En utvärdering av befintlig data från referensfasen av kontrollprogrammet för Grimstorp Lillesjön har utförts. De studerade parametrarna i rapporten är ytvatten- och grundvattenhalter (grundvattenrör och brunnar) av arsenik och tre utvalda PAH (acenaften, fluoren och naftalen) ämnen samt fysikaliska-kemiska stödparametrar. För att bidra med information till kontrollprogrammet har i denna rapport statistiska parametrar beräknats i form av kontrollmål för årsmedelvärde och stickprov för de studerade parametrarna. Det har även i förväg angetts den förändring från kontrollmålet som kan påvisas enligt planerad provtagning. Arsenikhalterna har 1-5 ggr mindre relativa standard avvikelsen (CV) än för de tre valda PAH ämnena, där CV i många fall är över ett. Det största bidraget till variationen i data kommer från säsongsvariationer, där temperaturen har den största inverkan till variationen. För ytvatten- samt brunnsdata för de undersökta parametrarna kan halvårsvisa säsongsmässiga indelningar ses och genom att dela in data enligt säsongsvariationen kan variationskoefficienten minskas. Från jämförelse med andra genomförda impregneringprojekt vid före detta impregneringsanläggningar kan konstateras att i entreprenadfasen sker ett läckage av arsenik. I uppföljningsfasen påverkas visa grundvattenrör nedströms det före detta impregneringsområdet med högre halter av arsenik och PAH. Dessa haltökningar kan påvisas tre år efter utförd sanering. Sammantaget är bättre att köra kontrollprogrammet för Grimstorp Lillesjön mindre intensivt men under en längre tidsperiod och då ta prover under samma säsong, vilket ger jämförbara resultat. Detta medför att totalt sett kan färre prov tas jämfört med planerad provtagning eller en mindre förändring av halter kan detekteras i entreprenad och uppföljningsfasen.

Polycyclic aromatic hydrocarbons (PAHs) are widely distributed in the environment and are generated by many sources. Though the potential of PAH-rich mixtures to cause health effects has been known for almost a century, there are still unanswered questions about the levels of PAHs in the environment, the potential for human exposure to PAHs, the health effects associated with exposure, and how genetic susceptibility influences the extent of health effects in individuals. The first objective of this research was to quantify concentrations of PAHs in samples of settled house dust collected from homes in Azerbaijan, China, and Texas. The trends of PAH surface loadings and percentage of carcinogenic PAHs were China > Azerbaijan > Texas, indicating that the risk of health effects from exposure to PAHs in house dust is highest in the Chinese population and lowest in the Texas population. PAHs in China and Azerbaijan were derived mainly from combustion sources; Texas PAHs were derived from unburned fossil fuels such as petroleum. The second objective of this research was to investigate the effect of pregnane X receptor (PXR) on the genotoxicity of benzo[a]pyrene (BaP). BaP treatment resulted in significantly lower DNA adduct levels in PXR-transfected HepG2 cells than in parental HepG2 cells. Total GST enzymatic activity and mRNA levels of several metabolizing enyzmes were significantly higher in cells overexpressing PXR. These results suggest that PXR protects cells against DNA damage by PAHs such as BaP, possibly through a coordinated regulation of genes involved in xenobiotic metabolism. The third objective of this research was to investigate biomarkers of exposure in house mice (Mus musculus) exposed to PAH mixtures in situ. Mice and soil were collected near homes in Sumgayit and Khizi, Azerbaijan. Mean liver adduct levels were significantly higher in Khizi than in Sumgayit. Mean lung and kidney adduct levels were similar in the two regions. The DNA lesions detected may be a combination of environmentally-induced DNA adducts and naturally-occurring I-compounds. PAHs were present at background levels in soils from both Khizi and Sumgayit. It appears that health risks posed to rodents by soil-borne PAHs are low in these two areas.

Capping is typically used to control contaminant release from the underlying sediments. However, the presence of conventional caps often eliminates or slows natural degradation that might otherwise occur at the surface sediment. This is primarily due to the development of reducing conditions within the sediment that discourage hydrocarbon degradation. The objective of this study was to develop a novel active capping method, an electrode enhanced cap, to manipulate the redox potential to produce conditions more favorable for hydrocarbon degradation and evaluate the approach for the remediation of PAH contaminated sediment. A preliminary study of electrode enhanced biodegradation of PAH in sediment slurries showed that naphthalene and phenanthrene concentration decreased significantly within 4 days, and PAH degrading genes increased by almost 2 orders of magnitude. In a sediment microcosm more representative of expected field conditions, graphite cloth was used to form an anode at the sediment-cap interface and a similar cathode was placed a few centimeters above within a thin sand layer. With the application of 2V voltage, ORP increased and pH dropped around the anode reflecting water electrolysis. Various cap amendments (buffers) were employed to moderate pH changes. Bicarbonate was found to be the most effective in laboratory experiments but a slower dissolving buffer, e.g. siderite, may be more effective under field conditions. Phenanthrene concentration was found to decrease slowly with time in the vicinity of the anode. In the sediment at 0-1 cm below the anode, phenanthrene concentrations decreased to ~70% of initial concentration with no bicarbonate, and to ~50% with bicarbonate over ~70 days, whereas those in the control remained relatively constant. PAH degrading gene increased compared with control, providing microbial evidence of PAH biodegradation. A voltage-current relationship, which incorporated separation distance and the area of the electrodes, was established to predict current. A coupled reactive transport model was developed to simulate pH profiles and model results showed that pH is neutralized at the anode with upflowing groundwater seepage. This study demonstrated that electrode enhanced capping can be used to control redox potential in a sediment cap, provide microbial electron acceptors, and stimulate PAH degradation. / text

abstract: Dust storms known as 'haboobs' occur in the City of Tempe, AZ during the North American monsoon season. A haboob classification method based on meteorological and air quality measurements is described. There were from 3 to 20 haboob events per year over the period from 2005 to 2014. The calculated annual TSP (total suspended particulate) dry deposition during haboobs is estimated to contribute 74% of the total particulate mass deposited in Tempe, AZ. Dry deposition is compared with the aqueous chemistry of Tempe Town Lake. Water management and other factors may have a stronger impact on Tempe Town Lake chemistry than haboob dry-deposition. Haboobs alter the Polycyclic Aromatic Hydrocarbon (PAH) concentrations and distributions in Tempe, AZ. PAH isomer ratios suggest PM2.5 (particulate matter with aerodynamic diameters less than or equal to 2.5 μm) sources consistent with approximate thunderstorm outflow paths. The importance of the atmospheric aqueous phase, fogs and clouds, for the processing and removal of PAHs is not well known. A multiphase model was developed to determine the fate and lifetime of PAHs in fogs and clouds. The model employed literature values that describe the partitioning between three phases (aqueous, liquid organic, and gas), in situ PAH measurements, and experimental and estimated (photo)oxidation rates. At 25 °C, PAHs with two, three and four rings were predicted to be primarily gas phase (fraction in the gas phase xg > 90 %) while five- and six-ring PAHs partitioned significantly into droplets (xg < 60 %) with aqueous phase fractions of 1 to 6 % and liquid organic phase fractions of 31 to 91 %. The predicted atmospheric lifetimes of PAHs in the presence of fog or cloud droplets (< 5 hours) were significantly shorter than literature predictions of PAH wet and dry deposition lifetimes (1 to 14 days and 5 to 15 months respectively) and shorter than or equal to predicted PAH gas phase / particle phase atmospheric lifetimes (1 to 300 hours). The aqueous phase cannot be neglected as a PAH sink due to the large aqueous volume (vs. organic volume) and the relatively fast aqueous reactions. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2016

Au cours de ma thèse je me suis intéressé à deux aspects de l’immunité dans les pathologies pulmonaires chroniques : l’immunité innée et l’inflammation dans le développement de l’hypertension artérielle pulmonaire (HTAP) ; l’immunité adaptative et la réponse vaccinale antigrippale chez des patients atteint de la broncho-pneumopathie chronique obstructive (BPCO).Ma première étude a porté sur l’implication de la voie de signalisation IL-1ß/IL-1R1/MyD88 dans le développement de l’HTAP, l’IL-1ß étant une cytokine majeure de l’immunité innée. Nos résultats montrent que le remodelage vasculaire pulmonaire et l'inflammation dans l’HTAP dépendent de la voie de signalisation IL-1R1/MyD88. L’IL-1R1 et MyD88 sont tout deux nettement surexprimés dans les vaisseaux pulmonaires de patients atteints d’HTAP idiopathique. Chez les souris exposées à une hypoxie chronique de 21 jours, l’augmentation de la production d'IL-1ß et de l'expression de IL-1R1 et MyD88 précèdent le développement de l’HTAP. Les souris IL-1R1-/- et MyD88-/- étant protégées similairement contre le développement de l’HTAP, nous avons pu identifier IL-1R1 comme un acteur majeur dans la pathogenèse de l’HTAP, affectant à la fois la prolifération des cellules musculaires lisses d’artères pulmonaires (CML-AP) et le recrutement des macrophages. La protection partielle contre la maladie des souris M.lys-Cre MyD88fl/fl indique que les effets de l’IL-1ß/IL-1R1 sur l’HTAP sont médiés en partie par l'activation des macrophages. De plus, l’anakinra (IL-1Ra) permet de reverser partiellement l’HTAP établie, chez les souris SM22-5HTT+ et chez les rats exposés à la monocrotaline.Ma seconde étude a porté sur l’efficacité de la réponse vaccinale antigrippale chez des patients atteints de BPCO. Sur une cohorte de 15 sujets atteints de BPCO et 15 sujets sains, nos résultats montrent une altération de la réponse humorale et de la réponse cellulaire au vaccin antigrippale où l’on observe une production d’anticorps anti-hémagglutinine affaiblie et une diminution de la production d’IFNγ par les lymphocytes T auxiliaires (CD4+). L’analyse des sous-populations lymphocytaires indique qu’il existe chez ces patients un défaut de différentiation des cellules B, où l’on observe un taux de cellules B naïves (CD21+CD27-) plus important et un taux de cellules B mémoires (CD21+CD27+) switchées moindre (CD27+IgD-) que chez les patients contrôles, pouvant expliquer l’altération de la réponse vaccinale. Enfin, nous avons observé que les sous-populations lymphocytaires, en particulier les cellules B naïves et mémoires, sont corrélées avec deux paramètres cliniques de la maladie, la DLCO et le score d’emphysème.Ces travaux de thèse montrent donc que les interventions pharmacologiques ciblant la voie IL-1ß/IL-1R1 peuvent être prometteuses pour le traitement de l'HTAP et que de nouvelles stratégies vaccinales antigrippales doivent être développées pour les patients atteints de BPCO afin d’augmenter l’efficacité du vaccin et de prévenir les exacerbations. / During my thesis, I was interested in two aspects of immunity in chronic lung diseases: innate immunity and inflammation in the development of pulmonary arterial hypertension (PAH); adaptive immunity and influenza vaccine response in patients with chronic obstructive pulmonary disease (COPD).My first study was focused on the involvement of the IL-1ß/IL-1R1/MyD88 signaling pathway in the development of PAH; IL-1ß is a major cytokine in innate immunity. Our results show that the pulmonary vascular remodeling and inflammation in PAH depend on IL-1R1/MyD88 signaling pathway. IL-1R1 and MyD88 are both significantly overexpressed in pulmonary vessels of patients with idiopathic PAH. In mice exposed to chronic hypoxia during 21 days, the increase in production of IL-1ß and expression of IL-1R1 and MyD88 are involved in the development of PAH. Mice deleted with IL-1R1 and MyD88 were similarly protected against the development of PAH. We identified IL-1R1 as a major player in the pathogenesis of PAH, affecting both pulmonary arteries smooth muscle (PA-SMC) proliferation and recruitment of macrophages. The partial protection against the disease in mice M.lys-Cre MyD88fl/fl indicates that the effects of IL-1ß/IL-1R1 on PAH are mediated partially by activation of macrophages. In addition, anakinra (IL-1Ra) partially reverse established PAH in SM22-5HTT + mice and rats exposed to monocrotaline.My second study was focused on the efficacy of influenza vaccine response in patients with COPD. In a cohort of 15 subject with COPD and 15 healthy subjects, our results show that both the humoral and the cellular responses to influenza vaccination are impaired in patients with COPD, with a blunted antibody response and decreased INFγ production by helper T lymphocytes (CD4+). Analysis of lymphocyte subpopulations indicates an impairment of B cell differentiation in these patients: naive (CD21+ CD27-) B cell counts were higher and switched memory B-cell (CD27+ IgD-) counts were lower in COPD patients, which could explain the impairment of vaccine response. Interestingly, these changes in B cell subsets correlated with DLCO and the CT emphysema score.This thesis work thus shows that pharmacological interventions targeted towards IL-1ß/IL-1R1 may be promising for the treatment of PAH and new influenza vaccine strategies should be developed for COPD patients to increase vaccine efficacy and prevent exacerbations.

A collection of 4,10-chrysene derivatives was prepared via the BHQ (Bull-Hutchings- Quayle) reaction, their electronic and morphological properties analysed and assessed for suitability as organic semiconductor (OSC) materials. Larger polycyclic aromatic hydrocarbons (PAHs) such as benzo[k]tetraphenes and dinaphtho[1,2,-b:1',2'- k]chrysenes were then prepared and similarly characterised. An acene-based OSC material TMTES-pentacene was also prepared. It is proposed that non-linear PAH- based OSC materials may provide an alternative to popular acene-based materials; offering advantages in stability, diversity and handling.

Background: Pulmonary arterial hypertension (PAH) is a rare but serious disease with symptoms as dyspnea, fatigue and intolerance to exercise. The treatment is mainly pharmacological with physical exercise as an important complement. The 6 minutes walking test (6MWT) is used today worldwide for assessment and follow-up of the PAH patient. Objective: The aim of this study was to, among a PAH-population in Norrland, examine the 6-minutes walking test variables walking distance, ∆dyspnea and Δsaturation according to change over time and correlation between the variables. A further objectice was to examine any differences between four different PAH risk groups according to ∆dyspné och Δsat. Method:  This study is a retrospective register study based on the Umeå/Sundsvall part of the Swedish patient registry SPAHR. A total of 69 patients were examined at the time of diagnosis and at follow-up after 12 ± 3 months regarding 6MWT. Results: A significantly longer walkning distance was measured at follow-up comepared to baseline (284 m (IQR 187-410) vs 322 m (IQR 240 - 435), p &lt; 0,001). A negative but weak correlation existed  at baseline between walking distance and Δsat (r = -0.23, p= 0.022) and at follow-up (r = -0.27, p= 0.033). No significant difference regarding Δsaturation and Δdyspnea could be seen between the risk groups.  Conclusion: Also this study demonstrates that the walking distance is the measure that is seen to vary over time, while Δsaturation and Δdyspnea have not been shown to do so. The weak correlation that could be detected between walking distance and Δsaturation raises the idea that it may be a factor that strengthens or weakens the result measured in meters and could thus possibly increase the informational value of the 6MWT. However, the results of this study indicate that desaturation and estimated dyspnea are not factors that correlate with the walking distance (and thus the patient's functional working capacity). Other variables such as quality of life and fear of movement may need to be estimated by the patient group to be able to evaluate and plan both pharmacological treatment and physical exercise, and to see if it can predict the outcome of the treatment. This should be studied scientifically.

Emissions of soot and polycyclic aromatic hydrocarbons (PAHs) from incomplete burning of hydrocarbon fuels pose a great threat to the environment and human health. To reduce such emissions, a comprehensive understanding of their evolution process is essential. In this work, a series of research studies were conducted to evaluate sooting tendencies and to experimentally and theoretically develop PAH mechanisms. The sooting tendencies of oxygenated fuels were quantitively investigated in counterflow diffusion flames. Sooting limits are described by critical fuel and oxygen mole fractions, measured with a laser scattering technique. The addition of dimethyl ether displays non-monotonic behavior on sooting tendencies at elevated pressures, which is attributed to the chemical effect from kinetic simulations. The tendency of incipient soot formation of other oxygenated fuels (e.g., alcohol, acid, ether, ketone, and carbonate ester) was also assessed, using a similar approach. As the precursor of soot, PAH measurement using laser induced fluoresecnce was implemented to track the evolution processes from PAHs to incipient soot. Developing a PAH mechanism is essential to the understanding of soot formation; however, PAH formation and its growth process are not well understood. Based on previous research, PAHs with 5-membered rings are abundant in flames. Therefore, the growth of PAHs with 5-membered rings was investigated, using acenaphthylene (A2R5) as the example. The density functional theory (DFT) and the transition state theory (TST) were adopted to calculate potential energy surfaces and reaction rate coefficients. The existence of 5-membered rings appreciably impacts PAH production by facilitating the formation of planar PAHs with C2H substitution, thereby improving existing PAH mechanisms. In PAH mechanisms, the thermochemistry properties are not all calculated, but are hypothesized to be equal to those of a similar structure. The simulation accuracy of the hypothesis is explored here by discussing the sensitivity of the thermochemistry parameters in flame simulations. The group additivity method utilizing THERM codes is used to calculate thermochemistry properties. PAH loading affects the sensitivity of thermochemistry properties to both flame temperature and product yields. These results show that either accurate thermochemistry properties, or reverse reaction rates should be provided in the mechanism to improve simulation accuracy.

Soot formation is one of the most complex phenomena in combustion science and an understanding of the underlying physico-chemical mechanisms is important. This work adopted both experimental and numerical approaches to study soot formation in laminar counterfl ow diffusion flames. As polycyclic aromatic hydrocarbons (PAHs) are the precursors of soot particles, a detailed gas-phase chemical mechanism describing PAH growth upto coronene for fuels with 1 to 4 carbon atoms was validated against laminar premixed and counter- flow diffusion fl ames. Built upon this gas-phase mechanism, a soot model was then developed to describe soot inception and surface growth. This soot model was sub- sequently used to study fuel mixing effect on soot formation in counterfl ow diffusion flames. Simulation results showed that compared to the baseline case of the ethylene flame, the doping of 5% (by volume) propane or ethane in ethylene tends to increase the soot volume fraction and number density while keeping the average soot size almost unchanged. These results are in agreement with experimental observations. Laser light extinction/scattering as well as laser induced fluorescence techniques were used to study the effect of strain rate on soot and PAH formation in counterfl ow diffusion ames. The results showed that as strain rate increased both soot volume fraction and PAH concentrations decreased. The concentrations of larger PAH were more sensitive to strain rate compared to smaller ones. The effect of CO2 addition on soot formation was also studied using similar experimental techniques. Soot loading was reduced with CO2 dilution. Subsequent numerical modeling studies were able to reproduce the experimental trend. In addition, the chemical effect of CO2 addition was analyzed using numerical data. Critical conditions for the onset of soot were systematically studied in counterfl ow diffusion ames for various gaseous hydrocarbon fuels and at different strain rates. A sooting temperature index (STI) and a sooting sensitivity index (SSI) were proposed to present the sooting tendencies of different fuels and their sensitivities to strain rates.

Fireworks on Independence Day have been identified as a nationwide but short-term source of particulate matter in the U.S. No study has specifically examined their impacts on ambient polycyclic aromatic hydrocarbons (PAHs). Based on data between 1990 and 2019 in the Air Quality System, we identified 76 unique events that had PAH measurements on both July 4th days and control days (within 15 days before and after July 4th). We compared concentrations and diagnostic ratios of 16 priority PAHs between event and control days using Wilcoxon signed-rank tests and multivariable regressions. A local PAH monitoring campaign was conducted at eight sites in Memphis, Tennessee, to obtain a close observation of PAH changes. The national geometric mean (GM) concentrations of summed 16 PAHs (ΣPAHs) were similar between event and control days (48.1 ng/m3 vs. 52.8 ng/m3, p = 0.98). About a quarter of events had elevated PAH concentrations compared with control days. Higher diagnostic ratios were found on event days, suggesting more contributions from fireworks sources. PAHs on July 4th were unlikely to cause acute or chronic health effects. While the local monitoring showed a 15% increase of ΣPAHs on July 4th, the difference was not significant (p = 0.62). Elevated PAH concentrations occurred at sites near fireworks sources and without major traffics, but did not occur at those in remote areas or near major interstate highways. In conclusion, this study finds that Independence Day fireworks have negligible impacts on atmospheric PAHs at the national level, and are unlikely to pose significant health risks. The firework effect is localized within a limited geographic scale, suggesting potential needs for local monitoring and control programs.