Secondary aerosol formation from atmospheric reactions of aliphatic amines

Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+) nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively) and photooxidation (23% and 8% respectively). The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase

Characterization and Quantification of Isoprene-Derived Epoxydiols in Ambient Aerosol in the Southeastern United States

Isoprene-derived epoxydiols (IEPOX) are identified in ambient aerosol samples for the first time, together with other previously identified isoprene tracers (i.e., 2-methyltetrols, 2-methylglyceric acid, C5-alkenetriols, and organosulfate derivatives of 2-methyltetrols). Fine ambient aerosol collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS) was analyzed using both gas chromatography/quadrupole mass spectrometry (GC/MS) and gas chromatography/time-of-flight mass spectrometry (GC/TOFMS) with prior trimethylsilylation. Mass concentrations of IEPOX ranged from ~1 to 24 ng m^(−3) in the aerosol collected from the two sites. Detection of particle-phase IEPOX in the AMIGAS samples supports recent laboratory results that gas-phase IEPOX produced from the photooxidation of isoprene under low-NO_x conditions is a key precursor of ambient isoprene secondary organic aerosol (SOA) formation. On average, the sum of the mass concentrations of IEPOX and the measured isoprene SOA tracers accounted for about 3% of the organic carbon, demonstrating the significance of isoprene oxidation to the formation of ambient aerosol in this region

Nitrogen deposition to the United States: distribution, sources, and processes

We simulate nitrogen deposition over the US in 2006–2008 by using the GEOS-Chem global chemical transport model at 1/2°×2/3° horizontal resolution over North America and adjacent oceans. US emissions of NO<sub>x</sub> and NH<sub>3</sub> in the model are 6.7 and 2.9 Tg N a<sup>−1</sup> respectively, including a 20% natural contribution for each. Ammonia emissions are a factor of 3 lower in winter than summer, providing a good match to US network observations of NH<sub>x</sub> (≡NH<sub>3</sub> gas + ammonium aerosol) and ammonium wet deposition fluxes. Model comparisons to observed deposition fluxes and surface air concentrations of oxidized nitrogen species (NO<sub>y</sub>) show overall good agreement but excessive wintertime HNO<sub>3</sub> production over the US Midwest and Northeast. This suggests a model overestimate N<sub>2</sub>O<sub>5</sub> hydrolysis in aerosols, and a possible factor is inhibition by aerosol nitrate. Model results indicate a total nitrogen deposition flux of 6.5 Tg N a<sup>−1</sup> over the contiguous US, including 4.2 as NO<sub>y</sub> and 2.3 as NH<sub>x</sub>. Domestic anthropogenic, foreign anthropogenic, and natural sources contribute respectively 78%, 6%, and 16% of total nitrogen deposition over the contiguous US in the model. The domestic anthropogenic contribution generally exceeds 70% in the east and in populated areas of the west, and is typically 50–70% in remote areas of the west. Total nitrogen deposition in the model exceeds 10 kg N ha<sup>−1</sup> a<sup>−1</sup> over 35% of the contiguous US

The marine isotope stage 1–5 cryptotephra record of Tenaghi Philippon, Greece:Towards a detailed tephrostratigraphic framework for the Eastern Mediterranean region

The iconic climate archive of Tenaghi Philippon (TP), NE Greece, allows the study of short-term palaeoclimatic and environmental change throughout the past 1.3 Ma. To provide high-quality age control for detailed palaeoclimate reconstructions based on the TP archive, (crypto)tephra studies of a peat core ‘TP-2005’ have been carried out for the 0–130 ka interval. The results show that the TP basin is ideally positioned to receive tephra fall from both the Italian and Aegean Arc volcanic provinces. Two visible tephra layers, the Santorini Cape Riva/Y-2 (c. 22 ka) and the Campanian Ignimbrite (CI)/Y-5 (c. 39.8 ka) tephras, and six primary cryptotephra layers, namely the early Holocene E1 tephra from the Aeolian Islands (c. 8.3 ka), the Campanian Y-3 (c. 29 ka) and X-6 tephras (c. 109.5 ka), as well as counterpart tephras TM-18-1d (c. 40.4 ka), TM-23-11 (c. 92.4 ka) and TM-33-1a (c. 116.7 ka) from the Lago Grande di Monticchio sequence (southern Italy), were identified along with repeatedly redeposited Y-2 and CI tephra material. Bayesian modelling of the ages of seven of the primary tephra layers, 60 radiocarbon measurements and 20 palynological control points have been applied to markedly improve the chronology of the TP archive. This revised chronology constrains the age of tephra TM-18-1d to 40.90–41.66 cal ka BP (95.4% range). Several tephra layers identified in the TP record form important isochrons for correlating this archive with other terrestrial (e.g., Lago Grande di Monticchio, Sulmona Basin and Lake Ohrid) and marine (e.g., Adriatic Sea core PRAD 1-2 and Aegean Sea core LC21) palaeoclimate records in the Mediterranean region

Immunological Outcomes of Allergen-Specific Immunotherapy in Food Allergy

IgE-mediated food allergies are caused by adverse immunologic responses to food proteins. Allergic reactions may present locally in different tissues such as skin, gastrointestinal and respiratory tract and may result is systemic life-threatening reactions. During the last decades, the prevalence of food allergies has significantly increased throughout the world, and considerable efforts have been made to develop curative therapies. Food allergen immunotherapy is a promising therapeutic approach for food allergies that is based on the administration of increasing doses of culprit food extracts, or purified, and sometime modified food allergens. Different routes of administration for food allergen immunotherapy including oral, sublingual, epicutaneous and subcutaneous regimens are being evaluated. Although a wealth of data from clinical food allergen immunotherapy trials has been obtained, a lack of consistency in assessed clinical and immunological outcome measures presents a major hurdle for evaluating these new treatments. Coordinated efforts are needed to establish standardized outcome measures to be applied in food allergy immunotherapy studies, allowing for better harmonization of data and setting the standards for the future research. Several immunological parameters have been measured in food allergen immunotherapy, including allergen-specific immunoglobulin levels, basophil activation, cytokines, and other soluble biomarkers, T cell and B cell responses and skin prick tests. In this review we discuss different immunological parameters and assess their applicability as potential outcome measures for food allergen immunotherapy that may be included in such a standardized set of outcome measures

Minimally invasive application of botulinum toxin A in patients with idiopathic rhinitis

<p>Abstract</p> <p>Background</p> <p>Nasal hypersecretion due to idiopathic rhinitis can often not be treated sufficiently by conventional medication. Botulinum toxin A (BTA) has been injected into the nasal mucosa in patients with nasal hypersecretion with a reduction of rhinorrhea lasting for about 4 to 8 weeks. Since the nasal mucosa is well supplied with glands and vessels, the aim of this study was to find out if the distribution of BTA in the nasal mucosa and a reduction of nasal hypersecretion can also be reached by a minimally invasive application by sponges without an injection.</p> <p>Methods</p> <p>Patients were randomly divided into two groups. The effect of BTA (group A, C, D) or saline as placebo (group B) was investigated in 20 patients with idiopathic rhinitis by applying it with a sponge soaked with BTA (40 units each nostril) or saline. Subgroups C and D contained these patients of group A and B who did not improve in symptoms one week after the original treatment (either BTA or saline) who then received the alternative medication. Changes of symptoms (rhinorrhea, nasal obstruction) were scored by the patients in a four point scale and counted (consumption of tissues, sneezing) in a diary. The patients were followed up weeks 1, 2, 4, 8 and 12.</p> <p>Results</p> <p>There was a clear reduction of the amount of secretion in group A compared to group B, C and D. This did not correlate with the tissue consumption, which was comparably reduced in group A and B, but reduced less in group C and D. Sneezing was clearly reduced in group A but comparably unchanged in group B and C and increased in group D. Nasal congestion remained unchanged.</p> <p>Conclusion</p> <p>In some patients with therapy-resistant idiopathic rhinitis BTA applied with a sponge is a long-lasting and minimal invasive therapy to reduce nasal hypersecretion.</p

The French Didactic Tradition in Mathematics

This chapter presents the French didactic tradition. It first describes theemergence and development of this tradition according to four key features (role ofmathematics and mathematicians, role of theories, role of design of teaching andlearning environments, and role of empirical research), and illustrates it through two case studies respectively devoted to research carried out within this traditionon algebra and on line symmetry-reflection. It then questions the influence of thistradition through the contributions of four researchers from Germany, Italy, Mexicoand Tunisia, before ending with a short epilogue