ADAPTAÇÃO DA METODOLOGIA DE ANÁLISE DE METEMOGLOBINA COMO BIOMARCADOR DE EFEITO DA EXPOSIÇÃO AO AGROTÓXICO DIFLUBENZURON

This work aimed to adapt the analysis of methemoglobin recommended by Evelyn - Malloy (visible spectrophotometry), in order to facilitate its application in the field, or to analysis in clinical laboratory, of existing sites of diflubenzuron application. The parameters changed included: centrifuge rotation speed; time between the collection of biological sample and analysis, and storage temperature of the samples; and the volume of reagents. The comparison of the rotation speed (rpm) of the reference methodology with the rpm of a "clinical centrifuge" did not reveal a statistically significant difference in the levels of methemoglobin. The time between the collection of biological sample and analysis was extended for a period of up to 48 hours for both conservation by refrigeration and ambient temperature, producing no statistically significant difference when compared to the standard duration of 2 hours. Regarding the reagents, the reference methodology already uses the volume necessary to ensure complete reaction, whereas a wider range from the recommended volume to a 5-fold reduction in comparison to the reference methodology could be used. It was concluded that the proposed changes to the methodology for adapting the analysis are applicable to studies of field / workplace exposure and ensure the reliability of results. The adapted methodology was inter-laboratory validated and the parameters changed can be selected according to the requirements of the laboratory at which the methemoglobin is to be measured.

Fiat nox

Soitinnus: lauluääni, piano.

Fiat nox

Soitinnus: lauluääni, orkesteri.

Electrochemical evidence of sulfinic acid derivative as an intermediate in the reduction of aromatic sulfonyl chloride in an aprotic medium

The electrochemical reduction of p-nitrobenzenesulfonyl chloride (NBSCl) in dimethylsulfoxide (DMSO) solution is used here as a model to investigate the role of sulfinic acid derivative in this compound's global reduction process. Cyclic voltammetric experiments reveal the production of sulfinic acid derivative, which is important in chemical reactions involving the original compound and other intermediates. This paper also discusses the probable mechanisms of the reduction.

Web-sovellus Google App Engine alustalle

App Engine on lyhenne englanninkielisistä termeistä application, sovellus ja engine, moottori. Kyseessä on Google, Inc. -konsernin toteuttama kaupallinen palvelu, joka noudattaa pilvimallin tietojenkäsittelyn periaatteita ja mahdollistaa asiakkaan oman sovelluskehityksen. Järjestelmään on mahdollista ohjelmoida itse ideoitu palvelu Internet - verkon välityksellä käytettäväksi, joko yksityisesti tai julkisesti. Kyse on siis hajautetusta palvelinjärjestelmästä, jonka tarjoaa dynaamisesti kuormitukseen sopeutuvan sovellusalustan, jossa asiakas ei vuokraa virtuaalikoneita. Myös järjestelmän tarjoama tallennuskapasiteetti on saatavilla joustavasti. Itse kandidaatintyössä syvennytään yksityiskohtaisemmin sovelluksen toteuttamiseen palvelussa, rajoitteisiin ja soveltuvuuteen. Alussa käydään läpi pilvikäsite, joista monilla tietokoneiden käyttäjillä on epäselvä käsitys. Erilaisia kokonaisuuksia voidaan luoda erittäin monella tavalla, joista rajaamme käsittelyn kohteeksi toteuttamiskelpoiset yleiset ratkaisut.

Role of oxidation-reduction cycle of iron in direct leaching of zinc concentrate

Direct leaching is an alternative to conventional roast-leach-electrowin (RLE) zinc production method. The basic reaction of direct leach method is the oxidation of sphalerite concentrate in acidic liquid by ferric iron. The reaction mechanism and kinetics, mass transfer and current modifications of zinc concentrate direct leaching process are considered. Particular attention is paid to the oxidation-reduction cycle of iron and its role in direct leaching of zinc concentrate, since it can be one of the limiting factors of the leaching process under certain conditions. The oxidation-reduction cycle of iron was experimentally studied with goal of gaining new knowledge for developing the direct leaching of zinc concentrate. In order to obtain this aim, ferrous iron oxidation experiments were carried out. Affect of such parameters as temperature, pressure, sulfuric acid concentration, ferrous iron and copper concentrations was studied. Based on the experimental results, mathematical model of the ferrous iron oxidation rate was developed. According to results obtained during the study, the reaction rate orders for ferrous iron concentration, oxygen concentration and copper concentration are 0.777, 0.652 and 0.0951 respectively. Values predicted by model were in good concordance with the experimental results. The reliability of estimated parameters was evaluated by MCMC analysis which showed good parameters reliability.

Adsorption isotherm studies of BOD, TSS and colour reduction from palm oil mill effluent (POME) using boiler fly ash

Palm oil is one of the two most important vegetable oils in the world's oil and fats market. The extraction and purification processes generate different kinds of waste generally known as palm oil mill effluent (POME). Earlier studies had indicated the possibility of using boiler fly ash to adsorb impurities and colour in POME treatment. The adsorption treatment of POME using boiler fly ash was further investigated in detail in this work with regards to the reduction of BOD, colour and TSS from palm oil mill effluent. The amount of BOD, colour and TSS adsorbed increased as the weight of the boiler fly ash used was increased. Also, the smaller particle size of 425µm adsorbed more than the 850µm size. Attempts were made to fit the experimental data with the Freundlich, Langmuir and Dubinin-Radushkevich isotherms. The R² values, which ranged from 0.8974-0.9898, 0.8848-0.9824 and 0.6235-0.9101 for Freundlich, Langmuir and Dubinin-Radushkevich isotherms respectively, showed that Freundlich isotherm gave a better fit followed by Langmuir and then Dubinin-Radushkevich isotherm. The sorption trend could be put as BOD > Colour > TSS. The apparent energy of adsorption was found to be 1.25, 0.58 and 0.97 (KJ/mol) for BOD, colour and TSS respectively, showing that sorption process occurs by physiosorption. Therefore, boiler fly ash is capable of reducing BOD, Colour and TSS from POME and hence could be used to develop a good adsorbent for POME treatment.

Development of chemical looping combustion process

Chemical looping combustion (CLC) provides a promising technology to help cut carbon dioxide emissions. CLC is based on separated oxidation and reduction processes. Oxygen carrier, which is made from metal and supporting material, is in continuous recirculation between the air and fuel reactors. The CLC process does not require separation unit for carbon dioxide. The fuel reactor can produce an almost pure carbon dioxide feed which decrease costs of carbon capture and storage (CCS). The CLC method is one of the most promising ones for energy efficient carbon capture. A large amount of literature was examined for this study and from it the most promising methods and designs were chosen. These methods and designs were combined as reactor system design which was then sized during the making of this thesis. Sizing was done with a mathematical model that was further improved during the study.

Fungicides, seed dresser adjuvants and storage time in the control of Drechslera teres in barley seeds

In experiments conducted in laboratory, the effect of fungicides, seed dresser adjuvants and storage time in the control of Drechslera teres in seeds of barley cultivar BRS Elis, with 58% incidence, was quantified. Fungicides indicated by barley research (carboxin + thiram, difenoconazole and triadimenol) compared with the mixture carbendazim + iprodione were tested. As seed dresser adjuvants, water (500m mL/100 Kg) and a polymer (150 mL/100 Kg) were used. Treated seeds were stored in paper bags and kept in the refrigerator at 5ºC. At 30-day intervals during six months, seeds were plated on semi-selective Reis's medium (1983). The best control was obtained by the mixtures carboxin + thiram and carbendazim + iprodione and the polymer as seed dresser. The control efficiency was improved by the storage time without negatively affecting seed germination. Due to the transmission efficiency, the fungus eradication in seeds should be pursued.

In vivo sensitivity reduction of Puccinia triticina races, causal agent of wheat leaf rust, to DMI and QoI fungicides

Experiments were carried out to determine in vivo the IC50 and the IC90 for demethylation-inhibitor fungicides (DMIs, triazoles) and quinone outside inhibitors (QoIs, strobilurins) to the five most frequent races of Puccinia triticina in 2007 growing season in Southern Brazil. The tests were done in a greenhouse with wheat seedlings. DMI fungicides were tested at the concentrations, in mg/L, 0.0; 0.02; 0.2; 2.0; 20.0; 100.0 and 200.0, and QoIs at the concentrations 0.0; 0.0001; 0.001; 0.01; 0.1; 1 and 10.0 mg of active ingredient/L water. Fungicides were preventively applied at 24 hours before the inoculation of seedlings with the fungal spores. The effect of treatments was assessed based on the number of uredia/cm². The lowest IC50 (inhibitory concentration) for DMI fungicides determined for MCG-MN, sensitive race, ranged from 0.33 to 0.91 mg/L, while the highest values for MDP-MR, MDT-MR, MDK-MR, MFH-HT races, varied from 9.63 to 85.64 mg/L (suspected insensitivity). QoI fungicide presented an IC50 varying from 0.0018 to 0.14 mg/L. The sensitivity reduction factor for DMIs varied from 8.8 to 238.8, and for QoIs from 0.3 to 1.5 mg/L. Sensitivity reduction was confirmed for the races MDP-MR, MDT-MR, MDK-MR, MFH-HT to DMIs, as well as their sensitivity to QoI fungicides.

Mycobiota evolution during storage of paddy, brown and milled rice in different genotypes

The rice grain is frequently infected by a series of pathogens (fungi) during its storage, producing damages to the economy and health of humans. The aim of this study was to identify the fungal genera present in different rice genotypes and to quantify their variation during storage. Paddy, brown and milled rice fractions of Nutriar, (N) H329-5(H329) and Don Ignacio genotypes were analyzed at 4, 8 and 12 months of storage. Fungi were identified based on their micromorphological characteristics and colonies. The observed genera according to their frequency were: Alternaria, Nigrospora, Epicoccum, Bipolaris, Curvularia, Cladosporium and Fusarium (field fungi) and Penicillium and Aspergillus (storage fungi). The mycobiota composition was different depending on the grain fraction and the period of storage: field fungi were located in the hulls and bran layers, while storage fungi were mainly in the endosperm. The different genotypes showed different susceptibility to contamination.

Sensitivity reduction in Blumeria graminis f. sp. hordei to triadimenol fungicide applied as barley seed treatment

Experiments were carried out in a growth chamber with controlled temperature and photoperiod to test two populations of Blumeria graminis f. sp. hordei from Guarapuava, Paraná State, and Passo Fundo, Rio Grande do Sul State, Brazil. Treatments consisted in application of the fungicide triadimenol (Baytan 150 SC®) at three rates of its commercial formulation: 150, 250, 350 mL/100 Kg barley seeds. The experiments were conducted separately in a growth chamber for each population, adopting the same temperature and photoperiod. For inoculation, pots containing barley seedlings colonized by the fungus were placed among the plots. After emergence of the first symptoms, the disease severity was assessed at two-day intervals. The experiments were repeated twice for each fungus population. Data were expressed as area under the disease progress curve and as powdery mildew control by comparing the severity after the fungicide treatments to that of control. Data were subjected to analysis of variance and regression analysis; the area under the disease progress curve was also calculated. Comparing the data obtained in the present study with those reported in the literature and the control, the maximum value of 26.1% is considered insufficient to prevent the damages caused by the disease. The control response to the fungicide rate was significant. We can conclude that there was a reduction in the sensitivity of both B. graminis f.sp. hordei populations to the fungicide triadimenol, which explains the control failure observed in barley farms.

In vitro sensitivity reduction of Fusarium graminearum to DMI and QoI fungicides

In Brazil, Fusarium head blight (FHB) affecting wheat can cause up to 39.8% damage. Resistant cultivars are not available yet; thus, short-term disease control relies on the use of fungicides. The first step to improve control is to monitor fungal populations that are sensitivity to chemicals in order to achieve efficient FHB management. In vitro experiments were conducted to evaluate the inhibitory concentration (IC50) of fungicides for both mycelial growth and conidial germination of ten Fusarium graminearum isolates. The following demethylation inhibitor (DMI) fungicides were tested: metconazole, prothioconazole and tebuconazole. In addition, pyraclostrobin and trifloxystrobin were included, representing QoI fungicides, as well as three co-formulations containing metconazole + pyraclostrobin, prothioconazole + trifloxystrobin, and tebuconazole + trifloxystrobin. For mycelial growth, the overall mean IC50 of isolates was: metconazole 0.07, prothioconazole 0.1, and tebuconazole 0.19 mg/L. For the co-formulations, it was: prothioconazole + trifloxystrobin 0.08, tebuconazole + trifloxystrobin 0.12, and metconazole + pyraclostrobin 0.14 mg/L. Regarding spore germination inhibition, IC50 for prothioconazole + trifloxystrobin was 0.06, for tebuconazole + trifloxystrobin, 0.12 mg/L, for QoI alone pyraclostrobin, was 0.09, and for trifloxystrobin, 0.28 mg/L. There was a sensitivity shift among isolates and the highest fungitoxicity to F. graminearum was confirmed for prothioconazole, metconazole and tebuconazole .

Jätteenpolton typenoksidipäästöjen vähentäminen

Työn tavoitteena oli selvittää jätteenpolton typenoksidipäästöjen puhdistusmahdollisuuksia. Työssä käydään läpi typen oksidien muodostuminen poltossa ja typen oksidien poistomenetelmät. Poistomenetelmiä käsiteltäessä painotus on arinapoltossa ja erityisesti selektiivisessä ei-katalyyttimenetelmässä (SNCR). Työn kokeellinen osa tehtiin Ekokem Oy Ab:n jätevoimalassa Riihimäellä. Kokeellisessa osassa selvitettiin ensin ammoniakkiveden massavirran, SNCR-laitteiston veden massavirran ja räjähdysnuohouksen vaikutusta typenoksidipitoisuuteen. Samalla selvitettiin muita typenoksidipitoisuuteen vaikuttavia tekijöitä sekä SNCR-laitteiston puhdistustehokkuus. Sen jälkeen selvitettiin parhaita toiminta-arvoja öljyisen veden massavirralle, SNCR-laitteiston massavirralle ja primääri- ja sekundääri-ilman suhteelle typenoksidipitoisuuden, ammoniakki-slip:n, ilokaasupitoisuuden, ammoniakkiveden kulutuksen ja höyryn tuotannon kannalta. Tulokseksi saatiin, että ammoniakkiveden massavirran lisääminen pienentää typenoksidipitoisuutta, mutta voi aiheuttaa ammoniakkipäästön. Paras SNCR-laitteiston veden massavirta on suurin tutkittu, 800 kg/h, jolloin typenoksidipitoisuus sekä typenoksidipitoisuuden hetkittäinen vaihtelu, ammoniakkiveden kulutus ja ammoniakkipäästö ovat pienimmät. Samalla tosin höyryn virtaama pienenee. SNCR-laitteiston puhdistustehokkuudeksi saatiin 60 %. Räjähdysnuohouksella ei ole havaittavaa, eikä öljyisen veden massavirralla merkittävää vaikutusta typenoksidipitoisuuteen. Ammoniakkiveden kulutuksen kannalta paras öljyisen veden määrä on 600 kg/h, kun taas ammoniakki-slip:n kannalta paras öljyisen veden määrä on 950 kg/h. Primääri-ilman osuuden pienentäminen pienentää ammoniakki-slip:iä ja ammoniakkiveden kulutusta.

Energia- ja ilmastotoimenpiteiden käynnistäminen pk-yrityksissä

Tämän diplomityön tarkoituksena oli kehittää toimintamalli pk-yritysten energia- ja ilmastotoimenpiteiden käynnistämiseksi HINKU-kunnissa. Esimerkkiyrityksenä työssä toimi Tehomet Oy:n Parikkalan tehdas. Työssä tutustuttiin ensimmäisenä erilaisiin jo olemassa oleviin toimintamalleihin, hiilijalanjäljen laskentastandardeihin sekä erilaisiin mahdollisuuksiin hiilineutraaliuden saavuttamiseksi. Lisäksi Tehomet Oy:n Parikkalan tehtaalta kerättiin tarvittavaa tietoa yrityksen ja tuotteen hiilijalanjälkien laskentaa varten. Kerätyn tiedon ja jo olemassa olevien standardien ja toimintamallien pohjalta kehitettiin toimintamalli, johon sisältyy laskentataulukko, jonka avulla yritykset voivat laskea hiilijalanjälkensä ja tunnistaa kasvihuonekaasupäästöjen merkittävyyden liiketoimintansa kehittämisen näkökulmasta. Tehomet Oy:n valmistaman puupylvään hiilijalanjälki pieneni merkittävästi, kun laskennassa huomioitiin hiilen sitoutuminen tuotteeseen sekä tuotteen käytöstä poisto. Parikkalan tehtaan tapauksessa suurin yksittäinen kasvihuonekaasujen päästölähde on sähkönkulutus. Energiankulutuksen kannalta merkittävin säästökohde olisi mitä todennäköisimmin teholtaan liian suuresta kompressorista luopuminen. Kasvihuonekaasupäästöjen hiilineutraaliksi saattamiseksi mahdolliset toimenpiteet olisivat tässä tapauksessa hiilivapaan sähkön ostaminen tai päästöjen kompensoiminen ostamalla päästöoikeuksia. Toimintamallin todellinen toimivuus nähdään tulevaisuudessa, kun sitä päästään testaamaan laajemmalti eri aloilla toimiviin yrityksiin.