Abstract. Model-measurement comparisons of HO x in extremely clean air ([NO]<3 ppt) are reported. Measurements were made during the second Southern Ocean Photochemistry Experiment (SOAPEX-2), held in austral summer 1999 at the Cape Grim Baseline Air Pollution Station in northwestern Tasmania, Australia.The free-radical chemistry was studied using a zerodimensional box-model based upon the Master Chemical Mechanism (MCM). Two versions of the model were used, with different levels of chemical complexity, to explore the role of hydrocarbons upon free-radical budgets under very clean conditions. The "detailed" model was constrained to measurements of CO, CH 4 and 17 NMHCs, while the "simple" model contained only the CO and CH 4 oxidation mechanisms, together with inorganic chemistry. The OH and HO 2 (HO x ) concentrations predicted by the two models agreed to within 5-10%.The model results were compared with the HO x concentrations measured by the FAGE (Fluorescence Assay by Gas Expansion) technique during four days of clean Southern Ocean marine boundary layer (MBL) air. The models overestimated OH concentrations by about 10% on two days and about 20% on the other two days. HO 2 concentrations were measured during two of these days and the models overestimated the measured concentrations by about 40%. Better agreement with measured HO 2 was observed by using data from several MBL aerosol measurements to estimate the aerosol surface area and by increasing the HO 2 uptake coefficient to unity. This reduced the modelled HO 2 overestimate by ∼40%, with little effect on OH, because of the poor HO 2 to OH conversion at the low ambient NO x concentrations.Local sensitivity analysis and Morris One-At-A-Time analysis were performed on the "simple" model, and showed

Abstract. The composition of organic aerosol formed from the gas phase ozonolysis of cyclohexene has been investigated in a smog chamber experiment. Comprehensive gas chromatography with time of flight mass spectrometric detection was used to determine that dicarboxylic acids and corresponding cyclic anhydrides dominated the small gas phase reaction products found in aerosol sampled during the first hour after initial aerosol formation. Structural analysis of larger more polar molecules was performed using liquid chromatography with ion trap tandem mass spectrometry. This indicated that the majority of identified organic mass was in dimer form, built up from combinations of the most abundant small acid molecules, with frequent indication of the inclusion of adipic acid. Trimers and tetramers potentially formed via similar acid combinations were also observed in lower abundances. Tandem mass spectral data indicated dimers with either acid anhydride or ester functionalities as the linkage between monomers. High-resolution mass spectrometry identified the molecular formulae of the most abundant dimer species to be C

The corrosion and dissolution of high- and low-carbon CoCrMo alloys, as used in orthopedic joint replacements, were studied by immersing samples in phosphate-buffered saline (PBS), water, and synovial fluid at 37 degrees C for up to 35 days. Bulk properties were analyzed with a fine ion beam microscope. Surface analyses by X-ray photoelectron spectroscopy and Auger electron spectroscopy showed surprisingly that synovial fluid produced a thin oxide/hydroxide layer. Release of ions into solution from the alloy also followed an unexpected pattern where synovial fluid, of all the samples, had the highest Cr concentration but the lowest Co concentration. The presence of carbide inclusions in the alloy did not affect the corrosion or the dissolution mechanisms, although the carbides were a significant feature on the metal surface. Only one mechanism was recognized as controlling the thickness of the oxide/hydroxide interface. The analysis of the dissolved metal showed two mechanisms at work: (1) a protein film caused ligand-induced dissolution, increasing the Cr concentration in synovial fluid, and was explained by the equilibrium constants; (2) corrosion at the interface increased the Co in PBS. The effect of prepassivating the samples (ASTM F-86-01) did not always have the desired effect of reducing dissolution. The release of Cr into PBS increased after prepassivation. The metal-synovial fluid interface did not contain calcium phosphate as a deposit, typically found where samples are exposed to calcium rich bodily fluids.