The effect of sub-zero temperature on the formation and composition of secondary organic aerosol from ozonolysis of alpha-pinene.

This study presents a newly constructed temperature controlled cold-room smog chamber at Aarhus University, Denmark. The chamber is herein utilized to study the effect of sub-zero temperature on the formation and chemical composition of secondary organic aerosol (SOA) from ozone initiated oxidation of α-pinene. The chemical composition of α-pinene SOA formed from dark ozonolysis of α-pinene at 293 K and 258 K was investigated using High-Resolution Time-of-Flight Aerosol Mass Spectrometry (HR-ToF-AMS) and Ultra-High Performance Liquid Chromatography/Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry (UHPLC/ESI-qToF-MS). For comparison, an OH-initiated oxidation experiment was performed at 293 K. In ozonolysis experiments it was found that oxygen-to-carbon (O : C) ratios were higher in the particles formed at 293 K compared to 258 K. A total of 16 different organic acids and 30 dimers esters were quantified in the collected particles composing up to 34% of the total α-pinene SOA mass with increased mass fraction of carboxylic acids in particles from α-pinene ozonolysis at 258 K compared to 293 K. In contrast, dimer esters showed suppressed formation at the sub-zero reaction temperature, thus contributing 3% to SOA mass at 258 K while contributing 9% at 293 K. SOA formed in the OH-initiated oxidation of α-pinene at 293 K resulted in low concentrations of dimer esters supporting Criegee intermediates as a possible pathway to dimer ester formation. Vapour pressure estimates of the identified carboxylic acids and dimer esters are presented and show how otherwise semi-volatile carboxylic acids at sufficiently low temperatures may classify as low or even extremely low volatile organic compounds (ELVOC), thus may add to an enhanced particle formation observed at the sub-zero temperature through gas-to-particle conversion. The change in chemical composition of the SOA particles with temperature is ascribed to a combination of effects: the decreased vapour pressures and hence increased condensation of carboxylic acids from the gas phase to the particle phase along with suppressed formation of the high molecular weight dimer esters and different gas and particle phase chemistry results in particles of different chemical composition as a consequence of low reaction temperatures.

Synthesis and characterization of O-acylated-ω-hydroxy fatty acids as skin-protecting barrier lipids.

A series of O-acylated-ω-hydroxy fatty acids (Acyl acids) of up to 34 carbons were synthesized and characterized through DSC, FTIR and Langmuir isotherm measurements to identify potential replacements to petrolatum, a highly used occlusive technology that if unrefined, it can potentially be classified as carcinogenic. Fourier transform infrared spectroscopy studies demonstrated that long acyl acids engender orthorhombic packing; packing behavior that is predominant in the lipid matrix of healthy stratum corneum, the outmost layer of the skin. In addition, Differential Scanning Calorimetry (DSC) and Langmuir isotherm studies suggested that the length of the hydrocarbon chain and the position of the ester bond influence the molecular organization of the acyl acids. For instance, 16-(tetradecanoyloxy)hexadecanoic acid (30 carbons) displayed a higher melting point (mp=68°C) than 10-(stearoyloxy)decanoic acid (28 carbons; mp=63°C) and 10-(tetradecanoyloxy)decanoic acid (24 carbons; mp=55°C) according to DSC. Moreover, Langmuir isotherm studies showed that mixtures of acyl acid with distearoylphosphatidylcholine improved packing behavior. Finally, Water Vapor Transmission Rate (WVTR) measurements showed that the compounds in fact decrease WVTR compared to untreated control (P<0.001) which demonstrates the potential of these ingredients as occlusive technologies to combat skin barrier diseases.

Regional and inter annual patterns of heavy metals, organochlorines and stable isotopes in narwhals (Monodon monoceros) from West Greenland.

Samples of 150 narwhals obtained in different years from two West Greenland areas, Avanersuaq and Uummannaq, were compared for concentrations of and regional differences in heavy metals and organochlorines and stable-carbon and nitrogen isotopes. Cadmium, Hg, and Se concentrations increased in the first 3-4 years of the animal's life, after which no dependence on age was observed. Females had significantly higher concentrations of Cd in all tissues and of Hg and Se in liver than males. No consistent difference in metal levels between narwhals from Avanersuaq and Uummannaq was found. Year-to-year variation in metal levels at one location was larger than the geographical variation. Metal levels were within the range of previous published results for narwhals from Arctic Canada. Organochlorine (OC) concentrations in blubber of narwhals were dependent on age and sex. Females showed decreasing OC concentration in the first 8-10 years, while for males increases were detected in the first few years of life, after which the concentrations became stable. Few statistical differences in mean OC concentrations among individuals were observed. However, narwhals from Avanersuaq in 1993 had the lowest levels, indicating a temporal decrease of SigmaPCBs. SigmaPCBs, DDTs, HCHs and toxaphenes seem to be at similar levels in West Greenland and Arctic Canada, which can be explained by the close winter distributions of populations as well as large ranges in concentrations, time span, number of analyses and the size/age composition of the data. PCB and DDT concentrations in West Greenland narwhals were half those found in East Greenland and Svalbard. Stable-carbon isotope ratios in muscle of 150 narwhals showed a decreasing trend in the first year when they gradually reduced their dependency on mother's milk, after which they became relatively stable. delta15 N values were significantly higher in samples from Uummannaq in 1993 compared to samples from Avanersuaq in 1984 and 1985 indicating that the diet of the narwhals in Uummannaq was at a higher trophic level. However, only a few significant correlations were found between stable isotope ratios and metal and OC concentrations.

Measurements of nitrogen dioxide in Greenland using Palmes diffusion tubes.

Measurements of nitrogen dioxide using the Palmes diffusion tubes in Uummannaq, Aasiaat, and Nuuk. all located along the west-coast of Greenland, have demonstrated that the levels of pollution at the most heavily impacted sites are comparable to levels in much larger towns in Denmark. The highest concentrations were, in general, observed near sites influenced by car traffic (peak concentrations of up to 16 ppbv), medium concentrations were observed in the residential areas (2 6 ppbv), and very low levels were found at the background locations in the town outskirts (1-2 ppbv). Observations of nitrogen dioxide concentrations less than 0.1 ppbv at a remote site, Akia, 25 km from Nuuk, indicate that, compared to local sources, long-range transport of nitrogen dioxide is not important in western Greenland.