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A. J. Huisman,
J. R. Hottle,
M. M. Galloway,
J. P. DiGangi,
K. L. Coens,
W. Choi,
I. C. Faloona,
J. B. Gilman,
W. C. Kuster,
J. Gouw de, [......],
R. C. Cohen, G. M. Wolfe,
J. A. Thornton,
K. S. Docherty,
D. K. Farmer,
M. J. Cubison,
J. L. Jimenez,
J. Mao,
W. H. Brune,
F. N. Keutsch
Atmos. Chem. Phys. 01/2011; 11(17):8883-8897.
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G. M. Wolfe,
J. A. Thornton,
N. C. Bouvier-Brown,
A. H. Goldstein,
J. -H. Park,
M. McKay,
D. M. Matross,
J. Mao,
W. H. Brune,
B. W. LaFranchi, [......],
K. -E. Min,
P. J. Wooldridge,
R. C. Cohen,
J. D. Crounse,
I. C. Faloona,
J. B. Gilman,
W. C. Kuster,
J. A. Gouw de,
A. Huisman,
F. N. Keutsch
Atmos. Chem. Phys. 01/2011; 11(3):1269-1294.
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G. M. Wolfe,
J. A. Thornton,
N. C. Bouvier-Brown,
A. H. Goldstein,
Park J.-H,
McKay M,
D. M. Matross,
Mao J,
W. H. Brune,
B. W. LaFranchi, [......],
Min K.-E,
P. J. Wooldridge,
R. C. Cohen,
J. D. Crounse,
I. C. Faloona,
J. B. Gilman,
W. C. Kuster,
J. A. de Gouw,
Huisman A,
F. N. Keutsch
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ABSTRACT: In a companion paper, we introduced the Chemistry of Atmosphere-Forest Exchange (CAFE) model, a vertically-resolved 1-D chemical transport model designed to probe the details of near-surface reactive gas exchange. Here, we apply CAFE to noontime observations from the 2007 Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX-2007). In this work we evaluate the CAFE modeling approach, demonstrate the significance of in-canopy chemistry for forest-atmosphere exchange and identify key shortcomings in the current understanding of intra-canopy processes. CAFE generally reproduces BEARPEX-2007 observations but requires an enhanced radical recycling mechanism to overcome a factor of 6 underestimate of hydroxyl (OH) concentrations observed during a warm (~29 °C) period. Modeled fluxes of acyl peroxy nitrates (APN) are quite sensitive to gradients in chemical production and loss, demonstrating that chemistry may perturb forest-atmosphere exchange even when the chemical timescale is long relative to the canopy mixing timescale. The model underestimates peroxy acetyl nitrate (PAN) fluxes by 50% and the exchange velocity by nearly a factor of three under warmer conditions, suggesting that near-surface APN sinks are underestimated relative to the sources. Nitric acid typically dominates gross dry N deposition at this site, though other reactive nitrogen (NOy) species can comprise up to 28% of the N deposition budget under cooler conditions. Upward NO2 fluxes cause the net above-canopy NOy flux to be ~30% lower than the gross depositional flux. CAFE under-predicts ozone fluxes and exchange velocities by ~20%. Large uncertainty in the parameterization of cuticular and ground deposition precludes conclusive attribution of non-stomatal fluxes to chemistry or surface uptake. Model-measurement comparisons of vertical concentration gradients for several emitted species suggests that the lower canopy airspace may be only weakly coupled with the upper canopy. Future efforts to model forest-atmosphere exchange will require a more mechanistic understanding of non-stomatal deposition and a more thorough characterization of in-canopy mixing processes.
Atmospheric Chemistry and Physics. 01/2011;
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Choi W,
I. C. Faloona,
N. C. Bouvier-Brown,
McKay M,
A. H. Goldstein,
Mao J,
W. H. Brune,
B. W. LaFranchi,
R. C. Cohen, G. M. Wolfe,
J. A. Thornton,
D. M. Sonnenfroh,
D. B. Millet
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ABSTRACT: To better understand the processing of biogenic VOCs (BVOCs) in the pine forests of the US Sierra Nevada, we measured HCHO at Blodgett Research Station using Quantum Cascade Laser Spectroscopy (QCLS) during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) of late summer 2007. Four days of the experiment exhibited particularly copious HCHO, with midday peaks between 15–20 ppbv, while the other days developed delayed maxima between 8–14 ppbv in the early evening. From the expansive photochemical data set, we attempt to explain the observed HCHO concentrations by quantifying the various known photochemical production and loss terms in its chemical budget. Overall, known chemistry predicts a factor of 3–5 times less HCHO than observed. By examining diurnal patterns of the various budget terms we conclude that, during the high HCHO period, local, highly reactive oxidation chemistry produces an abundance of formaldehyde at the site. The results support the hypothesis of previous work at Blodgett Forest suggesting that large quantities of oxidation products, observed directly above the ponderosa pine canopy, are evidence of profuse emissions of very reactive volatile organic compounds (VR-VOCs) from the forest. However, on the majority of days, under generally cooler and more moist conditions, lower levels of HCHO develop primarily influenced by the influx of precursors transported into the region along with the Sacramento plume.
Atmospheric Chemistry and Physics. 01/2010;
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ABSTRACT: We present the Chemistry of Atmosphere-Forest Exchange (CAFE) model, a vertically-resolved 1-D chemical transport model designed to probe the details of near-surface reactive gas exchange. CAFE integrates all key processes, including turbulent diffusion, emission, deposition and chemistry, throughout the forest canopy and mixed layer. It is the first model of its kind to incorporate the Master Chemical Mechanism (MCM) and a suite of reactions for the oxidation of monoterpenes and sesquiterpenes, providing a more comprehensive description of the oxidative chemistry occurring within and above the forest. We use CAFE to simulate a young Ponderosa pine forest in the Sierra Nevada, CA. Utilizing meteorological constraints from the BEARPEX-2007 field campaign, we assess the sensitivity of modeled fluxes to parameterizations of diffusion, laminar sublayer resistance and radiation extinction. To characterize the general chemical environment of this forest, we also present modeled mixing ratio profiles of biogenic hydrocarbons, hydrogen oxides and reactive nitrogen. The vertical profiles of these species demonstrate a range of structures and gradients that reflect the interplay of physical and chemical processes within the forest canopy, which can influence net exchange.
Atmospheric Chemistry and Physics Discussions. 01/2010;
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P. J. Wooldridge,
A. E. Perring,
T. H. Bertram,
F. M. Flocke,
J. M. Roberts,
H. B. Singh,
L. G. Huey,
J. A. Thornton, G. M. Wolfe,
J. G. Murphy,
J. L. Fry,
A. W. Rollins,
B. W. LaFranchi,
R. C. Cohen
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ABSTRACT: Peroxyacetyl nitrate (PAN) and its chemical analogues are increasingly being quantified in the ambient atmosphere by thermal dissociation (TD) followed by detection of either the peroxyacyl radical or the NO<sub>2</sub> product. Here we present details of the technique developed at University of California, Berkeley which detects the sum of all peroxynitrates (ΣPNs) via laser-induced fluorescence (LIF) of the NO<sub>2</sub> product. We review the various deployments and compare the Berkeley ΣPNs measurements with the sums of PAN and its homologue species detected individually by other instruments. The observed TD-LIF ΣPNs usually agree to within 10% with the summed individual species, thus arguing against the presence of significant concentrations of unmeasured PAN-type compounds in the atmosphere, as suggested by some photochemical mechanisms. Examples of poorer agreement are attributed to a sampling inlet design that is shown to be inappropriate for high NO<sub>x</sub> conditions. Interferences to the TD-LIF measurements are described along with strategies to minimize their effects.
Atmospheric Measurement Techniques. 01/2010;
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ABSTRACT: Interannual variations in background tropospheric trace gases (such as carbon monoxide, CO) are largely driven by variations in emissions (especially wildfires) and transport pathways. Understanding this variability is essential to quantify the intercontinental contribution to US air quality. We investigate the interannual variability of long-range transport of Asian pollutants to the Northeast Pacific via measurements from the Mt. Bachelor Observatory (MBO: 43.98° N, 121.69° W; 2.7 km a.s.l.) and GEOS-Chem chemical transport model simulations in spring 2005 vs. the INTEX-B campaign during spring 2006. Measurements of CO at MBO were significantly enhanced during spring 2005 relative to the same time in 2006 (the INTEX-B study period); a decline in monthly mean CO of 41 ppbv was observed between April 2005 and April 2006. A backtrajectory-based meteorological index shows that long-range transport of CO from the heavily industrialized region of East Asia was significantly greater in early spring 2005 than in 2006. In addition, spring 2005 was an anomalously strong biomass burning season in Southeast Asia. Data presented by Yurganov et al. (2008) using MOPITT satellite retrievals from this area reveal an average CO burden anomaly (referenced to March 2000–February 2002 mean values) between October 2004 through April 2005 of 2.6 Tg CO vs. 0.6 Tg CO for the same period a year later. The Naval Research Laboratory's global aerosol transport model, as well as winds from NCEP reanalysis, show that emissions from these fires were efficiently transported to MBO throughout April 2005. Asian dust transport, however, was substantially greater in 2006 than 2005, particularly in May. Monthly mean aerosol light scattering coefficient at 532 nm (σsp) at MBO more than doubled from 2.7 Mm−1 in May 2005 to 6.2 Mm−1 in May 2006. We also evaluate CO interannual variability throughout the western US via Earth System Research Laboratory ground site data and throughout the Northern Hemisphere via MOPITT and TES satellite observations. Both in the Northeast Pacific and on larger scales, we reveal a significant decrease (from 2–21%) in springtime maximum CO between 2005 and 2006, evident in all platforms and the GEOS-Chem model. We attribute this to (a) anomalously strong biomass burning in Southeast Asia during winter 2004 through spring 2005, and (b) the transport pattern in March and April 2006 which limited the inflow of Asian pollution to the lower free troposphere over western North America.
Atmospheric Chemistry and Physics. 01/2009;
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ABSTRACT: During the Biosphere Effects on AeRosols and Photochemistry EXperiment 2007 (BEARPEX-2007), we observed eddy covariance (EC) fluxes of speciated acyl peroxy nitrates (APNs), including peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN) and peroxymethacryloyl nitrate (MPAN), above a Ponderosa pine forest in the western Sierra Nevada. All APN fluxes are net downward during the day, with a median midday PAN exchange velocity of −0.3 cm s−1; nighttime storage-corrected APN EC fluxes are smaller than daytime fluxes but still downward. Analysis with a standard resistance model shows that loss of PAN to the canopy is not controlled by turbulent or molecular diffusion. Stomatal uptake can account for 25 to 50% of the observed downward PAN flux. Vertical gradients in the PAN thermal decomposition (TD) rate explain a similar fraction of the flux, suggesting that a significant portion of the PAN flux into the forest results from chemical processes in the canopy. The remaining "unidentified" portion of the net PAN flux (~15%) is ascribed to deposition or reactive uptake on non-stomatal surfaces (e.g. leaf cuticles or soil). Shifts in temperature, moisture and ecosystem activity during the summer – fall transition alter the relative contribution of stomatal uptake, non-stomatal uptake and thermochemical gradients to the net PAN flux. Daytime PAN and MPAN exchange velocities are a factor of 3 smaller than those of PPN during the first two weeks of the measurement period, consistent with strong intra-canopy chemical production of PAN and MPAN during this period. Depositional loss of APNs can be 3–21% of the gross gas-phase TD loss depending on temperature. As a source of nitrogen to the biosphere, PAN deposition represents approximately 4–19% of that due to dry deposition of nitric acid at this site.
Atmospheric Chemistry and Physics. 01/2009;
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B. W. LaFranchi, G. M. Wolfe,
J. A. Thornton,
S. A. Harrold,
E. C. Browne,
K. E. Min,
P. J. Wooldridge,
J. B. Gilman,
W. C. Kuster,
P. D. Goldan,
J. A. deGouw,
McKay M,
A. H. Goldstein,
Ren X,
Mao J,
R. C. Cohen
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ABSTRACT: Acyl peroxy nitrates (APNs, also known as PANs) are formed from the oxidation of aldehydes and other oxygenated VOC (oVOC) in the presence of NO2. Formation of APNs suppresses NOx (NOx≡NO+NO2) in urban areas and enhances NOx downwind in urban plumes, increasing the rate of ozone production throughout an urban plume. APNs also redistribute NOx on global scales, enhancing NOx and thus ozone production. There are both anthropogenic and biogenic oVOC precursors to APNs, but a detailed evaluation of their chemistry against observations has proven elusive. Here we describe measurements of PAN, PPN, and MPAN along with the majority of chemicals that participate in their production and loss, including OH, HO2, numerous oVOC, and NO2. Observations were made during the Biosphere Effects on AeRosols and Photochemistry Experiment (BEARPEX 2007) in the outflow of the Sacramento urban plume. These observations are used to evaluate a detailed chemical model of APN ratios and concentrations. We find the ratios of APNs are nearly independent of the loss mechanisms and thus an especially good test of our understanding of their sources. We show that oxidation of methylvinyl ketone, methacrolein, methyl glyoxal, biacetyl and acetaldehyde are all significant sources of the PAN+peroxy acetyl (PA) radical reservoir, with methylvinyl ketone (MVK) often being the primary non-acetaldehyde source. At high temperatures, oxidation of non-acetaldehyde PA radical sources contributes over 60% to the total PA production rate. An analysis of absolute APN concentrations reveals a missing APN sink that can be resolved by increasing the PA+∑RO2 rate constant by a factor of 3.
Atmospheric Chemistry and Physics Discussions. 01/2009;
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B. W. LaFranchi, G. M. Wolfe,
J. A. Thornton,
S. A. Harrold,
E. C. Browne,
K. E. Min,
P. J. Wooldridge,
J. B. Gilman,
W. C. Kuster,
P. D. Goldan,
J. A. de Gouw,
McKay M,
A. H. Goldstein,
Ren X,
Mao J,
R. C. Cohen
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ABSTRACT: Acyl peroxy nitrates (APNs, also known as PANs) are formed from the oxidation of aldehydes and other oxygenated VOC (oVOC) in the presence of NO2. There are both anthropogenic and biogenic oVOC precursors to APNs, but a detailed evaluation of this chemistry against observations has proven elusive. Here we describe measurements of PAN, PPN, and MPAN along with the majority of chemicals that participate in their production and loss, including OH, HO2, numerous oVOC, and NO2. Observations were made during the Biosphere Effects on AeRosols and Photochemistry Experiment (BEARPEX 2007) in the outflow of the Sacramento urban plume. These observations are used to evaluate a detailed chemical model of APN ratios and concentrations. We find that the ratios of APNs are nearly independent of the loss mechanisms and thus an especially good test of our understanding of their sources. We show that oxidation of methylvinyl ketone, methacrolein, methyl glyoxal, biacetyl and acetaldehyde are all significant sources of the PAN+peroxy acetyl (PA) radical reservoir, accounting for 26%, 2%, 7%, 20%, and 45%, of the production rate on average during the campaign, respectively. At high temperatures, when upwind isoprene emissions are highest, oxidation of non-acetaldehyde PA radical sources contributes over 60% to the total PA production rate, with methylvinyl ketone being the most important of the isoprene-derived sources. An analysis of absolute APN concentrations reveals a missing APN sink that can be resolved by increasing the PA+∑RO2 rate constant by a factor of 3.
Atmospheric Chemistry and Physics. 01/2009;
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ABSTRACT: We present month-long observations of speciated acyl peroxy nitrates (APNs), including PAN, PPN, MPAN, APAN, and the sum of PiBN and PnBN, measured at the Mount Bachelor Observatory (MBO) as part of the INTEX-B collaborative field campaign during spring 2006. APN abundances, measured by thermal dissociation-chemical ionization mass spectrometry (TD-CIMS), are discussed in terms of differing contributions from the boundary layer (BL) and the free troposphere (FT) and in the context of previous APN measurements in the NE Pacific region. PAN mixing ratios range from 11 to 3955 pptv, with a mean value of 334 pptv for the full measurement period. PPN is linearly correlated with PAN (r2=0.96), with an average abundance of 6.5% relative to PAN; other APNs are generally <1% of PAN. Diurnal cycles and relationships of APNs with ozone reveal a gradient in hydrocarbon chemistry between the BL and the FT. On average, levels of APNs, ozone and PPN/PAN are substantially higher in FT air relative to BL air, suggesting that this site is strongly influenced by distant pollution sources. To estimate the impact of long-range transport of Asian pollution on atmospheric composition at MBO, we perform a detailed analysis utilizing HYSPLIT back trajectories. This analysis suggests that trans-Pacific transport of Asian pollution leads to substantial increases in APN and ozone mixing ratios at MBO, especially when transport occurs via the free troposphere. The ensemble of trajectories indicate that Asian-influenced free tropospheric air was sampled in ~16% of our data and contained a median PAN mixing ratio double that of the full dataset.
Atmospheric Chemistry and Physics. 01/2007;
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ABSTRACT: Recent observations have detected surface active organics in atmospheric aerosols. We have studied the reaction of N<sub>2</sub>O<sub>5</sub> on aqueous natural seawater and NaCl aerosol as a function of sodium dodecyl sulfate (SDS) concentration to test the effect of varying levels of surfactant on gas-aerosol reaction rates. SDS was chosen as a proxy for naturally occurring long chain monocarboxylic acid molecules, such as palmitic or stearic acid, because of its solubility in water and well-characterized surface properties. Experiments were performed using a newly constructed aerosol flow tube coupled to a chemical ionization mass spectrometer for monitoring the gas phase, and a differential mobility analyzer/condensation particle counter for determining aerosol surface area. We find that the presence of ~3.5 wt% SDS in the aerosol, which corresponds to a monolayer surface coverage of ~2×10<sup>14</sup> molecules cm<sup>−2</sup>, suppresses the N<sub>2</sub>O<sub>5</sub> reaction probability, γ<sup>N2O5</sup>, by approximately a factor of ten, independent of relative humidity. Consistent with this observation is a similar reduction in the rate of ClNO<sub>2</sub> product generation measured simultaneously. However, the product yield remains nearly constant under all conditions. The degree of suppression is strongly dependent on SDS content in the aerosol, with no discernable effect at 0.1 wt% SDS, but significant suppression at what we predict to be submonolayer coverages with 0.3–0.6 wt% SDS on NaCl and natural seawater aerosols, respectively.
Atmospheric Chemistry and Physics Discussions. 01/2006;
