ALBERT

Description: Photochemical reactions represent the main pathway for the removal of non-methane volatile organic compounds (VOCs) in the atmosphere. VOCs may react with hydroxyl radical (OH), the most important atmospheric oxidant, or they can be photolyzed by actinic radiation. In the presence of clouds and fog, VOCs may partition into the aqueous phase where they can undergo aqueous photolysis and/or reaction with dissolved OH. The significance of direct aqueous photolysis is largely uncertain due to the lack of published absorption cross sections and photolysis quantum yields. In light of this, we strive to identify atmospherically relevant VOCs where removal by aqueous photolysis may be a significant sink. The relative importance of different photochemical sinks is assessed by calculating the ratios of the removal rates inside air parcels containing cloud and fog droplets. This relative approach provides useful information in spite of the limited aqueous photolysis data. Results of this work should help guide researchers in identifying molecules that are the most likely to undergo aqueous OH oxidation and photolysis. For example, we find that out of the 27 atmospherically relevant species investigated, the removal of glyceraldehyde and pyruvic acid by aqueous photolysis is potentially an important sink. We also determine the relative magnitudes of these four chemical sinks for the set of relevant organic compounds.

Description: Photochemical reactions represent the main pathway for the removal of non-methane volatile organic compounds (VOCs) in the atmosphere. VOCs may react with hydroxyl radical (OH), the most important atmospheric oxidant, or they can be photolyzed by actinic radiation. In the presence of clouds and fog, VOCs may partition into the aqueous phase where they can undergo aqueous photolysis and/or reaction with dissolved OH. The significance of direct aqueous photolysis is largely uncertain due to the lack of published absorption cross sections and photolysis quantum yields. In light of this, we strive to identify atmospherically relevant VOCs where removal by aqueous photolysis may be a significant sink. The relative importance of different photochemical sinks is assessed by calculating the ratios of the removal rates inside air parcels containing cloud and fog droplets. This relative approach provides useful information in spite of the limited aqueous photolysis data. Results of this work should help guide researchers in identifying molecules that are the most likely to undergo aqueous OH oxidation and photolysis. We find that out of the 27 atmospherically relevant species investigated, the removal of glyceraldehyde and pyruvic acid by aqueous photolysis is potentially an important sink. We also determine the relative magnitudes of these four chemical sinks for the set of relevant organic compounds.

Description: In topographically complex watersheds, landscape position and vegetation heterogeneity can alter the soil water regime through both lateral and vertical redistribution, respectively. These alterations of soil moisture may have significant impacts on the spatial heterogeneity of biogeochemical cycles throughout the watershed. To evaluate how landscape position and vegetation heterogeneity affect soil CO2 efflux (FSOIL) we conducted observations across the Weimer Run watershed (373 ha), located near Davis, West Virginia, for three growing seasons with varying precipitation (2010 – 1042 mm; 2011 – 1739 mm; 2012 – 1244 mm; precipitation data from BDKW2 station, MesoWest, University of Utah). An apparent soil temperature threshold of 11 °C at 12 cm depth on FSOIL was observed in our data – where FSOIL rates greatly increase in variance above this threshold. For analysis, FSOIL values above this threshold were isolated and examined. Differences in FSOIL among years were apparent by elevation (F4,633 = 3.17; p = 0.013) and by vegetation cover (F4, 633 = 2.96; p = 0.019). For the Weimer Run watershed, vegetation exerts the major control on soil CO2 efflux (FSOIL), with the plots beneath shrubs at all elevations for all years showing the greatest mean rates of FSOIL (6.07 μmol CO2 m-2 s-1) compared to plots beneath closed-forest canopy (4.69 μmol CO2 m-2 s-1) and plots located in open, forest gaps (4.09 μmol CO2 m-2 s-1) plots. During periods of high soil moisture, we find that CO2 efflux rates are constrained and that maximum efflux rates in this system occur during periods of average to below average soil water availability. These findings offer valuable insight into the processes occurring within these topographically complex, temperate and humid systems, and the interactions of abiotic and biotic factors mediating biogeochemical cycles. With possible changing rainfall patterns as predicted by climate models, it is important to understand the couplings between water and carbon cycling at the watershed and landscape scales, and their potential dynamics under global change scenarios.