Probing functional groups at the gas-aerosol interface using heterogeneous titration reactions: a tool for predicting aerosol health effects?

The complex chemical and physical nature of combustion and secondary organic aerosols (SOAs) in general precludes the complete characterization of both bulk and interfacial components. The bulk composition reveals the history of the growth process and therefore the source region, whereas the interface controls--to a large extent--the interaction with gases, biological membranes, and solid supports. We summarize the development of a soft interrogation technique, using heterogeneous chemistry, for the interfacial functional groups of selected probe gases [N(CH(3))(3), NH(2)OH, CF(3)COOH, HCl, O(3), NO(2)] of different reactivity. The technique reveals the identity and density of surface functional groups. Examples include acidic and basic sites, olefinic and polycyclic aromatic hydrocarbon (PAH) sites, and partially and completely oxidized surface sites. We report on the surface composition and oxidation states of laboratory-generated aerosols and of aerosols sampled in several bus depots. In the latter case, the biomarker 8-hydroxy-2'-deoxyguanosine, signaling oxidative stress caused by aerosol exposure, was isolated. The increase in biomarker levels over a working day is correlated with the surface density N(i)(O3) of olefinic and/or PAH sites obtained from O(3) uptakes as well as with the initial uptake coefficient, γ(0), of five probe gases used in the field. This correlation with γ(0) suggests the idea of competing pathways occurring at the interface of the aerosol particles between the generation of reactive oxygen species (ROS) responsible for oxidative stress and cellular antioxidants.

Implementation of population balances in simulation of gas-liquid reactors using a CFD-PBM coupled approach

In bubbly flow simulations, bubble size distribution is an important factor in determination of hydrodynamics. Beside hydrodynamics, it is crucial in the prediction of interfacial area available for mass transfer and in the prediction of reaction rate in gas-liquid reactors such as bubble columns. Solution of population balance equations is a method which can help to model the size distribution by considering continuous bubble coalescence and breakage. Therefore, in Computational Fluid Dynamic simulations it is necessary to couple CFD and Population Balance Model (CFD-PBM) to get reliable distribution. In the current work a CFD-PBM coupled model is implemented as FORTRAN subroutines in ANSYS CFX 10 and it has been tested for bubbly flow. This model uses the idea of Multi Phase Multi Size Group approach which was previously presented by Sha et al. (2006) [18]. The current CFD-PBM coupled method considers inhomogeneous flow field for different bubble size groups in the Eulerian multi-dispersed phase systems. Considering different velocity field for bubbles can give the advantageof more accurate solution of hydrodynamics. It is also an improved method for prediction of bubble size distribution in multiphase flow compared to available commercial packages.

Plasmapolttoprosessin kehittäminen ja optimointi

Ydinvoimaloidenprimaarivesikierron puhdistukseen käytetään ioninvaihtohartsia. Käytönjälkeen ioninvaihtohartsi luokitellaan matalaja keskiaktiivisiin jätteisiin. Plasmakäsittelyllä käytetyn ioninvaihtohartsin tilavuutta voidaan pienentää sekä sen orgaaninen luonne poistaa. Plasmakäsittelyn tarkoituksena on hapettaa orgaaninen aines oksideiksi, jotka poistuvat prosessista savukaasuina. Epäorgaaninen aines, joka sisältää radioaktiivisen aineksen, on tarkoitus hapettaa oksideiksi ja sulfideiksi, jotka voidaan kerätä talteen tuhkana. Tässä diplomityössä käsitellään käytetyn ioninvaihtohartsin käsittelyyn suunnitellun plasmapolttoprosessin kehittämistä ja optimointia. Ioninvaihtohartsin plasmakäsittelyssä syntyvien reaktiotuotteiden selvittäminen suoritettiin tarkastelemalla ainetaseita sekä aihetta käsitteleviä tutkimuksia. Näiden perusteella parannettiin jäähdytystä, suunniteltiin jatkuvatoiminen syöttömenetelmä sekä laadittiin toimintaalueen reunaehdot laitteistolle. Koelaitteistossa 6,5 kW:n rfteho syötetään sovitinpiirin ja kuparisen induktiokelan kautta plasmaan. Plasmakaasuna on käytetty hapenja argonin seoskaasua. Plasmapolttoa on seurattu massaspektrometrilla, optisella emissiospektrometrilla, lämpösekä painemittareilla. Laskennan ja kokeiden pohjalta selvitettiin optimaalinen seossuhde plasmakaasulle, paineen ja tehon noston vaikutus hartsin polttonopeuteen sekä jatkuvatoimisen syöttömenetelmän edut panostoimiseen syöttöön. Rfgeneraattorin teho rajoitti jatkuvatoimisen polttonopeuden 130 g/h ja hetkellisen polttonopeuden 175 g/h. Radioaktiivisten aineiden pidätys oli 93,5 % cesiumin osalta. Tulosten perusteella 4 kg/h ioninvaihtohartsia polttavan laitteiston tehon lähteeksi tarvitaan 65 kW rfgeneraattori. Palamattoman hartsin ja tuhkan kulkeutuminen partikkelisuodattimille sekä reaktiotuotteena syntyvien rikinoksidien käsittely vaatii vielä jatkotutkimusta.

Termodesorptiolaitoksen päästöt

Tässä diplomityössä tutkittiin pilaantuneen maan puhdistamiseen käytettävän termodesorptiolaitoksen päästöjä ilmaan. Tarkasteluun otettiin raskasmetallit ja happamista päästöistä rikkidioksidi (SO2) ja vetykloridi (HCl).Näiden haitta-aineiden puhdistusta tutkittiin mittaamalla niiden pitoisuuksia ennen ja jälkeen kaasunpuhdistuksen. Tutkimuksessa havaittiin raskasmetallien sekä happamien yhdisteiden puhdistuvan käytössä olevalla tekniikalla erittäin hyvin. Viranomaisten asettamat päästöraja-arvot alitettiinselvästi.

Graphitized carbon black in quartz tubes for the sampling of indoor air nicotine and analysis by microwave thermal desorption-capillary gas chromatography

Nicotine in a smoky indoor air environment can be determined using graphitized carbon black as a solid sorbent in quartz tubes. The temperature stability, high purity, and heat absorption characteristics of the sorbent, as well as the permeability of the quartz tubes to microwaves, enable the thermal desorption by means of microwaves after active sampling. Permeation and dynamic dilution procedures for the generation of nicotine in the vapor phase at low and high concentrations are used to evaluate the performances of the sampler. Tube preparation is described and the microwave desorption temperature is measured. Breakthrough volume is determined to allow sampling at 0.1-1 L/min for definite periods of time. The procedure is tested for the determination of gas and paticulate phase nicotine in sidestream smoke produced in an experimental chamber.

LEAF GAS EXCHANGE CHARACTERISTICS OF FOUR PAPAYA GENOTYPES DURING DIFFERENT STAGES OF DEVELOPMENT

In this research, was used four papaya (Carica papaya L.) genotypes: three from the 'Solo ( Sunrise Solo TJ, Sunrise Solo 72/12 and Baixinho de Santa Amália) group and one from the 'Formosa' group (Know-You 01). They were grown in plastic pots containing a sandy-clay-loam soil subjected to pH correction and fertilization, under greenhouse conditions. Throughout the experimental period plants were subjected to periodic irrigation to maintain the soil humitidy around field capacity. The experiment was conducted 73 days after sowing. In all genotypes, leaf gas exchange characteristics were determined. The net photosynthetic rate (A, mumol m-2 s-1 ), stomatal conductance (g s mol m-2 s-1), leaf temperature (T I, 0C) and intercellular carbon dioxide concentration (ci, muL L-1) on the 4th, 5th, 6th, 7th, 8th and 9th leaves from the plant apex were determined. No significant differences were observed for A, g s, c i, or Tl either among the leaves sampled from any of the genotypes. A was positively correlated with g s and in the other hand T I and g s were negatively correlated. The results suggest that, for 73 DAP, all the sampled papaya leaves functioned as sources of organs.

Fast gas chromatography and negative-ion chemical ionization tandem mass spectrometry for forensic analysis of cannabinoids in whole blood.

The present work describes a fast gas chromatography/negative-ion chemical ionization tandem mass spectrometric assay (Fast GC/NICI-MS/MS) for analysis of tetrahydrocannabinol (THC), 11-hydroxy-tetrahydrocannabinol (THC-OH) and 11-nor-9-carboxy-tetrahydrocannabinol (THC-COOH) in whole blood. The cannabinoids were extracted from 500 microL of whole blood by a simple liquid-liquid extraction (LLE) and then derivatized by using trifluoroacetic anhydride (TFAA) and hexafluoro-2-propanol (HFIP) as fluorinated agents. Mass spectrometric detection of the analytes was performed in the selected reaction-monitoring mode on a triple quadrupole instrument after negative-ion chemical ionization. The assay was found to be linear in the concentration range of 0.5-20 ng/mL for THC and THC-OH, and of 2.5-100 ng/mL for THC-COOH. Repeatability and intermediate precision were found less than 12% for all concentrations tested. Under standard chromatographic conditions, the run cycle time would have been 15 min. By using fast conditions of separation, the assay analysis time has been reduced to 5 min, without compromising the chromatographic resolution. Finally, a simple approach for estimating the uncertainty measurement is presented.

The Effect of Adding CO2 to Hypoxic Inspired Gas on Cerebral Blood Flow Velocity and Breathing during Incremental Exercise

Hypoxia increases the ventilatory response to exercise, which leads to hyperventilation-induced hypocapnia and subsequent reduction in cerebral blood flow (CBF). We studied the effects of adding CO2 to a hypoxic inspired gas on CBF during heavy exercise in an altitude naïve population. We hypothesized that augmented inspired CO2 and hypoxia would exert synergistic effects on increasing CBF during exercise, which would improve exercise capacity compared to hypocapnic hypoxia. We also examined the responsiveness of CO2 and O2 chemoreception on the regulation ventilation (E) during incremental exercise. We measured middle cerebral artery velocity (MCAv; index of CBF), E, end-tidal PCO2, respiratory compensation threshold (RC) and ventilatory response to exercise (E slope) in ten healthy men during incremental cycling to exhaustion in normoxia and hypoxia (FIO2 = 0.10) with and without augmenting the fraction of inspired CO2 (FICO2). During exercise in normoxia, augmenting FICO2 elevated MCAv throughout exercise and lowered both RC onset andE slope below RC (P<0.05). In hypoxia, MCAv and E slope below RC during exercise were elevated, while the onset of RC occurred at lower exercise intensity (P<0.05). Augmenting FICO2 in hypoxia increased E at RC (P<0.05) but no difference was observed in RC onset, MCAv, or E slope below RC (P>0.05). The E slope above RC was unchanged with either hypoxia or augmented FICO2 (P>0.05). We found augmenting FICO2 increased CBF during sub-maximal exercise in normoxia, but not in hypoxia, indicating that the 'normal' cerebrovascular response to hypercapnia is blunted during exercise in hypoxia, possibly due to an exhaustion of cerebral vasodilatory reserve. This finding may explain the lack of improvement of exercise capacity in hypoxia with augmented CO2. Our data further indicate that, during exercise below RC, chemoreception is responsive, while above RC the ventilatory response to CO2 is blunted.

Disseny de les instal·lacions de climatització, gas, electricitat i aigua calenta sanitària d'un edifici de 12 habitatges amb pàrquing

El projecte defineix les instal·lacions bàsiques en un edifici de 12 habitatges, incloent el disseny de la instal·lació d'ACS amb aportació per energies renovables. S'avaluen els sistemes més adequats per a cada instal·lació i es defineixen els materials i els elements constructius de l'edifici. Del pàrquing situat al soterrani s'estudiarà la ventilació que més s'escaigui i les proteccions contra incendis necessàries.

Reduction of Greenhouse Gas Emissions in North-West Russia - Finnish Business Opportunities

Tutkimus suomalaisten yritysten liiketoimintamahdollisuuksista hiilidoksidipäästöjen vähentämisen parissa Luoteis-Venäjällä.

Computational Analysis and Optimization of Real Gas Flow In Small Centrifugal Compressors

Small centrifugal compressors are more and more widely used in many industrialsystems because of their higher efficiency and better off-design performance comparing to piston and scroll compressors as while as higher work coefficient perstage than in axial compressors. Higher efficiency is always the aim of the designer of compressors. In the present work, the influence of four partsof a small centrifugal compressor that compresses heavy molecular weight real gas has been investigated in order to achieve higher efficiency. Two parts concern the impeller: tip clearance and the circumferential position of the splitter blade. The other two parts concern the diffuser: the pinch shape and vane shape. Computational fluid dynamics is applied in this study. The Reynolds averaged Navier-Stokes flow solver Finflo is used. The quasi-steady approach is utilized. Chien's k-e turbulence model is used to model the turbulence. A new practical real gas model is presented in this study. The real gas model is easily generated, accuracy controllable and fairly fast. The numerical results and measurements show good agreement. The influence of tip clearance on the performance of a small compressor is obvious. The pressure ratio and efficiency are decreased as the size of tip clearance is increased, while the total enthalpy rise keeps almost constant. The decrement of the pressure ratio and efficiency is larger at higher mass flow rates and smaller at lower mass flow rates. The flow angles at the inlet and outlet of the impeller are increased as the size of tip clearance is increased. The results of the detailed flow field show that leakingflow is the main reason for the performance drop. The secondary flow region becomes larger as the size of tip clearance is increased and the area of the main flow is compressed. The flow uniformity is then decreased. A detailed study shows that the leaking flow rate is higher near the exit of the impeller than that near the inlet of the impeller. Based on this phenomenon, a new partiallyshrouded impeller is used. The impeller is shrouded near the exit of the impeller. The results show that the flow field near the exit of the impeller is greatly changed by the partially shrouded impeller, and better performance is achievedthan with the unshrouded impeller. The loading distribution on the impeller blade and the flow fields in the impeller is changed by moving the splitter of the impeller in circumferential direction. Moving the splitter slightly to the suction side of the long blade can improve the performance of the compressor. The total enthalpy rise is reduced if only the leading edge of the splitter ismoved to the suction side of the long blade. The performance of the compressor is decreased if the blade is bended from the radius direction at the leading edge of the splitter. The total pressure rise and the enthalpy rise of thecompressor are increased if pinch is used at the diffuser inlet. Among the fivedifferent pinch shape configurations, at design and lower mass flow rates the efficiency of a straight line pinch is the highest, while at higher mass flow rate, the efficiency of a concave pinch is the highest. The sharp corner of the pinch is the main reason for the decrease of efficiency and should be avoided. The variation of the flow angles entering the diffuser in spanwise direction is decreased if pinch is applied. A three-dimensional low solidity twisted vaned diffuser is designed to match the flow angles entering the diffuser. The numerical results show that the pressure recovery in the twisted diffuser is higher than in a conventional low solidity vaned diffuser, which also leads to higher efficiency of the twisted diffuser. Investigation of the detailed flow fields shows that the separation at lower mass flow rate in the twisted diffuser is later than in the conventional low solidity vaned diffuser, which leads to a possible wider flow range of the twisted diffuser.

Numerical and ExperimentalModelling of Gas Flow and Heat Transfer in the Air Gap of An Electric Machine

This work deals with the cooling of high-speed electric machines, such as motors and generators, through an air gap. It consists of numerical and experimental modelling of gas flow and heat transfer in an annular channel. Velocity and temperature profiles are modelled in the air gap of a high-speed testmachine. Local and mean heat transfer coefficients and total friction coefficients are attained for a smooth rotor-stator combination at a large velocity range. The aim is to solve the heat transfer numerically and experimentally. The FINFLO software, developed at Helsinki University of Technology, has been used in the flow solution, and the commercial IGG and Field view programs for the grid generation and post processing. The annular channel is discretized as a sector mesh. Calculation is performed with constant mass flow rate on six rotational speeds. The effect of turbulence is calculated using three turbulence models. The friction coefficient and velocity factor are attained via total friction power. The first part of experimental section consists of finding the proper sensors and calibrating them in a straight pipe. After preliminary tests, a RdF-sensor is glued on the walls of stator and rotor surfaces. Telemetry is needed to be able to measure the heat transfer coefficients at the rotor. The mean heat transfer coefficients are measured in a test machine on four cooling air mass flow rates at a wide Couette Reynolds number range. The calculated values concerning the friction and heat transfer coefficients are compared with measured and semi-empirical data. Heat is transferred from the hotter stator and rotor surfaces to the coolerair flow in the air gap, not from the rotor to the stator via the air gap, althought the stator temperature is lower than the rotor temperature. The calculatedfriction coefficients fits well with the semi-empirical equations and precedingmeasurements. On constant mass flow rate the rotor heat transfer coefficient attains a saturation point at a higher rotational speed, while the heat transfer coefficient of the stator grows uniformly. The magnitudes of the heat transfer coefficients are almost constant with different turbulence models. The calibrationof sensors in a straight pipe is only an advisory step in the selection process. Telemetry is tested in the pipe conditions and compared to the same measurements with a plain sensor. The magnitudes of the measured data and the data from the semi-empirical equation are higher for the heat transfer coefficients than thenumerical data considered on the velocity range. Friction and heat transfer coefficients are presented in a large velocity range in the report. The goals are reached acceptably using numerical and experimental research. The next challenge is to achieve results for grooved stator-rotor combinations. The work contains also results for an air gap with a grooved stator with 36 slots. The velocity field by the numerical method does not match in every respect the estimated flow mode. The absence of secondary Taylor vortices is evident when using time averagednumerical simulation.

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.

Modeling dynamic behavior in tilting pad gas journal bearings

Thisresearch deals with the dynamic modeling of gas lubricated tilting pad journal bearings provided with spring supported pads, including experimental verification of the computation. On the basis of a mathematical model of a film bearing, a computer program has been developed, which can be used for the simulation of a special type of tilting pad gas journal bearing supported by a rotary spring under different loading conditions time dependently (transient running conditions due to geometry variations in time externally imposed). On the basis of literature, different transformations have been used in the model to achieve simpler calculation. The numerical simulation is used to solve a non-stationary case of a gasfilm. The simulation results were compared with literature results in a stationary case (steady running conditions) and they were found to be equal. In addition to this, comparisons were made with a number of stationary and non-stationary bearing tests, which were performed at Lappeenranta University of Technology using bearings designed with the simulation program. A study was also made using numerical simulation and literature to establish the influence of the different bearing parameters on the stability of the bearing. Comparison work was done with literature on tilting pad gas bearings. This bearing type is rarely used. One literature reference has studied the same bearing type as that used in LUT. A new design of tilting pad gas bearing is introduced. It is based on a stainless steel body and electron beam welding of the bearing parts. It has good operation characteristics and is easier to tune and faster to manufacture than traditional constructions. It is also suitable for large serial production.