was maintained by introduction of anions (OH-) and cations (H+) produced via electrolysis of water.

The potential of social networking sites in inpatriate adjustment

People make up one of the most important resources for a corporation and therefore it has to continuously seek an ever more diverse and international workforce. Inpatriation is another way of utilizing foreign expertise in a corporation. An inpatriate refers to a person that is on an international assignment at the headquarters of a corporation, where they have been sent either from a subsidiary abroad or from a third country outside the corporation. Strengthening the social network of the inpatriate and their family contributes to the adjustment process and furthermore the success of the work assignment. As social networking sites are currently the fastest developing personal networking tools in the world, it is interesting to see how they can help in inpatriate adjustment. The objective of this thesis is to explore the potential of social networking sites (SNS) in inpatriate adjustment. The main objective can be divided into three sub objectives: 1. What is SNS used for during the inpatriate assignment? 2. What are the inpatriates’ motivations to use SNS? 3. Could the three facets of adjustment (work, interaction and general) be gained through SNS? This qualitative study utilizes the theme interview data collection method and the thematic analysis approach for analysing the interview data. From the interviews with five Indian inpatriates in Finland the most mentioned uses of SNS were related to participating (sharing opinions, recommendations and discussing things and connecting to friends, family and colleagues) and consuming (collecting information for work and free time), the least mentioned use of SNS was producing (posting videos, photos and updates). An interesting finding was that the five interviewees did not use SNS for purely entertainment motives at all during their assignment. This thesis found that all three facets of adjustment could potentially be gained through SNS.

Modelling of potentiometric ion sensors

Potentiometric ion sensors are a very important subgroup of electrochemical sensors, very attractive for practical applications due to their small size, portability, low-energy consumption, relatively low cost and not changing the sample composition. They are investigated by the researchers from many fields of science. The continuous development of this field creates the necessity for a detailed description of sensor response and the electrochemical processes important in the practical applications of ion sensors. The aim of this thesis is to present the existing models available for the description of potentiometric ion sensors as well as their applicability and limitations. This includes the description of the diffusion potential occurring at the reference electrodes. The wide range of existing models, from most idealised phase boundary models to most general models, including migration, is discussed. This work concentrates on the advanced modelling of ion sensors, namely the Nernst-Planck-Poisson (NPP) model, which is the most general of the presented models, therefore the most widely applicable. It allows the modelling of the transport processes occurring in ion sensors and generating the potentiometric response. Details of the solution of the NPP model (including the numerical methods used) are shown. The comparisons between NPP and the more idealized models are presented. The applicability of the model to describe the formation of diffusion potential in reference electrode, the lower detection limit of both ion-exchanger and neutral carrier electrodes and the effect of the complexation in the membrane are discussed. The model was applied for the description of both types of electrodes, i.e. with the inner filling solution and solidcontact electrodes. The NPP model allows the electrochemical methods other than potentiometry to be described. Application of this model in Electrochemical Impedance Spectroscopy is discussed and a possible use in chrono-potentiometry is indicated. By combining the NPP model with evolutionary algorithms, namely Hierarchical Genetic Strategy (HGS), a novel method allowing the facilitation of the design of ion sensors was created. It is described in detail in this thesis and its possible applications in the field of ion sensors are indicated. Finally, some interesting effects occurring in the ion sensors (i.e. overshot response and influence of anionic sites) as well as the possible applications of NPP in biochemistry are described.

Critical aspects on the behavior of material from the mechanical tool-workpiece interaction in single point diamond turning

Some material aspects such as grain size, purity and anisotropy exert an important influence on surface quality, especially in single point diamond turning. The aim of this paper is to present and discuss some critical factors that can limit the accuracy of ultraprecision machining of non-ferrous metals and to identify the effects of them on the cutting mechanism with single point diamond tools. This will be carried out through observations of machined surfaces and chips produced using optical and scanning electron microscopy. Solutions to reduce the influence of some of these limiting factors related with the mechanism of generation of mirror-like surfaces will be discussed.

Ion mobility spectrometry in liquid analysis

Ion mobility spectrometry (IMS) is a straightforward, low cost method for fast and sensitive determination of organic and inorganic analytes. Originally this portable technique was applied to the determination of gas phase compounds in security and military use. Nowadays, IMS has received increasing attention in environmental and biological analysis, and in food quality determination. This thesis consists of literature review of suitable sample preparation and introduction methods for liquid matrices applicable to IMS from its early development stages to date. Thermal desorption, solid phase microextraction (SPME) and membrane extraction were examined in experimental investigations of hazardous aquatic pollutants and potential pollutants. Also the effect of different natural waters on the extraction efficiency was studied, and the utilised IMS data processing methods are discussed. Parameters such as extraction and desorption temperatures, extraction time, SPME fibre depth, SPME fibre type and salt addition were examined for the studied sample preparation and introduction methods. The observed critical parameters were extracting material and temperature. The extraction methods showed time and cost effectiveness because sampling could be performed in single step procedures and from different natural water matrices within a few minutes. Based on these experimental and theoretical studies, the most suitable method to test in the automated monitoring system is membrane extraction. In future an IMS based early warning system for monitoring water pollutants could ensure the safe supply of drinking water. IMS can also be utilised for monitoring natural waters in cases of environmental leakage or chemical accidents. When combined with sophisticated sample introduction methods, IMS possesses the potential for both on-line and on-site identification of analytes in different water matrices.

An interaction framework for deploying the knowledge of diasporas: Using Finland as an example

This study discusses the importance of diasporas’ knowledge with regard to the national competitive advantage of Finland. The purpose of this study is to suggest an interaction framework, which illustrates how diasporas can benefit the host country via intentional knowledge spillovers, with two sub-objectives: to seek which features are crucial for productive interaction between a host government and diasporas, and to scrutinize the modes of interaction currently effective in Finland. The theoretical background of the study consists of literature relating to the concepts of diaspora and knowledge. The empirical research conducted for this study is based on expert interviews. The interview data was collected between September and November 2013. Eight interviews were made; five with representatives of expert organizations, and three with immigrants. Thematic analysis was used to categorize and interpret the interview data. In addition, thematic networks were built to act as a basis of analysis. This study finds that knowledge, especially new combinations of knowledge, is a significant input in innovation. Innovation is found to be the basis of national competitive advantage. Thus the means through which knowledge is transferred are of key importance. Diasporas are found a good source of new knowledge, and thus may aid the innovative process. Host country stance and policy are found to have a major impact on the ability of the host country to benefit from diasporas’ knowledge. As a host country, this study finds Finland to have a very fragmented strategy field and a prejudiced attitude, which currently make it difficult to utilize the potential of diasporas. The interaction framework based on these findings suggests ways in which Finland can improve its national competitive advantage through acquiring the innovative potential of diasporas. Strategy revision and increased promotion are discussed as means towards improved interaction. In addition, the importance of learning is emphasized. The findings of this study enhance understanding of the relationship between the concepts of diaspora and knowledge. In addition, this study ties the relationship to economic benefit. Future research is, however, necessary in order to fully understand the meaning of the relationship, as well as to increase understanding of the generalizability of the interaction framework.

Resonant tunneling effects in semiconductor heterostructures

The thesis is devoted to a theoretical study of resonant tunneling phenomena in semiconductor heterostructures and nanostructures. It considers several problems relevant to modern solid state physics. Namely these are tunneling between 2D electron layers with spin-orbit interaction, tunnel injection into molecular solid material, resonant tunnel coupling of a bound state with continuum and resonant indirect exchange interaction mediated by a remote conducting channel. A manifestation of spin-orbit interaction in the tunneling between two 2D electron layers is considered. General expression is obtained for the tunneling current with account of Rashba and Dresselhaus types of spin-orbit interaction and elastic scattering. It is demonstrated that the tunneling conductance is very sensitive to relation between Rashba and Dresselhaus contributions and opens possibility to determine the spin-orbit interaction parameters and electron quantum lifetime in direct tunneling experiments with no external magnetic field applied. A microscopic mechanism of hole injection from metallic electrode into organic molecular solid (OMS) in high electric field is proposed for the case when the molecules ionization energy exceeds work function of the metal. It is shown that the main contribution to the injection current comes from direct isoenergetic transitions from localized states in OMS to empty states in the metal. Strong dependence of the injection current on applied voltage originates from variation of the number of empty states available in the metal rather than from distortion of the interface barrier. A theory of tunnel coupling between an impurity bound state and the 2D delocalized states in the quantum well (QW) is developed. The problem is formulated in terms of Anderson-Fano model as configuration interaction between the carrier bound state at the impurity and the continuum of delocalized states in the QW. An effect of this interaction on the interband optical transitions in the QW is analyzed. The results are discussed regarding the series of experiments on the GaAs structures with a -Mn layer. A new mechanism of ferromagnetism in diluted magnetic semiconductor heterosructures is considered, namely the resonant enhancement of indirect exchange interaction between paramagnetic centers via a spatially separated conducting channel. The underlying physical model is similar to the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction; however, an important difference relevant to the low-dimensional structures is a resonant hybridization of a bound state at the paramagnetic ion with the continuum of delocalized states in the conducting channel. An approach is developed, which unlike RKKY is not based on the perturbation theory and demonstrates that the resonant hybridization leads to a strong enhancement of the indirect exchange. This finding is discussed in the context of the known experimental data supporting the phenomenon.

Activity and functional interaction of alternative oxidase and uncoupling protein in mitochondria from tomato fruit

Cyanide-resistant alternative oxidase (AOX) is not limited to plant mitochondria and is widespread among several types of protists. The uncoupling protein (UCP) is much more widespread than previously believed, not only in tissues of higher animals but also in plants and in an amoeboid protozoan. The redox energy-dissipating pathway (AOX) and the proton electrochemical gradient energy-dissipating pathway (UCP) lead to the same final effect, i.e., a decrease in ATP synthesis and an increase in heat production. Studies with green tomato fruit mitochondria show that both proteins are present simultaneously in the membrane. This raises the question of a specific physiological role for each energy-dissipating system and of a possible functional connection between them (shared regulation). Linoleic acid, an abundant free fatty acid in plants which activates UCP, strongly inhibits cyanide-resistant respiration mediated by AOX. Moreover, studies of the evolution of AOX and UCP protein expression and of their activities during post-harvest ripening of tomato fruit show that AOX and plant UCP work sequentially: AOX activity decreases in early post-growing stages and UCP activity is decreased in late ripening stages. Electron partitioning between the alternative oxidase and the cytochrome pathway as well as H+ gradient partitioning between ATP synthase and UCP can be evaluated by the ADP/O method. This method facilitates description of the kinetics of energy-dissipating pathways and of ATP synthase when state 3 respiration is decreased by limitation of oxidizable substrate.

NIR-Vis Up-Conversion Luminescence in the Yb3+,Er3+ Doped Y2O2S, ZrO2, and NaYF4 Nanomaterials

Since the discovery of the up-conversion phenomenon, there has been an ever increasing interest in up-converting phosphors in which the absorption of two or more low energy photons is followed by emission of a higher energy photon. Most up-conversion luminescence materials operate by using a combination of a trivalent rare earth (lanthanide) sensitizer (e.g. Yb or Er) and an activator (e.g. Er, Ho, Tm or Pr) ion in a crystal lattice. Up-converting phosphors have a variety of potential applications as lasers and displays as well as inks for security printing (e.g. bank notes and bonds). One of the most sophisticated applications of lanthanide up-conversion luminescence is probably in medical diagnostics. However, there are some major problems in the use of photoluminescence based on the direct UV excitation in immunoassays. Human blood absorbs strongly UV radiation as well as the emission of the phosphor in the visible. A promising way to overcome the problems arising from the blood absorption is to use a long wavelength excitation and benefit from the up-conversion luminescence. Since there is practically no absorption by the whole-blood in the near IR region, it has no capability for up-conversion in the excitation wavelength region of the conventional up-converting phosphor based on the Yb3+ (sensitizer) and Er3+ (activator) combination. The aim of this work was to prepare nanocrystalline materials with high red (and green) up-conversion luminescence efficiency for use in quantitative whole-blood immunoassays. For coupling to biological compounds, nanometer-sized (crystallite size below 50 nm) up-converting phosphor particles are required. The nanocrystalline ZrO2:Yb3+,Er3+, Y2O2S:Yb3+,Er3+, NaYF4:Yb3+,Er3+ and NaRF4-NaR’F4 (R: Y, Yb, Er) materials, prepared with the combustion, sol-gel, flux, co-precipitation and solvothermal synthesis, were studied using the thermal analysis, FT-IR spectroscopy, transmission electron microscopy, EDX spectroscopy, XANES/EXAFS measurements, absorption spectroscopy, X-ray powder diffraction, as well as up-conversion and thermoluminescence spectroscopies. The effect of the impurities of the phosphors, crystallite size, as well as the crystal structure on the up-conversion luminescence intensity was analyzed. Finally, a new phenomenon, persistent up-conversion luminescence was introduced and discussed. For efficient use in bioassays, more work is needed to yield nanomaterials with smaller and more uniform crystallite sizes. Surface modifications need to be studied to improve the dispersion in water. On the other hand, further work must be carried out to optimize the persistent up-conversion luminescence of the nanomaterials to allow for their use as efficient immunoassay nanomaterials combining the advantages of both up-conversion and persistent luminescence.

DNA-lipid systems: A physical chemistry study

It is well known that the interaction of polyelectrolytes with oppositely charged surfactants leads to an associative phase separation; however, the phase behavior of DNA and oppositely charged surfactants is more strongly associative than observed in other systems. A precipitate is formed with very low amounts of surfactant and DNA. DNA compaction is a general phenomenon in the presence of multivalent ions and positively charged surfaces; because of the high charge density there are strong attractive ion correlation effects. Techniques like phase diagram determinations, fluorescence microscopy, and ellipsometry were used to study these systems. The interaction between DNA and catanionic mixtures (i.e., mixtures of cationic and anionic surfactants) was also investigated. We observed that DNA compacts and adsorbs onto the surface of positively charged vesicles, and that the addition of an anionic surfactant can release DNA back into solution from a compact globular complex between DNA and the cationic surfactant. Finally, DNA interactions with polycations, chitosans with different chain lengths, were studied by fluorescence microscopy, in vivo transfection assays and cryogenic transmission electron microscopy. The general conclusion is that a chitosan effective in promoting compaction is also efficient in transfection.

An EDTA-β-cyclodextrin adsorbent for the adsorption of rare earth elements and its application in preconcentration of ultratrace rare earth elements from seawater

The objectives of this work were synthesizing an EDTA-β-CD adsorbent and investigating its adsorption potential and applications in preconcentration of REEs from aqueous phase. The adsorption capacity of EDTA-β-CD was investigated. The adsorption studies were performed by batch techniques both in one- and multi-component systems. The effects of pH, contact time and initial concentration were evaluated. The analytical detection methods and characterization methods were presented. EDTA-β-CD adsorbent was synthesized successfully with high EDTA coverage. The maximum REEs uptake was 0.310 mmol g-1 for La(III), 0.337 mmol g-1 for Ce(III) and 0.353 mmol g-1 for Eu(III), respectively. The kinetics of REEs onto EDTA-β-CD fitted well to pseudo-second-order model and the adsorption rate was affected by intra-particle diffusion. The experimental data of one component studies fitted to Langmuir isotherm model indicating the homogeneous surface of the adsorbent. The extended Sips model was applicable for the isotherm studies in three-component system. The electrostatic interaction, chelation and complexation were all involved in the adsorption mechanism. The preconcentration of RE ions and regeneration of EDTA-β-CD were successful. Overall, EDTA-β-CD is an effective adsorbent in adsorption and preconcentration of REEs.