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The importance of organic compounds in the oxidative capacity of the atmosphere, and as cloud condensation and ice-forming nuclei, has been recognized for several decades. Organic compounds comprise a significant fraction of the suspended matter mass, leading to local (e.g. toxicity, health hazards) and global (e.g. climate change) impacts. The state of knowledge of the physical chemistry of organic aerosols has increased during the last few decades. However, due to their complex chemistry and the multifaceted processes in which they are involved, the importance of organic aerosols, particularly bioaerosols, in driving physical and chemical atmospheric processes is still very uncertain and poorly understood. Factors such as solubility, surface tension, chemical impurities, volatility, morphology, contact angle, deliquescence, wettability, and the oxidation process are pivotal in the understanding of the activation processes of cloud droplets, and their chemical structures, solubilities and even the molecular configuration of the microbial outer membrane, all impact ice and cloud nucleation processes in the atmosphere. The aim of this review paper is to assess the current state of knowledge regarding chemical and physical characterization of bioaerosols with a focus on those properties important in nucleation processes. We herein discuss the potential importance (or lack thereof) of physical and chemical properties of bioaerosols and illustrate how the knowledge of these properties can be employed to study nucleation processes using a modeling exercise. We also outline a list of major uncertainties due to a lack of understanding of the processes involved or lack of available data. We will also discuss key issues of atmospheric significance deserving future physical chemistry research in the fields of bioaerosol characterization and microphysics, as well as bioaerosol modeling. These fundamental questions are to be addressed prior to any definite conclusions on the potential significance of the role of bioaerosols on physico-chemical atmospheric processes and that of climate.

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Acetone plays an important role in the chemistry of both the atmosphere and the ocean, due to its potential effect on the tropospheric HO(x) (= HO + HO(2)) budget, as well as its environmental and health effects. We discuss the development of a mobile, sensitive, selective, economical and facile method for the determination of acetone in seawater. The method consists of derivatizing acetone to its pentafluorobenzyl oxime using 1,2,3,4,5-pentafluorobenzylhydroxylamine (PFBHA), followed by solid-phase microextraction (SPME) and analysis by gas chromatography/mass spectrometry (GC/MS). A detection limit of 3.0 nM was achieved. The buffering capacity of seawater imposes challenges in using the method's optimum pH (3.7) on seawater samples, requiring calibration standards to be made in buffered salt water and the acidification of seawater samples and standards prior to extraction. We employed the technique for analysis of selected surface seawater samples taken on the Nordic seas during the ARK-XX/1 cruise (R.V. Polarstern). An upper limit of 5.5-9.6 nM was observed for acetone in these waters, the first acetone measurements reported for far North Atlantic and Arctic waters. Simplified schematic of transformations of organic compounds at the atmosphere-ocean interface.

A new multidimensional chromatographic method is described in which material separated into lipid-class bands on silica-coated quartz thin-layer chromatography (TLC) rods (Chromarods) is desorbed using a pyrolysis unit interface and introduced directly into a gas chromatograph-mass spectrometer for molecular species analysis. Steryl esters, wax esters, hydrocarbons, ketones, and fatty-acid methyl esters (FAMEs) are thermally desorbed without pretreatment. In order to desorb free sterols, monoacylglycerols (MAGs), aliphatic alcohols, and free fatty acids, the esters are converted to trimethylsilyl derivatives on the rod. Triacylglycerols and phospholipids are converted to FAMEs by thermochemolysis with tetramethylammonium hydroxide. The method's utility is demonstrated with lipids from seawater particulate matter by first confirming the identity of lipid bands with the appropriate standards. The wax ester-steryl ester TLC band contained no more than 8% steryl esters. Wax esters of up to C42 are detected. In six individual acyl lipid classes, C14-C22 fatty acids are detected with C16 acids predominant in all but wax esters. C16-C22 MAGs are identified in the complex acetone-mobile polar lipid band. The method successfully extends the scope of latroscan TLC-flame-ionization detection on Chromarods, which is a widely used technique for lipid-class analysis. Modification of the pyrolysis probe to handle intact TLC rods is a future objective.