Freezing Point Depressions of Dilute Solutions of Alkali Metal Chlorides and Bromides

Freezing point depressions (¿Tf) of dilute solutions of several alkali metal chlorides and bromides were calculated by means of the best activity coefficient equations. In the calculations, Hückel, Hamer and Pitzer equationswere used for activity coefficients. The experimental ¿Tf values available in the literature for dilute LiCl, NaCl and KBr solutions can be predicted within experimental error by the Hückel equations used. The experimental ¿Tf values for dilute LiCl and KBr solutions can also be accurately calculated by corresponding Pitzer equations and those for dilute NaCl solutions by the Hamer equation for this salt. Neither Hamer nor Pitzer equations predict accurately the freezing points reported in the literature for LiBr and NaBr solutions. The ¿Tf values available for dilute solutions of RbCl, CsCl or CsBr are not known at the moment accurately because the existing data for these solutions are not precise. The freezing point depressions are tabulated in the present study for LiCl, NaCl and KBr solutions at several rounded molalities. The ¿Tf values in this table can be highly recommended. The activity coefficient equations used in the calculation of these values have been tested with almost allhigh-precision electrochemical data measured at 298.15 K.

Formation and Control of Trace Metal Emissions in Co-Firing of Biomass, Peat, and Wastes in Fluidised Bed Combustors

Environmentally harmful consequences of fossil fuel utilisation andthe landfilling of wastes have increased the interest among the energy producers to consider the use of alternative fuels like wood fuels and Refuse-Derived Fuels, RDFs. The fluidised bed technology that allows the flexible use of a variety of different fuels is commonly used at small- and medium-sized power plants ofmunicipalities and industry in Finland. Since there is only one mass-burn plantcurrently in operation in the country and no intention to build new ones, the co-firing of pre-processed wastes in fluidised bed boilers has become the most generally applied waste-to-energy concept in Finland. The recently validated EU Directive on Incineration of Wastes aims to mitigate environmentally harmful pollutants of waste incineration and co-incineration of wastes with conventional fuels. Apart from gaseous flue gas pollutants and dust, the emissions of toxic tracemetals are limited. The implementation of the Directive's restrictions in the Finnish legislation is assumed to limit the co-firing of waste fuels, due to the insufficient reduction of the regulated air pollutants in the existing flue gas cleaning devices. Trace metals emission formation and reduction in the ESP, the condensing wet scrubber, the fabric filter, and the humidification reactor were studied, experimentally, in full- and pilot-scale combustors utilising the bubbling fluidised bed technology, and, theoretically, by means of reactor model calculations. The core of the model is a thermodynamic equilibrium analysis. The experiments were carried out with wood chips, sawdust, and peat, and their refuse-derived fuel, RDF, blends. In all, ten different fuels or fuel blends were tested. Relatively high concentrations of trace metals in RDFs compared to the concentrations of these metals in wood fuels increased the trace metal concentrations in the flue gas after the boiler ten- to hundred-folds, when RDF was co-fired with sawdust in a full-scale BFB boiler. In the case of peat, lesser increase in trace metal concentrations was observed, due to the higher initial trace metal concentrations of peat compared to sawdust. Despite the high removal rate of most of the trace metals in the ESP, the Directive emission limits for trace metals were exceeded in each of the RDF co-firing tests. The dominat trace metals in fluegas after the ESP were Cu, Pb and Mn. In the condensing wet scrubber, the flue gas trace metal emissions were reduced below the Directive emission limits, whenRDF pellet was used as a co-firing fuel together with sawdust and peat. High chlorine content of the RDFs enhanced the mercuric chloride formation and hence the mercury removal in the ESP and scrubber. Mercury emissions were lower than theDirective emission limit for total Hg, 0.05 mg/Nm3, in all full-scale co-firingtests already in the flue gas after the ESP. The pilot-scale experiments with aBFB combustor equipped with a fabric filter revealed that the fabric filter alone is able to reduce the trace metal concentrations, including mercury, in the flue gas during the RDF co-firing approximately to the same level as they are during the wood chip firing. Lower trace metal emissions than the Directive limits were easily reached even with a 40% thermal share of RDF co-firing with sawdust.Enrichment of trace metals in the submicron fly ash particle fraction because of RDF co-firing was not observed in the test runs where sawdust was used as the main fuel. The combustion of RDF pellets with peat caused an enrichment of As, Cd, Co, Pb, Sb, and V in the submicron particle mode. Accumulation and release oftrace metals in the bed material was examined by means of a bed material analysis, mass balance calculations and a reactor model. Lead, zinc and copper were found to have a tendency to be accumulated in the bed material but also to have a tendency to be released from the bed material into the combustion gases, if the combustion conditions were changed. The concentration of the trace metal in the combustion gases of the bubbling fluidised bed boiler was found to be a summary of trace metal fluxes from three main sources. They were (1) the trace metal flux from the burning fuel particle (2) the trace metal flux from the ash in the bed, and (3) the trace metal flux from the active alkali metal layer on the sand (and ash) particles in the bed. The amount of chlorine in the system, the combustion temperature, the fuel ash composition and the saturation state of the bed material in regard to trace metals were discovered to be key factors affecting therelease process. During the co-firing of waste fuels with variable amounts of e.g. ash and chlorine, it is extremely important to consider the possible ongoingaccumulation and/or release of the trace metals in the bed, when determining the flue gas trace metal emissions. If the state of the combustion process in regard to trace metals accumulation and/or release in the bed material is not known,it may happen that emissions from the bed material rather than the combustion of the fuel in question are measured and reported.

Potentiometric titration as a method of determining the stoichiometric dissociation constants of weak acids from the thermodynamic dissociation constants of aqueous solutions at 298.15 K

The simple single-ion activity coefficient equation originating from the Debye-Hückel theory was used to determine the thermodynamic and stoichiometric dissociation constants of weak acids from data concerning galvanic cells. Electromotive force data from galvanic cells without liquid junctions, which was obtained from literature, was studied in conjuction with the potentiometric titration data relating to aqueous solutions at 298.15 K. The dissociation constants of weak acids could be determined by the presented techniques and almost all the experimental data studied could be interpreted within the range of experimental error. Potentiometric titration has been used here and the calculation methods were developed to obtain the thermodynamic and stoichiometric dissociation constants of some weak acids in aqueous solutions at 298.15 K. The ionic strength of titrated solutions were adjusted using an inert electrolyte, namely, sodium or potassium chloride. Salt content alonedetermines the ionic strength. The ionic strength of the solutions studied varied from 0.059 mol kg-1 to 0.37 mol kg-1, and in some cases up to 1.0 mol kg-1. The following substances were investigated using potentiometric titration: aceticacid, propionic acid, L-aspartic acid, L-glutamic acid and bis(2,2-dimethyl-3-oxopropanol) amine.

Pineapple yield and fruit quality effected by NPK fertilization in a tropical soil

There is a lack of information about fertilization of pineapple grown in the State of São Paulo, Brazil. So a field experiment with pineapple 'Smooth Cayenne' was carried out to study the effects of NPK rates on yield and fruit quality. The trial was located on an Alfisol in the central part of the State of São Paulo (Agudos county). The experimental design was an incomplete NPK factorial, with 32 treatments set up in two blocks. The P was applied only at planting, at the rates of 0; 80; 160 and 320 kg/ha of P2 0(5), as superphosphate. The N and K2O rates were 0; 175; 350, and 700 kg/ha, applied as urea and potassium chloride, respectively, divided in four applications during the growth period. Response functions were adjusted to yield or to fruit characteristics in order to estimate the nutrient rates required to reach maximum values. The results showed quadratic effects of N and K on yield and a maximum of 72 t/ha of fresh fruit was attained with rates of 498 and 394 kg/ha, respectively of N and K2O. In order to reach the maximum fruit size, and to improve the percentage of first class fruit (mass greater than 2.6 kg), were necessary rates of N and K respectively 11 and 43 % higher than those for maximum yield. No effect of P rates was observed on pineapple plant growth, despite the low availability of this nutrient in the soil. The effect of N rates was negative on total soluble solids and total acidity while the opposite occurred with K, which increased also the content of vitamin C. High yield and fruit size were closely related to N and K concentrations in the leaves.

Preharvest calcium sprays were not always needed to improve quality of 'gala' apples in Brazil

Calcium sprays have normally improved both the quality and the storage life of apples throughout the world because Ca helps to prevent many fruit disorders and that taken up from the soil does not often reach the fruit in adequate amounts. Since the efficacy of Ca sprays varies according to soil, apple cultivar, and weather conditions, this study was carried out from 1998 to 2004, in the Southern of Brazil, in order to assess the effect of Ca sprays on the quality and storability of 'Gala' fruits. The experiment was set up in an orchard planted in 1988, on a density of 1234 trees/ha. Treatments consisted of 0, 4, 8, and 12 annual sprays of 0.5% CaCl2 regularly distributed 30 days after petal fall until one week before harvest. Fruits of the same size and maturity level were annually analyzed at harvest and after five months of conventional cold storage (-1ºC and 90-95% of RH). In five out of six seasons, fruits from all treatments were free of any physiological disorder, and Ca sprays had no effect on leaf composition and on any fruit attribute (soluble solids, titratable acidity, starch pattern index, flesh firmness, and concentrations of N, K, Ca and Mg). In the season of 2000/2001, however, when yield was 18 t ha-1 and fruits had an average weight of 175 g, the incidence of bitter pit plus lenticel blotch pit on stored fruits was 24% in the treatment with no calcium sprays and it decreased up to 2% in that with 12 sprays. Two seasons later, yield was also low (25 t ha-1) and fruits were large (168 g each), but they did not show any physiological disorder regardless of the number of Ca sprays. It seems that the incidence of Ca related disorders in 'Gala' apples grown on limed soils in Brazil with no excess of any nutrient only occurs on seasons with low crop yield, as a result of large fruits and a high leaf/fruit ratio, associated with some unknown environmental conditions.

Prevalence of iodine inadequacy in Switzerland assessed by the estimated average requirement cut-point method in relation to the impact of iodized salt.

OBJECTIVE: To assess the iodine status of Swiss population groups and to evaluate the influence of iodized salt as a vector for iodine fortification. DESIGN: The relationship between 24 h urinary iodine and Na excretions was assessed in the general population after correcting for confounders. Single-day intakes were estimated assuming that 92 % of dietary iodine was excreted in 24 h urine. Usual intake distributions were derived for male and female population groups after adjustment for within-subject variability. The estimated average requirement (EAR) cut-point method was applied as guidance to assess the inadequacy of the iodine supply. SETTING: Public health strategies to reduce the dietary salt intake in the general population may affect its iodine supply. SUBJECTS: The study population (1481 volunteers, aged ≥15 years) was randomly selected from three different linguistic regions of Switzerland. RESULTS: The 24 h urine samples from 1420 participants were determined to be properly collected. Mean iodine intakes obtained for men (n 705) and women (n 715) were 179 (sd 68.1) µg/d and 138 (sd 57.8) µg/d, respectively. Urinary Na and Ca, and BMI were significantly and positively associated with higher iodine intake, as were men and non-smokers. Fifty-four per cent of the total iodine intake originated from iodized salt. The prevalence of inadequate iodine intake as estimated by the EAR cut-point method was 2 % for men and 14 % for women. CONCLUSIONS: The estimated prevalence of inadequate iodine intake was within the optimal target range of 2-3 % for men, but not for women.

Potassium fertilization for pineapple: effects on plant growth and fruit yield

A field experiment with pineapple (Smooth Cayenne) was carried out on an Ultisol located in the city of Agudos (22º30'S; 49º03'W), in the state of São Paulo, Brazil, with the objective of investigating the effects of rates and sources of potassium fertilizer on plant growth and fruit yield. The experiment was a complete factorial design (4x3) with four rates (0, 175, 350, and 700 kg ha-1 of K2O) and three combinations of K sources (100% KCl, 100% K2SO4, and 40% K2SO4 + 60% KCl). Plant growth and fruit yield were evaluated. Biomass accumulation of pineapple plants was impaired by chlorine added with potassium chloride. Fruit yield increased with potassium fertilization. At high rates of K application, fertilization with K2SO4 showed better results than with KCl. Detrimental effects of KCl were associated with excess of chlorine.

Potassium fertilization for pineapple: effects on soil chemical properties and plant nutrition

A field experiment was carried out on an Ultisol located at the city of Agudos (22º30'S; 49º03'W), in the state of São Paulo, Brazil, in order to determine the effects of rates and sources of potassium fertilizer on nutritional status of 'Smooth Cayenne' pineapple and on some soil chemical properties. The experiment was a complete factorial design with four rates (0, 175, 350, and 700 kg ha-1 of K2O) and three combinations of K sources (100% KCl, 100% K2SO4 and 40% K2SO4 + 60% KCl). Soil samples were taken from the depths 0-20 cm, 20-40 cm and 40-60 cm at planting and 14 months after. Nutritional status of pineapple plants was assessed by means of tissue analysis. Soil K availability increased with application of K fertilizer, regardless of K sources. Soil chlorine and Cl concentration in pineapple leaves increased with application of KCl or K2SO4+KCl. Plant uptake of potassium was shaped by soil K availability and by the application rates of K fertilizer, independently of K sources.

Arvometallien selektiivinen erottaminen kloridiliuoksista

Työssä tutkittiin jalometallien selektiivistä erottamista kloridiliuoksista synteettisten polymeerihartsien avulla. Laboratoriokokeissa keskityttiin tutkimaan kullan erottamista hydrofiilisen polymetakrylaattipohjaisen adsorbentin avulla. Lähtökohtana oli platinarikaste, joka sisälsi kullan lisäksi platinaa, palladiumia, hopeaa, kuparia, rautaa, vismuttia, seleeniä ja telluuria. Mittauksissa tutkittiin eri metallien ja puolimetallien adsorptiota hartsiin tasapaino-, kinetiikka- ja kolonnikokeilla. Työssä käytettiin myös adsorption simulointiin monikomponenttierotuksen dynaamiseen mallintamiseen tarkoitettua tietokoneohjelmaa, johon tarvittavat parametrit estimoitiin kokeellisen datan avulla. Tasapainokokeet yhtä metallia sisältäneistä liuoksista osoittivat, että hartsi adsorboi tehokkaasti kultaa kaikissa tutkituissa suolahappopitoisuuksissa (1-6 M). Kulta muodostaa hartsiin hyvin adsorboituvia tetrakloroauraatti(III)ioneja, [AuCl4]-, jotka ovat erittäin stabiileja pieniin kloridipitoisuuksiin saakka. Suolahappopitoisuudella oli merkitystä ainoastaan raudan adsorptioon, joka kasvoi huomattavasti suolahappopitoisuuden noustessa johtuen raudan taipumuksesta muodostaa hyvin adsorboituvia [FeCl4]--ioneja väkevissä suolahappopitoisuuksissa. Muiden tutkittujen alkuaineiden adsorptiot jäivät alhaisiksi kaikilla suolahappopitoisuuksilla. Rikasteliuoksella tehdyt tasapainokokeet osoittivat, että adsorptiokapasiteetti kullalle riippuu voimakkaasti muista läsnäolevista komponenteista. Kilpaileva adsorptio kuvattiin Langmuir-Freundlich-isotermillä. Kolonnikokeet osoittivat, että hartsi adsorboi kullan lisäksi hieman myös rautaa ja telluuria, jotka saatiin kuitenkin eluoitua hartsista täysin 5 M suolahappopesulla ja sitä seuraavalla 1 M suolahappopesulla. Tehokkaaksi liuokseksi kullan desorboimiseen osoittautui asetonin ja 1 M suolahapon seos. Kolonnierotuksen eri vaiheet pystyttiin tyydyttävästi kuvaamaan simulointimallilla.

Preservation of minimally processed 'aurora-1' peaches using additives

'Aurora-1' peaches establishes an interesting alternative as a minimally processed product, due to its characteristics like flavor, color, smell, and also because of its handling resistance. However, it has a short shelf life after a fresh-cut due to enzymatic browning and stone cavity collapse. The main purpose of this research was to test the additive with antioxidant effect to prevent browning in minimally processed 'Aurora-1' peaches. The minimal processing consists of washing, sanitizing, peelings and fruit stone extraction. After that, longitudinal cuts were made to obtain eight segments per fruit. The slices were immersed into the following treatment solutions: control (immersion in 2% ascorbic acid); 2% ascorbic acid + 2% calcium chloride; 1% sodium isoascorbate; 1% citric acid; 1% L-cysteine hydrochloride. The products were placed into rigid polystyrene trays branded MEIWA M-54, covered with 14 µm PVC film (OmnifilmTM) and kept in cold storage at 3ºC ± 2ºC and 65% RH for twelve days, and evaluated each three days. Appraised variables were appearance, soluble solids, titratable acidity, soluble carbohydrates and reducing sugars, total and soluble pectin, ascorbic acid, and peroxidase and polyphenol oxidase enzyme activity. L-cysteine gave to the minimally processed products a shelf life of twelve days, limmited by off-flavor. The treatment with ascorbic acid was efficient to maintainthe ascorbic acid content, with a shelf-life of nine days, limited by enzymatic browning.

Epäpuhtaudet sinkin uutossa

Työssä tutkittiin metalli- ja anioniepäpuhtauksien myötäuuttautumista sinkin mukana di(2-etyyliheksyyli)fosforihappoalla (D2EHPA). Laboratoriokokeissa selvitettiin pH:n vaikutusta metalliepäpuhtauksien uuttautumiseen pH-alueella -O, l... 3 sekä pesujen vaikutusta sinkillä ladatun orgaanisen faasin metallipitoisuuksiin. Kokeita tehtiin sekä synteettisillä että autenttisilla prosessiliuoksilla. Anionikokeissa tutkittiin raudan ja sinkin vaikutusta kloridin ja fluoridin uuttautumiseen. Synteettisillä liuoksilla tehdyissä kokeissa tutkittiin kadmiumin, koboltin, nikkelin, kuparin sekä antimonin uuttautumista sinkkisulfaattiliuoksesta. Kokeissa havaittiin D2EHPA:n uuttavan sinkkiä selvästi em. metalleja paremmin. Sinkki uuttautui sulfaattiliuoksesta lähes täydellisesti tasapaino-pH:n ollessa yli 2,3. Sinkin jälkeen muista metalleista uuttautui eniten kadmium ja järjestyksessä sitten kupari, koboltti ja nikkeli. Epäpuhtausmetallien myötäuuttautumista lisääntyi uuton tasapaino-pH:n kasvaessa ja väheni sinkkilatauksen kasvaessa. Kahdella peräkkäisellä pesuaskeleella, joissa ensimmäinen pesuliuos sisälsi 5 g/L rikkihappoa ja toinen sekä 15 g/L rikkihappoa että 5 g/L sinkkiä saatiin kaikkien epäpuhtausmetallien pitoisuudet jäämään alle 3 mg/L. Antimonin uuttokokeissa huomattiin antimonin uuttautuvan täydellisesti D2EHPA:lla pH:sta riippumatta pH-alueella0...3. Prosessiliuoksilla tehdyissä kokeissa todettiin D2EHPA:n pystyvän tehokkaasti erottamaan sinkin magnesiumista ßzn,Mg ˜107 ja kadmiumista ßzn,cd ˜106. Havaittiin myös, että mitä suurempi sinkki- ja rautalataus orgaanisessa faasissa on sitä vähemmän magnesiumia ja kadmiumia uuttautuu. Ensimmäisessä pesussa saatiin sekä kadmiumin että magnesiumin pitoisuudet putoamaan keskimäärin 0,1 mg/L eli 30 alkuperäisestä pitoisuudesta. Toisella pesuaskeleella ei enää ollut vaikutusta kadmiumin ja magnesiumin pitoisuuksiin orgaanisessa faasissa. Kokeissa havaittiin myös, että D2EHPA:n latausasteen ylittäessä 0,7 alkaa sinkki-D2EHPA-kompleksit polymeroitua ja faasit eivät enää selkeytyneet helposti. Anionikokeissa huomattiin, ettei D2EHPA uuttanut kloridi tai fluoridi sinkin tai raudan mukana. D2EHPA:n havaittiin myös itsessään sisältävän hieman kloridia.

Pitkäketjuisten keteenien valmistusreaktiot ja kinetiikka.

Tämän diplomityön tarkoituksena oli tutkia pitkäketjuisten rasvahappokloridien ja alkyyliketeenidimeerien (AKD) valmistusreaktioiden kinetiikkaa. Työn tavoitteena oli saada mittaustuloksia, joiden perusteella voitaisiin kehittää reaktioille kineettinen kineettinen malli ja suorittaa valmistusprosessien alustava optimointi. Teoreettisessa osassa on selvitetty rasvahappokloridien ja alkyyliketeenidimeerien (AKD) eri valmistustapoja. Lisäksi on perehdytty tarkemmin rasvahappokloridien dehydrohalogenointireaktioiden reaktiomekanismeihin ja valmistusprosessin problematiikkaan. Kokeellisessa osassa tutkittiin rasvahappokloridien valmistusta klooraamalla öljyhappoa 30 mol-% fosforitrikloridiylimäärällä lämpötiloissa 45, 50 ja 55OC. Alkyyliketeenidimeerien valmistusta tutkittiin dehydrohalogenoimalla palmitiini- ja öljyhappokloridia 0-30 mol-% trietyyliamiiniylimäärällä inertissä liuottimessa, lämpötiloissa 45 ja 50OC. Reaktiot toteutettiin puolipanosreaktiona, joissa reaktioastiassa olevaan reagenssin ja liuottimen seokseen lisättiin lähtöaine tasaisena massavirtana. Reaktioiden etenemistä seurattiin FT-IR- ja GC-analyysien avulla. Kalorimetrisilla kokeilla tutkittiin öljyhappokloridin dimeroitumisreaktion reaktiolämmön muodostumista ja UV-VIS-analyyseillä seurattiin öljyhappokloridin vanhenemista. Öljyhappokloridin valmistusreaktiolle saatiin hyvä kineettinen malli. Kineettisen mallin puutteena voidaan pitää sitä, ettei kokeissa saatu tietoa mahdollisten sivutuotteiden muodostumisesta. Sovitusohjelmalla saatiin sovitettua estimaatit reaktionopeusvakioille lämpötiloissa 45, 50 ja 55OC. Happokloridien dimeroitumisreaktioiden kineettisen mallin sopivuudelle saatiin suhteellisen hyvä kuva Kuten öljyhappokloridin tapauksessa, myöskään AKD:n valmistusreaktioissa syntynyt sivutuotteita, joten niiden osuutta oletettuun kineettiseen malliin ei tunneta. Sovitusohjelmalla saatiin sovitettua estimaatit reaktionopeusvakioille lämpötiloissa 45 ja 50OC.

Ilmakehan hiukkasmaisten ioniyhdisteiden online-mittaus

Ilmakehän hiukkaset aiheuttavat merkittäviä ympäristö- ja terveyshaittoja, joihin vaikuttaa hiukkasten kemiallinen koostumus. Hiukkasten kemiallisesta koostumuksesta voidaan hankkia tietoa hiukkasmittauksilla. Työn tavoitteena oli rakentaa jatkuvatoiminen mittausjärjestelmä, jolla voidaan mitata ilmakehän aerosolihiukkasten ionipitoisuuksia. Mittausjärjestelmä koostuu virtuaali-impaktorista, denuderputkista, PILS-laitteesta ja ionikromatografista. Näyteilmavirtaus kulkee ensin esierottimena toimivan virtuaali-impaktorm lävitse, joka poistaa aerodynaamiselta halkaisijaltaan 1,3 um:a suuremmat hiukkaset ilmavirtauksesta. Näyte, joka sisältää 1,3 um:a pienemmät hiukkaset kulkee virtuaali-impaktorin jälkeen kahden 1 % KOH-liuoksella käsitellyn denuderputken lävitse, joilla poistetaan hiukkasmääritystä häiritsevät happamat kaasut näytevirtauksesta. Denuderputkien jälkeen ilmavirtaus saapuu PILS-laitteeseen, jossa hiukkaset kasvatetaan vesihöyryn avulla aerosolipisaroiksi, törmäytetään keräyslevyyn ja sekoitetaan sen jälkeen sisäistä standardiainetta (NaBr) sisältavään kuljetusliuokseen. Kuljetusliuoksen ja aerosolipisaroiden seoksesta koostuva näyteliuos johdetaan PILS-laitteesta ionikromatografille analysoitavaksi. Mittausjärjestelmään liitetyllä ionikromatografilla voidaan analysoida neljä näytetta tunnissa. Näytteistä määritettävät anionit olivat sulfaatti, nitraatti ja kloridi. PILS-mittausjärjestelmää testattiin keräämällä hiukkasnäytteitä samanaikaisesti PILS-laitteella sekä virtuaali-impaktorilla tai suodatinkeräimellä ja vertaamalla saatuja aerosolihiukkasten sulfaattipitoisuuksia keskenään. Testeissa kerättiin joko VOAG-laitteella tuotettuja ammoniumsulfaattihiukkasia tai laboratorion huoneilmaa. PILS-mittausjärjestelmällä mitatut sulfaattipitoisuudet olivat 2-20 % pienempia kuin suodatinkeraimella mitatut, kun kerättiin keinotekoisesti tuotettuja ammoniumsulfaattihiukkasia. Huoneilmaa kerättäessä PILS-mittausjärjestelmällä saadut pitoisuudet olivat noin 10 % pienempiä kuin suodatinkeräystulokset. Koetulokset osoittivat, että mittausjärjestelmällä saadaan analysoiduksi luotettavasti hiukkasten sulfaattipitoisuudet.

Sisäisten donorien vaikutus Polypropeeni Ziegler-Natta katalyytissä

Tässä työssä tutkittiin erilaisten sisäisten donorien vaikutusta polypropeenin ominaisuuksiin käytettäessä Ziegler-Natta-katalyyttiä, joka valmistettiin Borealiksen aiemmin kehittämällä kaksifaasimenetelmällä. Tällä uudella menetelmällä katalyytti voidaan valmistaa ilman lisättyä sisäistä donoria ja kantajaa. Katalyyttihiukkaset saadaan kaksifaasisysteemin ansiosta muodoltaan pyöreiksi. Työn kokeellisessa osassa valmistettiin erilaisia Mg-komplekseja, jossa sisäinen donori muodostuu in-situ alkoholin ja karboksyylihappokloridin reagoidessa keskenään. Katalyyttisynteesissä Mg-kompleksi reagoi TiCl4:n kanssa. Saatujen katalyyttien ominaisuuksia testattiin polymeroimalla niillä propeenia 70 °C:ssa tunnin ajan. Polymeerien ominaisuuksia tutkittiin useiden eri karakterisointimenetelmien avulla. Lisäksi tutkittiin mahdollisuutta valmistaa katalyytti, joka ei sisältäisi ftalaattia. Työssä havaittiin, että katalyytin valmistusmenetelmä on käyttökelpoinen myös muilla sisäisillä donoreilla kuin referenssinä käytetyllä DOP:lla. Kaksiliuosfaasi-systeemi saatiin aikaan myös kahdella muulla työssä tutkitulla sisäisellä donorilla. Lisäksi faasitasapainokokeissa kahden liuosfaasin systeemi saatiin aikaan sisäisellä donorilla, joka ei sisältänyt ftalaattia. Kyseisellä katalyytillä havaittiin olevan muista katalyyteistä poikkeavia ominaisuuksia. Esimerkiksi se antoi matalamman isotaktisuuden kuin referenssikatalyytti ja se saattaisikin soveltua matalan isotaktisuuden pehmeille tuotteille. Työssä kokeiltiin yhdellä uudella katalyytillä myös eteenin polymerointia, sillä katalyytin donoripitoisuus oli hyvin matala. Katalyytin aktiivisuus eteenipolymeroinnissa oli varsin hyvä.

Use of the dried blood spot sampling process coupled with fast gas chromatography and negative-ion chemical ionization tandem mass spectrometry: application to fluoxetine, norfluoxetine, reboxetine, and paroxetine analysis.

The objective of this work was to combine the advantages of the dried blood spot (DBS) sampling process with the highly sensitive and selective negative-ion chemical ionization tandem mass spectrometry (NICI-MS-MS) to analyze for recent antidepressants including fluoxetine, norfluoxetine, reboxetine, and paroxetine from micro whole blood samples (i.e., 10 microL). Before analysis, DBS samples were punched out, and antidepressants were simultaneously extracted and derivatized in a single step by use of pentafluoropropionic acid anhydride and 0.02% triethylamine in butyl chloride for 30 min at 60 degrees C under ultrasonication. Derivatives were then separated on a gas chromatograph coupled with a triple-quadrupole mass spectrometer operating in negative selected reaction monitoring mode for a total run time of 5 min. To establish the validity of the method, trueness, precision, and selectivity were determined on the basis of the guidelines of the "Société Française des Sciences et des Techniques Pharmaceutiques" (SFSTP). The assay was found to be linear in the concentration ranges 1 to 500 ng mL(-1) for fluoxetine and norfluoxetine and 20 to 500 ng mL(-1) for reboxetine and paroxetine. Despite the small sampling volume, the limit of detection was estimated at 20 pg mL(-1) for all the analytes. The stability of DBS was also evaluated at -20 degrees C, 4 degrees C, 25 degrees C, and 40 degrees C for up to 30 days. Furthermore, the method was successfully applied to a pharmacokinetic investigation performed on a healthy volunteer after oral administration of a single 40-mg dose of fluoxetine. Thus, this validated DBS method combines an extractive-derivative single step with a fast and sensitive GC-NICI-MS-MS technique. Using microliter blood samples, this procedure offers a patient-friendly tool in many biomedical fields such as checking treatment adherence, therapeutic drug monitoring, toxicological analyses, or pharmacokinetic studies.