This thesis concerns various aspects of the influence of atmospheric particulate matter on the terrestrial system. In Part I, the radiative influence of particulate matter on the production of crops is explored using the CERES crop model. It is known that the presence of aerosols in the atmosphere simultaneously reduces the amount of sunlight reaching the surface and increases the fraction of that light which is diffuse. Reduction of the total amount of sunlight tends to slow the rate of photosynthesis occurring in plants while increasing the fraction which is diffuse tends to increase the net rate of photosynthesis by more evenly distributing sunlight throughout all layers of a plant canopy. The CERES crop model was modified to estimate the influence of both a reduction in total sunlight and an increase in the diffuse fraction. Model simulations were performed for rice, maize and wheat at a variety of locations and found the likely influence of aerosols on crop production to be a 0-10% reduction in yield compared to the base case. In Part II, the concentration and size distribution of water-insoluble aerosols (WIA) is explored. It has been well-established that atmospheric particulate matter influences the planetary radiation budget both directly and indirectly. The magnitude of these influences is related to particle solubility. A new technique was developed to provide these measurements in real-time. This instrumentation was evaluated in a laboratory setting and implemented into several field studies. Results from these sampling campaigns indicate that in areas heavily influenced by motor vehicle traffic, the WIA concentration is dominated by particulate soot. Many episodes of high levels of crustal dust were also observed. At these times, the WIA size distribution shifted toward larger sizes in a characteristic manner. This suggests that this method is useful for detecting insoluble mineral aerosols as well as particulate soot and that examination of the WIA size-distribution may provide a basis to distinguish between the two.

Diesel particulate matter (DPM) is the solid portion of diesel exhaust. DPM occurs primarily in the submicron range, and poses a number of respiratory and other health hazards including cardiovascular and pulmonary disease. Underground miners typically have the highest DPM exposures compared to other occupations. This is because many mines are characterized by confined work spaces and large diesel equipment fleets. Exposures can be a particularly high hazard in large opening mines where ventilation can be challenging. As such, DPM monitoring is critical to protecting miner health and informing a range of engineering decisions. DPM is primarily composed of two components, elemental carbon (EC) and organic carbon (OC), which are often summed to report total carbon (TC). The ratio of EC to OC, and presence of a number of other minor constituents such as sorbed metals, can vary with many factors such as engine operating conditions, maintenance, fuel types and additives, and the level and type of exhaust after-treatments used. Given its complexity, DPM cannot be measured directly, and either TC or EC are generally used as a surrogate. Currently, the Mining Safety and Health Administration (MSHA) limits personal exposures of underground metal/non-metal miners to 160 µg TC/m3 on an 8-hr time weighted average basis. Compliance is demonstrated by collecting full-shift personal filter samples, which are later analyzed using the NIOSH 5040 Standard Method. For engineering purposes, area samples can also be collected and analyzed. The typical lag time between sample collection and reporting of results is on the order of weeks, and this presents a real problem for identifying and remediating conditions that led to overexposures or high DPM in area samples. The handheld FLIR Airtec monitor was developed to provide real-time DPM data and allow immediate decision making. The monitor works on a laser extinction principle to measure EC, the black component of DPM, as mass accumulates on a filter. The Airtec has proven useful for personal monitoring and short-term DPM surveying. However, capabilities are needed for continuous, long-term monitoring. Continuous DPM monitoring would be highly valuable for applications such as design and operation of ventilation on demand systems, or engineering studies of new ventilation, exhaust treatment or other DPM controls. The work presented in this thesis considers three continuous monitors, two of which are already commercially available: Magee Scientific's AE33 black carbon (BC) Aethalometer and Sunset Laboratory's Semi-Continuous OCEC Field Analyzer. The third monitor, called the Airwatch, is still in development. The AE33 and Airwatch effectively operate on the same principle as the Airtec, but include a self-advancing filter tape to allow autonomous operation over relatively long periods of time. The OCEC field monitor is essentially a field version of the laboratory analyzer used for traditional 5040 Method analysis. The AE33 has been briefly demonstrated in mine environments in a couple of other studies, but further testing is needed. The current prototype of the Airwatch and the OCEC field monitor have never been mine-tested. Two separate studies are reported here. The first is a field study in an underground stone mine that tested the Airwatch prototype and AE33 head-to-head under relatively high DPM conditions. Results demonstrated that both instruments could track general trends, but that further work was needed to identify and resolve issues associated with use of both instruments in high-DPM environments – and with basic design elements of the Airwatch. Additionally, the need to calibrate the monitors' output data to the standard measure of EC (i.e., 5040 Method EC) was made clear. In the second study, laboratory testing was conducted under very controlled conditions to meet this need, and another round of field testing was also done. The second study also included the OCEC field monitor. The laboratory tests yielded data to allow interpretation of the AE33 and Airwatch results with respect to 5040 EC. These tests also shed light on the current range EC concentrations over which these monitors can provide reliable data – which is indeed a primary range of interest for mines. As expected, the OCEC field monitor was shown to produce lab-grade results across a wide range of concentrations. The field testing in the second study demonstrated that all three monitors could operate autonomously in a mine environment over extended periods of time (i.e., weeks to months). Overall, it can be concluded that the AE33 and OCEC field monitor represent off-the-shelf options for DPM monitoring in mines, and the Airwatch might be another option if fully developed in the future. Selection of a particular monitoring tool should include careful consideration of specific factors including data quality needs, conditions in the intended monitoring location(s), and general user friendliness of the monitor. / Master of Science

The research presented in this doctoral dissertation aimed to improve knowledge on methods to evaluate exposures to carbon-containing nanomaterials and to develop optimized respiratory filters properties to protect workers from these exposures while minimizing discomfort due to breathing resistance. In the initial study, a novel laboratory-based system generated aerosols of four carbon-containing powders (carbon black, a small-diameter (< 8 nm) multi-walled carbon nanotube (MWCNT), a large-diameter (50-80 nm) MWCNT, and a nickel-coated MWCNT) to evaluate the effectiveness of NIOSH Method 5040 for measuring masses as low as 1 μg. A targeted mass of a powder ranging from 1 to 30 μg was deposited on filters for gravimetric and elemental carbon (EC) analysis. The gravimetric mass was compared to the EC mass, and a regression model developed for each powder type. Additionally, the limit of detection (LOD) of the NIOSH Method 5040 for each powder type was determined. The regression models had significant slopes relative to zero for all powder types with all but carbon black demonstrating a statistical difference between the two methods. The LOD of NIOSH Method 5040 ranged from 4.5 for small-diameter MWCNTs to 31.8 μg for nickel-coated MWCNTs. Assuming a sample flow rate of 4.2 L/min and an 8-hour sample duration, the concentration-based LOD for NIOSH Method 5040 ranged from 2.2 μg/m3 for small-diameter MWCNTs to 15.8 μg/m3 for nickel-coated MWCNTs. These results indicate the analysis of EC is affected by the structure and elemental content of the CNTs. Additionally, based on the LOD determined for each powder type, the method may not be sufficient to assess exposures at and below the recommended exposure limit accurately without sampling durations longer than 8 hours. A second study used a laboratory-based system to evaluate an aethalometer response to carbon-containing nanomaterials including carbon black and MWCNTs. Concentrations ranging from 1 to 20 μg/m3 were generated to evaluate the device at concentrations expected in occupational settings. The concentration of the aerosol was measured by an aethalometer alongside a sample collected for EC analysis using NIOSH Method 5040. Additionally, NIOSH Method 7300 was used to determine the concentration of nickel during trials with a nickel-coated MWCNT to determine if the method along with the aethalometer can be used to assess metal-coated MWCNTs. A regression model was developed for each powder type, and the slopes for each were significant relative to zero. The LOD of the aethalometer ranged from 0.56 μg/m3 for nickel-coated MWCNTs to 7.2 μg/m3 for small-diameter MWCNTs. These results indicate the response of the aethalometer may be affected by particle structure and elemental content. NIOSH Method 5040 performed better than the aethalometer for all powder types except the nickel-coated MWCNT. Additionally, based on the LOD determined for each powder, an aethalometer may not be able to assess low-level exposures. In the third study, a mathematical model was used to predict the particle penetration and pressure drop of respirator filters with varying filter thickness, fiber diameter, solidity, and electrostatic charge. Particle penetration was determined experimentally for two different commercially available respirator filters against a sodium chloride aerosol using a scanning mobility particle sizer (SMPS). Optimized filter designs were developed using the model to minimize the pressure drop by adjusting the filter depth, fiber diameter, and solidity of the filter. The model and experimental data were used to maintain a 5% maximum penetration against nanoparticle exposures while minimizing breathing resistance. Model results indicated electrostatic charging played a significant role in improving collection efficiency of respirator filters while not increasing the breathing resistance of the filter. Filter thickness and solidity also played a key role in minimizing breathing resistance. Pressure drop decreased with decreasing solidity, however, the filter depth increased to maintain the collection efficiency of the filter. This increase in filter depth introduced a decision point of determining the practical implications of increased filter thickness on the end user. Filter depth increases dramatically as the solidity decreases below 0.20. The breathing resistance that corresponds to this design is heavily dependent on the face velocity and electrostatic charge of the filter. The electrostatic charge should be maximized during filter production as this was the dominant collection method for nanoparticle aerosols.

This manuscript based thesis examines and advances methods for constraining sources of atmospheric trace constituents with a Lagrangian particle dispersion model. The method of Bayesian inversion is demonstrated, and a new method is introduced to a class of similar problems where established methods are not applicable. First, A new regression based methodology was developed and applied to observations of atmospheric methanesulfonic acid mass concentrations at Alert, Nunavut. The methodology was used to compare the importance of phytoplankton blooms vs. the ice-free ocean as sources of the dimethylsulfide precursor, and to compare the importance of bromine monoxide vs. hydroxyl as agents oxidizing dimethylsul de to methanesulfonic acid. These issues are relevant to the application of methanesulfonic acid concentrations in ice cores to determine historic sea ice properties. The analysis indicated that source regions to Alert during the spring are primarily ice-free ocean with a significant contribution from ice edge blooms, and during the summer to be dominated by the ice-free ocean. The model also indicated that oxidation of DMS by BrO was the dominant source of MSA in the spring, while DMS oxidation by OH was the dominant source in the summer. Secondly, Bayesian inversion was applied to observations of atmospheric elemental carbon mass concentrations at Tsinghua University in Beijing, China. The analysis provided evidence that current bottom-up elemental carbon emissions estimates in northern China are likely underpredicted. Global chemical transport models show ubiquitous underestimates of the atmospheric burden of elemental carbon, especially near large sources of emissions. Northern China is among the regions with the most intensive elemental carbon emissions in the world, and an underestimate of emissions in this region may be partially responsible for the global chemical transport model underestimates.

This manuscript based thesis examines and advances methods for constraining sources of atmospheric trace constituents with a Lagrangian particle dispersion model. The method of Bayesian inversion is demonstrated, and a new method is introduced to a class of similar problems where established methods are not applicable. First, A new regression based methodology was developed and applied to observations of atmospheric methanesulfonic acid mass concentrations at Alert, Nunavut. The methodology was used to compare the importance of phytoplankton blooms vs. the ice-free ocean as sources of the dimethylsulfide precursor, and to compare the importance of bromine monoxide vs. hydroxyl as agents oxidizing dimethylsul de to methanesulfonic acid. These issues are relevant to the application of methanesulfonic acid concentrations in ice cores to determine historic sea ice properties. The analysis indicated that source regions to Alert during the spring are primarily ice-free ocean with a significant contribution from ice edge blooms, and during the summer to be dominated by the ice-free ocean. The model also indicated that oxidation of DMS by BrO was the dominant source of MSA in the spring, while DMS oxidation by OH was the dominant source in the summer. Secondly, Bayesian inversion was applied to observations of atmospheric elemental carbon mass concentrations at Tsinghua University in Beijing, China. The analysis provided evidence that current bottom-up elemental carbon emissions estimates in northern China are likely underpredicted. Global chemical transport models show ubiquitous underestimates of the atmospheric burden of elemental carbon, especially near large sources of emissions. Northern China is among the regions with the most intensive elemental carbon emissions in the world, and an underestimate of emissions in this region may be partially responsible for the global chemical transport model underestimates.

No description available.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2017-03-14T13:09:52Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE_DETERMINAÇÃO DO CARBONO E NITROGÊNIO ORGANICO PARTICULADO EM AMBIENTES OCEÂNICOS E ESTUARINO - COSTEIRO, NA REGIÃO N~1.pdf: 3127471 bytes, checksum: 07f07e56cbb161e91a0b19e2387b5734 (MD5) / Made available in DSpace on 2017-03-14T13:09:52Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE_DETERMINAÇÃO DO CARBONO E NITROGÊNIO ORGANICO PARTICULADO EM AMBIENTES OCEÂNICOS E ESTUARINO - COSTEIRO, NA REGIÃO N~1.pdf: 3127471 bytes, checksum: 07f07e56cbb161e91a0b19e2387b5734 (MD5) Previous issue date: 2016-07-14 / CAPES / O objetivo principal da presente tese constitui em agregar informações ao conhecimento sobre a fração orgânica do material em suspensão na região oceânica- costeira - estuarina do litoral de Pernambuco e na região costeira adjacente, principalmente no que se refere às suas concentrações, avaliando a distribuição do COP e NT. Em função da sua importância e estudos relacionados ao material em suspensão serem escassos para o carbono e nitrogênio nessas regiões. A tese é apresentada como um conjunto de capítulos interligados, nos quais foram apresentados resultados da distribuição do COP e NT nas plumas dos rios Capibaribe e Jaboatão e o arquipélago de Fernando de Noronha, com relativamente pouca influência humana, e foi escolhida como área de controle. A exportação de matéria orgânica via fluxo estuarino, ficou definida pelas medianas do Carbono Elementar de (2,04% e 0,97%) e Nitrogênio Elementar de (0,63% e 0,24%) e razão C/N de (6,60 e 9,30) nas plumas do Capibaribe e Jaboatão respectivamente. A análise de componentes principais aplicada aos dados sugeriu que os altos índices pluviométricos e o material carreado pelo fluxo fluvial para região costeira influenciaram a distribuição dessas frações e que tais diferenças podem resultar das diferentes cargas de ação antrópica e mecanismos de transporte estuário – região costeira revelando a complexidade da distribuição da matéria orgânica nestes ambientes. No segundo capítulo-artigo estudo caracterizou a matéria orgânica em função das razões elementares e isotópicas δ13C, δ15N, C/N do material particulado em suspensão na água superficial em 21 pontos amostrais sendo 12 no estuário do rio Capibaribe e 9 no estuário do rio Jaboatão. Os maiores valores de δ13C, δ15N, C/N (-17,75‰, 23,71‰ e 13,45‰) no Capibaribe e, (-21,97‰, 27,30‰ e 14,74‰) no Jaboatão, respectivamente. Os valores encontrados sugerem que uma grande parte da matéria em suspensão dos rios em estudo, se origina a partir de entradas de efluentes com alto teor de matéria orgânica, como também que a MO exportada pelos rios é fortemente influenciada pelo seu elevado estado de eutrofização, com acentuada produção autóctone. Nos estuários superiores os valores empobrecidos de 13C indicam maior presença de material tanto de origem continental quanto de origem mista. É também observado que δ13C e a razão C/N não são correlacionados no estuário do Capibaribe e estes resultados sugerem que existem áreas no estuário de preferência, fontes de matéria orgânica sob a influência tanto de autóctones (estuário inferior) como de alóctones (estuário superior). O terceiro e último capítulo - artigo ocorreu na região costeira de PE e foram agregadas as frações COP e NT à fração de COD, as quais não apresentaram correlação, indicando que elas não tenham a mesma fonte, destacando a influência alóctone para o aumento dessas frações e assim os efeitos de influencia do rio Capibaribe nas águas oligotróficas costeiras. / The main objective of this thesis is to add information to the existing knowledge of the organic fraction of suspended matter in the oceanic-coastal-estuarine region of the coast of Pernambuco, Brazil and the adjacent coastal zone, mainly in regard to its concentrations, by evaluating the distribution of POC and NT. In spite of the importance of this topic, studies on suspended matter for carbon and nitrogen are scarce in these regions. The thesis is presented as a set of interrelated chapters that contain the results of POC and NT distribution in the plumes of rivers Capibaribe and Jaboatão. The Fernando de Noronha Archipelago was chosen as a control area because of the minimal human influence in this region. The export of organic matter through estuarine flow was defined using the medians of elemental carbon (2.04% and 0.97%) and elemental nitrogen (0.63% and 0.24%), and C/N ratio (6.60 and 9.30) in the Capibaribe and Jaboatão plumes, respectively. The principal component analysis applied to the data suggests that the high rainfall and the matter carried by the river flow to the coastal region influence the distribution of these fractions. The analysis also suggests that the detected differences can be caused by different charges of human action and estuarycoastal mechanisms of transport, thus revealing the complexity of the distribution of organic matter in these environments. In the second chapter of the article, organic matter was characterised on the basis of elementary and isotopic ratios δ13C, δ15N, and C/N of the suspended particulate matter in surface water at 21 sampling points, of which 12 were in the estuary of river Capibaribe and 9 in the estuary of river Jaboatão. The highest values of δ13C, δ15N, and C/N (-17.75‰, 23.71‰, and 13.45 ‰) in Capibaribe and (-21.97‰, 27.30‰, and 14.74 ‰) in Jaboatao, respectively. The values found in this study suggest that a large proportion of suspended matter from the rivers originates from effluent inputs with high organic matter content. Also, the OM exported by the rivers is heavily influenced by a high state of eutrophication, with pronounced autochthonous production. In the upper estuary, the impoverished values of δ13C indicate a greater presence of matter of continental origin and of mixed origin. It was also observed that δ13C and C/N ratio are not correlated in the estuary of the Capibaribe, which suggests that there are areas at the estuary of preference where sources of organic matter are under the influence of autochthonous (lower estuary) or allochthonous (upper estuary) contributions. The third and final chapter-article occurred in the coastal zone of PE. Here, the fractions of POC and NT were added to the fraction of DOC and showed no correlation, which indicates that they do not share the same source. Moreover, this finding highlights the influence of allochthonous contributions to the increase of these fractions and the consequent effects of the influence of Capibaribe river in coastal oligotrophic waters.

No description available.

Interest in effects of carbonaceous particles in the atmosphere has recently taken an upswing due to knowledge of how these particles affect our environment. Carbonaceous aerosols are characterized by their dark color, giving them the ability to absorb both incoming and outgoing radiation of all wavelengths in the atmosphere. If these particles are deposited on snow or ice they blacken the surface, with an increased rate of melting as a consequence. These particles play a significant role in climate change and it is important to characterize the particles in order to determine their environmental impact and their origin. In this thesis, two non-destructive dielectric measurement approaches for characterizing carbonaceous particles at microwave frequencies were explored: measurements with an impedance analyzer and measurements using a cavity resonator. Measurements were carried out on quartz filters containing concentrations of carbon normally found in snow in northern Scandinavia. To validate the carbon concentration on the filters a field trip to northern Sweden was conducted. Snow samples were collected and analyzed in regards of carbon content, confirming that the amount of carbon on the filters were accurate. The impedance analyzer showed great uncertainty and the results were not precise enough to determine the credibility of the approach. Measurements with the cavity resonator showed some promising results due to its extreme sensitivity but require adjustments to distinguish different particle types from each other. Thus, it is expected that the use of a cavity resonator operating at microwave frequencies will become an applicable method for characterizing carbonaceous particles in the future.

Elemental carbon (EC), a product of incomplete combustion of fossil fuels and biomass, contributes to climate warming and poor air quality. In urban areas, diesel fuel trucks are the main source of EC emissions from mobile sources. After emission, EC is deposited to receptor surfaces via two main pathways: precipitation (wet deposition) and directly as particles (dry deposition). Urban trees may play an important role in removing EC from the atmosphere by intercepting and delivering it directly to the soil. The goal of this research was to quantify the magnitude of EC retention in leaf waxes (in-wax EC) and EC fluxes to the soil via leaf litterfall in the City of Denton, Texas. Denton is a rapidly growing urban location in the Dallas-Fort Worth metropolitan area. A foliar extraction technique was used to determine EC retention in leaf waxes. Foliar samples were collected monthly, from April through July, from pairs of Quercus stellata (post oak, n=10) and Quercus virginiana (live oak, n = 10) trees. Samples were rinsed with water and chloroform in a two-step process to determine EC retained in leaf waxes. A Sunset OC/EC aerosol analyzer was utilized to analyze the EC content of extracts filtered onto quartz-fiber filters. From April through July, leaf litter was collected bi-weekly under 35 trees (20 post oak, 15 live oak), and oven dried to determine dry weight. EC retained by tree canopies was estimated by multiplying in-wax EC by canopy leaf area index, while EC flux to soil was estimated by multiplying in-wax EC by leaf litterfall mass. This study shows that through retention of EC in leaf waxes, urban tree canopies represent important short-term sinks for soot in urban areas.