Association between in-utero exposure to diesel exhaust and N-acetyl-cysteine supplementation in hyperlipidemic pregnant mice and development of atherosclerosis at multiple vascular sites in the offspring

Thesis (Master's)--University of Washington, 2016-06

Traffic-Related PM2.5 Air Pollution and Schools in Proximity to Major Roadways in Shanghai, China

Thesis (Master's)--University of Washington, 2016-06

Preservation of York Minster historic limestone by hydrophobic surface coatings

Magnesian limestone is a key construction component of many historic buildings that is under constant attack from environmental pollutants notably by oxides of sulfur via acid rain, particulate matter sulfate and gaseous SO 2 emissions. Hydrophobic surface coatings offer a potential route to protect existing stonework in cultural heritage sites, however, many available coatings act by blocking the stone microstructure, preventing it from 'breathing' and promoting mould growth and salt efflorescence. Here we report on a conformal surface modification method using self-assembled monolayers of naturally sourced free fatty acids combined with sub-monolayer fluorinated alkyl silanes to generate hydrophobic (HP) and super hydrophobic (SHP) coatings on calcite. We demonstrate the efficacy of these HP and SHP surface coatings for increasing limestone resistance to sulfation, and thus retarding gypsum formation under SO/H O and model acid rain environments. SHP treatment of 19th century stone from York Minster suppresses sulfuric acid permeation.

Novel analytical methodologies for the monitoring of traditional and non-traditional pollutants in different environmental compartments of South Florida

Routine monitoring of environmental pollution demands simplicity and speed without sacrificing sensitivity or accuracy. The development and application of sensitive, fast and easy to implement analytical methodologies for detecting emerging and traditional water and airborne contaminants in South Florida is presented. A novel method was developed for quantification of the herbicide glyphosate based on lyophilization followed by derivatization and simultaneous detection by fluorescence and mass spectrometry. Samples were analyzed from water canals that will hydrate estuarine wetlands of Biscayne National Park, detecting inputs of glyphosate from both aquatic usage and agricultural runoff from farms. A second study describes a set of fast, automated LC-MS/MS protocols for the analysis of dioctyl sulfosuccinate (DOSS) and 2-butoxyethanol, two components of Corexit®. Around 1.8 million gallons of those dispersant formulations were used in the response efforts for the Gulf of Mexico oil spill in 2010. The methods presented here allow the trace-level detection of these compounds in seawater, crude oil and commercial dispersants formulations. In addition, two methodologies were developed for the analysis of well-known pollutants, namely Polycyclic Aromatic Hydrocarbons (PAHs) and airborne particulate matter (APM). PAHs are ubiquitous environmental contaminants and some are potent carcinogens. Traditional GC-MS analysis is labor-intensive and consumes large amounts of toxic solvents. My study provides an alternative automated SPE-LC-APPI-MS/MS analysis with minimal sample preparation and a lower solvent consumption. The system can inject, extract, clean, separate and detect 28 PAHs and 15 families of alkylated PAHs in 28 minutes. The methodology was tested with environmental samples from Miami. Airborne Particulate Matter is a mixture of particles of chemical and biological origin. Assessment of its elemental composition is critical for the protection of sensitive ecosystems and public health. The APM collected from Port Everglades between 2005 and 2010 was analyzed by ICP-MS after acid digestion of filters. The most abundant elements were Fe and Al, followed by Cu, V and Zn. Enrichment factors show that hazardous elements (Cd, Pb, As, Co, Ni and Cr) are introduced by anthropogenic activities. Data suggest that the major sources of APM were an electricity plant, road dust, industrial emissions and marine vessels.

Estimativa da poluição emitida pelos ônibus das linhas troncais da cidade de Uberlândia, MG

The transport of people and goods contributes to the deterioration of the environment in urban areas because of the generation of pollution, such as, air, noise, soil, water or visual degradation. The heavy vehicles that use diesel as fuel are mainly responsible for the emission of nitrogen oxides (NOx) and particulate matter (PM), contributing to participation of the transport sector in air pollution. In addition, there is emission of Greenhouse Gas (GHG) whose main component is carbon dioxide (CO2). In most major cities, public transportation is often considered as a less polluting alternative compared to the private vehicle, in view of the potential to reduce, per passenger, the emissions of GHG and air pollutants. The study area was the city of Uberlândia and the objects of study were the trunk lines of the Sistema Integrado de Transporte (SIT). The emissions of NOx, PM and CO2 were estimated through the bottom-up approach which used the route of each bus line and also fuel consumption obtained through simulation from the TSIS software. The software has some result limitations, there are no report about the emission of pollutants by bus, and it is not able to change specifications for the fuel used by the fleet. The results obtained through calculations of pollutants and GHG emission by the bottom-up approach show that the emission is higher when using fuel comsuption obtained in simulation than using distance. For the results considering fuel and distance there was a reduction in emissions comparing ethanol and diesel.

Quantitative determination of carbonaceous particle mixing state in Paris using single-particle mass spectrometer and aerosol mass spectrometer measurements

Single-particle mixing state information can be a powerful tool for assessing the relative impact of local and regional sources of ambient particulate matter in urban environments. However, quantitative mixing state data are challenging to obtain using single-particle mass spectrometers. In this study, the quantitative chemical composition of carbonaceous single particles has been determined using an aerosol time-of-flight mass spectrometer (ATOFMS) as part of the MEGAPOLI 2010 winter campaign in Paris, France. Relative peak areas of marker ions for elemental carbon (EC), organic aerosol (OA), ammonium, nitrate, sulfate and potassium were compared with concurrent measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), a thermal-optical OCEC analyser and a particle into liquid sampler coupled with ion chromatography (PILS-IC). ATOFMS-derived estimated mass concentrations reproduced the variability of these species well (R-2 = 0.67-0.78), and 10 discrete mixing states for carbonaceous particles were identified and quantified. The chemical mixing state of HR-ToF-AMS organic aerosol factors, resolved using positive matrix factorisation, was also investigated through comparison with the ATOFMS dataset. The results indicate that hydrocarbon-like OA (HOA) detected in Paris is associated with two EC-rich mixing states which differ in their relative sulfate content, while fresh biomass burning OA (BBOA) is associated with two mixing states which differ significantly in their OA/EC ratios. Aged biomass burning OA (OOA(2)-BBOA) was found to be significantly internally mixed with nitrate, while secondary, oxidised OA (OOA) was associated with five particle mixing states, each exhibiting different relative secondary inorganic ion content. Externally mixed secondary organic aerosol was not observed. These findings demonstrate the range of primary and secondary organic aerosol mixing states in Paris. Examination of the temporal behaviour and chemical composition of the ATOFMS classes also enabled estimation of the relative contribution of transported emissions of each chemical species and total particle mass in the size range investigated. Only 22% of the total ATOFMS-derived particle mass was apportioned to fresh, local emissions, with 78% apportioned to regional/continental-scale emissions. Single-particle mixing state information can be a powerful tool for assessing the relative impact of local and regional sources of ambient particulate matter in urban environments. However, quantitative mixing state data are challenging to obtain using single-particle mass spectrometers. In this study, the quantitative chemical composition of carbonaceous single particles has been determined using an aerosol time-of-flight mass spectrometer (ATOFMS) as part of the MEGAPOLI 2010 winter campaign in Paris, France. Relative peak areas of marker ions for elemental carbon (EC), organic aerosol (OA), ammonium, nitrate, sulfate and potassium were compared with concurrent measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), a thermal-optical OCEC analyser and a particle into liquid sampler coupled with ion chromatography (PILS-IC). ATOFMS-derived estimated mass concentrations reproduced the variability of these species well (R-2 = 0.67-0.78), and 10 discrete mixing states for carbonaceous particles were identified and quantified. The chemical mixing state of HR-ToF-AMS organic aerosol factors, resolved using positive matrix factorisation, was also investigated through comparison with the ATOFMS dataset. The results indicate that hydrocarbon-like OA (HOA) detected in Paris is associated with two EC-rich mixing states which differ in their relative sulfate content, while fresh biomass burning OA (BBOA) is associated with two mixing states which differ significantly in their OA/EC ratios. Aged biomass burning OA (OOA(2)-BBOA) was found to be significantly internally mixed with nitrate, while secondary, oxidised OA (OOA) was associated with five particle mixing states, each exhibiting different relative secondary inorganic ion content. Externally mixed secondary organic aerosol was not observed. These findings demonstrate the range of primary and secondary organic aerosol mixing states in Paris. Examination of the temporal behaviour and chemical composition of the ATOFMS classes also enabled estimation of the relative contribution of transported emissions of each chemical species and total particle mass in the size range investigated. Only 22% of the total ATOFMS-derived particle mass was apportioned to fresh, local emissions, with 78% apportioned to regional/continental-scale emissions.

Long-term chemical characterization of aerosols at CVAO from 2007 to 2011

The first long-term aerosol sampling and chemical characterization results from measurements at the Cape Verde Atmospheric Observatory (CVAO) on the island of São Vicente are presented and are discussed with respect to air mass origin and seasonal trends. In total 671 samples were collected using a high-volume PM10 sampler on quartz fiber filters from January 2007 to December 2011. The samples were analyzed for their aerosol chemical composition, including their ionic and organic constituents. Back trajectory analyses showed that the aerosol at CVAO was strongly influenced by emissions from Europe and Africa, with the latter often responsible for high mineral dust loading. Sea salt and mineral dust dominated the aerosol mass and made up in total about 80% of the aerosol mass. The 5-year PM10 mean was 47.1 ± 55.5 µg/m**2, while the mineral dust and sea salt means were 27.9 ± 48.7 and 11.1 ± 5.5 µg/m**2, respectively. Non-sea-salt (nss) sulfate made up 62% of the total sulfate and originated from both long-range transport from Africa or Europe and marine sources. Strong seasonal variation was observed for the aerosol components. While nitrate showed no clear seasonal variation with an annual mean of 1.1 ± 0.6 µg/m**3, the aerosol mass, OC (organic carbon) and EC (elemental carbon), showed strong winter maxima due to strong influence of African air mass inflow. Additionally during summer, elevated concentrations of OM were observed originating from marine emissions. A summer maximum was observed for non-sea-salt sulfate and was connected to periods when air mass inflow was predominantly of marine origin, indicating that marine biogenic emissions were a significant source. Ammonium showed a distinct maximum in spring and coincided with ocean surface water chlorophyll a concentrations. Good correlations were also observed between nss-sulfate and oxalate during the summer and winter seasons, indicating a likely photochemical in-cloud processing of the marine and anthropogenic precursors of these species. High temporal variability was observed in both chloride and bromide depletion, differing significantly within the seasons, air mass history and Saharan dust concentration. Chloride (bromide) depletion varied from 8.8 ± 8.5% (62 ± 42%) in Saharan-dust-dominated air mass to 30 ± 12% (87 ± 11%) in polluted Europe air masses. During summer, bromide depletion often reached 100% in marine as well as in polluted continental samples. In addition to the influence of the aerosol acidic components, photochemistry was one of the main drivers of halogenide depletion during the summer; while during dust events, displacement reaction with nitric acid was found to be the dominant mechanism. Positive matrix factorization (PMF) analysis identified three major aerosol sources: sea salt, aged sea salt and long-range transport. The ionic budget was dominated by the first two of these factors, while the long-range transport factor could only account for about 14% of the total observed ionic mass.

Extracellular cathepsin S and intracellular caspase 1 activation are surrogate biomarkers of particulate-induced lysosomal disruption in macrophages

BACKGROUND: Particulate matter has been shown to stimulate the innate immune system and induce acute inflammation. Therefore, while nanotechnology has the potential to provide therapeutic formulations with improved efficacy, there are concerns such pharmaceutical preparations could induce unwanted inflammatory side effects. Accordingly, we aim to examine the utility of using the proteolytic activity signatures of cysteine proteases, caspase 1 and cathepsin S (CTSS), as biomarkers to assess particulate-induced inflammation.

METHODS: Primary peritoneal macrophages and bone marrow-derived macrophages from C57BL/6 mice and ctss(-/-) mice were exposed to micro- and nanoparticulates and also the lysosomotropic agent, L-leucyl-L-leucine methyl ester (LLOME). ELISA and immunoblot analyses were used to measure the IL-1β response in cells, generated by lysosomal rupture. Affinity-binding probes (ABPs), which irreversibly bind to the active site thiol of cysteine proteases, were then used to detect active caspase 1 and CTSS following lysosomal rupture. Reporter substrates were also used to quantify the proteolytic activity of these enzymes, as measured by substrate turnover.

RESULTS: We demonstrate that exposure to silica, alum and polystyrene particulates induces IL-1β release from macrophages, through lysosomal destabilization. IL-1β secretion positively correlated with an increase in the proteolytic activity signatures of intracellular caspase 1 and extracellular CTSS, which were detected using ABPs and reporter substrates. Interestingly IL-1β release was significantly reduced in primary macrophages from ctss(-/-) mice.

CONCLUSIONS: This study supports the emerging significance of CTSS as a regulator of the innate immune response, highlighting its role in regulating IL-1β release. Crucially, the results demonstrate the utility of intracellular caspase 1 and extracellular CTSS proteolytic activities as surrogate biomarkers of lysosomal rupture and acute inflammation. In the future, activity-based detection of these enzymes may prove useful for the real-time assessment of particle-induced inflammation and toxicity assessment during the development of nanotherapeutics.

Exposure of children to ultrafine particles in primary schools in Portugal

Children spend a large part of their time at schools, which might be reflected as chronic exposure. Ultrafine particles (UFP) are generally associated with a more severe toxicity compared to fine and coarse particles, due to their ability to penetrate cell membranes. In addition, children tend to be more susceptible to UFP-mediated toxicity compared to adults, due to various factors including undeveloped immune and respiratory systems and inhalation rates. Thus, the purpose of this study was to determine indoor UFP number concentrations in Portuguese primary schools. Ultrafine particles were sampled between January and March 2014 in 10 public primary schools (35 classrooms) located in Porto, Portugal. Overall, the average indoor UFP number concentrations were not significantly different from outdoor concentrations (8.69 × 10(3) vs. 9.25 × 10(3) pt/cm(3), respectively; considering 6.5 h of indoor occupancy). Classrooms with distinct characteristics showed different trends of indoor UFP concentrations. The levels of carbon dioxide were negatively correlated with indoor UFP concentrations. Occupational density was significantly and positively correlated with UFP concentrations. Although the obtained results need to be interpreted with caution since there are no guidelines for UFP levels, special attention needs to be given to source control strategies in order to reduce major particle emissions and ensure good indoor air quality.

AN INVESTIGATION OF VARIABLE VALVE TIMING EFFECTS ON HCCI ENGINE PERFORMANCE

The Homogeneous Charge Compression Ignition (HCCI) engine is a promising combustion concept for reducing NOx and particulate matter (PM) emissions and providing a high thermal efficiency in internal combustion engines. This concept though has limitations in the areas of combustion control and achieving stable combustion at high loads. For HCCI to be a viable option for on-road vehicles, further understanding of its combustion phenomenon and its control are essential. Thus, this thesis has a focus on both the experimental setup of an HCCI engine at Michigan Technological University (MTU) and also developing a physical numerical simulation model called the Sequential Model for Residual Affected HCCI (SMRH) to investigate performance of HCCI engines. The primary focus is on understanding the effects of intake and exhaust valve timings on HCCI combustion. For the experimental studies, this thesis provided the contributions for development of HCCI setup at MTU. In particular, this thesis made contributions in the areas of measurement of valve profiles, measurement of piston to valve contact clearance for procuring new pistons for further studies of high geometric compression ratio HCCI engines. It also consists of developing and testing a supercharging station and the setup of an electrical air heater to extend the HCCI operating region. The HCCI engine setup is based on a GM 2.0 L LHU Gen 1 engine which is a direct injected engine with variable valve timing (VVT) capabilities. For the simulation studies, a computationally efficient modeling platform has been developed and validated against experimental data from a single cylinder HCCI engine. In-cylinder pressure trace, combustion phasing (CA10, CA50, BD) and performance metrics IMEP, thermal efficiency, and CO emission are found to be in good agreement with experimental data for different operating conditions. Effects of phasing intake and exhaust valves are analyzed using SMRH. In addition, a novel index called Fuel Efficiency and Emissions (FEE) index is defined and is used to determine the optimal valve timings for engine operation through the use of FEE contour maps.

Novel Analytical Methodologies for the Monitoring of Traditional and Non-traditional Pollutants in different Environmental Compartments of South Florida

Routine monitoring of environmental pollution demands simplicity and speed without sacrificing sensitivity or accuracy. The development and application of sensitive, fast and easy to implement analytical methodologies for detecting emerging and traditional water and airborne contaminants in South Florida is presented. A novel method was developed for quantification of the herbicide glyphosate based on lyophilization followed by derivatization and simultaneous detection by fluorescence and mass spectrometry. Samples were analyzed from water canals that will hydrate estuarine wetlands of Biscayne National Park, detecting inputs of glyphosate from both aquatic usage and agricultural runoff from farms. A second study describes a set of fast, automated LC-MS/MS protocols for the analysis of dioctyl sulfosuccinate (DOSS) and 2-butoxyethanol, two components of Corexit®. Around 1.8 million gallons of those dispersant formulations were used in the response efforts for the Gulf of Mexico oil spill in 2010. The methods presented here allow the trace-level detection of these compounds in seawater, crude oil and commercial dispersants formulations. In addition, two methodologies were developed for the analysis of well-known pollutants, namely Polycyclic Aromatic Hydrocarbons (PAHs) and airborne particulate matter (APM). PAHs are ubiquitous environmental contaminants and some are potent carcinogens. Traditional GC-MS analysis is labor-intensive and consumes large amounts of toxic solvents. My study provides an alternative automated SPE-LC-APPI-MS/MS analysis with minimal sample preparation and a lower solvent consumption. The system can inject, extract, clean, separate and detect 28 PAHs and 15 families of alkylated PAHs in 28 minutes. The methodology was tested with environmental samples from Miami. Airborne Particulate Matter is a mixture of particles of chemical and biological origin. Assessment of its elemental composition is critical for the protection of sensitive ecosystems and public health. The APM collected from Port Everglades between 2005 and 2010 was analyzed by ICP-MS after acid digestion of filters. The most abundant elements were Fe and Al, followed by Cu, V and Zn. Enrichment factors show that hazardous elements (Cd, Pb, As, Co, Ni and Cr) are introduced by anthropogenic activities. Data suggest that the major sources of APM were an electricity plant, road dust, industrial emissions and marine vessels.

Nanomolar Levels Of Pahs In Extracts From Urban Air Induce Mapk Signaling In Hepg2 Cells.

Polycyclic aromatic hydrocarbons (PAHs) are common environmental pollutants that occur naturally in complex mixtures. Many of the adverse health effects of PAHs including cancer are linked to the activation of intracellular stress response signaling. This study has investigated intracellular MAPK signaling in response to PAHs in extracts from urban air collected in Stockholm, Sweden and Limeira, Brazil, in comparison to BP in HepG2 cells. Nanomolar concentrations of PAHs in the extracts induced activation of MEK4 signaling with down-stream increased gene expression of several important stress response mediators. Involvement of the MEK4/JNK pathway was confirmed using siRNA and an inhibitor of JNK signaling resulting in significantly reduced MAPK signaling transactivated by the AP-1 transcription factors ATF2 and c-Jun. ATF2 was also identified as a sensitive stress responsive protein with activation observed at extract concentrations equivalent to 0.1 nM BP. We show that exposure to low levels of environmental PAH mixtures more strongly activates these signaling pathways compared to BP alone suggesting effects due to interactions. Taken together, this is the first study showing the involvement of MEK4/JNK/AP-1 pathway in regulating the intracellular stress response after exposure to nanomolar levels of PAHs in environmental mixtures.

Effect Of Particles Of Ashes Produced From Sugarcane Burning On The Respiratory System Of Rats.

The practice of burning sugarcane obtained by non-mechanized harvesting exposes workers and the people of neighboring towns to high concentrations of particulate matter (PM) that is harmful to health, and may trigger a series of cardiorespiratory diseases. The aim of this study was to analyze the chemical composition of the micro-particles coming from sugarcane burning residues and to verify the effects of this micro-particulate matter on lung and tracheal tissues. Micro-particulate matter (PM10) was obtained by dissolving filter paper containing burnt residues in NaCl solution. This material was instilled into the Wistar rats' nostrils. Histological analyses (hematoxylin and eosin - HE) of cardiac, lung and tracheal tissues were performed. Inflammatory mediators were measured in lung tissues by using ELISA. The chemical composition of the particulate material revealed a large quantity of the phthalic acid ester, high concentrations of phenolic compounds, anthracene and polycyclic aromatic hydrocarbons (PAH). Histological analysis showed a reduction in subjacent conjunctive tissue in the trachea, lung inflammation with inflammatory infiltrate formation and reduction of alveolar spaces and a significant increase (p<0.05) in the release of IL-1α, IL-1β, IL-6, and INF-γ in the group treated with PM10 when compared to the control group. We concluded that the burning sugarcane residues release many particles, which have toxic chemical compounds. The micro-particulate matter can induce alterations in the respiratory system.

Uma análise do coeficiente de remoção de poluentes em função do espectro de gotas de chuva em diferentes localidades no Brasil e Alemanha

The pollutant transference among reservoirs atmosphere-hydrosphere, relevant to the atmospheric chemistry, depends upon scavenging coefficient (Λ) calculus, which depends on the raindrop size distribution as well as on the rainfall systems, both different to each locality. In this work, the Λ calculus will be evaluated to gas SO2 and particulate matter fine and coarse among five sites in Germany and two in Brazil. The results show three possible classifications in function of Λ, comparable to literature, however with a greater range due to the differences of rainfall system sites. This preliminary study supports future researches

Air pollution and hospital admissions for respiratory diseases in the subequatorial Amazon: a time series approach

The objective of the study is to evaluate the effect of the daily variation in concentrations of fine particulate matter (diameter less than 2.5µm - PM2.5) resulting from the burning of biomass on the daily number of hospitalizations of children and elderly people for respiratory diseases, in Alta Floresta and Tangará da Serra in the Brazilian Amazon in 2005. This is an ecological time series study that uses data on daily number of hospitalizations of children and the elderly for respiratory diseases, and estimated concentration of PM2.5. In Alta Floresta, the percentage increases in the relative risk (%RR) of hospitalization for respiratory diseases in children were significant for the whole year and for the dry season with 3-4 day lags. In the dry season these measurements reach 6% (95%CI: 1.4-10.8). The associations were sig-nificant for moving averages of 3-5 days. The %RR for the elderly was significant for the current day of the drought, with a 6.8% increase (95%CI: 0.5-13.5) for each additional 10µg/m3 of PM2.5. No as-sociations were verified for Tangara da Serra. The PM2.5 from the burning of biomass increased hospitalizations for respiratory diseases in children and the elderly.