VIS-NIR SPECTROMETRY, SOIL PHOSPHATE EXTRACTION METHODS AND INTERACTIONS OF SOIL ATTRIBUTES

The objective of this study was to evaluate the relationships between the spectra in the Vis-NIR range and the soil P concentrations obtained from the PM and Prem extraction methods as well as the effects of these relationships on the construction of models predicting P concentration in Oxisols. Soil samples' spectra and their PM and Prem extraction solutions were determined for the Vis-NIR region between 400 and 2500 nm. Mineralogy and/or organic matter content act as primary attributes allowing correlation of these soil phosphorus fractions with the spectra, mainly at wavelengths between 450-550, 900-1100 nm, near 1400 nm and between 2200-2300 nm. However, the regression models generated were not suitable for quantitative phosphate analysis. Solubilization of organic matter and reactions during the PM extraction process hindered correlations between the spectra and these P soil fractions. For Prem,, the presence of Ca in the extractant and preferential adsorption by gibbsite and iron oxides, particularly goethite, obscured correlations with the spectra.

Iron determination by FAAS in fish feed and feces after ultrasound-assisted extraction

This paper proposes a method to determine iron in samples of fish feed and feces using ultrasound in the extraction of the analyte and in subsequent quantification by flame atomic absorption spectrometry. Using HCl 0.10 mol L -1 as the extraction solution, the optimal conditions of extraction were found to be: granulometry of the sample <60 μm; a sonication time of five cycles of 10 s and sonication power of 136 W. The method was applied in studies of the availability of iron in four food sources used in the diet of Nile Tilapia. The results obtained with the proposed extraction method allowed us to calculate the coefficients of apparent digestibility of iron in the food sources, which was not possible when using results obtained from samples mineralized by acid digestion. © Springer Science+Business Media, LLC 2008.

Content extraction: Identifying the main content in HTML documents

Except the article forming the main content most HTML documents on the WWW contain additional contents such as navigation menus, design elements or commercial banners. In the context of several applications it is necessary to draw the distinction between main and additional content automatically. Content extraction and template detection are the two approaches to solve this task. This thesis gives an extensive overview of existing algorithms from both areas. It contributes an objective way to measure and evaluate the performance of content extraction algorithms under different aspects. These evaluation measures allow to draw the first objective comparison of existing extraction solutions. The newly introduced content code blurring algorithm overcomes several drawbacks of previous approaches and proves to be the best content extraction algorithm at the moment. An analysis of methods to cluster web documents according to their underlying templates is the third major contribution of this thesis. In combination with a localised crawling process this clustering analysis can be used to automatically create sets of training documents for template detection algorithms. As the whole process can be automated it allows to perform template detection on a single document, thereby combining the advantages of single and multi document algorithms.

Kuparinuuttoliuosten adsorptiopuhdistus

Työssä tutkittiin laboratorio-olosuhteissa yhdeksän eri adsorbentin sopivuutta kuparinuuttoliuosten adsorptiopuhdistukseen eli savikäsittelyyn. Tarkoituksena oli poistaa uuttoliuoksesta laimentimen ja reagenssin hapettumis- ja hajoamistuotteita. Adsorbenttien sopivuus uuttoliuosten puhdistukseen määritettiin adsorptio-, kinetiikka- ja faasien selkeytymisaikakokeilla. Tehdyissä kokeissa käytettiin sekä hapetettua synteettistä uuttoliuosta että teollisuudesta saatuja autenttisia kuparinuuttoliuoksia. Uuttoreagenssit olivat hydroksi-oksiimeihin perustuvia. Teollisuudesta saaduista käytetyistä adsorbenteista eluoidun liuoksen kaasugromatografi- ja massaspektrometrianalyysissä ei havaittu selviä merkkejä reagenssin tai laimentimen hajoamistuotteista. Savikäsittely lyhensi faasien selkeytymisaikaa merkittävästi. Bentoniittipohjaisten savien havaittiin soveltuvan parhaiten uuttoliuosten adsorptiopuhdistukseen. IR-analyysin perusteella niiden pinnalle adsorboitui myös eniten karbonyyliryhmiä sisältäviä yhdisteitä. Faasien selkeytymisajan havaittiin huonontuvan itsestään liuosten seistessä savikäsittelyn jälkeen. Noin vuorokauden jälkeen selkeytymisaika tasaantui tasolle, joka oli kuitenkin huomattavasti parempi kuin käsittelemättömällä liuoksella. Savikäsittelyssä käytettävän saven optimimäärä oli noin 1 p-%:a ja sekoitusaika muutamia minuutteja. Savikäsittelyllä ei ollut merkittävää vaikutusta kuparinuuton kinetiikkaan. Työssä tutkittiin laboratorio-olosuhteissa yhdeksän eri adsorbentin sopivuutta kuparinuuttoliuosten adsorptiopuhdistukseen eli savikäsittelyyn. Tarkoituksena oli poistaa uuttoliuoksesta laimentimen ja reagenssin hapettumis- ja hajoamistuotteita. Adsorbe

Avaliação dos parâmetros de solubilidade de Hildebrand/Hansen na seleção de solventes para a extração de pesticidas organoclorados do solo

This work evaluated the use of the Hildebrand/Hansen solubility parameters for selection of solvents for extraction of the organochlorine pesticides pp' DDT, pp' DDE, Aldrin and a-Endossulfan from soil using columns packed with Al2O3. The mixtures hexane:dichloromethane (7:3; v/v), hexane:acetonitrile (1:1; v/v), hexane:acetone (1:1; v/v) and pure hexane were chosen as extracting solutions. In the addition and recovery tests, different extraction solutions provided high recoveries percentages (>75%) with coefficients of variation below 15%. The recoveries are in agreement with the Hildebrand/Hansen parameters, demonstrating its applicability in the selection of extracting solution and in the replacement of toxic solvents, as dichloromethane

Kullan uutto kloridiliuoksista

Työssä tutkittiin kullan neste-nesteuuttoa kloridiliuoksista kirjallisuustutkimuksen ja laboratoriokokeiden avulla. Uuttoreagenssina käytettiin Outotecin kehittämää kullanuuttoreagenssia. Teoreettisessa osassa tarkastellaan kullan käyttäytymistä happamissa vesiliuoksissa, jotka sisältävät kloridia ja bromidia. Lisäksi työssä käsitellään kultakloridiyhdisteiden käyttöturvallisuutta. Teollisuudessa vuonna 2012 käytettäviä neste-nesteuuttoon perustuvia kullan talteenottomenetelmiä esitellään lyhyesti. Kirjallisuusosassa käsitellään myös joidenkin teollisesti käytettävien polymeeristen rakennemateriaalien ominaisuuksia. Kokeellisessa osassa määritettiin kullanuuttoreagenssin fysikaalisia ominaisuuksia, kuten sen tiheys, viskositeetti, liukoisuus veteen sekä faasien selkeytyminen uuttoprosessissa. Tuloksista havaittiin, että eri modifiointiaineet vaikuttavat huomattavasti kullanuuttoliuoksen fysikaalisiin ominaisuuksiin. Kullan uuttoa tutkittiin pienen mittakaavan laboratoriokokein käyttämällä synteettisiä kultaa sisältäviä lähtöliuoksia. Kokeissa tutkittiin lähtöliuoksen happopitoisuuden ja bromidipitoisuuden, sekä uuttoreagenssin modifiointiaineiden vaikutuksia kullan uuttotasapainoon. Lisäksi tutkittiin joidenkin epäpuhtausmetallien myötäuuttautumista. Materiaalitutkimuksissa tarkasteltiin kullanuuttoreagenssin ja autenttisen kullan halidiliuoksen vaikutuksia polymeerimateriaaleihin pitkäaikaisessa kontaktissa. Uuttoliuosten havaittiin aiheuttavan turpoamaa sekä pinnan pehmenemistä joissakin teollisissa muoveissa.

Avaliação dos parâmetros de solubilidade de Hildebrand/Hansen na seleção de solventes para a extração de pesticidas organoclorados do solo

This work evaluated the use of the Hildebrand/Hansen solubility parameters for selection of solvents for extraction of the organochlorine pesticides pp' DDT, pp' DDE, Aldrin and a-Endossulfan from soil using columns packed with Al2O3. The mixtures hexane:dichloromethane (7:3; v/v), hexane:acetonitrile (1:1; v/v), hexane:acetone (1:1; v/v) and pure hexane were chosen as extracting solutions. In the addition and recovery tests, different extraction solutions provided high recoveries percentages (>75%) with coefficients of variation below 15%. The recoveries are in agreement with the Hildebrand/Hansen parameters, demonstrating its applicability in the selection of extracting solution and in the replacement of toxic solvents, as dichloromethane

Isocyanates and Amines – Sampling and Analytical Procedures

This thesis covers sampling and analytical procedures for isocyanates (R-NCO) and amines (R-NH2), two kinds of chemicals frequently used in association with the polymeric material polyurethane (PUR). Exposure to isocyanates may result in respiratory disorders and dermal sensitisation, and they are one of the main causes of occupational asthma. Several of the aromatic diamines associated with PUR production are classified as suspected carcinogens. Hence, the presence of these chemicals in different exposure situations must be monitored. In the context of determining isocyanates in air, the methodologies included derivatisation with the reagent di-n-butylamine (DBA) upon collection and subsequent determination using liquid chromatography (LC) and mass spectrometric detection (MS). A user-friendly solvent-free sampler for collection of airborne isocyanates was developed as an alternative to a more cumbersome impinger-filter sampling technique. The combination of the DBA reagent together with MS detection techniques revealed several new exposure situations for isocyanates, such as isocyanic acid during thermal degradation of PUR and urea-based resins. Further, a method for characterising isocyanates in technical products used in the production of PUR was developed. This enabled determination of isocyanates in air for which pure analytical standards are missing. Tandem MS (MS/MS) determination of isocyanates in air below 10-6 of the threshold limit values was achieved. As for the determination of amines, the analytical methods included derivatisation into pentafluoropropionic amide or ethyl carbamate ester derivatives and subsequent MS analysis. Several amines in biological fluids, as markers of exposure for either the amines themselves or the corresponding isocyanates, were determined by LC-MS/MS at amol level. In aqueous extraction solutions of flexible PUR foam products, toluene diamine and related compounds were found. In conclusion, this thesis demonstrates the usefulness of well characterised analytical procedures and techniques for determination of hazardous compounds. Without reliable and robust methodologies there is a risk that exposure levels will be underestimated or, even worse, that relevant compounds will be completely missed.

Phosphorus fractions in soil of the Jena Experiment (Main Experiment, year 2007)

This data set contains measurements of phosphorus fractions (Hedley fractions) in soil collected 2007 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Soil sampling and analysis: Five independent soil samples per plot were taken in a depth of 0-15 cm using a soil corer with an inner diameter of 1 cm. The five samples per plot were combined to one composite sample per plot. A four-step sequential P fractionation (Hedley fractions) was applied. Sequentially, 20 ml NaHCO3 (adjusted to pH 8.5), 30 ml NaOH, and 35 ml HCl were used as extraction solutions for 0.5 g soil. The last step comprised the combustion (550 °C) of the remaining soil to destroy all organic material followed by shaking with 20 ml H2SO4. Organic P concentrations of the respective fractions were calculated as the difference between total dissolved P and inorganic P. Duplicate phosphate concentrations of P fractions in soil were measured photometrically (molybdenum blue-reactive P) with a Continuous Flow Analyzer (Bran&Luebbe, Germany).

Batch Liquid-Liquid Extraction of Phenol from Aqueous Solutions

The aim of this work is the study of batch liquid-liquid extraction of phenol from aqueous solutions in a bench-scale well-mixed reactor. The influence of the ratio of phase volumes, temperature, and rotational speed on phenol removal (0.72-1.1% w/w) was investigated using methyl isobutyl ketone as an extracting solvent. For this purpose, the ratio of phase volumes were set at 0.1 and 0.2, the temperature at 10, 20, and 30 degrees C, and the rotational speed at 300, 400, and 500 rpm. A physical model based on the material balance of the phases as well as the equation of mass flux between the phases allowed the estimation of the overall coefficient of mass transfer coupled with the superficial area. Moreover, it proved to fit, satisfactorily well, the experimental data of residual phenol concentration in the organic phase versus time under all the conditions investigated.

The electronic structure of anionic halide complexes of element 105 in aqueous solutions and their extraction by aliphatic amines

To study the complex formation of group 5 elements (Nb, Ta, Ha, and pseudoanalog Pa) in aqueous HCI solutions of medium and high concentrations the electronic structures of anionic complexes of these elements [MCl_6]^-, [MOCl_4]^-, [M(OH)-2 Cl_4]^-, and [MOCl_5]^2- have been calculated using the relativistic Dirac-Slater Discrete-Variational Method. The charge density distribution analysis has shown that tantalum occupies a specific position in the group and has the highest tendency to form the pure halide complex, [TaCl_6-. This fact along with a high covalency of this complex explains its good extractability into aliphatic amines. Niobium has equal trends to form pure halide [NbCl_6]^- and oxyhalide [NbOCl_5]^2- species at medium and high acid concentrations. Protactinium has a slight preference for the [PaOCl_5]^2- form or for the pure halide complexes with coordination number higher than 6 under these conditions. Element 105 at high HCl concentrations will have a preference to form oxyhalide anionic complex [HaOCl_5]^2- rather than [HaCl_6]^-. For the same sort of anionic oxychloride complexes an estimate has been done of their partition between the organic and aqueous phases in the extraction by aliphatic amines, which shows the following succession of the partition coefficients: P_Nb < P_Ha < P_Pa.

The solvent-solvent extraction of uranium from sulfuric acid solutions with oil soluble amines /

Fifty oil soluble amines were screened for possible use as extractants for uranium from sulfuric acid solutions. The most promising of these were studied further to obtain the optimum conditions for operation of such a process. Kerosene was used as the diluent.

Power Secant Method applied to natural frequency extraction of Timoshenko beam structures

This work deals with an improved plane frame formulation whose exact dynamic stiffness matrix (DSM) presents, uniquely, null determinant for the natural frequencies. In comparison with the classical DSM, the formulation herein presented has some major advantages: local mode shapes are preserved in the formulation so that, for any positive frequency, the DSM will never be ill-conditioned; in the absence of poles, it is possible to employ the secant method in order to have a more computationally efficient eigenvalue extraction procedure. Applying the procedure to the more general case of Timoshenko beams, we introduce a new technique, named ""power deflation"", that makes the secant method suitable for the transcendental nonlinear eigenvalue problems based on the improved DSM. In order to avoid overflow occurrences that can hinder the secant method iterations, limiting frequencies are formulated, with scaling also applied to the eigenvalue problem. Comparisons with results available in the literature demonstrate the strength of the proposed method. Computational efficiency is compared with solutions obtained both by FEM and by the Wittrick-Williams algorithm.

Simultaneous flow injection preconcentration of lead and cadmium using cloud point extraction and determination by atomic absorption spectrometry

A flow injection (FI) micelle-mediated separation/preconcentration procedure for the determination of lead and cadmium by flame atomic absorption spectrometry (FAAS) has been proposed. The analytes reacted with 1-(2-thiazolylazo)-2-naphthol (TAN) to form hydrophobic chelates, which were extracted into the micelles of 0.05% (w/v) Triton X-114 in a solution buffered at pH 8.4. In the preconcentration stage, the micellar solution was continuously injected into a flow system with four mini-columns packed with cotton, glass wool. or TNT compresses for phase separation. The analytes-containing micelles were eluted from the mini-columns by a stream of 3 mol L(-1) HCl solution and the analytes were determined by FAAS. Chemical and flow variables affecting the preconcentration of the analytes were studied. For 15 mL. of preconcentrated solution, the enhancement factors varied between 15.1 and 20.3, the limits of detection were approximately 4.5 and 0.75 mu g L(-1) for lead and cadmium, respectively. For a solution containing 100 and 10 mu g L(-1) of lead and cadmium, respectively, the R.S.D. values varied from 1.6 to 3.2% (n = 7). The accuracy of the preconcentration system was evaluated by recovery measurements on spiked water samples. The method was susceptible to matrix effects, but these interferences were minimized by adding barium ions as masking agent in the sample solutions, and recoveries from spiked sample varied in the range of 95.1-107.3%. (C) 2008 Elsevier B.V. All rights reserved.

Synthesis, characterization and evaluation of phosphorylated resins in the removal of Pb(2+) from aqueous solutions

Phosphinic-derivative poly(styrene-co-divinylbenzene)-based on PS-DVB copolymers with different porosity degrees have been prepared by aromatic electrophilic substitution reaction using PCl(3)/AlCl(3) followed by base-promoted hydrolysis. The phosphorylation reaction was analyzed by infra-red spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetry (TG/DTG). In addition, the phosphorous content of the phosphorylated copolymers was determined by spectrophotometry using the method based on sodium molybdate reactant so that the extension of that modification could be assessed. The performance of the phosphorylated resins in the extraction of Pb(2+) from aqueous solutions in a batch system was also evaluated. The Pb(2+) content was determined by atomic absorption spectrometry (AAS). These materials presented excellent extraction capacity under the contact time of 30 min and pH 6.