Flow injection visible diffuse reflectance quantitative analysis of total sulfur in biodiesel, in plant leaves and in natural waters

Flow injection (FI) methodology, using diffuse reflectance in the visible region of the spectrum, for the analysis of total sulfur in the form of sulfate, precipitated in the form of barium sulfate, is presented. The method was applied to biodiesel, to plant leaves and to natural waters analysis. The analytical signal (S) correlates linearly with sulfate concentration (C) between 20 and 120 ppm, through the equation S=-1.138+0.0934 C (r = 0.9993). The experimentally observed limit of detection is about 10 ppm. The mean R.S.D. is about 3.0 %. Real samples containing sulfate were analyzed and the results obtained by the FI and by the reference batch turbidimetric method using the statistical Student's t-test and F-test were compared.

Determination of sulfur in diesel using ATR/FTIR and multivariate calibration

The aim of this present work was to provide a more fast, simple and less expensive to analyze sulfur content in diesel samples than by the standard methods currently used. Thus, samples of diesel fuel with sulfur concentrations varying from 400 and 2500 mgkg-1 were analyzed by two methodologies: X-ray fluorescence, according to ASTM D4294 and by Fourier transform infrared spectrometry (FTIR). The spectral data obtained from FTIR were used to build multivariate calibration models by partial least squares (PLS). Four models were built in three different ways: 1) a model using the full spectra (665 to 4000 cm-1), 2) two models using some specific spectrum regions and 3) a model with variable selected by classic method of variable selection stepwise. The model obtained by variable selection stepwise and the model built with region spectra between 665 and 856 cm-1 and 1145 and 2717 cm-1 showed better results in the determination of sulfur content.

Cluster structure of atomic nuclei

Kirjallisuusarvostelu

Early detection of injuries in leaves of Clusia hilariana Schltdl. (Clusiaceae) caused by particulate deposition of iron

This study aims to evaluate the prognostic value of microscopic parameters of asymptomatic leaves of Clusia hilariana Schltdl. subjected to particulate deposition of iron (2.14 mg cm-2 day-1) for 45 consecutive days. Samples of young and expanded leaves without symptoms were collected and subjected to light and scanning electron microscopy techniques. The height of the epidermal cells on both surfaces of the leaf and the thickness of the hypodermis, the chlorophyll parenchyma, and the leaf blade were measured. Micromorphological injury occurred in the abaxial surface of young leaves and on both surfaces of expanded leaves. Erosion of the epicuticular wax and cuticle rupture were frequent on the adaxial surface, while on the abaxial surface of both leaves there was a loss of sinuosity on the anticlinal wall of the epidermal cells, stomatal deformity and obstruction. Micromorphometric alterations were seen in all leaf tissues except in the height of epidermic cells, probably due to the thick cuticle and prominent cuticular flanges. The highest difference in thickness of the leaf blade was seen in young leaves of plants subjected to SPMFe, indicating greater sensibility to particulate iron in comparison to the expanded leaves. The micromorphological and micromorphometric alterations in the leaf blade of Clusia hilariana Schltdl. showed the prognostic potential of these tools on the evaluation of impacts caused by the deposition of particulate matter, especially in the 'Restinga' natural vegetation, where the exposure is increasing due to the presence of iron ore industry in their surroundings.

Activation of supply relationships : a study of main providers in the Turku logistics cluster

Företag inom industri och handel väljer allt oftare att låta ett logistikföretag sköta stora delar av sina logistiska processer. Logistikföretagen i sin tur överlåter utförandet av enskilda tjänster, som t.ex. olika typer av transport, till olika samarbetspartners inom branschen. I avhandlingen studeras hur logistikföretag går till väga då de väljer vilka av deras samarbetspartners som ska engageras för att delta i utförandet av ett logistiktjänstepaket, en arbetsprocess som här kallas aktivering. Fokus ligger på aktiveringens innehåll och de faktorer som inverkar på hur den går till och vilka samarbetsparter som kommer att engageras. Arbetet bygger på nätverksansatsen för studier av företagsrelationer på industriella marknader. Aktiveringsprocessen uppfattas som en rätt ordinär, rutinmässig verksamhet i företaget, men den kan också förväntas inverka på hur företagets samarbetsnätverk utvecklas över tiden, genom att vissa relationer förstärks medan andra försvagas. I den empi riska undersökningen deltog 29 logistikföretag i Åboregionen som utgående från ett diskussionsunderlag fick berätta om hur de går till väga vid aktivering.

Spatial variability of leaf nutrient contents in a drip irrigated citrus orchard

This study aimed to evaluate the spatial variability of leaf content of macro and micronutrients. The citrus plants orchard with 5 years of age, planted at regular intervals of 8 x 7 m, was managed under drip irrigation. Leaf samples were collected from each plant to be analyzed in the laboratory. Data were analyzed using the software R, version 2.5.1 Copyright (C) 2007, along with geostatistics package GeoR. All contents of macro and micronutrients studied were adjusted to normal distribution and showed spatial dependence.The best-fit models, based on the likelihood, for the macro and micronutrients were the spherical and matern. It is suggest for the macronutrients nitrogen, phosphorus, potassium, calcium, magnesium and sulfur the minimum distances between samples of 37; 58; 29; 63; 46 and 15 m respectively, while for the micronutrients boron, copper, iron, manganese and zinc, the distances suggests are 29; 9; 113; 35 and 14 m, respectively.

Adaptation of "Niagara Rosada" grape must to winemaking by partial cluster dehydration

This study aimed to verify the influence of partial dehydration of "Niagara Rosada" grape clusters in physicochemical quality of the pre- fermentation must. In Brazil, during the winemaking process it is common to need to adjust the grape must when the physicochemical characteristics of the raw material are insufficient to produce wines in accordance with the Brazilian legislation for classification of beverages, which establishes the minimum alcohol content of 8.6 % for the beverage to be considered wine. Therefore, given that the reduction in the water content of grape berries allows the concentration of chemical compounds present in its composition, especially the concentration of total soluble solids, we proceeded with the treatments that were formed by the combination of two temperatures (T1-37.1ºC and T2-22.9 ºC) two air speeds (S1: 1.79 m s-1 and S2: 3.21 m s-1) and a control (T0) that has not gone through the dehydration treatment. Analysis of pH, Total Titratable Acidity (TTA) were performed in mEq L-1, Total Soluble Solids (TSS) in ºBrix, water content on a dry basis and Concentration of Phenolic Compounds (CPC) in mg of gallic acid per 100g of must. The average comparison test identified statistically significant modifications for the adaptation of must for winemaking purposes, having the treatment with 22.9 ºC and air speed of 1.79 m s-1 shown the largest increase in the concentration of total soluble solids, followed by the second best result for concentration of phenolic compounds.

Quasiclassical Approach to the Vortex State in Iron-based Superconductors

The quasiclassical approach was applied to the investigation of the vortex properties in the ironbased superconductors. The special attention was paid to manifestation of the nonlocal effects of the vortex core structure. The main results are as follows: (i) The effects of the pairing symmetries (s+ and s₊₊) on the cutoff parameter of field distribution, ξh, in stoichiometric (like LiFeAs) and nonstoichiometric (like doped BaFe₂As₂) iron pnictides have been investigated using Eilenberger quasiclassical equations. Magnetic field, temperature and impurity scattering dependences of ξh have been calculated. Two opposite behavior have been discovered. The ξh /ξc2 ratio is less in s+ symmetry when intraband impurity scattering (Γ₀) is much larger than one and much larger than interband impurity scattering (Γπ), i.e. in nonstoichiometric iron pnictides. Opposite, the value ξh /ξc2 is higher in s+ case and the field dependent curve is shifted upward from the "clean" case (Γ₀ = Γπ = 0) for stoichiometric iron pnictides (Γ₀ = Γπ ≪ 1). (ii) Eilenberger approach to the cutoff parameter, ξh, of the field distribution in the mixed state of high

Acidic dissolution of iron oxides and regeneration of a ceramic filter medium

The dewatering of iron ore concentrates requires large capacity in addition to producing a cake with low moisture content. Such large processes are commonly energy intensive and means to lower the specific energy consumption are needed. Ceramic capillary action disc filters incorporate a novel filter medium enabling the harnessing of capillary action, which results in decreased energy consumption in comparison to traditional filtration technologies. As another benefit, the filter medium is mechanically and chemically more durable than, for example, filter cloths and can, thus, withstand harsh operating conditions and possible regeneration better than other types of filter media. In iron ore dewatering, the regeneration of the filter medium is done through a combination of several techniques: (1) backwashing, (2) ultrasonic cleaning, and (3) acid regeneration. Although it is commonly acknowledged that the filter medium is affected by slurry particles and extraneous compounds, published research, especially in the field of dewatering of mineral concentrates, is scarce. Whereas the regenerative effect of backwashing and ultrasound are more or less mechanical, regeneration with acids is based on chemistry. The chemistry behind the acid regeneration is, naturally, dissolution. The dissolution of iron oxide particles has been extensively studied over several decades but those studies may not necessarily be directly applicable in the regeneration of the filter medium which has undergone interactions with the slurry components. The aim of this thesis was to investigate if free particle dissolution indeed correlates with the regeneration of the filter medium. For this purpose, both free particle dissolution and dissolution of surface adhered particles were studied. The focus was on acidic dissolution of iron oxide particles and on the study of the ceramic filter medium used in the dewatering of iron ore concentrates. The free particle dissolution experiments show that the solubility of synthetic fine grained iron oxide particles in oxalic acid could be explained through linear models accounting for the effects of temperature and acid concentration, whereas the dissolution of a natural magnetite is not so easily explained by such models. In addition, the kinetic experiments performed both support and contradict the work of previous authors: the suitable kinetic model here supports previous research suggesting solid state reduction to be the reaction mechanism of hematite dissolution but the formation of a stable iron oxalate is not supported by the results of this research. Several other dissolution mechanisms have also been suggested for iron oxide dissolution in oxalic acid, indicating that the details of oxalate promoted reductive dissolution are not yet agreed and, in this respect, this research offers added value to the community. The results of the regeneration experiments with the ceramic filter media show that oxalic acid is highly effective in removing iron oxide particles from the surface of the filter medium. The dissolution of those particles did not, however, exhibit the expected behaviour, i.e. complete dissolution. The results of this thesis show that although the regeneration of the ceramic filter medium with acids incorporates the dissolution of slurry particles from the surface of the filter medium, the regeneration cannot be assessed purely based upon free particle dissolution. A steady state, dependent on temperature and on the acid concentration, was observed in the dissolution of particles from the surface even though the limit of solubility of free iron oxide particles had not been reached. Both the regeneration capacity and efficiency, with regards to the removal of iron oxide particles, was found to be temperature dependent, but was not affected by the acid concentration. This observation further suggests that the removal of the surface adhered particles does not follow the dissolution of free particles, which do exhibit a dependency on the acid concentration. In addition, changes in the permeability and in the pore structure of the filter medium were still observed after the bulk concentration of dissolved iron had reached a steady state. Consequently, the regeneration of the filter medium continued after the dissolution of particles from the surface had ceased. This observation suggests that internal changes take place at the final stages of regeneration. The regeneration process could, in theory, be divided into two, possibly overlapping, stages: (1) dissolution of surface-adhered particles, and (2) dissolution of extraneous compounds from within the pore structure. In addition to the fundamental knowledge generated during this thesis, tools to assess the effects of parameters on the regeneration of the ceramic filter medium are needed. It has become clear that the same tools used to estimate the dissolution of free particles cannot be used to estimate the regeneration of a filter medium unless only a robust characterisation of the order of regeneration efficiency is needed.

CO2 sparging for improving the filtration properties of iron ore slurries

Iron ore treatment processes are usually continuous and high tonnage and filtration equipment has to meet these requirements. In magnetite (Fe3O4) treatment process continuous rotary disc filters are often used for filtration. Carbon dioxide (CO2) treatment is a fairly novel and un-known filtration enhancing process. The interest to use CO2 is quite high because CO2 is a greenhouse gas that is abundant, readily available and capture and use of CO2 would be environmentally beneficial. The focus of this thesis was to investigate if CO2 could be used to enhance the filtration of magnetite with ceramic disc filter. Previous studies have suggested that CO2 could be used to enhance the filtration properties of different iron ores thus increasing the filtration capacity. In the literature part, the basic theory of filtration and the particle properties affecting filtration were discussed. The basic steps of a typical ore treatment process were presented. The reasons why CO2 might enhance the filtration properties of different ores were investigated. A literature survey of earlier studies of CO2 addition as a filter aid was presented and the basic chemical properties and reactions of CO2 were also discussed. The experimental part was done at the LUT Laboratory of Separation Technology using different magnetite samples from the industry. The filtration experiments indicated that CO2 had a positive influence on the filtration properties of magnetite slurry. Zeta potential of untreated and CO2 treated magnetite was measured and CO2 treated magnetite had lower zeta potential values than the untreated magnetite. The filtration capacity was increased while the cake moisture levels were only slightly increased.

Development of an environmentally friendly method of starch oxidation by hydrogen peroxide and a complex water-soluble Iron catalyst

Oxidized starch is a key component in the paper industry, where it is used as both surfacing sizer and filler. Large quantities are annually used for this purpose; however, the methods for the oxidation are not environmentally friendly. In our research, we have studied the possibility to replace the harmful oxidation agents, such as hypochlorite or iodates and transition metal catalysts, with a more environmentally friendly oxidant, hydrogen peroxide (H2O2), and a special metal complex catalyst (FePcS), of which only a small amount is needed. The work comprised batch and semi-batch studies by H2O2, ultrasound studies of starch particles, determination of low-molecular by-products and determination of the decomposition kinetics of H2O2 in the presence of starch and the catalyst. This resulted in a waste-free oxidation method, which only produces water and oxygen as side products. The starch oxidation was studied in both semi-batch and batch modes in respective to the oxidant (H2O2) addition. The semi-batch mode proved to yield a sufficient degree of substitution (COOH groups) for industrial purposes. Treatment of starch granules by ultrasound was found to improve the reactivity of starch. The kinetic results were found out to have a rather complex pattern – several oxidation phases were observed, apparently due to the fact that the oxidation reaction in the beginning only took place on the surface, whereas after a prolonged reaction time, partial degradation of the solid starch granules allowed further reaction in the interior parts. Batch-mode experiments enabled a more detailed study of the mechanisms of starch in the presence of H2O2 and the catalyst, but yielded less oxidized starch due to rapid decomposition of H2O2 due to its high concentrations. The effect of the solid-liquid (S/L) ratio in the reaction system was studied in batch experiments. These studies revealed that the presence of the catalyst and the starch enhance the H2O2 decomposition.