M. L. Alexander

Effect of hydrophilic organic seed aerosols on secondary organic aerosol formation from ozonolysis of α-pinene.

Gas-particle partitioning theory is widely used in atmospheric models to predict organic aerosol loadings. This theory predicts that secondary organic aerosol (SOA) yield of an oxidized volatile organic compound product will increase as the mass loading of preexisting organic aerosol increases. In a previous work, we showed that the presence of model hydrophobic primary organic aerosol (POA) had no detectable effect on the SOA yields from ozonolysis of α-pinene, suggesting that the condensing SOA compounds form a separate phase from the preexisting POA. However, a substantial faction of atmospheric aerosol is composed of polar, hydrophilic organic compounds. In this work, we investigate the effects of model hydrophilic organic aerosol (OA) species such as fulvic acid, adipic acid, and citric acid on the gas-particle partitioning of SOA from α-pinene ozonolysis. The results show that only citric acid seed significantly enhances the absorption of α-pinene SOA into the particle-phase. The other two seed particles have a negligible effect on the α-pinene SOA yields, suggesting that α-pinene SOA forms a well-mixed organic aerosol phase with citric acid and a separate phase with adipic acid and fulvic acid. This finding highlights the need to improve the thermodynamics treatment of organics in current aerosol models that simply lump all hydrophilic organic species into a single phase, thereby potentially introducing an erroneous sensitivity of SOA mass to emitted OA species.

A capillary absorption spectrometer for stable carbon isotope ratio (13C/12C) analysis in very small samples

A capillary absorption spectrometer (CAS) suitable for IR laser isotope analysis of small CO(2) samples is presented. The system employs a continuous-wave (cw) quantum cascade laser to study nearly adjacent rovibrational transitions of different isotopologues of CO(2) near 2307 cm(-1) (4.34 μm). This initial CAS system can achieve relative isotopic precision of about 10 ppm (13)C, or ∼1 per thousand (per mil in delta notation relative to Vienna Pee Dee Belemnite) with 20-100 picomoles of entrained sample within the hollow waveguide for CO(2) concentrations ∼400-750 ppm. Isotopic analyses of such gas fills in a 1-mm ID hollow waveguide of 0.8 m overall physical path length can be carried out down to ∼2 Torr. Overall (13)C∕(12)C ratios can be calibrated to ∼2 per thousand accuracy with diluted CO(2) standards. A novel, low-cost method to reduce cw-fringing noise resulting from multipath distortions in the hollow waveguide is presented, which allows weak absorbance features to be studied at the few ppm level (peak-to-rms) after 1000 scans are co-added in ∼10 s. The CAS is meant to work directly with converted CO(2) samples from a laser ablation-catalytic combustion micro-sampler to provide (13)C∕(12)C ratios of small biological isolates currently operating with spatial resolutions ∼50 μm.