Fluorinated compounds are environmentally persistent and have been demonstrated to bioaccumulate and contribute to climate change. The focus of this work was to better understand the atmospheric chemistry of poly- and per-fluorinated compounds in order to appreciate their impacts on the environment. Several fluorinated compounds exist for which data on climate impacts do not exist. Radiative efficiencies (REs) and atmospheric lifetimes of two new long-lived greenhouse gases (LLGHGs) were determined using smog chamber techniques: perfluoropolyethers and perfluoroalkyl amines. Through this, it was observed that RE was not directly related to the number of carbon-fluorine bonds. A structure-activity relationship was created to allow the determination of RE solely from the chemical structure of the compound. Also, a novel method was developed to detect polyfluorinated LLGHGs in the atmosphere. Using carbotrap, thermal desorption and cryogenic extraction coupled to GC-MS, atmospheric measurements can be made for a number of previously undetected compounds. A perfluoroalkyl amine was detected in the atmosphere using this technique, which is the compound with the highest RE ever detected in the atmosphere. Perfluorocarboxylic acids (PFCAs) are water soluble and non-volatile, suggesting they are not susceptible to long-range transport. A hypothesis was derived to explain the ubiquitous distribution of these compounds involving atmospheric formation of PFCAs from volatile precursors. Using smog chamber techniques with offline analysis, perfluorobutenes and fluorotelomer iodides were shown to yield PFCAs from atmospheric oxidation. Dehydrofluorination of perfluorinated alcohols (PFOHs) is poorly understood in the mechanism of PFCA atmospheric formation. Using density functional techniques, overtone-induced photolysis was shown to lead to dehydrofluorination of PFOHs. In the presence of water, this mechanism could be a sink of PFOHs in the atmosphere. Confirmation of the importance of volatile precursors was derived from examination of snow from High Arctic ice caps. This provided the first empirical evidence of atmospheric deposition. Through the analytes observed, fluxes and temporal trends, it was concluded that atmospheric oxidation of volatile precursors is an important source of PFCAs to the Arctic.

Denton, Texas consistently reaches ozone nonattainment levels. This has led to a large focus of air pollution monitoring efforts in the region, with long-range transport being explored as a key contributor. For this study, the University of North Texas Discovery Park campus was chosen as a prospective location for an extensive air quality monitoring station. Sixteen years of ozone and meteorological data for five state-run monitoring sites within a 25 mile radius, including the nearest Denton Airport site, was gathered from TCEQ online database for the month of April for the years 2000 to 2015. The data was analyzed to show a historical, regional perspective of ozone near the proposed site. The maximum ozone concentration measured at the Denton Airport location over the 16 year period was measured at 96 ppb in 2001. Experimental ozone and meteorological measurements were collected at the Discovery Park location from March 26 to April 3 and April 8 to April, 2016 and compared to the Denton Airport monitoring site. A time lag in ozone trends and an increase in peak ozone concentrations at the proposed location were observed at the proposed site in comparison to the Denton Airport site. Historical and experimental meteorological data agreed in indicating that southern winds that rarely exceed 20 miles per hour are the predominant wind pattern. Back trajectories, wind roses, pollution roses, and bivariate plots created for peak ozone days during experimental periods support long range transport as a considerable cause of high ozone levels in Denton. Furthermore, a study of the precursor characteristics at the Denton Airport site indicated the site was being affected by a local source of nitrogen dioxide that was not affecting the proposed location. The differences in the Denton Airport site and the proposed site indicate that further monitoring at Discovery Park would be insightful. An outline of an expansive mobile monitoring station and suggestions for effective utilization are provided to guide future studies in Denton and the surrounding North Texas region.

No description available.

Fluorinated compounds are environmentally persistent and have been demonstrated to bioaccumulate and contribute to climate change. The focus of this work was to better understand the atmospheric chemistry of poly- and per-fluorinated compounds in order to appreciate their impacts on the environment. Several fluorinated compounds exist for which data on climate impacts do not exist. Radiative efficiencies (REs) and atmospheric lifetimes of two new long-lived greenhouse gases (LLGHGs) were determined using smog chamber techniques: perfluoropolyethers and perfluoroalkyl amines. Through this, it was observed that RE was not directly related to the number of carbon-fluorine bonds. A structure-activity relationship was created to allow the determination of RE solely from the chemical structure of the compound. Also, a novel method was developed to detect polyfluorinated LLGHGs in the atmosphere. Using carbotrap, thermal desorption and cryogenic extraction coupled to GC-MS, atmospheric measurements can be made for a number of previously undetected compounds. A perfluoroalkyl amine was detected in the atmosphere using this technique, which is the compound with the highest RE ever detected in the atmosphere. Perfluorocarboxylic acids (PFCAs) are water soluble and non-volatile, suggesting they are not susceptible to long-range transport. A hypothesis was derived to explain the ubiquitous distribution of these compounds involving atmospheric formation of PFCAs from volatile precursors. Using smog chamber techniques with offline analysis, perfluorobutenes and fluorotelomer iodides were shown to yield PFCAs from atmospheric oxidation. Dehydrofluorination of perfluorinated alcohols (PFOHs) is poorly understood in the mechanism of PFCA atmospheric formation. Using density functional techniques, overtone-induced photolysis was shown to lead to dehydrofluorination of PFOHs. In the presence of water, this mechanism could be a sink of PFOHs in the atmosphere. Confirmation of the importance of volatile precursors was derived from examination of snow from High Arctic ice caps. This provided the first empirical evidence of atmospheric deposition. Through the analytes observed, fluxes and temporal trends, it was concluded that atmospheric oxidation of volatile precursors is an important source of PFCAs to the Arctic.

The aim of this study was to examine if perfluorinated alkylated substances (PFASs) reaches north of Sweden by long-range atmospheric transport. This was done by monitoring the levels of PFASs in reindeer livers at two locations in 2002 and 2010, respectively. The reindeers have lived all of their lives in the mountains and therefore the main source of exposure for PFASs is through air. The samples were extracted and analysed for 24 different PFASs using ultra performance liquid chromatography tandem mass spectrometer (UPLC-MS/MS). The most significant change concerns perfluorooctane sulfonic acid (PFOS) which decreased significantly from 6.1 ng/g at the most northern location (Ammarnäs/Biergenis) in 2002 to 0.87 ng/g 2010. At the other sampling location, Glen, PFOS decreased from 5.0 to 3.2 ng/g during the eight years. Mainly PFOS and longer chain carboxylates were found. The results revealed that the levels of many compounds decreased in time. The location seems to have an impact on the level of perfluorinated compounds present and most likely the distribution of them in the air, since certain PFASs have increased and decreased differently in time between the two locations. Since PFASs are non-volatile, they are believed to be degradation products of volatile compounds such as fluorotelomer alcohols (FTOHs) and perfluoroalkylated sulfonamido alcohols (FOSEs). FTOHs and FOSEs are released, translocated by long-range atmospheric transport and degraded to perfluorinated compounds in organisms or atmosphere.

Bulk atmospheric deposition samples were taken every two months for a year in 2009-2010 at two sites in northern Sweden and analyzed for a suite of legacy and emerging persistent organic chemicals including legacy organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs)  and novel flame retardants (NFRs).  To further investigate the urban occurrence and contribution to remote contamination of flame retardants, indoor air, ventilation system air, and dust were sampled in several microenvironments in Stockholm during the winter of 2012 for analysis of PBDEs, isomer-specific hexabromocyclododecane (HBCDD), and NFRs.  Outdoor air and soil samples were also sampled around the same time period for analysis of the same compounds.  Five emerging pollutants were detected in atmospheric deposition: the current-use pesticides trifluralin and chlorothalonil; and the NFRs 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), 1,2-bis(tribromophenoxy)ethane (BTBPE), and Dechlorane Plus (DP).  A decrease in the fraction of the anti isomer of DP was observed at the more remote site, indicating isomer-selective degradation or isomerization during long range atmospheric transport.  The more remote site also received more total deposition of organic pollutants despite its receiving less precipitation.  Although PBDEs and emerging organic pollutants were detected, the bulk of the deposition consisted of PCBs and hexachlorocyclohexanes (HCHs) at both sites.   Several NFRs were identified in indoor and ventilation air samples including TBECH, pentabromotoluene (PBT), hexabromobenzene (HBB), 1,2-bis(pentabromodiphenyl)ethane (DBDPE), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB), and bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (TBPH).  There was no significant difference between concentrations of contaminants in ventilation system air and indoor air indicating that the flame retardants included in this study reach the outdoor environment via ventilation systems.  Dust and outdoor air samples have only been analyzed for HBCDDs so far.  HBCDD concentrations in apartments, offices, and schools were lower than reported concentrations for other countries in similar microenvironments.   However, an enrichment of α-HBCDD compared to γ-HBCDD was observed in dust taken from near treated products in stores when compared to dust taken directly from those products.  Very low concentrations of HBCDDs were detected in outdoor air.

Persistent organic pollutants (POPs) are toxic chemicals that can be found in various matrices in all corners of the planet, including remote areas such as the Arctic.  Several POPs are known and monitored but given the abundance of new chemicals in commerce about which little is known, chemicals that may be new POPs are constantly being screened for. The use of flame retardants, particularly brominated flame retardants (BFRs), has been increasing for decades. PBDEs and HBCDDs are two types of BFRs that have historically been used in large volumes but recently faced legislative restrictions. However, in order to meet fire safety standards, these BFRs have been replaced by a variety of emerging flame retardants (EFRs) about which little is known especially concerning their toxicity, production volumes, and environmental behavior. The main purpose of this thesis was to investigate the occurrence and fate in indoor and outdoor environments of several EFRs and compare them with PBDEs, HBCDDs, and legacy POPs. Several indoor environments in the city of Stockholm, Sweden were sampled for dust, indoor air, and ventilation system air (Paper II).  Results from these samples revealed a number of EFRs that humans are exposed to and that are emitted from buildings through ventilation systems. These included DDC-CO, DBE-DBCH, PBT, HBB, EHTBB, and BEH-TEBP. PBDE levels seem to be declining compared to previous studies in Stockholm.  Outdoor air and soil were sampled across transects of Stockholm (Paper II) and Birmingham, United Kingdom (Paper III).  Results from these samples showed the presence of many of the same EFRs in the outdoor environment that were found in indoor environments.  Urban pulses in air were discovered for PBDEs in both cities and for some EFRs in Stockholm, indicating that the cities are sources of EFRs to the outdoor environment.  Atmospheric deposition samples were taken at two sites in northern Sweden (Paper I).  Three EFRs (DDC-CO, DBE-DBCH, and BTBPE) and two current-use pesticides (trifluralin and chlorothalonil) were identified, indicating these compounds’ potential for long range transport and global contamination.  Other legacy POPs such as HCH, PCBs, and PBDEs were measured in the deposition samples as well.  The bulk of deposition was comprised of HCH and PCBs with only minor contributions from PBDEs, chlordanes, and emerging compounds.  Finally, passive and active air sampling methods were compared for BFRs in offices in Beijing, China.  Some EFRs were identified in indoor air from China; however, BDE-209 was the most predominant compound found (Paper IV).  Air samples collected with passive samplers generally had measured FR concentrations within a factor of 2-3 of those collected with active samplers. The use of a GFF in the passive samplers resulted in concentrations of particle-bound contaminants such as BDE-209 that were more comparable to those in active samples. The positioning of the PUF in the passive samplers affected the sampling rates for gaseous compounds and particle retention on PUFs was shown to be a large source of uncertainty in passive sampling. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.</p><p> </p>

The environmental occurrence and behaviour of the brominated flame retardant (BFR) decabromodiphenyl ethane (dbdpe) has only been studied to a limited extent. It is structurally similar to decabromodiphenyl ether (decaBDE), which makes it conceivable that dbdpe may also become an environmental contaminant of concern. A method for environmental analysis and comparative assessments of dbdpe and decaBDE was developed. Both BFRs were studied in: a mass balance of the Henriksdal WWTP in Stockholm (Paper I); an international survey of sewage sludge (Paper II); sediment along a transect from Henriksdal WWTP to the outer archipelago of Stockholm and from isolated Swedish lakes (Paper III); and a benthic food web from the Scheldt estuary (Paper IV). Dbdpe was found in sludge from every country surveyed, indicating that it may be a worldwide concern. The WWTP mass balance showed that virtually all of the BFRs were transferred from wastewater to sludge. A small fraction was emitted via the effluent, confirming emissions to the aquatic environment. In the marine sediment, the BFR levels close to the WWTP outfall were high. They decreased along the transect to low levels in the outer archipelago. The study of lake sediment showed a widespread presence of dbdpe in the Swedish environment and provided evidence that it originates from long range atmospheric transport. In the food web, dbdpe did bioaccumulate to a small extent which was similar to decaBDE. The transfer of the BFRs from sediment to benthic invertebrates was low, while transfer from prey to predator was higher. Biodilution was observed rather than biomagnification. This work suggests that the persistence, the susceptibility to long range atmospheric transport, and the potential for bioaccumulation are similar for dbdpe and the regulated decaBDE that it is replacing. Thus, there is a risk that a problematic environmental pollutant is being replaced with a chemical that is equally problematic. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 4: Manuscript.

The horizontal and vertical distributions of ozone and its precursors over North America during spring and summer are frequently determined by several factors: cloud convection, lightning NOx production, mixing depth, and long-range transport. The critical factors that contribute to the spatial distribution of air pollutants are studied using the Regional chEmical trAnsport Model (REAM) with diverse satellite measurements as well as in-situ surface and aircraft measurements. Surface and aircraft measurements show a large amount of reactive nitrogen tracers over the Antarctic plateau during summer. These enhanced measurements are investigated, and their photochemical impact is accessed by 1-D CTM and REAM.

Daily aerosol samples were collected at the &Ccedil / andarli which is located on Aegean coast of Turkey. A rural site was selected to monitor atmospheric pollution by long range transport. Sampling was performed in both summer and winter seasons, and in total 151 samples were obtained. Concentrations of elements in the samples were measured in order to identify sources and possible source locations of pollutants. Measured concentrations of trace elements at the &Ccedil / andarli station were compared with those measured at various sites around the world and, also in Turkey. As a result of comparison, level of pollution at the Aegean Region was found to be lower than the Mediterranean Region and Black Sea Region. Air flow climatology at &Ccedil / andarli was investigated in order to determine potential source regions for pollutants. Frequency of air flows from Russia and Western Europe are higher suggesting that emissions from these industrial regions affect the chemical composition of particulate matter. Besides these, it was concluded that contributions from Central and Eastern European countries are significantly high because of frequent air mass transport. Concentrations of elements measured at &Ccedil / andarli station were found to show short and seasonal variations. Such variations in concentrations are explained by variations in the source strengths and transport patterns. Positive matrix factorization (PMF) was applied to determine sources of elements and contribution of sources to each element. This analysis revealed 5 sources, two local anthropogenic emissions factor, one soil factor, one sea salt factor and one long range transport factor. Distribution of Potential Source Contribution Function (PSCF) values showed that main sources of SO42- are observed in Bulgaria, Romania, Poland, Ukraine and central part of Aegean region.