Effect of physico-chemical conditions and operating parameters on flux and retention of different components in ultrafiltration and nanofiltration fractionation of sweet whey

Tässä väitöstutkimuksessa tutkittiin fysikaaliskemiallisten olosuhteiden ja toimintaparametrien vaikutusta juustoheran fraktiointiin. Kirjallisuusosassa on käsitelty heran ympäristövaikutusta, heran hyödyntämistä ja heran käsittelyä kalvotekniikalla. Kokeellinen osa on jaettu kahteen osaan, joista ensimmäinen käsittelee ultrasuodatusta ja toinen nanosuodatusta juustoheran fraktioinnissa. Ultrasuodatuskalvon valinta tehtiin perustuen kalvon cut-off lukuun, joka oli määritetty polyetyleeniglykoliliuoksilla olosuhteissa, joissa konsentraatiopolariosaatioei häiritse mittausta. Kriittisen vuon konseptia käytettiin sopivan proteiinikonsentraation löytämiseksi ultrasuodatuskokeisiin, koska heraproteiinit ovat tunnetusti kalvoa likaavia aineita. Ultrasuodatuskokeissa tutkittiin heran eri komponenttien suodattumista kalvon läpi ja siihen vaikuttavia ominaisuuksia. Herapermeaattien peptidifraktiot analysoitiin kokoekskluusiokromatografialla ja MALDI-TOF massaspektrometrillä. Kokeissa käytettävien nanosuodatuskalvojen keskimääräinen huokoskoko analysoitiin neutraaleilla liukoisilla aineilla ja zeta-potentiaalit virtauspotentiaalimittauksilla. Aminohappoja käytettiin malliaineina tutkittaessa huokoskoon ja varauksen merkitystä erotuksessa. Aminohappojen retentioon vaikuttivat pH ja liuoksen ionivahvuus sekä molekyylien väliset vuorovaikutukset. Heran ultrasuodatuksessa tuotettu permeaatti, joka sisälsi pieniä peptidejä, laktoosia ja suoloja, nanosuodatettiin happamassa ja emäksisessä pH:ssa. Emäksisissä oloissa tehdyssä nanosuodatuksessa foulaantumista tapahtui vähemmän ja permeaattivuo oli parempi. Emäksisissä oloissa myös selektiivisyys laktoosin erotuksessa peptideistä oli parempi verrattuna selektiivisyyteen happamissa oloissa.

Washing and Dewatering of Different Starches in Pressure Filters

The main objective of this thesis was togenerate better filtration technologies for effective production of pure starchproducts, and thereby the optimisation of filtration sequences using created models, as well as the synthesis of the theories of different filtration stages, which were suitable for starches. At first, the structure and the characteristics of the different starch grades are introduced and each starch grade is shown to have special characteristics. These are taken as the basis of the understanding of the differences in the behaviour of the different native starch grades and their modifications in pressure filtration. Next, the pressure filtration process is divided into stages, which are filtration, cake washing, compression dewatering and displacement dewatering. Each stage is considered individually in their own chapters. The order of the different suitable combinations of the process stages are studied, as well as the proper durations and pressures of the stages. The principles of the theory of each stageare reviewed, the methods for monitoring the progress of each stage are presented, and finally, the modelling of them is introduced. The experimental results obtained from the different stages of starch filtration tests are given and the suitability of the theories and models to the starch filtration are shown. Finally, the theories and the models are gathered together and shown, that the analysis of the whole starch pressure filtration process can be performed with the software developed.

Practical applications of a systematic approach to the chemical abatement of pollutants in water and air

The present dissertation is devoted to the systematic approach to the development of organic toxic and refractory pollutants abatement by chemical decomposition methods in aqueous and gaseous phases. The systematic approach outlines the basic scenario of chemical decomposition process applications with a step-by-step approximation to the most effective result with a predictable outcome for the full-scale application, confirmed by successful experience. The strategy includes the following steps: chemistry studies, reaction kinetic studies in interaction with the mass transfer processes under conditions of different control parameters, contact equipment design and studies, mathematical description of the process for its modelling and simulation, processes integration into treatment technology and its optimisation, and the treatment plant design. The main idea of the systematic approach for oxidation process introduction consists of a search for the most effective combination between the chemical reaction and the treatment device, in which the reaction is supposed to take place. Under this strategy,a knowledge of the reaction pathways, its products, stoichiometry and kinetics is fundamental and, unfortunately, often unavailable from the preliminary knowledge. Therefore, research made in chemistry on novel treatment methods, comprisesnowadays a substantial part of the efforts. Chemical decomposition methods in the aqueous phase include oxidation by ozonation, ozone-associated methods (O3/H2O2, O3/UV, O3/TiO2), Fenton reagent (H2O2/Fe2+/3+) and photocatalytic oxidation (PCO). In the gaseous phase, PCO and catalytic hydrolysis over zero valent ironsare developed. The experimental studies within the described methodology involve aqueous phase oxidation of natural organic matter (NOM) of potable water, phenolic and aromatic amino compounds, ethylene glycol and its derivatives as de-icing agents, and oxygenated motor fuel additives ¿ methyl tert-butyl ether (MTBE) ¿ in leachates and polluted groundwater. Gas-phase chemical decomposition includes PCO of volatile organic compounds and dechlorination of chlorinated methane derivatives. The results of the research summarised here are presented in fifteenattachments (publications and papers submitted for publication and under preparation).

"In vitro" comparative experimental study of antimicrobial action of mouth washing products

Regular use of mouth rinses modifies the oral habitat, since bacterial populations are submitted to a high selective pressure during the treatment exercised by the active presence of the disinfectant. Mostly mouth rinses are based on the antibacterial effect of Chlorhexidine, Triclosan, essential oils and other antibacterials although other pharmaceutical characteristics can also affect their effectiveness. In this paper we compare"in vitro" the antibacterial effect of different oral rinsing solutions. Minimal Inhibitory Concentrations (MIC) and Minimal Bactericidal Concentrations (MBC) were determined as well as the kinetics of bacterial death in the presence of letal concentrations of the mouth rinses. MIC values expressed as Maximal Inhibitory Dilution (MID) of the mouth rinse ranged from 1 to 1/2048 depending on the microorganism and product, whereas Minimal Biocidal Concentration (MBC), expressed as Maximal Biocidal Dilution (MBD) ranged from 1 to 1/1024, being in general one dilution less than MIC. Maximal Biocidal Dilution is a good tool to measure the actual efficiency of mouth washing solutions. However, kinetics of death seems to be better in our work killing curves demonstrate that bacterial populations are mostly eliminated during the first minute after the contact of bacterial suspension and the mouth-washing solution. In all tested bacterial species mouth-washing solutions tested were able to reduce until suspension treated except 1 and 5

Effects of DMPP on the growth and chemical composition of ryegrass (Lolium perenne L.) raised on calcareous soil

Se llevó a cabo un experimento de 406 días en macetas para evaluar el nuevo inhibidor de la nitrificación, 3,4-dimetilpirazol fosfato (DMPP), añadido a purines de cerdo. Se utilizaron macetas que contenían tierra franca calcárea que fueron sujetas a los siguientes tratamientos: sin purín, 73,7; 147,3 y 221 cm3 de purín por maceta, todas con o sin tratamiento de DMPP. A los 18 días las macetas fueron sembradas con Lolium perenne L. El mayor rendimiento (36,3 g maceta-1) se obtuvo para el tratamiento con la dosis superior de purín y DMPP, siendo un 7,4% superior al mismo tratamiento sin inhibidor y un 46,1% superior al tratamiento control. Las plantas tratadas con dosis alta y mediana, más el DMPP, absorbieron el 70% del total del N durante la primera fase del experimento (104 días) mientras que sin inhibidor absorbieron el 55,3 y el 62% respectivamente. Se observó una reducción significativa del 17% en el N lixiviado en los tratamientos sin cultivo al aplicar DMPP. El inhibidor aumentó significativamente la eficiencia agronómica del purín (g materia seca g-1 N aplicado).

Physical and chemical characterization of yellow mangosteen fruits

The work had as objective the physico-chemical characterization of yellow mangosteen fruits. Six samples of 25 fruits were harvested in yellow mangosteen plants of the Active Germoplasm Bank of São Paulo State University and characterized by evaluation of length and width, weight, percentage and number of seeds per fruit, peel and pulp percentage, soluble solid (SS), titratable acidity (TA), vitamin C and SS/TA rate. Yellow mangosteen fruit is an intermediate vitamin C source with an average content 120.33 mg/100g of fresh fruit and has good technological quality.

First systematic chemical profiling of cocaine police seizures in Finland in the framework of an intelligence-led approach

For the first time in Finland, the chemical profiling of cocaine specimens was performed at the National Bureau of Investigation (NBI). The main goals were to determine the chemical composition of cocaine specimens sold in the Finnish market and to study the distribution networks of cocaine in order to provide intelligence related to its trafficking. An analytical methodology enabling through one single GC-MS injection the determination of the added cutting agents (adulterants and diluents), the cocaine purity and the chemical profile (based on the major and minor alkaloids) for each specimen was thus implemented and validated. The methodology was found to be efficient for the discrimination between specimens coming from the same source and specimens coming from different sources. The results highlighted the practical utility of the chemical profiling, especially for supporting the investigation through operational intelligence and improving the knowledge related to the cocaine trafficking through strategic intelligence.

Physico-chemical characterization and oxidative reactivity evaluation of aged brake wear particles

Brake wear dust is a significant component of traffic emissions and has been linked to adverse health effects. Previous research found a strong oxidative stress response in cells exposed to freshly generated brake wear dust. We characterized aged dust collected from passenger vehicles, using microscopy and elemental analyses. Reactive oxygen species (ROS) generation was measured with acellular and cellular assays using 2′7-dichlorodihydrofluorescein dye. Microscopy analyses revealed samples to be heterogeneous particle mixtures with few nanoparticles detected. Several metals, primarily iron and copper, were identified. High oxygen concentrations suggested that the elements were oxidized. ROS were detected in the cell-free fluorescent test, while exposed cells were not dramatically activated by the concentrations used. The fact that aged brake wear samples have lower oxidative stress potential than fresh ones may relate to the highly oxidized or aged state of these particles, as well as their larger size and smaller reactive surface area.

Application of Information Statistical Theory to the Description of the Effect of Heat Conduction on the Chemical Reaction Rate in Gases

The effect of the heat flux on the rate of chemical reaction in dilute gases is shown to be important for reactions characterized by high activation energies and in the presence of very large temperature gradients. This effect, obtained from the second-order terms in the distribution function (similar to those obtained in the Burnett approximation to the solution of the Boltzmann equation), is derived on the basis of information theory. It is shown that the analytical results describing the effect are simpler if the kinetic definition for the nonequilibrium temperature is introduced than if the thermodynamic definition is introduced. The numerical results are nearly the same for both definitions

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.

Spectroscopic ellipsometry study of the In1-x Gax Asy P1-y / InP Heterojunctions grown by metalorganic chemical-vapor deposition

The dielectric functions of InP, In0.53Ga0.47As, and In0.75Ga0.25As0.5P0.5 epitaxial layers have been measured using a polarization modulation spectroscopic ellipsometer in the 1.5 to 5.3 eV region. The oxide removal procedure has been carefully checked by comparing spectroscopic ellipsometry and x ray photoelectron spectroscopy measurements. These reference data have been used to investigate the structural nature of metalorganic chemical vapor deposition grown In0.53Ga0.47As/InP and In0.75Ga0.25As0.5P0.5/InP heterojunctions, currently used for photodiodes and laser diodes. The sharpness of the interfaces has been systematically compared for the two types of heterojunctions: In1 xGaxAsy/InP and InP/In1 xGaxAsyP1 y. The sharpest interface is obtained for InP growth on In0.75Ga0.25As0.5P0.5 where the interface region is estimated to be (10±10) Å thick. The importance of performing in situ SE measurements is emphasized.

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.

Puumassapesurin suotautumisolojen kartoitus ja simulointi

Työn tavoitteena oli tutkia sellumassan suotautumiseen liittyviä tekijöitä Ahlstrom Machineryn Drum Displacer™ -puumassapesurissa (DD-pesuri). Teoriaosassa tarkasteltiin aluksi suotautumisen teoriaa kuitu-vesi-suspensiossa, minkä jälkeen esiteltiin suotautumisnopeuteen vaikuttavia fysikaalisia ja kemiallisia vaikutusmekanismeja. Seuraavaksi kuvattiin massan pesun yleisiä perusteita sekä teoriaa puumassapesureissa. Lopuksi tarkasteltiin pesurien kytkeytymistä muuhun kuitulinjaan sekä prosessista johtuvia pesun toiminnan ulkoisia häiriötekijöitä. Kokeellisen osan aluksi tarkasteltiin paine- ja lämpötilamittauksien avulla massapesurissa vallitsevia prosessioloja. Mittaustulosten perusteella pumppausolot pesurin suodoslinjoissa ovat vaikeahkot ja häiriötilanteita voi esiintyä, mutta käytäntö on osoittanut tästä olevan vain harvoin haittaa prosessin toiminnalle. Pesureissa toteutuneet syrjäytysnopeudet laskettiin ja niitä verrattiin syrjäytystestien antamiin tuloksiin. Kuitulinjasta riippuen testin vastaavuus tehdasprosessiin vaihteli suuresti. Syrjäytystesteillä kokeiltiin myös tehdasprosesseissa usein esiintyvien muuttujien vaikutusta sellukakun syrjäytettävyyteen. Kakun paksuus ja syrjäytyslämpötila vaikuttivat syrjäytysnopeuteen Darcyn lain mukaisesti. Alipaineen massakakun alapuolella havaittiin huonontavan syrjäytysnopeutta verrattuna tilanteeseen, jossa kakun alla vallitsi ilmanpaine. Tämä havainto on selvästi ristiriidassa suotautumisen teorian kanssa. Massakakun muodostumis-pH osoittautui ratkaisevaksi lopulliselle syrjäytysnopeudelle, sillä alkalisissa oloissa muodostetun kuitukakun syrjäytysnopeus ei enää parantunut happamalla syrjäytysnesteellä. Happamissa oloissa muodostetun kakun syrjäytysnopeus oli alkalisista parempi, mutta se alkoi hitaasti alentua, kun syrjäytysneste vaihtui alkaliseen. Massan laimentaminen ennen syrjäytystä alkalisella tehdassuodoksella puhtaan veden sijasta alensi ligniinipitoisella massalla lopullista syrjäytysnopeutta. Shirato-Tillerin mallilla ja Jönssonin staattisella mallilla simuloitiin numeerisesti syrjäytystestiä kahdessa eri pH:ssa, ja simulointituloksia verrattiin vastaavissa oloissa tehtyihin syrjäytystesteihin. Shirato-Tillerin mallin antamien syrjäytysnopeuksien havaittiin olevan lähellä syrjäytystestien nopeuksia, kun Jönssonin mallin antamat tulokset jäivät huomattavasti testituloksia alemmiksi. Herkkyystarkastelussa havaittiin mallien olevan varsin herkkiä parametrien virheille. Hajonta vaadittavien kuituparametrien määrityksissä ja menetelmien työläys rajoittavat numeerisen simuloinnin käytettävyyttä, sillä kuituparametrien määrityksen vaatima työmäärä on ainakin toistaiseksi syrjäytystestiä suurempi. Lopuksi todettiin, että oikeiden syrjäytysolosuhteiden käyttö on ensiarvoisen tärkeää oikeiden tulosten saamiseksi sekä kokeellisessa että numeerisessa simuloinnissa. Nykyinen syrjäytystestilaitteisto on pienin muutoksin käyttökelpoinen, kun massan testaus prosessioloissa tulee rutiininomaiseksi.