Ultrafine particle emissions in motor-vehicle exhaust are associated with cardiopulmonary health impacts and increased mortality. The emission, evolution, and exposure-uptake of these particles, one hundred nanometers and smaller in diameter, are fundamentally quantified by the number concentration as a function of particle size. Ultrafine particle number distributions are widely varying and fast changing as they are strongly influenced by local environmental conditions and variation in vehicle operation and maintenance. Research and regulation to quantify and control such emissions rely on measurement of the number distribution of ultrafine particles in vehicle exhaust and by the roadside. Instruments to make such measurements are commercially available, but they are expensive, non-portable, and have slow response times. A new instrument, the NanoAPA, is being developed for these in-situ applications as an inexpensive, portable, and real-time instrument. The instrument is designed to perform ultrafine particle sizing and counting through electronic control of a microfabricated device that charges sampled airborne particles with a corona ionizer and then incrementally size-separates, collects, and counts the number of particles in the aerosol. The focus of this thesis was the development and characterization of the smallest device known that can perform these sizing and counting functions. The device miniaturizes a classical instrument from the aerosol field, the double-condenser of Whipple (1960) used for the sizing and counting of atmospheric ions, into a microfabricated device designed to utilize voltage-and-flowrate-variable electrophoresis to measure ultrafine particle aerosols. Performance characterization of the microfabricated device required development of an apparatus for the generation and conditioning of aerosols appropriate to this application. This Standard Aerosol apparatus was demonstrated to produce repeatable, temperature and humidity stable, charge-neutral, monodisperse exhaust-analog aerosols of particles 10 to 100 nanometer in diameter. The microfabricated device was characterized with the Standard Aerosol apparatus for the operating conditions of 0.1 to 1.5 liter per minute flow rate and 0 to 3000 volt separator voltage. Results of the characterization demonstrated effective selection and collection of solvent droplets in the diameter range 10-100nm. The selection and collection results for engine-exhaust analog particles were inconclusive, likely due to particle re-entrainment. Repeatable measurements of particle number proved elusive, likely due to electrical field interference, the limited particle concentration obtainable from the Standard Aerosol apparatus, and signal-to-noise and temporal stability issues with the electrometer electronics. Recommendations are made for approaches likely to overcome these issues.

No description available.

<p>Flertalet studier har påvisat ett samband mellan koncentrationen av partiklar ≤ 10µm i luftföroreningar och cardiovaskulär- och pulmonell morbiditet och mortalitet. Vid resektion, koagulering/bränning med diatermipenna under operationer alstras rök. Denna rök innehåller bland annat mutagena och carcinogena partiklar i inhalerbar storlek (partiklar ≤ 10µm).</p><p>Ett första syfte med denna studie var att kvantifiera den mängd ultra-fina partiklar (UFP) och partiklar ≤ 10µm som operationspersonal exponeras för i operationsrummet, vid användande av diatermi med mobilt rökutsug. Ett andra syfte var också att ta reda på om operations-personal exponeras olika mycket beroende på var i rummet de befinner sig, samt undersöka om partikelnivåerna skiljer sig på olika operationssalar. Partikelmätningar utfördes under 14 ortopediska operationer där diatermi med rökutsug använts.</p><p>Medelvärdena av UFP visar på relativt låga partikelkoncentrationer på höftprotes- och ryggoperationer, med mycket korta stunder av höga värden upp till ett maxvärde på 88 396pt/ml vid operationsområdet. Även partiklar i storleken 1-10µm låg inom låga nivåer och under gränsvärdena vid jämförelse med organisk damm. Resultaten i studien indikerar att personal som står vid operationssåret exponeras av högre partikelkoncentrationer av ultra-fina partiklar och partiklar 1-10µm än övrig personal, även vid användande av mobilt rökutsug. Vid jämförelse av partikelnivåer av ultra-fina partiklar på två olika operationssalar framkom det att på den sal med lägst antal luftväxlingar i operationsrummet, var partikelkoncentrationen signifikant högre.</p>

QC20100709

Flertalet studier har påvisat ett samband mellan koncentrationen av partiklar ≤ 10µm i luftföroreningar och cardiovaskulär- och pulmonell morbiditet och mortalitet. Vid resektion, koagulering/bränning med diatermipenna under operationer alstras rök. Denna rök innehåller bland annat mutagena och carcinogena partiklar i inhalerbar storlek (partiklar ≤ 10µm). Ett första syfte med denna studie var att kvantifiera den mängd ultra-fina partiklar (UFP) och partiklar ≤ 10µm som operationspersonal exponeras för i operationsrummet, vid användande av diatermi med mobilt rökutsug. Ett andra syfte var också att ta reda på om operations-personal exponeras olika mycket beroende på var i rummet de befinner sig, samt undersöka om partikelnivåerna skiljer sig på olika operationssalar. Partikelmätningar utfördes under 14 ortopediska operationer där diatermi med rökutsug använts. Medelvärdena av UFP visar på relativt låga partikelkoncentrationer på höftprotes- och ryggoperationer, med mycket korta stunder av höga värden upp till ett maxvärde på 88 396pt/ml vid operationsområdet. Även partiklar i storleken 1-10µm låg inom låga nivåer och under gränsvärdena vid jämförelse med organisk damm. Resultaten i studien indikerar att personal som står vid operationssåret exponeras av högre partikelkoncentrationer av ultra-fina partiklar och partiklar 1-10µm än övrig personal, även vid användande av mobilt rökutsug. Vid jämförelse av partikelnivåer av ultra-fina partiklar på två olika operationssalar framkom det att på den sal med lägst antal luftväxlingar i operationsrummet, var partikelkoncentrationen signifikant högre.

No description available.

No description available.

The demands for copper and rare earth elements (REEs) in the U.S. will keep rising due to their applications in green energy technologies. Meanwhile, copper production in the U.S. has been declining over the past five years due to the depletion of high-grade ore deposits. The situation for REEs is worse; there is no domestic supply chain of REEs in the U.S. since the demise of Molycorp, Inc. in 2016. Studies have shown that the rejected materials from copper and coal processing plants contain significant amounts of valuable metals. As such, this rejected material can be considered as potential secondary sources for extracting copper and REEs, which may help combat future supply risks for the supply of copper and REEs in the U.S. However, the valuable mineral particles in these resources are ultrafine in size, which poses considerable challenges to the most widely used fine particle beneficiation technique, i.e., froth flotation. A novel technology called the Hydrophobic-Hydrophilic Separation (HHS) process, developed at Virginia Tech, has been successfully applied to recover fine coal in previous research. The results of research into the HHS process showed that the process has no lower particle size limit, similar to solvent extraction. Therefore, the primary objective of this research is to explore the feasibility of using the new process to recover ultrafine particles of coal, copper minerals, and rare earth minerals (REMs) associated with coal byproducts. In the present work, a series of laboratory-scale oil agglomeration and HHS tests have been carried out on coal with the objectives of assisting the HHS tests in pilot-scale, and the scale-up of the process. The knowledge gained from this study was successfully applied to solving the problems encountered in the pilot-scale tests. Additionally, a new and more efficient equipment known as the Morganizer has been designed and constructed to break up the agglomerates in oil phase as a means to remove entrained gangue minerals and water. The effectiveness of the new Morganizers has been demonstrated in laboratory-scale HHS tests, which may potentially result in the reduction of capital costs in commercializing the HHS process. Furthermore, the prospect of using the HHS process for processing high-sulfur coals has been explored. The results of this study showed that the HHS process can be used to increase the production of cleaner coal from waste streams. Application of the HHS process was further extended to recover the micron-sized REMs from a thickener underflow sample from the LW coal preparation plant, Kentucky. The results showed that the HHS process was far superior to the forced-air flotation process. In one test conducted during the earlier stages of the present study, a concentrate assaying 17,590 ppm total REEs was obtained from a 300 ppm feed. In this test, the Morganizer was not used to upgrade the rougher concentrate due to the lack of proper understanding of the fundamental mechanisms involved in converting oil-in-water (o/w) Pickering emulsions to water-in-oil (w/o) Pickering emulsions. Many of the studies has, therefore, been focused on the studies of phase inversion mechanisms. The results showed that phase inversion requires that i) the oil contact angles (θo) of the particles be increased above 90o, ii) the phase volume of oil (ϕo) be increased, and iii) the o/w emulsion be subjected to a high-shear agitation. It has been found that the first criterion can be readily met by using a hydrophobicity-enhancing agent. These findings were applied to produce high-grade REM concentrates from an artificial mixture of micron-sized monazite and silica. Based on the improved understanding of phase inversion, a modified HHS process has been developed to recover ultrafine particles of copper minerals. After successfully demonstrating the efficacy and effectiveness of this process on a series of artificial copper ore samples, the modified HHS process was used to produce high-grade copper concentrates from a series of cleaner scavenger tails obtained from operating plants. / Doctor of Philosophy / Recovery and dewatering of ultrafine particles have been the major challenges in the minerals and coal industries. Based on the thermodynamic advantage that oil droplets form contact angles about twice as large as those obtainable with air bubbles, a novel separation technology called the hydrophobic-hydrophilic separation (HHS) process was developed at Virginia Tech to address this issues. The research into the HHS process previously was only conducted on the recovery of ultrafine coal particles; also, the fundamental aspects of the HHS process were not fully understood, particularly the mechanisms of phase inversion of oil-in-water emulsions to water-in-oil emulsions. As a follow-up to the previous studies, emulsification tests have been conducted using ultrafine silica and chalcopyrite particles as emulsifiers, and the results showed that phase inversion requires high contact angles, high phase volumes, and high-shear agitation. These findings were applied to improve the HHS process for the recovery of ultrafine particles of coal, copper minerals, and rare earth minerals (REMs). The results obtained in the present work show that the HHS process can be used to efficiently recover and dewater fine particles without no lower particle size limits.

The drivers of human health and changing climate are important areas of environmental and atmospheric studies. Among many environmental factors present in our biosphere, small particles, also known as ultrafine particles or UFPs, have direct and indirect pathways to affect human health and climatic processes. The rapid change in their properties makes UFPs dynamic and often challenging to quantify their effect on health and radiative forcing. To reduce uncertainty in the climate effects of UFPs and to strengthen the evidence on health effects, accurate characterizations of physical and chemical properties of UFPs are needed. In this thesis, two broad aspects of UFPs were investigated: (1) the development of particle instrumentation to study particle properties; and (2) measurement of physical and chemical properties of UFPs relevant to human health and climate. These two broad aspects are divided into four specific aims in this thesis. The measurement of UFP concentration at different locations in an urban location, from roadside to various residential areas, can be improved by using a mobile particle counter. A TSI 3786 Condensation Particle Counter (CPC) was modified for mobile battery-power operation. This design provided high-frequency, one second time resolution measurements of particle number and carbon dioxide (CO2). An independent electric power system, a central controller and robust data acquisition system, and a GPS system are the major components of this mobile unit. These capabilities make the system remotely deployable, and also offer flexibility to integrate other analog and digital sensors. A Volatility Tandem Differential Mobility Analyzer (V-TDMA) system was designed and built to characterize the volatility behavior of UFPs. The physical and chemical properties of UFPs are often challenging to measure due to limited availability of instruments, detection limit in terms of particle size and concentration, and sampling frequency. Indirect methods such as V-TDMA are useful, for small mass (<1 µg/m3), and nuclei mode particles (<30nm). Another advantage of V-TDMA is its fast response in terms of sampling frequency. A secondary motivation for building a V-TDMA system was to improve instrumentation capability of our group, thus enabling study of kinetic and thermodynamic properties of novel aerosols. Chapter four describes the design detail of the built V-TDMA system, which measures the change in UFP size and concentration during heated and non-heated (or ambient) condition. The V-TDMA system has an acceptable penetration efficiency of 85% for 10 nm and maintains a uniform temperature profile in the heating system. Calibration of V-TDMA using ammonium sulfate particles indicated that the system produces comparable evaporation curves (in terms of volatilization temperature) or volatility profiles to other published V-TDMA designs. Additionally the system is fully programmable with respect to particle size, temperature and sampling frequency and can be run autonomously after initial set up. The thesis describes a part of yearlong study to provide a complete perspective on particle formation and growth in a rural and agricultural Midwestern site. Volatility characterizations of UFPs were conducted to enable inference about particle chemistry, and formation of low volatile core or evaporation resistant residue in the UFP in the Midwest. This study addresses identification of the volatility signature of particles in the UFP size range, quantification of physical differences of UFPs between NPF1 and non-NPF events and relation of evaporation resistant residue with particle size, seasonality and mixing state. K-means clustering was applied to determine three unique volatility clusters in 15, 30, 50 and 80 nm particle sizes. Based on the proposed average volatility, the identified volatility clusters were classified into high volatile, intermediate volatile and least volatile group. Although VFR alone is insufficient to establish chemical composition definitively, least volatile cluster based on average volatility may be characteristically similar to the pure ammonium sulfate. The amount of evaporation residue at 200 °C was positively correlated with particle size and showed significant correlation with ozone, sulfur dioxide and solar radiation. Residue also indicated the presence of external mixture, often during morning and night time. Air quality science and management of an accidental urban tire fire occurring in Iowa City in May and June of 2012 were investigated. Urban air quality emergencies near populated areas are difficult to evaluate without a proper air quality management and response system. To support the development of an appropriate air quality system, this thesis identified and created a rank for health-related acute and chronic compounds in the tire smoke. For health risk assessment, the study proposed an empirical equation for estimating multi-pollutant air quality index. Using mobile measurements and a dispersion model in conjunction with the proposed air quality index, smoke concentrations and likely health impact were evaluated for Iowa City and surrounding areas. It was concluded that the smoke levels reached unhealthy outdoor levels for sensitive groups out to distances of 3.1 km and 18 km at 24 h and 1h average times. Tire smoke characterization was another important aspect of this study which provided important and new information about tire smoke. Revised emission factors for coarse particle mass and aerosol-PAH and new emission factors and enhancement ratios values for a wide range of fine particulate mass, particle size (0.001-2.5 µm), and trace gas were estimated. Overall the thesis added new instrumentation in our research group to measure various physical properties such as size, concentration, and volatility UFP. The built instruments, data processing algorithm and visualization tools will be useful in estimation of accurate concentration and emission factors of UFP for health exposure studies, and generate a fast response measurement of kinetic and thermodynamics properties of ambient particles. This thesis also makes a strong case for the development of an air quality emergency system for accidental fires for urban location. It provides useful evaluation and estimation of many aspects of such system such as smoke characterization, method of air quality monitoring and impact assessment, and develops communicable method of exposure risk assessment.

The purpose of this study was to investigate whether or not differing base metals and filler wires used during welding processes contributed to differing amounts of ultrafine particles (UFP) and nanoparticles being emitted during the welding procedure. The study was also conducted to determine UFP and nanoparticle exposure in the breathing zones of the welders as well as the breathing zones of pipefitters and fire watchers, who commonly sit 6ft behind the welding arc. In order to determine if UFP and NP exposures differed with base metal and filler wire, all welding processes utilized the same welding machine for metal inert gas (MIG), the same wire speed, and the same voltages during each welding process. The only variation in welding procedures were cover gases used, base metals, and filler wires. Measurements gathered during welding procedures were conducted in the breathing zone of the welder and pipefitters consisted of UFP measurements taken by two different condensation particle counters (CPC), which operated in synchrony at the start and cessation of the welding process. NP measurements were taken by a NanoScan Scanning Mobility Particle Sizer (SMPS) and were also placed in the breathing zone of the welder. Lastly, particle characterization measurements for transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) were gathered using a filter attached to a high flow pump, which was placed in the breathing zone of the welder. According to the results, base metal and filler wire do emit differing amounts of NP and UFP during the welding processes. Carbon steel emits the highest amount of nanoparticles, while stainless steel emits the second highest amount, and inconel emits the least. The results also concluded that welders are exposed to a greater concentration of nanoparticles and UFPs than those experienced by pipefitters who stand 6ft from the welding arc.