Approximately 2000 daily aerosol samples were collected at Antalya (30&deg / 34&amp / #900 / 30.54 E, 36&deg / 47&amp / #8217 / 30.54N) on the Mediterranean coast of Turkey between 1993 and 2001. High volume PM10 sampler was used for the collection of samples on Whatman&amp / #8211 / 41 filters. Collected samples were analyzed by a combination of analytical techniques. Energy Dispersive X-Ray Fluorescence (EDXRF) and Inductively Coupled Plasma Mass Spectrometry (ICPMS) was used to measure trace element content of the collected samples from Li to U. Major ions, namely, SO42- and NO3-, were determined by employing Ion Chromatography (IC). Samples were analyzed in terms of their NH4+ contents by means of Colorimetry. Evaluation of short term trends of measured parameters have been shown that elements with marine and crustal origin are more episodic as compared to anthropogenic ones. Most of the parameters showed well defined seasonal cycles, for example, concentrations of crustal elements increased in summer season while winter concentrations of marine elements were considerably higher than associated values for summer. Seasonal Kendall statistic depicted that there was a decreasing trend for crustal elements such as Be, Co, Al, Na, Mg, K, Dy, Ho, Tm, Cs and Eu. Lead, As, Se and Ge were the anhtropogenic elements that decreasing trend was detected in the course of study period. Cluster and Residence time analysis were performed to find the origin of air masses arrving to Eastern Mediterranena Basin. It has been found that air masses reaching to our station resided more on Balkans and Eastern Europe. Positive Matrix Factorization (PMF) resolved eight factors influencing the chemical composition of Eastern Mediterranean aerosols as local dust, Saharan dust, oil combustion, coal combustion, crustal-anthropogenic mixed, sea salt, motor vehicle emission, and local Sb factor.

Long term data generated at four rural stations are compared to determine similarities and differences in aerosol compositions and factors contributing to observed differences at different regions in Turkey. The stations used in this study are located at Mediterranean coast (20 km to the west of Antalya city), Black Sea coast (20 km to the east of Amasra town), Central Anatolia (&Ccedil / ubuk, Ankara) and Northeastern part of the Anatolian Plateau (at Mt. Uludag). Data used in comparisons were generated in previous studies. However, some re-analysis of data were also performed / (1) to improve the similarities of the parameters compared and (2) to be able to apply recently-developed methodologies to data sets. Data from Mediterranean and Black Sea stations were identical in terms of parameters measured and were suitable for extensive comparison. However, fewer parameters were measured at &Ccedil / ubuk and Uludag stations, which limited the comparisons involving these two stations. Comparison included levels of major ions and elements, short-term and seasonal variations in concentrations, background (baseline) concentrations of elements, flow climatology of regions, correlations between elements, potential source areas affecting regions, and source types affecting chemical composition of particles. Comparison of levels of measured parameters in four regions showed that there are some differences in concentrations that arise from differences in the local characteristics of the sampling points. For example very high concentrations of elements such as Na and Cl in the Mediterranean region is attributed to closer proximity of the Antalya station to coast and not a general feature of the Mediterranean aerosol. There are also significant regional differences in the concentrations of measured elements and ions as well. Concentrations of anthropogenic elements are very similar at two coastal stations (Antalya and Amasra), but they are approximately a factor of two smaller at the two stations that are located on the Anatolian Plateau. This difference between coastal and high altitude plateau stations, which is common to all anthropogenic species, is attributed to different source regions and transport mechanisms influencing coastal regions and Anatolian Plateau. Some statistically significant differences were also observed in the temporal variations of elements and ions measured in different stations. The elements with crustal origin showed similar seasonal pattern at all stations, with higher concentrations in summer and lower concentrations in winter. This difference between summer and winter is attributed to suppression of re-suspension of crustal aerosol from wet or ice-covered surface soil in winter. Concentrations of anthropogenic elements, on the other hand, did not show a statistically significant seasonal trend at Amasra, &Ccedil / ubuk and Uludag stations, but they have higher concentrations during summer months at the Antalya station. This difference between Mediterranean aerosol and aerosol at the Central and Northern Turkey is due to influence of more local sources on &Ccedil / ubuk, Amasra and Uludag stations and domination of more distant source in determining aerosol composition at the Mediterranean region. A similar conclusion of strong influence of local sources on chemical composition of particles at the Central Anatolia was also suggested by the comparison of baseline concentrations in each station. General features in flow climatology (residence times of upper atmospheric air masses) in each region are found to be similar with more frequent flow from W, WNW, NW and NNW wind sectors. Since these are the sectors that include high emitting countries in Eastern and Western Europe and Russia, transport from these sectors are expected to bring pollution from both distant European countries and more local Balkan countries and western parts of Turkey. Flow climatology in stations showed small, but statistically significant, differences between summer and winter seasons. These variations suggested that the station at the Central Anatolia and Black Sea (&Ccedil / ubuk Amasra and Uludag stations) are affected from sources located at the Western Europe in winter season and from sources located at the Eastern Europe in summer. Mediterranean aerosol, on the other hand, are affected from sources at the Western Europe and do not show any seasonal differences. This variation in flow climatology between summer and winter seasons (and lack of variation at the Mediterranean station) is supported by the seasonal variation (and lack of variation at the Mediterranean station) in SO42-/NO3- ratio measured at the stations. Potential source contribution function (PSCF) values are calculated for selected elements and ions in each station. Statistical significance of calculated PSCF values is tested using bootstrapping technique. Results showed that specific grids at Russia and at Balkan countries are common source regions affecting concentrations of anthropogenic elements at all four regions in Turkey. However, each station is also affected from specific source regions as well. Aerosol composition at the Anatolian Plateau are affected from sources closer to the sampling points whereas Mediterranean and Black Sea aerosol are affected from source regions that farther away from the receptors. It should be noted that the same conclusion is also reached in comparison of seasonal patterns and baseline concentrations at these stations. Types of sources affecting aerosol composition at Black Sea, Mediterranean and Central Anatolia are also compared. Source types affecting atmospheric composition in these regions were calculated using positive matrix factorization (PMF). The results showed that aerosol at the Black Sea, Central Anatolia and Mediterranean atmosphere consists of 8, 6 and 7 components, respectively. Two of these components, namely a crustal component and a long-range transport component are common in all three stations. The chemical compositions of these common components are shown to the same within 95% statistical significance interval. Three factors, namely a fertilizer factor, which is highly enriched in NH4+ ion, a sea salt component and an arsenic factor are common in the Mediterranean and Black Sea aerosol but not observed at the Central Anatolia. Other factors found in the regions are specific for that region.

This dissertation is a collection of studies that investigates the issue of air pollution in the field of environmental chemistry. My thesis consists of research works done to measure the concentration of particulate matter (PM) and gas-phase species in ambient air. High concentrations of PM is a significant problem in Utah and in other regions of the world. Particles having an aerodynamic diameter of 2.5 micrometers and smaller play a crucial role in air pollution and pose serious health risks when inhaled. PM is composed of both organic and inorganic components. The organic fraction in PM ranges from 10-90% of the total particle mass. Several methods have been employed to measure the organic fraction of PM, but these techniques require extensive laboratory analysis, expensive bench top equipment, and do a poor job of capturing diurnal variations of the concentrations of ambient organic compounds. The Hansen Lab has developed a new instrument called the Organic Aerosol Monitor (OAM) which is based on gas chromatography followed by mass spectrometry detection platform for measuring the carbonaceous component of PM2.5 on an hourly averaged basis. Organic marker data collected in 2016 using the OAM was used in a Positive Matrix Factorization (PMF) analysis to identify the sources of PM in West Valley City, Utah. Additionally, data was collected in Richfield and Vernal, UT in 2017 - 2018 to quantitatively monitor the composition of organic markers of PM2.5. Some previously unidentified organic compounds in PM were successfully identified during this study, including terpenes, polycyclic aromatic hydrocarbons (PAHs), diethyl phthalate, some herbicides, and pesticides. Gas-phase species play a significant role in driving the formation of air pollutants in Earth's atmosphere. Traditional gas detection methods do not provide high temporally and spatially resolved data; therefore, it becomes important to detect and measure gas-phase species both qualitatively and quantitatively to better understand the sources of air pollution. An incoherent broadband cavity enhanced absorption spectrometer (IBBCEAS) combines a broadband incoherent light source, a stable optical cavity formed by two highly reflective mirrors and a charged-coupled device (CCD) detector to quantitatively measure the gas-phase compounds present in the atmosphere. The concentrations of formaldehyde (HCHO) were measured using IBBCEAS to investigate the sources of this hydrocarbon in Bountiful, Utah during 2019. Another important species is OH radical. It is one of the most predominant oxidizing species present in the atmosphere. It is found in low concentrations, 0.1 ppt. Detecting concentrations this low is challenging. A new IBBCEAS instrument has been designed and elements of this instrument were tested by measuring the OH overtones in a variety of short chained alcohols. A set of experiments were conducted to measure the absorption cross-sections for the 5th and 6th OH vibrational overtones in a series of short chained alcohols by IBBCEAS. Because OH radical's lowest energy electronic state occurs in the same wavelength region (i.e., 308 nm) that SO2 absorbs (300-310 nm), a study was conducted in which the concentrations of SO2 were measured using an IBBCEAS and compared with a commercially available SO2 monitor.

In the studies underlying this thesis, various source tracing techniques were applied to environmental samples from the Baltic region. Comprehensive sampling and analysis of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in surface sediments in Swedish coastal and offshore areas resulted in a unique data set for this region. Nearly 150 samples of surface sediments were analyzed for all tetra- to octa-chlorinated PCDD/Fs. The levels showed large spatial variability with hotspots in several coastal regions. Neither Sweden nor the EU has introduced guideline values for PCDD/Fs in sediment, but comparisons to available guidelines and quality standards from other countries indicate that large areas of primarily coastal sediments may constitute a risk to marine organisms. Multivariate pattern analysis techniques and receptor models, such as Principal Component Analysis (PCA) and Positive Matrix Factorization (PMF), were used to trace sources. These analyses suggested that three to six source types can explain most of the observed pattern variations found in the sediment samples. Atmospheric deposition was suggested as the most important source to offshore areas, thus confirming earlier estimates. However, spatial differences indicated a larger fraction of local/regional atmospheric sources, characterized by PCDFs, in the south. This was indicated by the identification of several patterns of atmospheric origin. In coastal areas, the influence of direct emission sources was larger, and among these, chlorophenol used for wood preservation and emissions from pulp/paper production and other wood related industry appeared to be most important. The historic emissions connected to processes involving chemical reactions with chlorine (e.g. pulp bleaching) were found to be of less importance except at some coastal sites. The analysis of PCDD/Fs in Baltic herring also revealed spatial variations in the levels and pollution patterns along the coast. The geographical match against areas with elevated sediment levels indicated that transfer from sediments via water to organisms was one possible explanation. Fugacity, a concept used to predict the net transport direction between environmental matrices, was used to explore the gas exchange of hexachlorocyclohexanes (HCHs) and polychlorinated biphenyls (PCBs) between air and water. These estimates suggested that, in the Kattegat Sea, the gaseous exchange of HCHs primarily resulted in net deposition while PCBs were net volatilized under certain environmental conditions. The study also indicated that, while the air concentrations of both PCBs and γ-HCH are mostly dependent upon the origin of the air mass, the fluctuations in α-HCH were primarily influenced by seasonal changes.

High levels of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in edible fish in the Baltic Sea have raised health concerns in the Baltic region and the rest of Europe. Thus, there are urgent needs to characterize sources in order to formulate effective mitigation strategies. The aim of this thesis is to contribute to a better understanding of past and present sources of PCDD/Fs in the Baltic Sea environment by exploring chemical fingerprints in sediments, air, and biota. The spatial and temporal patterns of PCDD/F distributions in the Baltic Sea during the 20th century were studied in Swedish coastal and offshore sediment cores. The results showed that PCDD/F levels peaked in 1975 (± 7 years) in coastal and 1991 (± 5 years) in offshore areas. The time trends of PCDD/Fs in the sediment cores also showed that environmental half-lives of these pollutants have been shorter in coastal than in offshore areas (15 ± 5 and 29 ± 14 years, respectively). Consequently, there have been remarkable recoveries in coastal areas, but slower recovery in offshore areas with 81 ± 12% and 38 ± 11% reductions from peak levels, respectively. Source-to-receptor multivariate modeling by Positive Matrix Factorization (PMF) showed that six types of PCDD/F sources are and have been important for the Baltic Sea environment: PCDD/Fs related to i) atmospheric background, ii) thermal processes, iii) manufacture and use of tetra-chlorophenol (TCP) and iv) penta-chlorophenol (PCP), v) industrial use of elementary chlo- rine and the chloralkali-process (Chl), and vi) hexa-CDD sources. The results showed that diffuse sources (i and ii) have consistently contributed >80% of the total amounts in the Southern Baltic Sea. In the Northern Baltic Sea, where the biota is most heavily contaminated, impacts of local sources (TCP, PCP and Chl) have been higher, contributing ca. 50% of total amounts. Among the six sources, only Thermal and chlorophenols (ii-iv) have had major impacts on biota. The impact of thermal sources has, however, been declining as shown from source apportioned time-trend data of PCDD/Fs in Baltic herring. In contrast, impacts of chlorophenol-associated sources generally increased, remained at steady-state or slowly decreased during 1990-2010, suggesting that these sources have substantially contributed to the persistently high levels of PCDD/Fs in Baltic biota. Atmospheric sources of PCDD/Fs for the Baltic region (Northern Europe) were also investigated, and specifically whether the inclusion of parallel measurements of metals in the analysis of air would help back-tracking sources. PCDD/Fs and metals in high-volume air samples from a rural field station near the shore of the central Baltic Sea were measured. The study focused on the winter season and air from the S and E sectors, as these samples showed elevated levels of PCDD/Fs, particularly PCDFs. Several metals were found to correlate significantly with the PCDFs. The wide range of candidate metals as source markers for PCDD/F emissions, and the lack of an up-to-date extensive compilation of source characteristics for metal emission from vari- ous sources, limited the use of the metals as source markers. The study was not able to pin-point primary PCDD/F sources for Baltic air, but it demonstrated a new promising approach for source tracing of air emissions. The best leads for back-tracking primary sources of atmospheric PCDD/Fs in Baltic air were seasonal trends and PCDD/F congener patterns, pointing at non-industrial related thermal sources related to heating. The non-localized natures of the sources raise challenges for managing the emissions and thus societal efforts are required to better control atmospheric emissions of PCDD/Fs. / EcoChange / BalticPOPs