Carbonyl sulfide (OCS): Large-scale distributions over North America during INTEX-NA and relationship to CO2

An extensive set of carbonyl sulfide (OCS) observations were made as part of the NASA Intercontinental Chemical Transport Experiment-North America (INTEX-NA) study, flown from 1 July to 14 August 2004 mostly over the eastern United States and Canada. These data show that summertime OCS mixing ratios at low altitude were dominated by surface drawdown and were highly correlated with CO2. Although local plumes were observed on some low-altitude flight legs, anthropogenic OCS sources were small compared to this sink. These INTEX-NA observations were in marked contrast to the early springtime 2001 Transport and Chemical Evolution over the Pacific experiment, which sampled Asian outflow dominated by anthropogenic OCS emissions. To test the gridded OCS fluxes used in past models, the INTEX-NA observations were combined with the sulfur transport Eulerian model (STEM) regional atmospheric chemistry model for a top-down assessment of bottom-up OCS surface fluxes for North America. Initial STEM results suggest that the modeled fluxes underestimate the OCS plant sink by more than 200%. Copyright 2008 by the American Geophysical Union

Surface-Enhanced Nitrate Photolysis on Ice

Heterogeneous nitrates photolysis is the trigger for many chemical processes occurring in the polar boundary layer and is widely believed to occur in a quasi-liquid layer (QLL) at the surface of ice. The dipole forbidden character of the electronic transition relevant to boundary layer atmospheric chemistry and the small photolysis/photoproducts quantum yields in ice (and in water) may confer a significant enhancement and interfacial specificity to this important photochemical reaction at the surface of ice. Using amorphous solid water films at cryogenic temperatures as models for the disordered interstitial air/ice interface within the snowpack suppresses the diffusive uptake kinetics thereby prolonging the residence time of nitrate anions at the surface of ice. This approach allows their slow heterogeneous photolysis kinetics to be studied providing the first direct evidence that nitrates adsorbed onto the first molecular layer at the surface of ice are photolyzed more effectively than those dissolved within the bulk. Vibrational spectroscopy allows the ~3-fold enhancement in photolysis rates to be correlated with the nitrates’ distorted intramolecular geometry thereby hinting at the role played by the greater chemical heterogeneity in their solvation environment at the surface of ice than in the bulk. A simple 1D kinetic model suggests 1-that a 3(6)-fold enhancement in photolysis rate for nitrates adsorbed onto the ice surface could increase the photochemical NO[subscript 2] emissions from a 5(8) nm thick photochemically active interfacial layer by 30%(60)%, and 2-that 25%(40%) of the NO[subscript 2] photochemical emissions to the snowpack interstitial air are released from the top-most molecularly thin surface layer on ice. These findings may provide a new paradigm for heterogeneous (photo)chemistry at temperatures below those required for a QLL to form at the ice surface

Ultrafast photochemistry of methyl hydroperoxide on ice particles

Simulations show that photodissociation of methyl hydroperoxide, CH3OOH, on water clusters produces a surprisingly wide range of products on a subpicosecond time scale, pointing to the possibility of complex photodegradation pathways for organic peroxides on aerosols and water droplets. Dynamics are computed at several excitation energies at 50 K using a semiempirical PM3 potential surface. CH3OOH is found to prefer the exterior of the cluster, with the CH3O group sticking out and the OH group immersed within the cluster. At atmospherically relevant photodissociation wavelengths the OH and CH3O photofragments remain at the surface of the cluster or embedded within it. However, none of the 25 completed trajectories carried out at the atmospherically relevant photodissociation energies led to recombination of OH and CH3O to form CH3OOH. Within the limited statistics of the available trajectories the predicted yield for the recombination is zero. Instead, various reactions involving the initial fragments and water promptly form a wide range of stable molecular products such as CH2O, H2O, H2, CO, CH3OH, and H2O2

Carbonyl sulfide (OCS): Large-scale distributions over North America during INTEX-NA and relationship to CO2

An extensive set of carbonyl sulfide (OCS) observations were made as part of the NASA Intercontinental Chemical Transport Experiment-North America (INTEX-NA) study, flown from 1 July to 14 August 2004 mostly over the eastern United States and Canada. These data show that summertime OCS mixing ratios at low altitude were dominated by surface drawdown and were highly correlated with CO2. Although local plumes were observed on some low-altitude flight legs, anthropogenic OCS sources were small compared to this sink. These INTEX-NA observations were in marked contrast to the early springtime 2001 Transport and Chemical Evolution over the Pacific experiment, which sampled Asian outflow dominated by anthropogenic OCS emissions. To test the gridded OCS fluxes used in past models, the INTEX-NA observations were combined with the sulfur transport Eulerian model (STEM) regional atmospheric chemistry model for a top-down assessment of bottom-up OCS surface fluxes for North America. Initial STEM results suggest that the modeled fluxes underestimate the OCS plant sink by more than 200%. Copyright 2008 by the American Geophysical Union

Breath sulfides and pulmonary function in cystic fibrosis

We have determined the concentrations of carbonyl sulfide (OCS), dimethylsulfide, and carbon disulfide (CS(2)) in the breath of a group of cystic fibrosis (CF) patients and one of healthy controls. At the detection sensitivity in these experiments, room air always contained measurable quantities of these three gases. For each subject the inhaled room concentrations were subtracted from the time-coincident concentrations in exhaled breath air. The most significant differences between the CF and control cohorts in these breath-minus-room values were found for OCS. The control group demonstrated a net uptake of 250 ± 20 parts-per-trillion-by-volume (pptv), whereas the CF cohort had a net uptake of 110 ± 60 pptv (P = 0.00003). Three CF patients exhaled more OCS than they inhaled from the room. The OCS concentrations in the CF cohort were strongly correlated with pulmonary function. The dimethylsulfide concentrations in breath were greatly enhanced over ambient, but no significant difference was observed between the CF and healthy control groups. The net (breath minus room) CS(2) concentrations for individuals ranged between +180 and -100 pptv. They were slightly greater in the CF cohort (+26 ± 38 pptv) vs. the control group (-17 ± 15 pptv; P = 0.04). Lung disease in CF is accompanied by the subsistence of chronic bacterial infections. Sulfides are known to be produced by bacteria in various systems and were therefore the special target for this investigation. Our results suggest that breath sulfide content deserves attention as a noninvasive marker of respiratory colonization

Measuring Particulate Emissions of Light Duty Passenger Vehicles Using Integrated Particle Size Distribution (IPSD)

The California Air Resources Board (ARB) adopted the low emission vehicle (LEV) III particulate matter (PM) standards in January 2012, which require, among other limits, vehicles to meet 1 mg/mi over the federal test procedure (FTP). One possible alternative measurement approach evaluated to support the implementation of the LEV III standards is integrated particle size distribution (IPSD), which reports real-time PM mass using size distribution and effective density. The IPSD method was evaluated using TSI’s engine exhaust particle sizer (EEPS, 5.6–560 nm) and gravimetric filter data from more than 250 tests and 34 vehicles at ARB’s Haagen-Smit Laboratory (HSL). IPSD mass was persistently lower than gravimetric mass by 56–75% over the FTP tests and by 81–84% over the supplemental FTP (US06) tests. Strong covariance between the methods suggests test-to-test variability originates from actual vehicle emission differences rather than measurement accuracy, where IPSD offered no statistical improvement over gravimetric measurement variability