The influence of oxygenated organic aerosols (OOA) and its volatile organic content on the oxidative potential of diesel particulate mater

Airborne particulate matter pollution is of concern for a number of reasons and has been widely recognised as an important risk factor to human health. A number of toxicological and epidemiological studies reported negative health effects on both respiratory and cardiovascular system. Despite the availability of a huge body of research, the underlying toxicological mechanisms by which particles induce adverse health effects are not yet entirely understood. The production of reactive oxygen species (ROS) has been shown to induce oxidative stress, which is proposed as a mechanism for many of the adverse health outcomes associated with exposure to particulate matter (PM). Therefore, it is crucial to introduce a technique that will allow rapid and routine screenings of the oxidative potential of PM.

An investigation of gaseous and particulate emissions from compression ignition engines operated with alternative fuels, injection technologies, and combustion strategies

Whilst the compression ignition (CI) engine exhibits many design advantages relative to its spark ignition engine counterpart; such as: high thermal efficiency, fuel economy and low carbon monoxide and hydrocarbon emissions, the issue of Diesel Particulate Matter (DPM) emissions continues to be an unresolved problem for the CI engine. Primarily, this thesis investigates a range of DPM mitigation strategies such as alternative fuels, injection technologies and combustion strategies conducted with a view to determine their impact on the physico-chemical properties of DPM emissions, and consequently to shed light on their likely human health impacts. Regulated gaseous emissions, Nitric oxide (NO), Carbon monoxide (CO), and Hydrocarbons (HCs), were measured in all experimental campaigns, although the major focus in this research program was on particulate emissions...

Effect of pulsed power on particle matter in diesel engine exhaust using a DBD plasma reactor

Nonthermal plasma (NTP) treatment of exhaust gas is a promising technology for both nitrogen oxides (NOX) and particulate matter (PM) reduction by introducing plasma into the exhaust gases. This paper considers the effect of NTP on PM mass reduction, PM size distribution, and PM removal efficiency. The experiments are performed on real exhaust gases from a diesel engine. The NTP is generated by applying high-voltage pulses using a pulsed power supply across a dielectric barrier discharge (DBD) reactor. The effects of the applied high-voltage pulses up to 19.44 kVpp with repetition rate of 10 kHz are investigated. In this paper, it is shown that the PM removal and PM size distribution need to be considered both together, as it is possible to achieve high PM removal efficiency with undesirable increase in the number of small particles. Regarding these two important factors, in this paper, 17 kVpp voltage level is determined to be an optimum point for the given configuration. Moreover, particles deposition on the surface of the DBD reactor is found to be a significant phenomenon, which should be considered in all plasma PM removal tests.

Influence of oxygen content of the certain types of biodiesels on particulate oxidative potential

Oxidative potential (OP) is related to the organic phase, specifically to its oxygenated organic fraction (OOA). Furthermore, the oxygen content of fuel molecules has significant influence on particulate OP. Thus, this study aimed to explore the actual dependency of the OOA and ROS to the oxygen content of the fuel. In order to reach the goal, different biodiesels blends, with various ranges of oxygen content; have been employed. The compact time of flight aerosol mass spectrometer (c-ToF AMS) enabled better identification of OOA. ROS monitored by using two assays: DTT and BPEA-nit. Despite emitting lower mass, both assays agreed that oxygen content of a biodiesel is directly correlated with its OOA, and highly related to its OP. Hence, the more oxygen included in the considered biodiesels, the higher the OP of PM emissions. This highlights the importance of taking oxygen content into account while assessing emissions from new fuel types, which is relevant from a health effects standpoint.

Chemical mass closure and source-specific composition of atmospheric particles

It has been known for decades that particles can cause adverse health effects as they are deposited within the respiratory system. Atmospheric aerosol particles influence climate by scattering solar radiation but aerosol particles act also as the nuclei around which cloud droplets form. The principal objectives of this thesis were to investigate the chemical composition and the sources of fine particles in different environments (traffic, urban background, remote) as well as during some specific air pollution situations. Quantifying the climate and health effects of atmospheric aerosols is not possible without detailed information of the aerosol chemical composition. Aerosol measurements were carried out at nine sites in six countries (Finland, Germany, Czech, Netherlands, Greece and Italy). Several different instruments were used in order to measure both the particulate matter (PM) mass and its chemical composition. In the off-line measurements the samples were collected first on a substrate or filter and gravimetric and chemical analysis were conducted in the laboratory. In the on-line measurements the sampling and analysis were either a combined procedure or performed successively within the same instrument. Results from the impactor samples were analyzed by the statistical methods. This thesis comprises also a work where a method for the determination carbonaceous matter size distribution by using a multistage impactor was developed. It was found that the chemistry of PM has usually strong spatial, temporal and size-dependent variability. In the Finnish sites most of the fine PM consisted of organic matter. However, in Greece sulfate dominated the fine PM and in Italy nitrate made the largest contribution to the fine PM. Regarding the size-dependent chemical composition, organic components were likely to be enriched in smaller particles than inorganic ions. Data analysis showed that organic carbon (OC) had four major sources in Helsinki. Secondary production was the major source in Helsinki during spring, summer and fall, whereas in winter biomass combustion dominated OC. The significant impact of biomass combustion on OC concentrations was also observed in the measurements performed in Central Europe. In this thesis aerosol samples were collected mainly by the conventional filter and impactor methods which suffered from the long integration time. However, by filter and impactor measurements chemical mass closure was achieved accurately, and a simple filter sampling was found to be useful in order to explain the sources of PM on the seasonal basis. The online instruments gave additional information related to the temporal variations of the sources and the atmospheric mixing conditions.

The importance of organic detritus in lotic ecosystems: Aspects of trophic interactions

Very little research has been carried out on detrital energetics and pathways in lotic ecosystems. Most investigations have concentrated on the degradation of allochthonous plant litter by fungi, with a glance at heterotrophic bacteria associated with decaying litter. In this short review, the author describes what is known of the detrition of plant litter in lotic waters, which results from the degradative activities of colonising saprophytic fungi and bacteria, and goes on to relate this process to those invertebrates that consume coarse and/or fine particulate detritus, or dissolved organic matter that aggregates into colloidal exopolymer particles. It is clear that many of the key processes involved in the relationships between the physical, chemical, biotic and biochemical elements present in running waters are very complex and poorly understood. Those few aspects for which there are reliable models with predictive power have resulted from data collections made over periods of 20 years or more. Comprehensive research of single catchments would provide a fine opportunity to collect data over a long period.

Observação do transporte de sedimentos em suspensão ao longo do Canal Norte do rio Amazonas durante condições de baixa descarga (outubro 2008)

The Amazon river, located in northernBrazil, discharges between 80,000 and 250,000 m3s-1 of water onto the adjacent shelf, creating a plume of brackish water that extends hundreds of kilometers away from the river mouth. This river also carries a large amount of fine sediments to the ocean where fluid mud has been found in the topset and upper foreset layers of the subaqueous delta formed on the mid-shelf. One of the main goals of this dissertation is to describe how turbulence and suspended sediment concentration vary along the Northern Channel of the Amazon river. Water column measurements were carried out in October 2008 at six anchor stations (P1, P3, P5, P6, P8 e P9) located seaward of the river mouth; P1 and P9 were 125 km apart. Each station was occupied during 13 hours during which current speed and direction were continuously sampled with a 600 kHz Teledyne-RDI ADCP; hourly profiles of temperature, salinity, turbidity and depth were also obtained. Water samples were collected for determination of Suspended Particulate Matter (SPM) concentration and calibration of the turbidity sensor. Current speed reached values above 1.5 m s1 in the along-channel direction (NE-SW); a remarkable ebb-flood asymmetry was observed and flows were strongly ebb-dominated. Throughout the water column, SPM concentration at stations P1 and P3 varied between 100 and 300 mg L1 in association with the presence of freshwater. In contrast, a strong salinity gradient was observed between stations P6 and P9, coinciding with the occurrence of concentrations of SPM above 10 g L-1 (fluid mud). At stations P3, P5 and P6, interface between freshwater from the Amazon river and salt water from the continental shelf, shear stresses wereestimated through four diferents methods: Reynolds, Turbulent Kinetic Energy (TKE), modified TKE and Quadratic Law; in the nearbed region (3 mab) the computed values varied between 0 and 3 Pa. At the three stations (P3, P5 and P6) the lowest and the highest shear stress values were obtained through, respectively, the Reynolds and the TKE methods. Over the whole water column turbulence intensity was estimated through the standard deviation of the turbulent component of the along-channel current velocity (root-mean square of u); from these values, it was estimated the turbulent dissipation of energy (G), whose values at 3 mab varied between zero and 20 s1.

Nutrient enhanced coastal ocean productivity in the north Gulf of Mexico: understanding the effects of nutrients on a coastal ecosystem

The continental shelf adjacent to the Mississippi River is a highly productive system, often referred to as the fertile fisheries crescent. This productivity is attributed to the effects of the river, especially nutrient delivery. In the later decades of the 2oth century, though, changes in the system were becoming evident. Nutrient loads were seen to be increasing and reports of hypoxia were becoming more frequent. During most recent summers, a broad area (up to 20,000 krn2) of near bottom, inner shelf waters immediately west of the Mississippi River delta becomes hypoxic (dissolved oxygen concentrations less than 2 mgll). In 1990, the Coastal Ocean Program of the National Oceanic and Atmospheric Administration initiated the Nutrient Enhanced Coastal Ocean Productivity (NECOP) study of this area to test the hypothesis that anthropogenic nutrient addition to the coastal ocean has contributed to coastal eutrophication with a significant impact on water quality. Three major goals of the study were to determine the degree to which coastal productivity in the region is enhanced by terrestrial nutrient input, to determine the impact of enhanced productivity on water quality, and to determine the fate of fixed carbon and its impact on living marine resources. The study involved 49 federal and academic scientists from 14 institutions and cost $9.7 million. Field work proceeded from 1990 through 1993 and analysis through 1996, although some analyses continue to this day. The Mississippi River system delivers, on average, 19,000 m3/s of water to the northern Gulf of Mexico. The major flood of the river system occurs in spring following snow melt in the upper drainage basin. This water reaches the Gulf of Mexico through the Mississippi River birdfoot delta and through the delta of the Atchafalaya River. Much of this water flows westward along the coast as a highly stratified coastal current, the Louisiana Coastal Current, isolated from the bottom by a strong halocline and from mid-shelf waters by a strong salinity front. This stratification maintains dissolved and particulate matter from the rivers, as well as recycled material, in a well-defined flow over the inner shelf. It also inhibits the downward mixing of oxygenated surface waters from the surface layer to the near bottom waters. This highly stratified flow is readily identifiable by its surface turbidity, as it carries much of the fine material delivered with the river discharge and resuspended by nearshore wave activity. A second significant contribution to the turbidity of the surface waters is due to phytoplankton in these waters. This turbidity reduces the solar radiation penetrating to depth through the water column. These two aspects of the coastal current, isolation of the inner shelf surface waters and maintenance of a turbid surface layer, precondition the waters for the development of near bottom summer hypoxia.

Trends in heavy metal levels in the dissolved and particulate phase in the Dutch rhine-meuse (MAAS) delta*

Levels of the heavy metals Cd, Cr, Cu, Pb and Zn, in both the dissolved and particulate phase, were determined in two sampling campaigns in August 1978 and August 1984 in the Dutch Rhine-Meuse (Maas) Delta. Besides the heavy metal concentrations, other important parameters were determined, such as the concentrations of seston, chlorophyll and nutrients. The concentrations of dissolved Cd and of Cd, Pb and Cu in particulate matter were much higher in 1978 than in 1984, especially for Cd. This may be due to the strict regulations implemented in Germany to reduce the pollution of natural waters by heavy metals. The correlation between the high Cd content and the chlorophyll content is explained by the binding of Cd to living and dead organisms. The distribution of the metals between the dissolved and the particulate phase, indicated by the distribution quotient Kd , increases from low values of Kd for Cu and Zn, to higher values for Cd and Cr, and the highest values for Pb. The differences are explained by various binding forms of each of these metals in natural waters

Particulate allergens potentiate allergic asthma in mice through sustained IgE-mediated mast cell activation.

Allergic asthma is characterized by airway hyperresponsiveness, inflammation, and a cellular infiltrate dominated by eosinophils. Numerous epidemiological studies have related the exacerbation of allergic asthma with an increase in ambient inhalable particulate matter from air pollutants. This is because inhalable particles efficiently deliver airborne allergens deep into the airways, where they can aggravate allergic asthma symptoms. However, the cellular mechanisms by which inhalable particulate allergens (pAgs) potentiate asthmatic symptoms remain unknown, in part because most in vivo and in vitro studies exploring the pathogenesis of allergic asthma use soluble allergens (sAgs). Using a mouse model of allergic asthma, we found that, compared with their sAg counterparts, pAgs triggered markedly heightened airway hyperresponsiveness and pulmonary eosinophilia in allergen-sensitized mice. Mast cells (MCs) were implicated in this divergent response, as the differences in airway inflammatory responses provoked by the physical nature of the allergens were attenuated in MC-deficient mice. The pAgs were found to mediate MC-dependent responses by enhancing retention of pAg/IgE/FcεRI complexes within lipid raft–enriched, CD63(+) endocytic compartments, which prolonged IgE/FcεRI-initiated signaling and resulted in heightened cytokine responses. These results reveal how the physical attributes of allergens can co-opt MC endocytic circuitry and signaling responses to aggravate pathological responses of allergic asthma in mice.

Survey of the potential environmental and health impacts in the immediate aftermath of the coal ash spill in Kingston, Tennessee.

An investigation of the potential environmental and health impacts in the immediate aftermath of one of the largest coal ash spills in U.S. history at the Tennessee Valley Authority (TVA) Kingston coal-burning power plant has revealed three major findings. First the surface release of coal ash with high levels of toxic elements (As = 75 mg/kg; Hg = 150 microg/kg) and radioactivity (226Ra + 228Ra = 8 pCi/g) to the environment has the potential to generate resuspended ambient fine particles (< 10 microm) containing these toxics into the atmosphere that may pose a health risk to local communities. Second, leaching of contaminants from the coal ash caused contamination of surface waters in areas of restricted water exchange, but only trace levels were found in the downstream Emory and Clinch Rivers due to river dilution. Third, the accumulation of Hg- and As-rich coal ash in river sediments has the potential to have an impact on the ecological system in the downstream rivers by fish poisoning and methylmercury formation in anaerobic river sediments.

Use of particulate surrogates for assessing microbial mobility in subsurface ecosystems.

Particulate matter can play a vital role in delivering nutrients and micro organisms to groundwater. This paper uses bacteriophage and microsphere surrogates to study the delivery of particles to the subsurface and demonstrates the potential role that pH and ionic strength can play in limiting particle mobility.

Biomarkers reveal the effects of hydrography on the sources and fate of marine and terrestrial organic matter in the western Irish Sea

A suite of lipid biomarkers were investigated from surface sediments and particulate matter across hydrographically distinct zones associated with the western Irish Sea gyre and the seasonal bloom. The aim was to assess the variation of organic matter (OM) composition, production, distribution and fate associated with coastal and southern mixed regions and also the summer stratified region. Based on the distribution of a suite of diagnostic biomarkers, including phospholipid fatty acids, source-specific sterols, wax esters and C₂₅ highly branched isoprenoids, diatoms, dinoflagellates and green algae were identified as major contributors of marine organic matter (MOM) in this setting. The distribution of cholesterol, wax esters and C₂₀ and C₂₂ polyunsaturated fatty acids indicate that copepod grazing represents an important process for mineralising this primary production. Net tow data from 2010 revealed much greater phytoplankton and zooplankton biomass in well-mixed waters compared to stratified waters. This appears to be largely reflected in MOM input to surface sediments. Terrestrial organic matter (TOM), derived from higher plants, was identified as a major source of OM regionally, but was concentrated in proximity to major riverine input at the Boyne Estuary and Dundalk Bay. Near-bottom residual circulation and the seasonal gyre also likely play a role in the fate of TOM in the western Irish Sea.

A methodology to estimate the residence time of estuaries

The residence time has long been used as a classification parameter for estuaries and other semi- enclosed water bodies. It aims to quantify the time water remains inside the estuary, being used as an indicator both for pollution assessment and for ecological processes. Estuaries with a short residence time will export nutrients from upstream sources more rapidly then estuaries with longer residence time. On the other hand the residence time determines if micro-algae can stay long enough to generate a bloom. As a consequence, estuaries with very short residence time are expected to have much lower algae blooms, then estuaries with longer residence time. In addition, estuaries with residence times shorter than the doubling time of algae cells will inhibit formation of algae blooms (EPA, 2001). The residence time is also an important issue for processes taking place in the sediment. The fluxes of particulate matter and associated adsorbed species from the water column to the sediment depends of the particle’s vertical velocity, water depth and residence time. This is particularly important for the fine fractions with lower sinking velocities. The question is how to compute the residence time and how does it depend on the computation method adopted.

Analysis of polycyclic aromatic hydrocarbons in atmospheric particulate samples by microwaveassisted extraction and liquid chromatography

A methodology based on microwave-assisted extraction (MAE) and LC with fluorescence detection (FLD) was investigated for the efficient determination of 15 polycyclic aromatic hydrocarbons (PAHs) regarded as priority pollutants by the US Environmental Protection Agency and dibenzo(a,l)pyrene in atmospheric particulate samples. PAHs were successfully extracted from real outdoor particulate matter (PM) samples with recoveries ranging from 81.4±8.8 to 112.0±1.1%, for all the compounds except for naphthalene (62.3±18.0%) and anthracene (67.3±5.7%), under the optimum MAE conditions (30.0 mL of ACN for 20 min at 110ºC). No clean-up steps were necessary prior to LC analysis. LOQs ranging from 0.0054 ng/m3 for benzo( a)anthracene to 0.089 ng/m3 for naphthalene were reached. The validated MAE methodology was applied to the determination of PAHs from a set of real world PM samples collected in Oporto (north of Portugal). The sum of particulate-bound PAHs in outdoor PM ranged from 2.5 and 28 ng/m3.