scholarly journals Methyl chavicol: characterization of its biogenic emission rate, abundance, and oxidation products in the atmosphere

2009 ◽  
Vol 9 (6) ◽  
pp. 2061-2074 ◽  
Author(s):  
N. C. Bouvier-Brown ◽  
A. H. Goldstein ◽  
D. R. Worton ◽  
D. M. Matross ◽  
J. B. Gilman ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Atmospheric Chemistry ◽  
Ponderosa Pine ◽  
Emission Rate ◽  
Oxidation Products ◽  
Ambient Atmosphere ◽  
Needle Age ◽  
Biogenic Emission ◽  
Methyl Chavicol ◽  
Mixing Ratios

Abstract. We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments – a gas chromatograph with mass spectrometer detector (GC-MS), a proton transfer reaction mass spectrometer (PTR-MS), and a thermal desorption aerosol GC-MS (TAG) – and found to be abundant within and above Blodgett Forest. Methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten-2-ol (MBO), a light- and temperature-dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4–68% of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72–10.2 μgCg−1 h−1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde) in the ambient atmosphere. Methyl chavicol is a major essential oil component of many plant species. This work suggests that methyl chavicol plays a significant role in the atmospheric chemistry of Blodgett Forest, and potentially other sites, and should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models.

scholarly journals Methyl chavicol: characterization of its biogenic emission rate, abundance, and oxidation products in the atmosphere

2008 ◽  
Vol 8 (6) ◽  
pp. 19707-19741 ◽  
Author(s):  
N. C. Bouvier-Brown ◽  
A. H. Goldstein ◽  
D. R. Worton ◽  
D. M. Matross ◽  
J. B. Gilman ◽  
...  
Keyword(s):  
Sierra Nevada ◽  
Atmospheric Chemistry ◽  
Ponderosa Pine ◽  
Emission Rate ◽  
Oxidation Products ◽  
Biogenic Emission ◽  
Methyl Chavicol ◽  
Mixing Ratios ◽  
Sierra Nevada Mountains ◽  
Ponderosa Pine Forest

Abstract. We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments – a gas chromatograph with mass spectrometer detector (GC-MS), a proton transfer reaction mass spectrometer (PTR-MS), and a thermal desorption aerosol GC-MS (TAG) – and found to be abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten-2-ol (MBO), a light- and temperature-dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4–68% of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72–10.2 μgCg−1h−1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde) in the ambient atmosphere. Methyl chavicol is a major essential oil component of many plant species. This work suggests that methyl chavicol plays a significant role in the atmospheric chemistry of Blodgett Forest, and potentially other sites, and should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models.

scholarly journals Mainz Isoprene Mechanism 2 (MIM2): an isoprene oxidation mechanism for regional and global atmospheric modelling

2008 ◽  
Vol 8 (4) ◽  
pp. 14033-14085 ◽  
Author(s):  
D. Taraborrelli ◽  
M. G. Lawrence ◽  
T. M. Butler ◽  
R. Sander ◽  
J. Lelieveld
Keyword(s):  
Atmospheric Chemistry ◽  
Oxidation Mechanism ◽  
Tropospheric Chemistry ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Good Representation ◽  
Chemical Production ◽  
Global Models ◽  
Mixing Ratios ◽  
Isoprene Oxidation

Abstract. We present an oxidation mechanism of intermediate size for isoprene (2-methyl-1,3-butadiene) suitable for simulations in regional and global atmospheric chemistry models, which we call MIM2. It is a reduction of the corresponding detailed mechanism in the Master Chemical Mechanism (MCM v3.1) and intended as the second version of the well-established Mainz Isoprene Mechanism (MIM). Our aim is to improve the representation of tropospheric chemistry in regional and global models under all NOx regimes. We evaluate MIM2 and re-evaluate MIM through comparisons with MCM v3.1. We find that MIM and MIM2 compute similar O3, OH and isoprene mixing ratios. Unlike MIM, MIM2 produces small relative biases for NOx and organic nitrogen-containing species due to a good representation of the alkyl and peroxy acyl nitrates (RONO2 and RC(O)OONO2). Moreover, MIM2 computes only small relative biases with respect to hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), methanol (CH3OH), formaldehyde (HCHO), peroxy acetyl nitrate (PAN), and formic and acetic acids (HCOOH and CH3C(O)OH), being always below ≈6% in all NOx scenarios studied. Most of the isoprene oxidation products are represented explicitly, including methyl vinyl ketone (MVK), methacrolein (MACR), hydroxyacetone and methyl glyoxal. MIM2 is mass-conserving with respect to carbon, including CO2 as well. Therefore, it is suitable for studies assessing carbon monoxide (CO) from biogenic sources, as well as for studies focused on the carbon cycle. Compared to MIM, MIM2 considers new species like acetaldehyde (CH3CHO), propene (CH2=CHCH3) and glyoxal (CHOCHO) with global chemical production rates for the year 2005 of 7.3, 9.5 and 33.8 Tg/yr, respectively. Our new mechanism is expected to substantially improve the results of atmospheric chemistry models by more accurately representing the interplay between atmospheric chemistry, transport and deposition, especially of nitrogen reservoir species. MIM2 allows regional and global models to easily incorporate new experimental results on the chemistry of organic species.

scholarly journals OH and HO<sub>2</sub> radical chemistry in a midlatitude forest: Measurements and model comparisons

2019 ◽  
Author(s):  
Michelle L. Lew ◽  
Pamela S. Rickly ◽  
Brandon P. Bottorff ◽  
Sofia Sklaveniti ◽  
Thierry Léonardis ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Global Climate ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Ozone Production ◽  
Peroxy Radicals ◽  
Mixing Ratios ◽  
Photolysis Rates ◽  
Model Predictions ◽  
Ho2 Radical

Abstract. Reactions of the hydroxyl (OH) and peroxy radicals (HO2 and RO2) play a central role in the chemistry of the atmosphere. In addition to controlling the lifetimes of many trace gases important to issues of global climate change, OH radical reactions initiate the oxidation of volatile organic compounds (VOCs) which can lead to the production of ozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicals in forest environments characterized by high mixing ratios of isoprene and low mixing ratios of nitrogen oxides (NOx) have shown serious discrepancies with modeled concentrations. These results bring into question our understanding of the atmospheric chemistry of isoprene and other biogenic VOCs under low NOx conditions. During the summer of 2015, OH and HO2 radical concentrations as well as total OH reactivity were measured using Laser-Induced Fluorescence - Fluorescence Assay by Gas Expansion (LIF-FAGE) techniques as part of the Indiana Radical, Reactivity and Ozone Production Intercomparison (IRRONIC). This campaign took place in a forested area near the Indiana University, Bloomington campus characterized by high mixing ratios of isoprene and low mixing ratios of NOx. Supporting measurements of photolysis rates, VOCs, NOx, and other species were used to constrain a zero-dimensional box model based on the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism (MCM). Using an OH chemical scavenger technique, the study revealed the presence of an interference with the LIF-FAGE measurements of OH that increased with both ambient concentrations of ozone and temperature. Subtraction of the interference resulted in measured OH concentrations that were in better agreement with model predictions, although the model still underestimated the measured concentrations, likely due to an underestimation of the concentration of NO at this site. Measurements of HO2 radical concentrations during the campaign included a fraction of isoprene-based peroxy radicals (HO2* = HO2 + αRO2) and were found to agree with model predictions. On average, the measured reactivity was consistent with that calculated from measured OH sinks to within 20 %, with modeled oxidation products accounting for the missing reactivity, although significant missing reactivity (approximately 40 % of the total measured reactivity) was observed on some days.

scholarly journals Origins and composition of fine atmospheric carbonaceous aerosol in the Sierra Nevada Mountains, California

2011 ◽  
Vol 11 (19) ◽  
pp. 10219-10241 ◽  
Author(s):  
D. R. Worton ◽  
A. H. Goldstein ◽  
D. K. Farmer ◽  
K. S. Docherty ◽  
J. L. Jimenez ◽  
...  
Keyword(s):  
Sierra Nevada ◽  
Ponderosa Pine ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Carbonaceous Aerosol ◽  
Research Station ◽  
Particle Phase ◽  
Methyl Chavicol ◽  
Biogenic Components ◽  
Urban Emissions

Abstract. In this paper we report chemically resolved measurements of organic aerosol (OA) and related tracers during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) at the Blodgett Forest Research Station, California from 15 August–10 October 2007. OA contributed the majority of the mass to the fine atmospheric particles and was predominately oxygenated (OOA). The highest concentrations of OA were during sporadic wildfire influence when aged plumes were impacting the site. In situ measurements of particle phase molecular markers were dominated by secondary compounds and along with gas phase compounds could be categorized into six factors or sources: (1) aged biomass burning emissions and oxidized urban emissions, (2) oxidized urban emissions (3) oxidation products of monoterpene emissions, (4) monoterpene emissions, (5) anthropogenic emissions and (6) local methyl chavicol emissions and oxidation products. There were multiple biogenic components that contributed to OA at this site whose contributions varied diurnally, seasonally and in response to changing meteorological conditions, e.g. temperature and precipitation events. Concentrations of isoprene oxidation products were larger when temperatures were higher during the first half of the campaign (15 August–12 September) due to more substantial emissions of isoprene and enhanced photochemistry. The oxidation of methyl chavicol, an oxygenated terpene emitted by ponderosa pine trees, contributed similarly to OA throughout the campaign. In contrast, the abundances of monoterpene oxidation products in the particle phase were greater during the cooler conditions in the latter half of the campaign (13 September–10 October), even though emissions of the precursors were lower, although the mechanism is not known. OA was correlated with the anthropogenic tracers 2-propyl nitrate and carbon monoxide (CO), consistent with previous observations, while being comprised of mostly non-fossil carbon (>75%). The correlation between OA and an anthropogenic tracer does not necessarily identify the source of the carbon as being anthropogenic but instead suggests a coupling between the anthropogenic and biogenic components in the air mass that might be related to the source of the oxidant and/or the aerosol sulfate. Observations of organosulfates of isoprene and α-pinene provided evidence for the likely importance of aerosol sulfate in spite of neutralized aerosol although acidic plumes might have played a role upwind of the site. This is in contrast to laboratory studies where strongly acidic seed aerosols were needed in order to form these compounds. These compounds together represented only a minor fraction (<1%) of the total OA mass, which may be the result of the neutralized aerosol at the site or because only a small number of organosulfates were quantified. The low contribution of organosulfates to total OA suggests that other mechanisms, e.g. NOx enhancement of oxidant levels, are likely responsible for the majority of the anthropogenic enhancement of biogenic secondary organic aerosol observed at this site.

scholarly journals Sensitivity of tropospheric chemical composition to halogen-radical chemistry using a fully coupled size-resolved multiphase chemistry/global climate system – Part 1: Halogen distributions, aerosol composition, and sensitivity of climate-relevant gases

2013 ◽  
Vol 13 (3) ◽  
pp. 6067-6129 ◽  
Author(s):  
M. S. Long ◽  
W.C. Keene ◽  
R. C. Easter ◽  
R. Sander ◽  
X. Liu ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Planetary Boundary Layer ◽  
Atmospheric Chemistry ◽  
Climate Model ◽  
Global Climate ◽  
Global Climate Model ◽  
Tropospheric Chemistry ◽  
Oxidation Products ◽  
Aerosol Composition ◽  
Mixing Ratios

Abstract. Observations and model studies suggest a significant but highly non-linear role for halogens, primarily Cl and Br, in multiphase atmospheric processes relevant to tropospheric chemistry and composition, aerosol evolution, radiative transfer, weather, and climate. The sensitivity of global atmospheric chemistry to the production of marine aerosol and the associated activation and cycling of inorganic Cl and Br was tested using a size-resolved multiphase coupled chemistry/global climate model (National Center for Atmospheric Research's Community Atmosphere Model (CAM); v3.6.33). Simulation results showed strong meridional and vertical gradients in Cl and Br species. The simulation reproduced most available observations with reasonable confidence permitting the formulation of potential mechanisms for several previously unexplained halogen phenomena including the enrichment of Br− in submicron aerosol, and the presence of a BrO maximum in the polar free troposphere. However, simulated total volatile Br mixing ratios were generally high in the troposphere. Br in the stratosphere was lower than observed due to the lack of long-lived organobromine species in the simulation. Comparing simulations using chemical mechanisms with and without reactive Cl and Br species demonstrated a significant temporal and spatial sensitivity of primary atmospheric oxidants (O3, HOx, NOx), CH4, and non-methane hydrocarbons (NMHC's) to halogen cycling. Simulated O3 and NOx were globally lower (65% and 35%, respectively, less in the planetary boundary layer based on median values) in simulations that included halogens. Globally, little impact was seen in SO2 and non-sea-salt SO42− processing due to halogens. Significant regional differences were evident: the lifetime of nss-SO42− was extended downwind of large sources of SO2. The burden and lifetime of DMS (and its oxidation products) were lower by a factor of 5 in simulations that included halogens, versus those without, leading to a 20% reduction in nss-SO42− in the Southern Hemisphere planetary boundary layer based on median values.

scholarly journals Large estragole fluxes from oil palms in Borneo

2010 ◽  
Vol 10 (1) ◽  
pp. 1517-1557 ◽  
Author(s):  
P. K. Misztal ◽  
S. M. Owen ◽  
A. B. Guenther ◽  
R. Rasmussen ◽  
C. Geron ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Oil Palm ◽  
Ponderosa Pine ◽  
Elaeis Guineensis ◽  
Ambient Air ◽  
Biogenic Emissions ◽  
Main Peak ◽  
Aerosol Formation ◽  
Mixing Ratios ◽  
Oil Palms

Abstract. During two field campaigns (OP3 and ACES), which ran in Borneo in 2008, we measured large emissions of estragole (methyl chavicol; IUPAC systematic name 1-allyl-4-methoxybenzene; CAS number 140-67-0) in ambient air above oil palm canopies (0.81 mg m−2 h−1 and 3.2 ppbv for mean midday fluxes and mixing ratios, respectively) and subsequently from flower enclosures. However, we did not detect this compound at a nearby rainforest. Estragole is a known attractant of the African oil palm weevil (Elaeidobius kamerunicus), which pollinates oil palms (Elaeis guineensis). There has been recent interest in the biogenic emissions of estragole but it is normally not included in atmospheric models of biogenic emissions and atmospheric chemistry despite its relatively high potential for secondary organic aerosol formation from photooxidation and high reactivity with OH radical. We report the first direct canopy-scale measurements of estragole fluxes from tropical oil palms by the virtual disjunct eddy covariance technique and compare them with previously reported data for estragole emissions from Ponderosa pine. Flowers, rather than leaves, appear to be the main source of estragole from oil palms; we derive a global estimate of estragole emissions from oil palm plantations of ~0.5 Tg y−1. The observed ecosystem mean fluxes (0.44 mg m−2 h−1) and mean ambient volume mixing ratios (3.0 ppbv) of estragole are the highest reported so far. The value for midday mixing ratios is not much different from the total average as, unlike other VOCs (e.g. isoprene), the main peak occurred in the evening rather than in the middle of the day. Despite this, we show that the estragole flux can be parameterised using a combination of a modified G06 algorithm for emission and a canopy resistance approach for deposition. However, the model underestimates the afternoon peak even though a similar approach works well for isoprene. Our measurements suggest that this biogenic compound may have an impact on regional atmospheric chemistry that previously has not been accounted for in models and could become more important in the future due to expansion of the areas of oil palm plantation.

scholarly journals Large estragole fluxes from oil palms in Borneo

2010 ◽  
Vol 10 (9) ◽  
pp. 4343-4358 ◽  
Author(s):  
P. K. Misztal ◽  
S. M. Owen ◽  
A. B. Guenther ◽  
R. Rasmussen ◽  
C. Geron ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Oil Palm ◽  
Ponderosa Pine ◽  
Elaeis Guineensis ◽  
Ambient Air ◽  
Biogenic Emissions ◽  
Main Peak ◽  
Aerosol Formation ◽  
Mixing Ratios ◽  
Oil Palms

Abstract. During two field campaigns (OP3 and ACES), which ran in Borneo in 2008, we measured large emissions of estragole (methyl chavicol; IUPAC systematic name 1-allyl-4-methoxybenzene; CAS number 140-67-0) in ambient air above oil palm canopies (0.81 mg m−2 h−1 and 3.2 ppbv for mean midday fluxes and mixing ratios respectively) and subsequently from flower enclosures. However, we did not detect this compound at a nearby rainforest. Estragole is a known attractant of the African oil palm weevil (Elaeidobius kamerunicus), which pollinates oil palms (Elaeis guineensis). There has been recent interest in the biogenic emissions of estragole but it is normally not included in atmospheric models of biogenic emissions and atmospheric chemistry despite its relatively high potential for secondary organic aerosol formation from photooxidation and high reactivity with OH radical. We report the first direct canopy-scale measurements of estragole fluxes from tropical oil palms by the virtual disjunct eddy covariance technique and compare them with previously reported data for estragole emissions from Ponderosa pine. Flowers, rather than leaves, appear to be the main source of estragole from oil palms; we derive a global estimate of estragole emissions from oil palm plantations of ~0.5 Tg y−1. The observed ecosystem mean fluxes (0.44 mg m−2 h−1) and mean ambient volume mixing ratios (3.0 ppbv) of estragole are the highest reported so far. The value for midday mixing ratios is not much different from the total average as, unlike other VOCs (e.g. isoprene), the main peak occurred in the evening rather than in the middle of the day. Despite this, we show that the estragole flux can be parameterised using a modified G06 algorithm for emission. However, the model underestimates the afternoon peak even though a similar approach works well for isoprene. Our measurements suggest that this biogenic compound may have an impact on regional atmospheric chemistry that previously has not been accounted for in models and could become more important in the future due to expansion of the areas of oil palm plantation.

scholarly journals Observations of oxidation products above a forest imply biogenic emissions of very reactive compounds

2005 ◽  
Vol 5 (1) ◽  
pp. 67-75 ◽  
Author(s):  
R. Holzinger ◽  
A. Lee ◽  
K. T. Paw ◽  
U. A. H. Goldstein
Keyword(s):  
Ponderosa Pine ◽  
Forest Canopy ◽  
Large Fraction ◽  
Oxidation Products ◽  
Biogenic Emissions ◽  
Central California ◽  
Mixing Ratios ◽  
Volatile Organic ◽  
Current Emission ◽  
Ponderosa Pine Forest

Abstract. Vertical gradients of mixing ratios of volatile organic compounds have been measured in a Ponderosa pine forest in Central California (38.90° N, 120.63° W, 1315m). These measurements reveal large quantities of previously unreported oxidation products of short lived biogenic precursors. The emission of biogenic precursors must be in the range of 13-66µmol m-2h-1 to produce the observed oxidation products. That is 6-30 times the emissions of total monoterpenes observed above the forest canopy on a molar basis. These reactive precursors constitute a large fraction of biogenic emissions at this site, and are not included in current emission inventories. When oxidized by ozone they should efficiently produce secondary aerosol and hydroxyl radicals.

scholarly journals Airborne intercomparison of HO<sub>x</sub> measurements using laser-induced fluorescence and chemical ionization mass spectrometry during ARCTAS

2012 ◽  
Vol 5 (2) ◽  
pp. 2529-2565 ◽  
Author(s):  
X. Ren ◽  
J. Mao ◽  
W. H. Brune ◽  
C. A. Cantrell ◽  
R. L. Mauldin III ◽  
...  
Keyword(s):  
Correlation Coefficient ◽  
Mass Spectrometer ◽  
Atmospheric Chemistry ◽  
Chemical Ionization ◽  
Uv Light ◽  
Laser Induced Fluorescence ◽  
Tropospheric Chemistry ◽  
Ionization Mass ◽  
Data Set ◽  
Mixing Ratios

Abstract. The hydroxyl (OH) and hydroperoxyl (HO2) radicals, collectively called HOx, play central roles in tropospheric chemistry. Accurate measurements of OH and HO2 are critical to examine our understanding of atmospheric chemistry. Intercomparisons of different techniques for detecting OH and HO2 are vital to evaluate their measurement capabilities. Three instruments that measured OH and/or HO2 radicals were deployed on the NASA DC-8 aircraft throughout Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS), in the spring and summer of 2008. One instrument was the Penn State Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) for OH and HO2 measurements based on Laser-Induced Fluorescence (LIF) spectroscopy. A second instrument was the NCAR Selected-Ion Chemical Ionization Mass Spectrometer (SI-CIMS) for OH measurement. A third instrument was the NCAR Peroxy Radical Chemical Ionization Mass Spectrometer (PeRCIMS) for HO2 measurement. Formal intercomparison of LIF and CIMS was conducted for the first time on a same aircraft platform. The three instruments were calibrated by quantitative photolysis of water vapor by UV light at 184.9 nm with three different calibration systems. The absolute accuracies were ±32% (2σ) for the LIF instrument, ±65% (2σ) for the SI-CIMS instrument, and ±50% (2σ) for the PeRCIMS instrument. In general, good agreement was obtained between the CIMS and LIF measurements of both OH and HO2 measurements. Linear regression of the entire data set yields [OH]CIMS = 0.89 × [OH]LIF + 2.8 × 105 cm−3 with a correlation coefficient, r2 = 0.72 for OH and [HO2]CIMS = 0.86 × [HO2]LIF + 3.9 parts per trillion by volume (pptv, equivalent to pmol mol−1) with a correlation coefficient, r2 = 0.72 for HO2. In general, the difference between CIMS and LIF instruments for OH and HO2 measurements can be explained by their combined measurement uncertainties. Comparison with box model results shows some similarities for both the CIMS and LIF measurements. First, the observed-to-modeled HO2 ratio increases greatly for higher NO mixing ratios, indicating that the model may not properly account for HOx sources that correlate with NO. Second, the observed-to-modeled OH ratio increases with increasing isoprene mixing ratios, suggesting either incomplete understanding of isoprene chemistry in the model or interferences in the measurements in environments where biogenic emissions dominate ambient volatile organic compounds.

scholarly journals Photochemical modeling of glyoxal at a rural site: observations and analysis from BEARPEX 2007

2011 ◽  
Vol 11 (17) ◽  
pp. 8883-8897 ◽  
Author(s):  
A. J. Huisman ◽  
J. R. Hottle ◽  
M. M. Galloway ◽  
J. P. DiGangi ◽  
K. L. Coens ◽  
...  
Keyword(s):  
High Temperature ◽  
Sierra Nevada ◽  
Ponderosa Pine ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Rural Site ◽  
High Time Resolution ◽  
Mixing Ratios ◽  
Dry Conditions ◽  
Oxidation Chemistry

Abstract. We present roughly one month of high time-resolution, direct, in situ measurements of gas-phase glyoxal acquired during the BEARPEX 2007 field campaign. The research site, located on a ponderosa pine plantation in the Sierra Nevada mountains, is strongly influenced by biogenic volatile organic compounds (BVOCs); thus this data adds to the few existing measurements of glyoxal in BVOC-dominated areas. The short lifetime of glyoxal of ~1 h, the fact that glyoxal mixing ratios are much higher during high temperature periods, and the results of a photochemical model demonstrate that glyoxal is strongly influenced by BVOC precursors during high temperature periods. A zero-dimensional box model using near-explicit chemistry from the Leeds Master Chemical Mechanism v3.1 was used to investigate the processes controlling glyoxal chemistry during BEARPEX 2007. The model showed that MBO is the most important glyoxal precursor (~67 %), followed by isoprene (~26 %) and methylchavicol (~6 %), a precursor previously not commonly considered for glyoxal production. The model calculated a noon lifetime for glyoxal of ~0.9 h, making glyoxal well suited as a local tracer of VOC oxidation in a forested rural environment; however, the modeled glyoxal mixing ratios over-predicted measured glyoxal by a factor 2 to 5. Loss of glyoxal to aerosol was not found to be significant, likely as a result of the very dry conditions, and could not explain the over-prediction. Although several parameters, such as an approximation for advection, were found to improve the model measurement discrepancy, reduction in OH was by far the most effective. Reducing model OH concentrations to half the measured values decreased the glyoxal over-prediction from a factor of 2.4 to 1.1, as well as the overprediction of HO2 from a factor of 1.64 to 1.14. Our analysis has shown that glyoxal is particularly sensitive to OH concentration compared to other BVOC oxidation products. This relationship arises from (i) the predominantly secondary- or higher-generation production of glyoxal from (mainly OH-driven, rather than O3-driven) BVOC oxidation at this site and (ii) the relative importance of photolysis in glyoxal loss as compared to reaction with OH. We propose that glyoxal is a useful tracer for OH-driven BVOC oxidation chemistry.

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