Desenvolvimento de uma câmara para combustão de combustíveis líquidos, operando sob regime de combustão sem chama visível

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Combustion of coal, bagasse and blends thereof Part II: Speciation of PAH emissions

This work reports on emissions of unburned hydrocarbon species from batch combustion of fixed beds of coal, sugar-cane bagasse, and blends thereof in a pre-heated two-stage laboratory furnace operated in the temperature range of 800-1000 degrees C. The effects of fuel blending, combustion staging, and operating furnace temperatures on emissions of pollutants were assessed. Furnace effluents were analyzed for products of incomplete combustion (PICs) including CO, volatile and semi-volatile hydrocarbons, and particulate matter, as has been reported in Ref. [1]. Emitted unburned hydrocarbons include traces of potentially health-hazardous Polycyclic Aromatic Hydrocarbons (PAHs), which are the focus of this work. Under the batch combustion conditions implemented herein, PAH were only generated during the volatile combustion phase of the fuels. The most prevalent species were in descending order: naphthalene, acenaphthylene, phenanthrene, fluoranthene, pyrene, dibenzofuran, benzofuran, byphenyl, fluorene, 9H-fluoren-9-one, acephenantrylene, benzo[b] fluoranthene, 1-methyl-naphthalene; 2-methyl-naphthalene, benz[a] anthracene and benzo[a] pyrene. PAH yields were the highest from combustion of neat bagasse. Combustion of the blends resulted in lower yields of PAH, than combustion of either of their neat fuel constituents. Increasing the furnace operating temperature enhanced the PAH emissions from bagasse, but had little effect on those from the coal or from the blends. Flue gas treatment in a secondary-stage furnace, upon with additional air, typically reduced PAH yields by promoting oxidation of the primary-stage furnace effluents. (C) 2011 Elsevier Ltd. All rights reserved.

Models of the Distribution of Persistent Organic Pollutants in the Marine Environment

Persistent organic pollutants (POPs) is a group of chemicals that are toxic, undergo long-range transport and accumulate in biota. Due to their persistency the distribution and recirculation in the environment often continues for a long period of time. Thereby they appear virtually everywhere within the biosphere, and poses a toxic stress to living organisms. In this thesis, attempts are made to contribute to the understanding of factors that influence the distribution of POPs with focus on processes in the marine environment. The bioavailability and the spatial distribution are central topics for the environmental risk management of POPs. In order to study these topics, various field studies were undertaken. To determine the bioavailable fraction of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated naphthalenes (PCNs), and polychlorinated biphenyls (PCBs) the aqueous dissolved phase were sampled and analysed. In the same samples, we also measured how much of these POPs were associated with suspended particles. Different models, which predicted the phase distribution of these POPs, were then evaluated. It was found that important water characteristics, which influenced the solid-water phase distribution of POPs, were particulate organic matter (POM), particulate soot (PSC), and dissolved organic matter (DOM). The bioavailable dissolved POP-phase in the water was lower when these sorbing phases were present. Furthermore, sediments were sampled and the spatial distribution of the POPs was examined. The results showed that the concentration of PCDD/Fs, and PCNs were better described using PSC- than using POM-content of the sediment. In parallel with these field studies, we synthesized knowledge of the processes affecting the distribution of POPs in a multimedia mass balance model. This model predicted concentrations of PCDD/Fs throughout our study area, the Grenlandsfjords in Norway, within factors of ten. This makes the model capable to validate the effect of suitable remedial actions in order to decrease the exposure of these POPs to biota in the Grenlandsfjords which was the aim of the project. Also, to evaluate the influence of eutrophication on the marine occurrence PCB data from the US Musselwatch and Benthic Surveillance Programs are examined in this thesis. The dry weight based concentrations of PCB in bivalves were found to correlate positively to the organic matter content of nearby sediments, and organic matter based concentrations of PCB in sediments were negatively correlated to the organic matter content of the sediment.

Hygroskopische Eigenschaften atmosphärischer Partikel in kontinentalen Luftmassen

Die hygroskopischen Eigenschaften sind wichtige Parameter des atmosphärischen Aerosols. Sie beeinflussen sowohl direkt über den Strahlungsantrieb, als auch indirekt über die Wechselwirkung von Aerosol und Wolken die globale Strahlungsbilanz und somit das Klima. Auch die Sichtweiteveränderung ist von ihnen abhängig. Sie beeinflussen die Partikeldeposition in der Lunge und müssen zur Vermeidung von Artefaktbildung bei der Aerosolmessung berücksichtigt werden.
Die vorliegende Dissertation beinhaltet Messungen des wasserlöslichen Volumenanteils und des hygroskopischen Wachstumsfaktors des atmosphärischen Aerosols. Mit diesen Untersuchungen konnte der überwiegende Teil (50 nm bis 4 µm Partikeldurchmesser) des für atmosphärische Prozesse relevanten Größenbereichs gleichzeitig größenaufgelöst und detailliert erfasst werden. Messungen wurden in ruralen, semi-urbanen und frei-troposphärischen Luftmassen durchgeführt. Messverfahren sind die SoFA (Water-Soluble Fraction of Large and Giant Atmospheric Particles)-Methode und der HTDMA (Hygroscopic Tandem Differential Mobility Analyzer). Im Rahmen dieser Arbeit wurde die SoFA-Methode weiterentwickelt.
Ein umfangreiches Messprogramm zeigt, dass der mittlere lösliche Volumenanteil des Aerosols mit Werten von ca. 59 % geringe Variationen zwischen den Messstandorten aufweist, lediglich in frei-troposphärischen Luftmassen liegt er mit 66 % erwartungsgemäß höher. Betrachtet man die Daten größenaufgelöst, so zeigt sich, dass im Größenbereich zwischen 200 und 500 nm Partikeldurchmesser der lösliche Volumenanteil ein Maximum aufweist. Ein in semi-urbanem Aerosol gemessener Jahresgang weist, vor allem für Partikel kleiner 300 nm, im Sommer geringere Werte als im Winter auf. Unterhalb 300 nm Partikeldurchmesser treten üblicherweise zwei, oberhalb bis zu drei Partikeltypen unterschiedlicher Hygroskopizität auf: der fast unlösliche Partikeltyp mit löslichen Volumenanteilen bis 12 %, der wahrscheinlich aus Ruß, sekundärem organischem, mineralischem und biologischem Material besteht; der teilweise lösliche Partikeltyp (50 bis 75 %), der als Mischpartikel anzusprechen ist; schließlich der überwiegend lösliche Partikeltyp (ca. 90 %), der wahrscheinlich durch Wolkenprozessierung entsteht. Der Unterschied zwischen den Messstandorten ist auch hier gering. Üblicherweise dominieren die löslicheren Partikeltypen mit relativen Anteilen von 60 bis 95 %, wobei sich ein Minimum der Häufigkeit der löslicheren Partikel zwischen 1.5 und 2.5 µm zeigt. Abschließende größenaufgelöste Modellrechnungen zum Aerosol-Feuchtewachstum unterstreichen die Relevanz dieser Untersuchungen für Strahlungs- und Wolkenprozesse.

A numerical methodology for the multi-objective optimization of the DI Diesel engine combustion

DI Diesel engine are widely used both for industrial and automotive applications due to their durability and fuel economy. Nonetheless, increasing environmental concerns force that type of engine to comply with increasingly demanding emission limits, so that, it has become mandatory to develop a robust design methodology of the DI Diesel combustion system focused on reduction of soot and NOx simultaneously while maintaining a reasonable fuel economy. In recent years, genetic algorithms and CFD three-dimensional combustion simulations have been successfully applied to that kind of problem. However, combining GAs optimization with actual CFD three-dimensional combustion simulations can be too onerous since a large number of calculations is usually needed for the genetic algorithm to converge, resulting in a high computational cost and, thus, limiting the suitability of this method for industrial processes. In order to make the optimization process less time-consuming, CFD simulations can be more conveniently used to generate a training set for the learning process of an artificial neural network which, once correctly trained, can be used to forecast the engine outputs as a function of the design parameters during a GA optimization performing a so-called virtual optimization. In the current work, a numerical methodology for the multi-objective virtual optimization of the combustion of an automotive DI Diesel engine, which relies on artificial neural networks and genetic algorithms, was developed.

Measurement and modeling of cloud condensation nuclei in continental air

Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. Knowledge of the spatial and temporal distribution of CCN in the atmosphere is essential to understand and describe the effects of aerosols in meteorological models. In this study, CCN properties were measured in polluted and pristine air of different continental regions, and the results were parameterized for efficient prediction of CCN concentrations.The continuous-flow CCN counter used for size-resolved measurements of CCN efficiency spectra (activation curves) was calibrated with ammonium sulfate and sodium chloride aerosols for a wide range of water vapor supersaturations (S=0.068% to 1.27%). A comprehensive uncertainty analysis showed that the instrument calibration depends strongly on the applied particle generation techniques, Köhler model calculations, and water activity parameterizations (relative deviations in S up to 25%). Laboratory experiments and a comparison with other CCN instruments confirmed the high accuracy and precision of the calibration and measurement procedures developed and applied in this study.The mean CCN number concentrations (NCCN,S) observed in polluted mega-city air and biomass burning smoke (Beijing and Pearl River Delta, China) ranged from 1000 cm−3 at S=0.068% to 16 000 cm−3 at S=1.27%, which is about two orders of magnitude higher than in pristine air at remote continental sites (Swiss Alps, Amazonian rainforest). Effective average hygroscopicity parameters, κ, describing the influence of chemical composition on the CCN activity of aerosol particles were derived from the measurement data. They varied in the range of 0.3±0.2, were size-dependent, and could be parameterized as a function of organic and inorganic aerosol mass fraction. At low S (≤0.27%), substantial portions of externally mixed CCN-inactive particles with much lower hygroscopicity were observed in polluted air (fresh soot particles with κ≈0.01). Thus, the aerosol particle mixing state needs to be known for highly accurate predictions of NCCN,S. Nevertheless, the observed CCN number concentrations could be efficiently approximated using measured aerosol particle number size distributions and a simple κ-Köhler model with a single proxy for the effective average particle hygroscopicity. The relative deviations between observations and model predictions were on average less than 20% when a constant average value of κ=0.3 was used in conjunction with variable size distribution data. With a constant average size distribution, however, the deviations increased up to 100% and more. The measurement and model results demonstrate that the aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. Depending on the required and applicable level of detail, the measurement results and parameterizations presented in this study can be directly implemented in detailed process models as well as in large-scale atmospheric and climate models for efficient description of the CCN activity of atmospheric aerosols.

Kinetic modeling and experiments on gas uptake and chemical transformation of organic aerosol in the atmosphere

Aerosolpartikel beeinflussen das Klima durch Streuung und Absorption von Strahlung sowie als Nukleations-Kerne für Wolkentröpfchen und Eiskristalle. Darüber hinaus haben Aerosole einen starken Einfluss auf die Luftverschmutzung und die öffentliche Gesundheit. Gas-Partikel-Wechselwirkunge sind wichtige Prozesse, weil sie die physikalischen und chemischen Eigenschaften von Aerosolen wie Toxizität, Reaktivität, Hygroskopizität und optische Eigenschaften beeinflussen. Durch einen Mangel an experimentellen Daten und universellen Modellformalismen sind jedoch die Mechanismen und die Kinetik der Gasaufnahme und der chemischen Transformation organischer Aerosolpartikel unzureichend erfasst. Sowohl die chemische Transformation als auch die negativen gesundheitlichen Auswirkungen von toxischen und allergenen Aerosolpartikeln, wie Ruß, polyzyklische aromatische Kohlenwasserstoffe (PAK) und Proteine, sind bislang nicht gut verstanden.rn Kinetische Fluss-Modelle für Aerosoloberflächen- und Partikelbulk-Chemie wurden auf Basis des Pöschl-Rudich-Ammann-Formalismus für Gas-Partikel-Wechselwirkungen entwickelt. Zunächst wurde das kinetische Doppelschicht-Oberflächenmodell K2-SURF entwickelt, welches den Abbau von PAK auf Aerosolpartikeln in Gegenwart von Ozon, Stickstoffdioxid, Wasserdampf, Hydroxyl- und Nitrat-Radikalen beschreibt. Kompetitive Adsorption und chemische Transformation der Oberfläche führen zu einer stark nicht-linearen Abhängigkeit der Ozon-Aufnahme bezüglich Gaszusammensetzung. Unter atmosphärischen Bedingungen reicht die chemische Lebensdauer von PAK von wenigen Minuten auf Ruß, über mehrere Stunden auf organischen und anorganischen Feststoffen bis hin zu Tagen auf flüssigen Partikeln. rn Anschließend wurde das kinetische Mehrschichtenmodell KM-SUB entwickelt um die chemische Transformation organischer Aerosolpartikel zu beschreiben. KM-SUB ist in der Lage, Transportprozesse und chemische Reaktionen an der Oberfläche und im Bulk von Aerosol-partikeln explizit aufzulösen. Es erforder im Gegensatz zu früheren Modellen keine vereinfachenden Annahmen über stationäre Zustände und radiale Durchmischung. In Kombination mit Literaturdaten und neuen experimentellen Ergebnissen wurde KM-SUB eingesetzt, um die Effekte von Grenzflächen- und Bulk-Transportprozessen auf die Ozonolyse und Nitrierung von Protein-Makromolekülen, Ölsäure, und verwandten organischen Ver¬bin-dungen aufzuklären. Die in dieser Studie entwickelten kinetischen Modelle sollen als Basis für die Entwicklung eines detaillierten Mechanismus für Aerosolchemie dienen sowie für das Herleiten von vereinfachten, jedoch realistischen Parametrisierungen für großskalige globale Atmosphären- und Klima-Modelle. rn Die in dieser Studie durchgeführten Experimente und Modellrechnungen liefern Beweise für die Bildung langlebiger reaktiver Sauerstoff-Intermediate (ROI) in der heterogenen Reaktion von Ozon mit Aerosolpartikeln. Die chemische Lebensdauer dieser Zwischenformen beträgt mehr als 100 s, deutlich länger als die Oberflächen-Verweilzeit von molekularem O3 (~10-9 s). Die ROIs erklären scheinbare Diskrepanzen zwischen früheren quantenmechanischen Berechnungen und kinetischen Experimenten. Sie spielen eine Schlüsselrolle in der chemischen Transformation sowie in den negativen Gesundheitseffekten von toxischen und allergenen Feinstaubkomponenten, wie Ruß, PAK und Proteine. ROIs sind vermutlich auch an der Zersetzung von Ozon auf mineralischem Staub und an der Bildung sowie am Wachstum von sekundären organischen Aerosolen beteiligt. Darüber hinaus bilden ROIs eine Verbindung zwischen atmosphärischen und biosphärischen Mehrphasenprozessen (chemische und biologische Alterung).rn Organische Verbindungen können als amorpher Feststoff oder in einem halbfesten Zustand vorliegen, der die Geschwindigkeit von heterogenen Reaktionenen und Mehrphasenprozessen in Aerosolen beeinflusst. Strömungsrohr-Experimente zeigen, dass die Ozonaufnahme und die oxidative Alterung von amorphen Proteinen durch Bulk-Diffusion kinetisch limitiert sind. Die reaktive Gasaufnahme zeigt eine deutliche Zunahme mit zunehmender Luftfeuchte, was durch eine Verringerung der Viskosität zu erklären ist, bedingt durch einen Phasenübergang der amorphen organischen Matrix von einem glasartigen zu einem halbfesten Zustand (feuchtigkeitsinduzierter Phasenübergang). Die chemische Lebensdauer reaktiver Verbindungen in organischen Partikeln kann von Sekunden bis zu Tagen ansteigen, da die Diffusionsrate in der halbfesten Phase bei niedriger Temperatur oder geringer Luftfeuchte um Größenordnungen absinken kann. Die Ergebnisse dieser Studie zeigen wie halbfeste Phasen die Auswirkung organischeer Aerosole auf Luftqualität, Gesundheit und Klima beeinflussen können. rn

Laboratory study on the optical properties of absorbing atmospheric aerosols and field applications

The interaction between aerosols and sun light plays an important role in the radiative balance of Earth’s atmosphere. This interaction is obtained by measuring the removal (extinction), redistribution (scattering), and transformation into heat (absorption) of light by the aerosols; i.e. their optical properties. Knowledge of these properties is crucial for our understanding of the atmospheric system. rn Light absorption by aerosols is a major contributor to the direct and indirect effects on our climate system, and an accurate and sensitive measurement method is crucial to further our understanding. A homebuilt photoacoustic sensor (PAS), measuring at a 532nm wavelength, was fully characterized and its functionality validated for measurements of absorbing aerosols. The optical absorption cross-sections of absorbing polystyrene latex spheres, to be used as a standard for aerosol absorption measurements, were measured and compared to literature values. Additionally, a calibration method using absorbing aerosol of known complex refractive index was presented.rn A new approach to retrieve the effective broadband refractive indices (mbroad,eff) of aerosol particles by a white light aerosol spectrometer (WELAS) optical particle counter (OPC) was achieved. Using a tandem differential mobility analyzer (DMA)-OPC system, the nbroad,eff are obtained for both laboratory and field applications. This method was tested in the laboratory using substances with a wide range of optical properties and it was used in ambient measurements to retrieve the nbroad,eff of biomass burning aerosols in a nationwide burning event in Israel. The retrieved effective broadband refractive indices for laboratory generated scattering aerosols were: ammonium sulfate (AS), glutaric acid (GA), and sodium chloride, all within 4% of literature values. For absorbing substances, nigrosine and various mixtures of nigrosine with AS and GA were measured, as well as a lightly absorbing substance, Suwannee river fulvic acid (SRFA). For the ambient measurements, the calibration curves generated from this method were to follow the optical evolution of biomass burning (BB) aerosols. A decrease in the overall aerosol absorption and scattering for aged aerosols during the day after the fires compared to the smoldering phase of the fires was found. rn The connection between light extinction of aerosols, their chemical composition and hygroscopicity for particles with different degrees of absorption was studied. The extinction cross-section (σext) at 532nm for different mobility diameters was measured at 80% and 90% relative humidity (RH), and at an RH<10%. The ratio of the humidified aerosols to the dry ones, fRHext(%RH,Dry), is presented. For purely scattering aerosols, fRHext(%RH,Dry) is inversely proportional with size; this dependence was suppressed for lightly absorbing ones. In addition, the validity of the mixing rules for water soluble absorbing aerosols is explored. The difference between the derived and calculated real parts of the complex RIs were less than 5.3% for all substances, wavelengths, and RHs. The obtained imaginary parts for the retrieved and calculated RIs were in good agreement with each other, and well within the measurement errors of retrieval from pulsed CRD spectroscopy measurements. Finally, a core-shell structure model is also used to explore the differences between the models, for substances with low growth factors, under these hydration conditions. It was found that at 80% RH and for size parameters less than 2.5, there is less than a 5 % difference between the extinction efficiencies calculated with both models. This difference is within measurement errors; hence, there is no significant difference between the models in this case. However, for greater size parameters the difference can be up to 10%. For 90% RH the differences below a size parameter of 2.5 were up to 7%.rn Finally, the fully characterized PAS together with a cavity ring down spectrometer (CRD), were used to study the optical properties of soot and secondary organic aerosol (SOA) during the SOOT-11 project in the AIDA chamber in Karlsruhe, Germany. The fresh fractal-like soot particles were allowed to coagulate for 28 hours before stepwise coating them with SOA. The single scattering albedo for fresh fractal-like soot was measured to be 0.2 (±0.03), and after allowing the soot to coagulate for 28 hours and coating it with SOA, it increased to 0.71(±0.01). An absorption enhancement of the coated soot of up to 1.71 (±0.03) times from the non-coated coagulated soot was directly measured with the PAS. Monodisperse measurements of SOA and soot coated with SOA were performed to derive the complex refractive index (m) of both aerosols. A complex refractive index of m = 1.471(±0.008) + i0.0(±0.002) for the SOA-αO3 was retrieved. For the compact coagulated soot a preliminary complex refractive index of m = 2.04(+0.21/-0.14) + i0.34(+0.18/-0.06) with 10nm(+4/-6) coating thickness was retrieved.rn These detail properties can be use by modelers to decrease uncertainties in assessing climatic impacts of the different species and to improve weather forecasting.rn

Untersuchungen von Aerosolpartikeln und Wolkenresidualpartikeln mittels Einzelpartikel-Massenspektrometrie und optischen Methoden

Atmosphärische Partikel beeinflussen das Klima durch Prozesse wie Streuung, Reflexion und Absorption. Zusätzlich fungiert ein Teil der Aerosolpartikel als Wolkenkondensationskeime (CCN), die sich auf die optischen Eigenschaften sowie die Rückstreukraft der Wolken und folglich den Strahlungshaushalt auswirken. Ob ein Aerosolpartikel Eigenschaften eines Wolkenkondensationskeims aufweist, ist vor allem von der Partikelgröße sowie der chemischen Zusammensetzung abhängig. Daher wurde die Methode der Einzelpartikel-Laserablations-Massenspektrometrie angewandt, die eine größenaufgelöste chemische Analyse von Einzelpartikeln erlaubt und zum Verständnis der ablaufenden multiphasenchemischen Prozesse innerhalb der Wolke beitragen soll.rnIm Rahmen dieser Arbeit wurde zur Charakterisierung von atmosphärischem Aerosol sowie von Wolkenresidualpartikel das Einzelpartikel-Massenspektrometer ALABAMA (Aircraft-based Laser Ablation Aerosol Mass Spectrometer) verwendet. Zusätzlich wurde zur Analyse der Partikelgröße sowie der Anzahlkonzentration ein optischer Partikelzähler betrieben. rnZur Bestimmung einer geeigneten Auswertemethode, die die Einzelpartikelmassenspektren automatisch in Gruppen ähnlich aussehender Spektren sortieren soll, wurden die beiden Algorithmen k-means und fuzzy c-means auf ihrer Richtigkeit überprüft. Es stellte sich heraus, dass beide Algorithmen keine fehlerfreien Ergebnisse lieferten, was u.a. von den Startbedingungen abhängig ist. Der fuzzy c-means lieferte jedoch zuverlässigere Ergebnisse. Darüber hinaus wurden die Massenspektren anhand auftretender charakteristischer chemischer Merkmale (Nitrat, Sulfat, Metalle) analysiert.rnIm Herbst 2010 fand die Feldkampagne HCCT (Hill Cap Cloud Thuringia) im Thüringer Wald statt, bei der die Veränderung von Aerosolpartikeln beim Passieren einer orographischen Wolke sowie ablaufende Prozesse innerhalb der Wolke untersucht wurden. Ein Vergleich der chemischen Zusammensetzung von Hintergrundaerosol und Wolkenresidualpartikeln zeigte, dass die relativen Anteile von Massenspektren der Partikeltypen Ruß und Amine für Wolkenresidualpartikel erhöht waren. Dies lässt sich durch eine gute CCN-Aktivität der intern gemischten Rußpartikel mit Nitrat und Sulfat bzw. auf einen begünstigten Übergang der Aminverbindungen aus der Gas- in die Partikelphase bei hohen relativen Luftfeuchten und tiefen Temperaturen erklären. Darüber hinaus stellte sich heraus, dass bereits mehr als 99% der Partikel des Hintergrundaerosols intern mit Nitrat und/oder Sulfat gemischt waren. Eine detaillierte Analyse des Mischungszustands der Aerosolpartikel zeigte, dass sich sowohl der Nitratgehalt als auch der Sulfatgehalt der Partikel beim Passieren der Wolke erhöhte. rn

GSR deposition along the bullet path in contact shots to composite models

In contact shots, all the materials emerging from the muzzle (combustion gases, soot, powder grains, and metals from the primer) will be driven into the depth of the entrance wound and the following sections of the bullet track. The so-called "pocket" ("powder cavity") under the skin containing soot and gunpowder particles is regarded as a significant indicator of a contact entrance wound since one would expect that the quantity of GSR deposited along the bullet's path rapidly declines towards the exit hole. Nevertheless, experience has shown that soot, powder particles, and carboxyhemoglobin may be found not only in the initial part of the wound channel, but also far away from the entrance and even at the exit. In order to investigate the propagation of GSRs under standardized conditions, contact test shots were fired against composite models of pig skin and 25-cm-long gelatin blocks using 9-mm Luger pistol cartridges with two different primers (Sinoxid® and Sintox®). Subsequently, 1-cm-thick layers of the gelatin blocks were examined as to their primer element contents (lead, barium, and antimony as discharge residues of Sinoxid® as well as zinc and titanium from Sintox®) by means of X-ray fluorescence spectroscopy. As expected, the highest element concentrations were found in the initial parts of the bullet tracks, but also the distal sections contained detectable amounts of the respective primer elements. The same was true for amorphous soot and unburned/partly burned powder particles, which could be demonstrated even at the exit site. With the help of a high-speed motion camera it was shown that for a short time the temporary cavitation extends from the entrance to the exit thus facilitating the unlimited spread of discharge residues along the whole bullet path.

An ice-core based history of Siberian forest fires since AD 1250

Forest fires play a key role in the global carbon cycle and thus, can affect regional and global climate. Although fires in extended areas of Russian boreal forests have a considerable influence on atmospheric greenhouse gas and soot concentrations, estimates of their impact on climate are hampered by a lack of data on the history of forest fires. Especially regions with strong continental climate are of high importance due to an intensified development of wildfires. In this study we reconstruct the fire history of Southern Siberia during the past 750 years using ice-core based nitrate, potassium, and charcoal concentration records from Belukha glacier in the continental Siberian Altai. A period of exceptionally high forest-fire activity was observed between AD 1600 and 1680, following an extremely dry period AD 1540-1600. Ice-core pollen data suggest distinct forest diebacks and the expansion of steppe in response to dry climatic conditions. Coherence with a paleoenvironmental record from the 200 km distant Siberian lake Teletskoye shows that the vegetational shift AD 1540-1680, the increase in fire activity AD 1600-1680, and the subsequent recovery of forests AD 1700 were of regional significance. Dead biomass accumulation in response to drought and high temperatures around AD 1600 probably triggered maximum forest-fire activity AD 1600-1680. The extreme dry period in the 16th century was also observed at other sites in Central Asia and is possibly associated with a persistent positive mode of the Pacific Decadal Oscillation (PDO). No significant increase in biomass burning occurred in the Altai region during the last 300 years, despite strongly increasing temperatures and human activities. Our results imply that precipitation changes controlled fire-regime and vegetation shifts in the Altai region during the past 750 years. We conclude that high sensitivity of ecosystems to occasional decadal-scale drought events may trigger unprecedented environmental reorganizations under global-warming conditions.

Recent increase in black carbon concentrations from a Mt. Everest ice core spanning 1860-2000 AD

A Mt. Everest ice core spanning 1860–2000 AD and analyzed at high resolution for black carbon (BC) using a Single Particle Soot Photometer (SP2) demonstrates strong seasonality, with peak concentrations during the winter-spring, and low concentrations during the summer monsoon season. BC concentrations from 1975–2000 relative to 1860–1975 have increased approximately threefold, indicating that BC from anthropogenic sources is being transported to high elevation regions of the Himalaya. The timing of the increase in BC is consistent with BC emission inventory data from South Asia and the Middle East, however since 1990 the ice core BC record does not indicate continually increasing BC concentrations. The Everest BC and dust records provide information about absorbing impurities that can contribute to glacier melt by reducing the albedo of snow and ice. There is no increasing trend in dust concentrations since 1860, and estimated surface radiative forcing due to BC in snow exceeds that of dust in snow. This suggests that a reduction in BC emissions may be an effective means to reduce the effect of absorbing impurities on snow albedo and melt, which affects Himalayan glaciers and the availability of water resources in major Asian rivers.

Diesel spray mixing limited vaporization with non-ideal and multi-component fuel thermophysical property effects

Internal combustion engines are, and will continue to be, a primary mode of power generation for ground transportation. Challenges exist in meeting fuel consumption regulations and emission standards while upholding performance, as fuel prices rise, and resource depletion and environmental impacts are of increasing concern. Diesel engines are advantageous due to their inherent efficiency advantage over spark ignition engines; however, their NOx and soot emissions can be difficult to control and reduce due to an inherent tradeoff. Diesel combustion is spray and mixing controlled providing an intrinsic link between spray and emissions, motivating detailed, fundamental studies on spray, vaporization, mixing, and combustion characteristics under engine relevant conditions. An optical combustion vessel facility has been developed at Michigan Technological University for these studies, with detailed tests and analysis being conducted. In this combustion vessel facility a preburn procedure for thermodynamic state generation is used, and validated using chemical kinetics modeling both for the MTU vessel, and institutions comprising the Engine Combustion Network international collaborative research initiative. It is shown that minor species produced are representative of modern diesel engines running exhaust gas recirculation and do not impact the autoignition of n-heptane. Diesel spray testing of a high-pressure (2000 bar) multi-hole injector is undertaken including non-vaporizing, vaporizing, and combusting tests, with sprays characterized using Mie back scatter imaging diagnostics. Liquid phase spray parameter trends agree with literature. Fluctuations in liquid length about a quasi-steady value are quantified, along with plume to plume variations. Hypotheses are developed for their causes including fuel pressure fluctuations, nozzle cavitation, internal injector flow and geometry, chamber temperature gradients, and turbulence. These are explored using a mixing limited vaporization model with an equation of state approach for thermopyhysical properties. This model is also applied to single and multi-component surrogates. Results include the development of the combustion research facility and validated thermodynamic state generation procedure. The developed equation of state approach provides application for improving surrogate fuels, both single and multi-component, in terms of diesel spray liquid length, with knowledge of only critical fuel properties. Experimental studies are coupled with modeling incorporating improved thermodynamic non-ideal gas and fuel

Dynamic modeling of active regeneration in catalyzed and non-catalyzed diesel particulate filters

Particulate matter (PM) emissions standards set by the US Environmental Protection Agency (EPA) have become increasingly stringent over the years. The EPA regulation for PM in heavy duty diesel engines has been reduced to 0.01 g/bhp-hr for the year 2010. Heavy duty diesel engines make use of an aftertreatment filtration device, the Diesel Particulate Filter (DPF). DPFs are highly efficient in filtering PM (known as soot) and are an integral part of 2010 heavy duty diesel aftertreatment system. PM is accumulated in the DPF as the exhaust gas flows through it. This PM needs to be removed by oxidation periodically for the efficient functioning of the filter. This oxidation process is also known as regeneration. There are 2 types of regeneration processes, namely active regeneration (oxidation of PM by external means) and passive oxidation (oxidation of PM by internal means). Active regeneration occurs typically in high temperature regions, about 500 - 600 °C, which is much higher than normal diesel exhaust temperatures. Thus, the exhaust temperature has to be raised with the help of external devices like a Diesel Oxidation Catalyst (DOC) or a fuel burner. The O2 oxidizes PM producing CO2 as oxidation product. In passive oxidation, one way of regeneration is by the use of NO2. NO2 oxidizes the PM producing NO and CO2 as oxidation products. The passive oxidation process occurs at lower temperatures (200 - 400 °C) in comparison to the active regeneration temperatures. Generally, DPF substrate walls are washcoated with catalyst material to speed up the rate of PM oxidation. The catalyst washcoat is observed to increase the rate of PM oxidation. The goal of this research is to develop a simple mathematical model to simulate the PM depletion during the active regeneration process in a DPF (catalyzed and non-catalyzed). A simple, zero-dimensional kinetic model was developed in MATLAB. Experimental data required for calibration was obtained by active regeneration experiments performed on PM loaded mini DPFs in an automated flow reactor. The DPFs were loaded with PM from the exhaust of a commercial heavy duty diesel engine. The model was calibrated to the data obtained from active regeneration experiments. Numerical gradient based optimization techniques were used to estimate the kinetic parameters of the model.

LIFE CYCLE ASSESSMENT OF BIOFUEL PRODUCED FROM ALGAE

Algae are considered a promising source of biofuels in the future. However, the environmental impact of algae-based fuel has high variability in previous LCA studies due to lack of accurate data from researchers and industry. The National Alliance for Advanced Biofuels and Bioproducts (NAABB) project was designed to produce and evaluate new technologies that can be implemented by the algal biofuel industry and establish the overall process sustainability. The MTU research group within NAABB worked on the environmental sustainability part of the consortium with UOP-Honeywell and with the University of Arizona (Dr. Paul Blowers). Several life cycle analysis (LCA) models were developed within the GREET Model and SimaPro 7.3 software to quantitatively assess the environment viability and sustainability of algal fuel processes. The baseline GREET Harmonized algae life cycle was expanded and replicated in SimaPro software, important differences in emission factors between GREET/E-Grid database and SimaPro/Ecoinvent database were compared, and adjustments were made to the SimaPro analyses. The results indicated that in most cases SimaPro has a higher emission penalty for inputs of electricity, chemicals, and other materials to the algae biofuels life cycle. A system-wide model of algae life cycle was made starting with preliminary data from the literature, and then progressed to detailed analyses based on inputs from all NAABB research areas, and finally several important scenarios in the algae life cycle were investigated as variations to the baseline scenario. Scenarios include conversion to jet fuel instead of biodiesel or renewable diesel, impacts of infrastructure for algae cultivation, co-product allocation methodology, and different usage of lipid-extracted algae (LEA). The infrastructure impact of algae cultivation is minimal compared to the overall life cycle. However, in the scenarios investigating LEA usage for animal feed instead of internal recycling for energy use and nutrient recovery the results reflect the high potential variability in LCA results. Calculated life cycle GHG values for biofuel production scenarios where LEA is used as animal feed ranged from a 55% reduction to 127% increase compared to the GREET baseline scenario depending on the choice of feed meal. Different allocation methods also affect LCA results significantly. Four novel harvesting technologies and two extraction technologies provided by the NAABB internal report have been analysis using SimaPro LCA software. The results indicated that a combination of acoustic extraction and acoustic harvesting technologies show the most promising result of all combinations to optimize the extraction of algae oil from algae. These scenario evaluations provide important insights for consideration when planning for the future of an algae-based biofuel industry.