Análise de agrotóxicos em água usando extração líquido-líquido com partição em baixa temperatura por cromatografia líquida de alta eficiência

This study optimized and validated the liquid-liquid extraction technique with partition at low temperature (LLE-PLT) for identification and quantification of four pesticides (chlorpyrifos, λ-cyhalothrin, permethrin, bifenthrin) in water samples. Analyses were performed by HPLC-UV. The technique was efficient for pesticide recovery with extraction exceeding 86%. Chromatographic response was linear for the four compounds in the 10-45 µg L-1 range, with correlation coefficients greater than 0.99. Limits of detection and quantitation were less than 3.5 µg L-1 and equal to 10 µg L-1, respectively. The proposed method was applied to 29 water samples from the Jaíba Project in northern Minas Gerais.

Otimização, validação e aplicação de método para determinação da concentração residual de difenoconazol em morangos após múltiplas aplicações

Difenoconazole residues in strawberry fruit cultivated in pots were estimated using the solid-liquid extraction with low temperature partition (SLE/LTP) method for sample preparation and gas chromatography with electron capture detection (GC/ECD) for analysis. The optimized method presented excellent recovery values from fortified samples and reproducibility (average recovery values ≥ 98%; CV values < 15%). Linearity of response was demonstrated (r = 0.995) with a detection limit of 9 µg kg-1. The method was successfully applied for the determination of difenoconazole residues in strawberries. Based on these results, the fungicide dissipates quickly, but the residual concentration increases after multiple applications.

Desenvolvimento do método de extração sólido-líquido com partição em baixa temperatura para determinação de inseticidas em grãos de milho ozonizados

The objective of this study was to optimize and validate a solid-liquid extraction method with low-temperature partitioning (SLE/LTP) for the analysis of pesticides. This method was coupled with gas chromatography (GC/ECD) and used to evaluate the degradation of bifenthrin and pirimiphos-methyl in maize grains on exposure to ozone. The optimized SLE/LTP-GC/ECD method is simple, effective and consumes low quantities of the solvent. It can be routinely used for the determination of bifenthrin and pirimiphos-methyl in maize samples. The use of this method of analysis determined that the levels of the insecticides in maize grains were reduced on exposure of the grains to the ozone gas. The observed reduction in the levels of insecticide was directly proportional to the increase in the concentration of the ozone gas.

Otimização e validação da extração sólido-líquido e purificação em baixa temperatura de HPAs em lodo de esgoto

In this study, a method of solid-liquid extraction and purification at low temperature (SLE-PLT) to determine 16 polycyclic aromatic hydrocarbons (PAHs) in sewage sludge was optimized and validated. The analyses were performed by HPLC-UV. The extraction phase, homogenization procedure, influence of pH, ionic strength and clean-up of the extracts were optimized. Recoveries were higher than 63.4% for 11 PAHs. The correlation coefficients were greater than 0.99 and limits of detection and quantitation were less than 0.060 and 0.15 µg g-1, respectively. These values were lower than the maximum residue limits of PAHs established by European legislation. SLE-PLT proved a more practical, economical method with fewer steps compared to Soxhlet extraction (reference method) for PAHs in sewage sludge.

Desenvolvimento de procedimento de extração para análise de sedativos e B-bloqueadores em rim suíno

A procedure was developed for determination of 5 sedatives and 14 β-blockers in swine kidney and subsequent analysis by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Three different procedures for extraction were tested, evaluated through recovery studies. The procedure using acetonitrile for extraction and cleanup with freezing at low temperature and dispersive solid phase extraction using 500 mg celite® 545 before the concentration step presented the better results. The dried samples were redissolved with methanol and analyzed using a LC-MS/MS system with electrospray ionization (ESI) operating in positive MRM mode. The recovery values for this procedure were in the 75-88% range. The robustness of the method was tested against small variations. The method was used to analyze carazolol, azaperone and azaperol in collaborative assay, obtaining results close to designed value.

Distribuição dos Hydrozoa até agora conhecidos nas costas do Brasil

This work was done with the aim of computing all the species of Hydrozoa (Siphonophora excluded) that have been collected on the Brazilian coast, or in the pelagial, near the coast (some of the "Meteor" Stations). Nutting's (1900, 1904, 1915) and Mayer's (1910) monographs were taken as starting points and later papers and the Zoological Record used to check posterior findings. As a whole, 116 different valid names, among species and forms, have been mentioned from the Brazilian coast, distributed among 60 genera. Of the 116 species, 82 are represented by hydropolyps, 30 by hydromedusae (11 of which belong to the Trachylina and therefore lack a polypoid generation) and finally, by 4 species of which are known both polypoid and medusoid generations. The subdivision of the coast has been made at random, on account of the scarcity of the findings, except for the best known district, that goes from the latitude of Vitoria (State of Espirito Santo, at about 20ºlat.S.) to the bay of Santos (State of São Paulo, about 24ºlat.S.). The latitude of Cabo Frio (23ºlat.S.) was considered as a possible natural barrier, and the results of the global counting of the distribution of the hydropolyps North and South of 23ºlat.S. is the following: 29 species are known only North of Cabo Frio, 26 only from the same latitude (see direction of the coast, along parallel 23ºS.) or further South and 28 species are known both North and South of the coast (of these, 5 species are "cosmopolitan"). Therefore it seems quite possible that Cabo Frio really is a barrier to the distribution of 55 species. 26 species are endemic to the Brazilian coast, of these, only 5 are found both North and South of the Cape, while-14 are found only North and 7 only South. No studies can be done, on the bathymetric distribution in relation to the latitude. These results must be considered as provisory since more extensive researches will probably alter these figures. However, I believe that they are significative as a mean index of the condition of the hydrozoan fauna of the Brazilian coast. A tentative working hypothesis is presented as to the possible factors that confer such a zoogeographic importance to the region of Cabo Frio, a fact that has been foreseen by Ekman (1935, p. 73). Geographic position, currents, latitude and nature of the sea bottom between the continent and the oceanic island of Trindade have been taken in consideration, and all of them seem to be possible eficient factors of separation. Furthermore, according to the data obtained by the "Meteor" Expedition in July 2, 1926, at station 164 (23º8'lat.S. - 42º5'long.W.) and station 165 (23º35'lat.S. - 40º52'long.W.) and by what is known by hearsay and local experience of the region (exact continued study is urgently needed), it seems possible that, off from the sharp curve that the coast has at Cabo Frio, there may be an irregularity of the general scheme of the current and local upwelling may be present that would explain the local low temperature, low salinity and high density of the superficial layers as well as the abundance of fishes; these factors might contribute towards the establishement of a zoogeographical barrier. Further work is needed and nothing more than an hypothesis can be presented for the moment.

Polttomoottorivoimalan energiatehokkuuden parantaminen hukkalämpövirtojen sähköksi muunnolla

Tämä diplomityö on osa FCEP hankeen Lappeenrannan teknillisessä yliopistossa tehtävää tutkimusta polttomoottoreiden energiatehokkuuden parantamisesta. Työn tavoitteena on saada tutkimustietoa polttomoottoreiden hukkalämpövirtojen hyödyntämisestä sähköntuotannossa. Tavoitteena on kartoittaa polttomoottorin hukkalämpövirtojen sähköksi muunnon potentiaalia valituilla menetelmillä ja tekniikoilla. Työssä tarkasteltavaksi moottoriksi valittiin DF- monipolttoainemoottori. DF-moottorin polttoaineena voidaan käyttää joko kaasua tai polttoöljyä. Laskennat suoritettiin moottorin valmistajan antamien hukkalämpövirtojen arvojen ja moottorin lämpötaseen avulla. Laskennan perusperiaatteena oli vesihöyryprosessin ja ORC-prosessien vertailu pakokaasulämmön hyödyntämisessä sekä matalalämpöisten hukkalämpövirtojen hyödyntäminen ORC-prosesseilla. Lisäksi työssä tutkittiin korkealla painesuhteella ja korkealla hyötysuhteella toimivan turboahtimen vaikutusta hukkalämpövirroista saatavaan tehoon. Diplomityössä tarkasteltiin moottorin lämpötaseen mukaisten arvojen lisäksi moottorin parametrien muuttamisen vaikutusta hukkalämpövirroista saatavaan tehoon. Moottorin parametrien muuttamisen vaikutusta moottorin akselitehoon tai moottorin lämpötaseeseen ei kuitenkaan tämän tutkimuksen puitteissa tarkasteltu. Työssä saatiin arvokasta tietoa polttomoottoreiden hukkalämpövirtojen muuntamisesta sähköksi eri menetelmillä sekä moottorin energiatehokkuuden parantamisesta.

Leaf-Targeted Ferredoxin-NADP+-Oxidoreductase (FNR): Electron Transfer Properties and Thylakoid Association in Arabidopsis thaliana

Photosynthetic reactions are divided in two parts: light-driven electron transfer reactions and carbon fixation reactions. Electron transfer reactions capture solar energy and split water molecules to form reducing energy (NADPH) and energy-carrying molecules (ATP). These end-products are used for fixation of inorganic carbon dioxide into organic sugar molecules. Ferredoxin-NADP⁺ oxidoreductase (FNR) is an enzyme that acts at the branch point between the electron transfer reactions and reductive metabolism by catalyzing reduction of NADP+ at the last step of the electron transfer chain. In this thesis, two isoforms of FNR from A rabidopsis thaliana, FNR1 and FNR2, were characterized using the reverse genetics approach. The fnr1 and fnr2 mutant plants resembled each other in many respects. Downregulation of photosynthesis protected the single fnr mutant plants from excess formation of reactive oxygen species (ROS), even without significant upregulation of antioxidative mechanisms. Adverse growth conditions, however, resulted in phenotypic differences between fnr1 and fnr2. While fnr2 plants showed downregulation of photosynthetic complexes and upregulation of antioxidative mechanisms under low-temperature growth conditions, fnr1 plants had the wild-type phenotype, indicating that FNR2 may have a specific role in redistribution of electrons under unfavorable conditions. The heterozygotic double mutant (fnr1xfnr2) was severely devoid of chloroplastic FNR, which clearly restricted photosynthesis. The fnr1xfnr2 plants used several photoprotective mechanisms to avoid oxidative stress. In wild-type chloroplasts, both FNR isoforms were found from the stroma, the thylakoid membrane, and the inner envelope membrane. In the absence of the FNR1 isoform, FNR2 was found only in the stroma, suggesting that FNR1 and FNR2 form a dimer, by which FNR1 anchors FNR2 to the thylakoid membrane. Structural modeling predicted formation of an FNR dimer in complex with ferredoxin. In this thesis work, Tic62 was found to be the main protein that binds FNR to the thylakoid membrane, where Tic62 and FNR formed high molecular weight complexes. The formation of such complexes was shown to be regulated by the redox state of the chloroplast. The accumulation of Tic62-FNR complexes in darkness and dissociation of complexes from the membranes in light provide evidence that the complexes may have roles unrelated to photosynthesis. This and the high viability of fnr1 mutant plants lacking thylakoid-bound FNR indicate that the stromal pool of FNR is photosynthetically active.

Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.

Polymer surface modification by atomic layer deposition

Current industrial atomic layer deposition (ALD) processes are almost wholly confined to glass or silicon substrates. For many industrial applications, deposition on polymer substrates will be necessary. Current deposition processes are also typically carried out at temperatures which are too high for polymers. If deposition temperatures in ALD can be reduced to the level applicable for polymers, it will open new interesting areas and applications for polymeric materials. The properties of polymers can be improved for example by coatings with functional and protective properties. Although the ALD has shown its capability to operate at low temperatures suitable for polymer substrates, there are other issues related to process efficiency and characteristics of different polymers where new knowledge will assist in developing industrially conceivable ALD processes. Lower deposition temperature in ALD generally means longer process times to facilitate the self limiting film growth mode characteristic to ALD. To improve process efficiency more reactive precursors are introduced into the process. For example in ALD oxide processes these can be more reactive oxidizers, such as ozone and oxygen radicals, to substitute the more conventionally used water. Although replacing water in the low temperature ALD with ozone or plasma generated oxygen radicals will enable the process times to be shortened, they may have unwanted effects both on the film growth and structure, and in some cases can form detrimental process conditions for the polymer substrate. Plasma assistance is a very promising approach to improve the process efficiency. The actual design and placement of the plasma source will have an effect on film growth characteristics and film structure that may retard the process efficiency development. Due to the fact that the lifetime of the radicals is limited, it requires the placement of the plasma source near to the film growth region. Conversely this subjects the substrate to exposure byother plasma species and electromagnetic radiation which sets requirements for plasma conditions optimization. In this thesis ALD has been used to modify, activate and functionalize the polymer surfaces for further improvement of polymer performance subject to application. The issues in ALD on polymers, both in thermal and plasma-assisted ALD will be further discussed.

Growth, magnetic and transport properties of InSb and II-IV-As2 semiconductors doped with manganese

This thesis is devoted to growth and investigations of Mn-doped InSb and II-IV-As2 semiconductors, including Cd1-xZnxGeAs2:Mn, ZnSiAs2:Mn bulk crystals, ZnSiAs2:Mn/Si heterostructures. Bulk crystals were grown by direct melting of starting components followed by fast cooling. Mn-doped ZnSiAs2/Si heterostructures were grown by vacuum-thermal deposition of ZnAs2 and Mn layers on Si substrates followed by annealing. The compositional and structural properties of samples were investigated by different methods. The samples consist of micro- and nano- sizes clusters of an additional ferromagnetic Mn-X phases (X = Sb or As). Influence of magnetic precipitations on magnetic and electrical properties of the investigated materials was examined. With relatively high Mn concentration the main contribution to magnetization of samples is by MnSb or MnAs clusters. These clusters are responsible for high temperature behavior of magnetization and relatively high Curie temperature: up to 350 K for Mn-doped II-IV-As2 and about 600 K for InMnSb. The low-field magnetic properties of Mn-doped II-IV-As2 semiconductors and ZnSiAs2:Mn/Si heterostructures are connected to the nanosize MnAs particles. Also influence of nanosized MnSb clusters on low-field magnetic properties of InMnSb have been observed. The contribution of paramagnetic phase to magnetization rises at low temperatures or in samples with low Mn concentration. Source of this contribution is not only isolated Mn ions, but also small complexes, mainly dimmers and trimmers formed by Mn ions, substituting cation positions in crystal lattice. Resistivity, magnetoresistance and Hall resistivity properties in bulk Mn-doped II-IV-As2 and InSb crystals was analyzed. The interaction between delocalized holes and 3d shells of the Mn ions together with giant Zeeman splitting near the cluster interface are respond for negative magnetoresistance. Additionally to high temperature critical pointthe low-temperature ferromagnetic transition was observed Anomalous Hall effect was observed in Mn doped samples and analyzed for InMnSb. It was found that MnX clusters influence significantly on magnetic scattering of carriers.

Color change and quality response of ‘lane late’ orange submitted to degreening process

This study aimed at evaluating the effects of ethylene on peel color and compositional changes in ‘Lane late’ orange stored under refrigerated and ambient conditions. Physiologically mature, but green-peeled, oranges were exposed to ethylene gas under room temperature and high relative humidity for 24 hours. Storage chamber was ventilated with fresh air after 12 hours to mitigate consequences derived from fruit respiration. Both nondestructive analysis, such as peel color (hue angle, chromaticity, and brightness) and weight loss, and destructive ones (soluble solids, titratable acidity, pH, soluble solids to acidity ratio, and puncture force) were performed upon harvest, after degreening, and every three days during eighteen days in storage. Experiment was carried out using an entirely randomized design with thirty replications for nondestructive and four replications for destructive analyses, in a split plot scheme. Exposure to ethylene ensured a golden yellow peel for both fruit stored under ambient and refrigerated conditions. High relative humidity, associated with low temperature prevented fruit from losing moisture. Fruit exposure to ethylene did not affect weight loss, soluble solids, titratable acidity, pH, soluble solids, acidity ratio, or puncture force.

Comparison of diffusion models for description of osmotic dehydration of radish slices dipped in brine

ABSTRACT This paper aims at describing the osmotic dehydration of radish cut into cylindrical pieces, using one- and two-dimensional analytical solutions of diffusion equation with boundary conditions of the first and third kind. These solutions were coupled with an optimizer to determine the process parameters, using experimental data. Three models were proposed to describe the osmotic dehydration of radish slices in brine at low temperature. The two-dimensional model with boundary condition of the third kind well described the kinetics of mass transfers, and it enabled prediction of moisture and solid distributions at any given time.

Advanced welding technologies used for arctic metal structures

Rapid depletion of easy-to-access fossil fuel, predominantly, oil and gas resources has now necessitated increase in need to develop new oil and gas sources in ever more remote and hostile environments. This is necessary in order to explore more oil and gas resources to meet rapidly rising long-term energy demand in the world, both at present and in the nearest future. Arctic is one of these harsh environments, where enormous oil and gas resources are available, containing about 20% of the world total oil and gas, but the environmental conditions are very harsh and hostile. However, virtually all the facilities required for the exploration and development of this new energy source are constructed with metals as well as their alloys and are predominantly joined together by welding processes and technologies. Meanwhile, due to entirely different environment from the usual moderate temperate region, conventional welding technologies, common metals and their alloys cannot be applied as this Arctic environment demand metals structures with very high toughness and strength properties under extremely low temperature. This is due to the fact that metals transit from ductility to brittleness as the temperature moves toward extreme negative values. Hence, this research work investigates and presents the advanced welding technologies applicable to Arctic metal structures which can give satisfactory weldments under active Arctic service conditions. .

Lujien hitsattavien terästen käyttäytyminen -60 °C:ssa

Opinnäytetyö on osa Arctic Materials Technologies Development -projektia, jonka tavoitteena on kehittää perusteita arktisten alueiden sovelluksiin suunnittelun ja valmistuksen kannalta. Arktisella alueella sijaitsee useita potentiaalisia öljy- ja maakaasuesiintymiä, joiden hyödyn-täminen tulee vuosi vuodelta kannattavammaksi ilmaston lämpenemisestä johtuvan merijään heikkenemisen vuoksi. Alin suunnittelulämpötila arktisilla alueilla on -60 °C, mikä aiheuttaa haasteita sekä materiaalinvalinnalle että hitsaukselle. Ferriittisillä teräksillä esiintyy lämpötilasta riippuvaa sitkeyden vaihtelua, jota kutsutaan transi-tiokäyttäytymiseksi. Lämpötilan laskiessa teräksen iskusitkeys sekä murtumissitkeys laske-vat. Arktisissa sovelluskohteissa käytetään yleisesti niukkaseosteisia, mikroseostettuja hie-noraeteräksiä, joille on ominaista erinomaiset sitkeys-, lujuus- sekä hitsattavuusominaisuudet vaativissakin olosuhteissa. Lujat termomekaanisesti valssatut ja nuorrutetut hienoraeteräkset kattavat myötölujuusluokat 355…700 MPa. Tutkimuksissa on saatu vaihtelevia tuloksia ma-teriaalien isku- ja murtumissitkeydestä -60 °C:ssa. Erityisesti sitkeysominaisuudet hitsiaineen ja muutosvyöhykkeen alueiden välillä ovat vaihtelevia. Pienemmällä lämmöntuonnilla ja seostetuilla lisäaineilla saavutetaan kuitenkin pääsääntöisesti parempia sitkeysarvoja. Asiku-laarinen ferriitti sekä alabainiitti ovat toivottavia mikrorakenteita liitoksessa, niiden pienen raekoon johdosta.