The use of disjunct eddy sampling methods for the determination of ecosystem level fluxes of trace gases

The concept of disjunct eddy sampling (DES) for use in measuring ecosystem-level micrometeorological fluxes is re-examined. The governing equations are discussed as well as other practical considerations and guidelines concerning this sampling method as it is applied to either the disjunct eddy covariance (DEC) or disjunct eddy accumulation (DEA) techniques. A disjunct eddy sampling system was constructed that could either be combined with relatively slow sensors (response time of 2 to 40 s) to measure fluxes using DEC, or could also be used to accumulate samples in stable reservoirs for later laboratory analysis (DEA technique). Both the DEC and DEA modes of this sampler were tested against conventional eddy covariance (EC) for fluxes of either CO2 (DEC) or isoprene (DEA). Good agreement in both modes was observed relative to the EC systems. However, the uncertainty in a single DEA flux measurement was considerable (40%) due to both the reduced statistical sampling and the analytical precision of the concentration difference measurements. We have also re-investigated the effects of nonzero mean vertical wind velocity on accumulation techniques as it relates to our DEA measurements. Despite the higher uncertainty, disjunct eddy sampling can provide an alternative technique to eddy covariance for determining ecosystem-level fluxes for species where fast sensors do not currently exist

A steady-state continuous flow chamber for the study of daytime and nighttime chemistry under atmospherically relevant NO levels

Experiments performed in laboratory chambers have contributed significantly to the understanding of the fundamental kinetics and mechanisms of the chemical reactions occurring in the atmosphere. Two chemical regimes, classified as high-NO vs. zero-NO conditions, have been extensively studied in previous chamber experiments. Results derived from these two chemical scenarios are widely parameterized in chemical transport models to represent key atmospheric processes in urban and pristine environments. As the anthropogenic NO_x emissions in the United States have decreased remarkably in the past few decades, the classic high-NO and zero-NO conditions are no longer applicable to many regions that are constantly impacted by both polluted and background air masses. We present here the development and characterization of the NCAR Atmospheric Simulation Chamber, which is operated in steady-state continuous flow mode for the study of atmospheric chemistry under intermediate NO conditions. This particular chemical regime is characterized by constant sub-ppb levels of NO and can be created in the chamber by precise control of the inflow NO concentration and the ratio of chamber mixing to residence timescales. Over the range of conditions achievable in the chamber, the lifetime of peroxy radicals (RO_2), a key intermediate from the atmospheric degradation of volatile organic compounds (VOCs), can be extended to several minutes, and a diverse array of reaction pathways, including unimolecular pathways and bimolecular reactions with NO and HO_2, can thus be explored. Characterization experiments under photolytic and dark conditions were performed and, in conjunction with model predictions, provide a basis for interpretation of prevailing atmospheric processes in environments with intertwined biogenic and anthropogenic activities. We demonstrate the proof of concept of the steady-state continuous flow chamber operation through measurements of major first-generation products, methacrolein (MACR) and methyl vinyl ketone (MVK), from OH- and NO_3- initiated oxidation of isoprene

A steady-state continuous flow chamber for the study of daytime and nighttime chemistry under atmospherically relevant NO levels

Experiments performed in laboratory chambers have contributed significantly to the understanding of the fundamental kinetics and mechanisms of the chemical reactions occurring in the atmosphere. Two chemical regimes, classified as high-NO vs. zero-NO conditions, have been extensively studied in previous chamber experiments. Results derived from these two chemical scenarios are widely parameterized in chemical transport models to represent key atmospheric processes in urban and pristine environments. As the anthropogenic NO_x emissions in the United States have decreased remarkably in the past few decades, the classic high-NO and zero-NO conditions are no longer applicable to many regions that are constantly impacted by both polluted and background air masses. We present here the development and characterization of the NCAR Atmospheric Simulation Chamber, which is operated in steady-state continuous flow mode for the study of atmospheric chemistry under intermediate NO conditions. This particular chemical regime is characterized by constant sub-ppb levels of NO and can be created in the chamber by precise control of the inflow NO concentration and the ratio of chamber mixing to residence timescales. Over the range of conditions achievable in the chamber, the lifetime of peroxy radicals (RO_2), a key intermediate from the atmospheric degradation of volatile organic compounds (VOCs), can be extended to several minutes, and a diverse array of reaction pathways, including unimolecular pathways and bimolecular reactions with NO and HO_2, can thus be explored. Characterization experiments under photolytic and dark conditions were performed and, in conjunction with model predictions, provide a basis for interpretation of prevailing atmospheric processes in environments with intertwined biogenic and anthropogenic activities. We demonstrate the proof of concept of the steady-state continuous flow chamber operation through measurements of major first-generation products, methacrolein (MACR) and methyl vinyl ketone (MVK), from OH- and NO_3- initiated oxidation of isoprene

Airborne Flux Measurements of BVOCs above Californian Oak Forests: Experimental Investigation of Surface and Entrainment Fluxes, OH Densities, and Damköhler Numbers

The article of record as published may be located at http://dx.doi.org/10.1175/JAS-D-13-054.1Airborne flux measurements of isoprene were performed over the Californian oak belts surrounding the Central Valley. The authors demonstrate for the first time 1) the feasibility of airborne eddy covariance measurements of reactive biogenic volatile organic compounds; 2) the effect of chemistry on the vertical transport of reactive species, such as isoprene; and 3) the applicability of wavelet analysis to estimate regional fluxes of biogenic volatile organic compounds. These flux measurements demonstrate that instrumentation operating at slower response times (e.g., 1–5 s) can still be used to determine eddy covariance fluxes in the mixed layer above land, where typical length scales of 0.5–3km were observed. Flux divergence of isoprene measured in the planetary boundary layer (PBL) is indicative of OH densities in the range of 4–7 3 106 molecules per cubic centimeter and allows extrapolation of airborne fluxes to the surface with Damk€ohler numbers (ratio between the mixing time scale and the chemical time scale) in the range of 0.3–0.9. Most of the isoprene is oxidized in the PBL with entrainment fluxes of about 10% compared to the corresponding surface fluxes. Entrainment velocities of 1–10 cm s21 were measured. The authors present implications for parameterizing PBL schemes of reactive species in regional and global models

Airborne flux measurements of bvocs above californian oak forests: Experimental investigation of surface and entrainment fluxes, OH densities, and damköhler numbers

Airborne flux measurements of isoprene were performed over the Californian oak belts surrounding the Central Valley. The authors demonstrate for the first time 1) the feasibility of airborne eddy covariance measurements of reactive biogenic volatile organic compounds; 2) the effect of chemistry on the vertical transport of reactive species, such as isoprene; and 3) the applicability of wavelet analysis to estimate regional fluxes of biogenic volatile organic compounds. These flux measurements demonstrate that instrumentation operating at slower response times (e.g., 1-5 s) can still be used to determine eddy covariance fluxes in the mixed layer above land, where typical length scales of 0.5-3km were observed. Flux divergence of isoprene measured in the planetary boundary layer (PBL) is indicative of OH densities in the range of 4-7 3 106 molecules per cubic centimeter and allows extrapolation of airborne fluxes to the surface with Damköhler numbers (ratio between the mixing time scale and the chemical time scale) in the range of 0.3-0.9. Most of the isoprene is oxidized in the PBL with entrainment fluxes of about 10% compared to the corresponding surface fluxes. Entrainment velocities of 1-10 cm s21 were measured. The authors present implications for parameterizing PBL schemes of reactive species in regional and global models. © 2013 American Meteorological Society

A steady-state continuous flow chamber for the study of daytime and nighttime chemistry under atmospherically relevant NO levels

Experiments performed in laboratory chambers have contributed significantly to the understanding of the fundamental kinetics and mechanisms of the chemical reactions occurring in the atmosphere. Two chemical regimes, classified as high-NO vs. zero-NO conditions, have been extensively studied in previous chamber experiments. Results derived from these two chemical scenarios are widely parameterized in chemical transport models to represent key atmospheric processes in urban and pristine environments. As the anthropogenic NOx emissions in the United States have decreased remarkably in the past few decades, the classic high-NO and zero-NO conditions are no longer applicable to many regions that are constantly impacted by both polluted and background air masses. We present here the development and characterization of the NCAR Atmospheric Simulation Chamber, which is operated in steady-state continuous flow mode for the study of atmospheric chemistry under intermediate NO conditions. This particular chemical regime is characterized by constant sub-ppb levels of NO and can be created in the chamber by precise control of the inflow NO concentration and the ratio of chamber mixing to residence timescales. Over the range of conditions achievable in the chamber, the lifetime of peroxy radicals (RO2), a key intermediate from the atmospheric degradation of volatile organic compounds (VOCs), can be extended to several minutes, and a diverse array of reaction pathways, including unimolecular pathways and bimolecular reactions with NO and HO2, can thus be explored. Characterization experiments under photolytic and dark conditions were performed and, in conjunction with model predictions, provide a basis for interpretation of prevailing atmospheric processes in environments with intertwined biogenic and anthropogenic activities. We demonstrate the proof of concept of the steady-state continuous flow chamber operation through measurements of major first-generation products, methacrolein (MACR) and methyl vinyl ketone (MVK), from OH- and NO3-initiated oxidation of isoprene

The use of disjunct eddy sampling methods for the determination of ecosystem level fluxes of trace gases

The concept of disjunct eddy sampling (DES) for use in measuring ecosystem-level micrometeorological fluxes is re-examined. The governing equations are discussed as well as other practical considerations and guidelines concerning this sampling method as it is applied to either the disjunct eddy covariance (DEC) or disjunct eddy accumulation (DEA) techniques. A disjunct eddy sampling system was constructed that could either be combined with relatively slow sensors (response time of 2 to 40 s) to measure fluxes using DEC, or could also be used to accumulate samples in stable reservoirs for later laboratory analysis (DEA technique). Both the DEC and DEA modes of this sampler were tested against conventional eddy covariance (EC) for fluxes of either CO2 (DEC) or isoprene (DEA). Good agreement in both modes was observed relative to the EC systems. However, the uncertainty in a single DEA flux measurement was considerable (∼40%) due to both the reduced statistical sampling and the analytical precision of the concentration difference measurements. We have also re-investigated the effects of nonzero mean vertical wind velocity on accumulation techniques as it relates to our DEA measurements. Despite the higher uncertainty, disjunct eddy sampling can provide an alternative technique to eddy covariance for determining ecosystem-level fluxes for species where fast sensors do not currently exist