scholarly journals Improved simulation of isoprene oxidation chemistry with the ECHAM5/MESSy chemistry-climate model: lessons from the GABRIEL airborne field campaign

2008 ◽  
Vol 8 (2) ◽  
pp. 6273-6312 ◽  
Author(s):  
T. M. Butler ◽  
D. Taraborrelli ◽  
C. Brühl ◽  
H. Fischer ◽  
H. Harder ◽  
...  
Keyword(s):  
Rate Constant ◽  
Atmospheric Chemistry ◽  
Climate Model ◽  
Effective Rate Constant ◽  
Effective Rate ◽  
Current Generation ◽  
Mixing Ratios ◽  
Oxidation Chain ◽  
Isoprene Oxidation ◽  
Oxidation Chemistry

Abstract. The GABRIEL airborne field measurement campaign, conducted over the Guyanas in October 2005, produced measurements of hydroxyl radical (OH) concentration which are significantly higher than can be simulated using current generation models of atmospheric chemistry. Based on the hypothesis that this "missing OH" is due to an as-yet undiscovered mechanism for recycling OH during the oxidation chain of isoprene, we determine that an OH recycling of about 40–50% (compared with 5–10% in current generation isoprene oxidation mechanisms) is necessary in order for our modelled OH to approach the lower error bounds of the OH observed during GABRIEL. Such a large amount of OH in our model leads to unrealistically low mixing ratios of isoprene. In order for our modelled isoprene mixing ratios to match those observed during the campaign, we also require that the effective rate constant for the reaction of isoprene with OH be reduced by about 50% compared with the lower bound of the range recommended by IUPAC. We show that a reasonable explanation for this lower effective rate constant could be the segregation of isoprene and OH in the mixed layer. Our modelling results are consistent with a global, annual isoprene source of about 500 Tg(C) yr−1, allowing experimentally derived and established isoprene flux rates to be reconciled with global models.

scholarly journals Improved simulation of isoprene oxidation chemistry with the ECHAM5/MESSy chemistry-climate model: lessons from the GABRIEL airborne field campaign

2008 ◽  
Vol 8 (16) ◽  
pp. 4529-4546 ◽  
Author(s):  
T. M. Butler ◽  
D. Taraborrelli ◽  
C. Brühl ◽  
H. Fischer ◽  
H. Harder ◽  
...  
Keyword(s):  
Rate Constant ◽  
Atmospheric Chemistry ◽  
Climate Model ◽  
Effective Rate Constant ◽  
Effective Rate ◽  
Current Generation ◽  
Mixing Ratios ◽  
Oxidation Chain ◽  
Isoprene Oxidation ◽  
Oxidation Chemistry

Abstract. The GABRIEL airborne field measurement campaign, conducted over the Guyanas in October 2005, produced measurements of hydroxyl radical (OH) concentration which are significantly higher than can be simulated using current generation models of atmospheric chemistry. Based on the hypothesis that this "missing OH" is due to an as-yet undiscovered mechanism for recycling OH during the oxidation chain of isoprene, we determine that an OH recycling of about 40–50% (compared with 5–10% in current generation isoprene oxidation mechanisms) is necessary in order for our modelled OH to approach the lower error bounds of the OH observed during GABRIEL. Such a large amount of OH in our model leads to unrealistically low mixing ratios of isoprene. In order for our modelled isoprene mixing ratios to match those observed during the campaign, we also require that the effective rate constant for the reaction of isoprene with OH be reduced by about 50% compared with the lower bound of the range recommended by IUPAC. We show that a reasonable explanation for this lower effective rate constant could be the segregation of isoprene and OH in the mixed layer. Our modelling results are consistent with a global, annual isoprene source of about 500 Tg(C) yr−1, allowing experimentally derived and established isoprene flux rates to be reconciled with global models.

scholarly journals The influence of small-scale variations in isoprene concentrations on atmospheric chemistry over a tropical rainforest

2011 ◽  
Vol 11 (9) ◽  
pp. 4121-4134 ◽  
Author(s):  
T. A. M. Pugh ◽  
A. R. MacKenzie ◽  
B. Langford ◽  
E. Nemitz ◽  
P. K. Misztal ◽  
...  
Keyword(s):  
Rate Constant ◽  
Atmospheric Chemistry ◽  
Tropical Rainforest ◽  
Effective Rate Constant ◽  
Effective Rate ◽  
Ozone Production ◽  
Small Scale ◽  
Aerosol Formation ◽  
Upper Limit ◽  
Model Measurement

Abstract. Biogenic volatile organic compounds (BVOCs) such as isoprene constitute a large proportion of the global atmospheric oxidant sink. Their reactions in the atmosphere contribute to processes such as ozone production and secondary organic aerosol formation. However, over the tropical rainforest, where 50 % of the global emissions of BVOCs are believed to occur, atmospheric chemistry models have been unable to simulate concurrently the measured daytime concentration of isoprene and that of its principal oxidant, hydroxyl (OH). One reason for this model-measurement discrepancy may be incomplete mixing of isoprene within the convective boundary layer, leading to patchiness or segregation in isoprene and OH mixing ratios and average concentrations that appear to be incompatible with each other. One way of capturing this effect in models of atmospheric chemistry is to use a reduced effective rate constant for their reaction. Recent studies comparing atmospheric chemistry global/box models with field measurements have suggested that this effective rate reduction may be as large as 50 %; which is at the upper limit of that calculated using large eddy simulation models. To date there has only been one field campaign worldwide that has reported co-located measurements of isoprene and OH at the necessary temporal resolution to calculate the segregation of these compounds. However many campaigns have recorded sufficiently high resolution isoprene measurements to capture the small-scale fluctuations in its concentration. Assuming uniform distributions of other OH production and loss processes, we use a box model of atmospheric chemistry, constrained by the spectrum of isoprene concentrations measured, as a virtual instrument, to estimate the variability in OH at a point and hence, to estimate the segregation intensity of isoprene and OH from high-frequency isoprene time series. The method successfully reproduces the only directly observed segregation, using measurements made in a deciduous forest in Germany. The effective rate constant reduction for the reaction of isoprene and OH over a South-East Asian rainforest is calculated to be typically <15 %. Although there are many unconstrained uncertainties, the likely nature of those processes suggests that this value represents an upper limit. The estimate is not sensitive to heterogeneities in NO at this remote site, unless they are correlated with those of isoprene, or to OH-recycling schemes in the isoprene oxidation mechanism, unless the recycling happens in the first reaction step. Segregation alone is therefore unlikely to be the sole cause of model-measurement discrepancies for isoprene and OH above a rainforest.

scholarly journals The influence of small-scale variations in isoprene concentrations on atmospheric chemistry over a tropical rainforest

2010 ◽  
Vol 10 (7) ◽  
pp. 18197-18234 ◽  
Author(s):  
T. A. M. Pugh ◽  
A. R. MacKenzie ◽  
B. Langford ◽  
E. Nemitz ◽  
P. K. Misztal ◽  
...  
Keyword(s):  
Rate Constant ◽  
Atmospheric Chemistry ◽  
Tropical Rainforest ◽  
Oxidation Mechanism ◽  
Effective Rate Constant ◽  
Effective Rate ◽  
Ozone Production ◽  
Small Scale ◽  
Aerosol Formation ◽  
Model Measurement

Abstract. Biogenic volatile organic compounds (BVOCs) such as isoprene constitute a large proportion of the global atmospheric oxidant sink. Their reactions in the atmosphere contribute to processes such as ozone production and secondary organic aerosol formation. However, over the tropical rainforest, where 50% of the global emissions of BVOCs are believed to occur, atmospheric chemistry models have been unable to simultaneously simulate the measured daytime concentration of isoprene and that of its principal oxidant, hydroxyl (OH). One reason for this model-measurement discrepancy may be incomplete mixing of isoprene within the convective boundary layer, leading to patchiness or segregation in isoprene and OH mixing ratios and average concentrations that appear to be incompatible with each other. One way of capturing this effect in models of atmospheric chemistry is to use a reduced effective rate constant for their reaction. Recent studies comparing atmospheric chemistry global/box models with field measurements have suggested that this effective rate reduction may be as large as 50%; which is at the upper limit of that calculated using large eddy simulation models. To date there has only been one field campaign worldwide that has reported co-located measurements of isoprene and OH at the necessary temporal resolution to calculate the segregation of these compounds. However many campaigns have recorded sufficiently high resolution isoprene measurements to capture the small-scale fluctuations in its concentration. We use a box model of atmospheric chemistry, constrained by the spectrum of isoprene concentrations measured, to estimate segregation intensity of isoprene and OH from high-frequency isoprene time series. The method successfully reproduces the only directly observed segregation. The effective rate constant reduction for the reaction of isoprene and OH over a South-East Asian rainforest is calculated to be typically <15%. This estimate is not sensitive to heterogeneities in NO at this remote site, unless they are correlated with those of isoprene, or to OH-recycling schemes in the isoprene oxidation mechanism, unless the recycling happens in the first reaction step. Segregation alone is therefore unlikely to be the sole cause of model-measurement discrepancies for isoprene and OH above a rainforest.

Diffusion‐controlled reactions: Upper bounds on the effective rate constant

1991 ◽  
Vol 94 (12) ◽  
pp. 7967-7971 ◽  
Author(s):  
J. Blawzdziewicz ◽  
G. Szamel ◽  
H. Van Beijeren
Keyword(s):  
Rate Constant ◽  
Effective Rate Constant ◽  
Effective Rate ◽  
Upper Bounds ◽  
Diffusion Controlled

scholarly journals Modelling marine emissions and atmospheric distributions of halocarbons and DMS: the influence of prescribed water concentration vs. prescribed emissions

2015 ◽  
Vol 15 (12) ◽  
pp. 17553-17598
Author(s):  
S. T. Lennartz ◽  
G. Krysztofiak-Tong ◽  
C. A. Marandino ◽  
B.-M. Sinnhuber ◽  
S. Tegtmeier ◽  
...  
Keyword(s):  
Wind Speed ◽  
Atmospheric Chemistry ◽  
Climate Model ◽  
Trace Gases ◽  
Surface Wind ◽  
Water Concentration ◽  
Absolute Magnitude ◽  
Actual State ◽  
Transfer Velocity ◽  
Mixing Ratios

Abstract. Marine produced short-lived trace gases such as dibromomethane (CH2Br2), bromoform (CHBr3), methyliodide (CH3I) and dimethylsulfide (DMS) significantly impact tropospheric and stratospheric chemistry. Describing their marine emissions in atmospheric chemistry models as accurately as possible is necessary to quantify their impact on ozone depletion and the Earth's radiative budget. So far, marine emissions of trace gases have mainly been prescribed from emission climatologies, thus lacking the interaction between the actual state of the atmosphere and the ocean. Here we present simulations with the chemistry climate model EMAC with online calculation of emissions based on surface water concentrations, in contrast to directly prescribed emissions. Considering the actual state of the model atmosphere results in a concentration gradient consistent with model real-time conditions at ocean surface and atmosphere, which determine the direction and magnitude of the computed flux. This method has a number of conceptual and practical benefits, as the modelled emission can respond consistently to changes in sea surface temperature, surface wind speed, sea ice cover and especially atmospheric mixing ratio. This online calculation could enhance, dampen or even invert the fluxes (i.e. deposition instead of emissions) of VSLS. We show that differences between prescribing emissions and prescribing concentrations (−28 % for CH2Br2 to +11 % for CHBr3) result mainly from consideration of the actual, time-varying state of the atmosphere. The absolute magnitude of the differences depends mainly on the surface ocean saturation of each particular gas. Comparison to observations from aircraft, ships and ground stations reveals that computing the air–sea flux interactively leads in most of the cases to more accurate atmospheric mixing ratios in the model compared to the computation from prescribed emissions. Calculating emissions online also enables effective testing of different air–sea transfer velocity parameterizations k, which was performed here for eight different parameterizations. The testing of these different k values is of special interest for DMS, as recently published parameterizations derived by direct flux measurements using eddy covariance measurements suggest decreasing k values at high wind speeds or a linear relationship with wind speed. Implementing these parameterizations reduces discrepancies in modelled DMS atmospheric mixing ratios and observations by a factor of 1.5 compared to parameterizations with a quadratic or cubic relationship to wind speed.

scholarly journals Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields

2009 ◽  
Vol 9 (2) ◽  
pp. 8857-8902 ◽  
Author(s):  
A. W. Rollins ◽  
A. Kiendler-Scharr ◽  
J. Fry ◽  
T. Brauers ◽  
S. S. Brown ◽  
...  
Keyword(s):  
First Generation ◽  
Secondary Organic Aerosol ◽  
Model Simulation ◽  
Effective Rate Constant ◽  
Organic Aerosol ◽  
Effective Rate ◽  
Oxidation Products ◽  
Alkyl Nitrates ◽  
Alkyl Nitrate ◽  
Isoprene Oxidation

Abstract. Alkyl nitrates and secondary organic aerosol (SOA) produced during the oxidation of isoprene by nitrate radicals has been observed in the SAPHIR chamber. We find the yield of nitrates is 70±8% from the isoprene+NO3 reaction, and the yield for secondary dinitrates produced in the reaction of primary isoprene nitrates with NO3 is 40±20%. We find an effective rate constant for reaction of NO3 with the group of first generation oxidation products to be 7×10−14 cm3 s−1. At the low total organic aerosol concentration in the chamber (max ≈0.6 μg m−3) we observed a mass yield (ΔSOA mass/Δisoprene mass) of 2% for the entire 16 h experiment. However a comparison of the timing of the observed SOA production to a box model simulation of first and second generation oxidation products shows that the yield from the first generation products was <0.2% while the further oxidation of the initial products leads to a yield of 10% (defined as ΔSOA/Δisoprene2x where Δisoprene2x is the mass of isoprene which reacted twice with NO3). The SOA yield of 10% is consistent with equilibrium partitioning of highly functionalized C5 products of isoprene oxidation.

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 Revision of the convective transport module CVTRANS 2.4 in the EMAC atmospheric chemistry–climate model

2015 ◽  
Vol 8 (8) ◽  
pp. 2435-2445 ◽  
Author(s):  
H. G. Ouwersloot ◽  
A. Pozzer ◽  
B. Steil ◽  
H. Tost ◽  
J. Lelieveld
Keyword(s):  
Atmospheric Chemistry ◽  
Climate Model ◽  
Convective Transport ◽  
Computational Time ◽  
Cloud Base ◽  
Mixing Ratio ◽  
Time Step ◽  
Mixing Ratios ◽  
Time Stepping ◽  
Intermediate Time

Abstract. The convective transport module, CVTRANS, of the ECHAM/MESSy Atmospheric Chemistry (EMAC) model has been revised to better represent the physical flows and incorporate recent findings on the properties of the convective plumes. The modifications involve (i) applying intermediate time stepping based on a settable criterion, (ii) using an analytic expression to account for the intra-time-step mixing ratio evolution below cloud base, and (iii) implementing a novel expression for the mixing ratios of atmospheric compounds at the base of an updraft. Even when averaged over a year, the predicted mixing ratios of atmospheric compounds are affected considerably by the intermediate time stepping. For example, for an exponentially decaying atmospheric tracer with a lifetime of 1 day, the zonal averages can locally differ by more than a factor of 6 and the induced root mean square deviation from the original code is, weighted by the air mass, higher than 40 % of the average mixing ratio. The other modifications result in smaller differences. However, since they do not require additional computational time, their application is also recommended.

Investigation of strongly enhanced methane Part I: Chemical feedbacks and rapid adjustments.

2020 ◽  
Author(s):  
Franziska Winterstein ◽  
Patrick Jöckel ◽  
Martin Dameris ◽  
Michael Ponater ◽  
Fabian Tanalski ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Radiative Forcing ◽  
Climate Model ◽  
Numerical Study ◽  
Stratospheric Ozone ◽  
Lower Boundary ◽  
Tropospheric Chemistry ◽  
Substantial Part ◽  
Mixing Ratios ◽  
The Impact

&lt;p&gt;Methane (CH&lt;sub&gt;4&lt;/sub&gt;) is the second most important greenhouse gas, which atmospheric concentration is influenced by human activities and currently on a sharp rise. We present a study with numerical simulations using a Chemistry-Climate-Model (CCM), which are performed to assess possible consequences of strongly enhanced CH&lt;sub&gt;4&lt;/sub&gt; concentrations in the Earth's atmosphere for the climate.&lt;/p&gt;&lt;p&gt;Our analysis includes experiments with 2xCH&lt;sub&gt;4&lt;/sub&gt; and 5xCH&lt;sub&gt;4&lt;/sub&gt; present day (2010) lower boundary mixing ratios using the CCM EMAC. The simulations are conducted with prescribed oceanic conditions, mimicking present day tropospheric temperatures as its changes are largely suppressed. By doing so we are able to investigate the quasi-instantaneous chemical impact on the atmosphere. We find that the massive increase in CH&lt;sub&gt;4&lt;/sub&gt; strongly influences the tropospheric chemistry by reducing the OH abundance and thereby extending the tropospheric CH&lt;sub&gt;4&lt;/sub&gt; lifetime as well as the residence time of other chemical pollutants. The region above the tropopause is impacted by a substantial rise in stratospheric water vapor (SWV). The stratospheric ozone (O&lt;sub&gt;3&lt;/sub&gt;) column increases overall, but SWV induced stratospheric cooling also leads to enhanced ozone depletion in the Antarctic lower stratosphere. Regional&amp;#160; patterns of ozone change are affected by modification of stratospheric dynamics, i.e. increased tropical up-welling and stronger meridional transport&amp;#160; towards the polar regions. We calculate the net radiative impact (RI) of the 2xCH&lt;sub&gt;4&lt;/sub&gt; experiment to be 0.69 W m&lt;sup&gt;-2&lt;/sup&gt; and for the 5xCH&lt;sub&gt;4&lt;/sub&gt; experiment to be 1.79 W m&lt;sup&gt;-2&lt;/sup&gt;. A substantial part of the RI is contributed by chemically induced O&lt;sub&gt;3&lt;/sub&gt; and SWV changes, in line with previous radiative forcing estimates and is for the first time splitted and spatially asigned to its chemical contributors.&lt;/p&gt;&lt;p&gt;This numerical study using a CCM with prescibed oceanic conditions shows the rapid responses to significantly enhanced CH&lt;sub&gt;4&lt;/sub&gt; mixing ratios, which is the first step towards investigating the impact of possible strong future CH&lt;sub&gt;4&lt;/sub&gt; emissions on atmospheric chemistry and its feedback on climate.&lt;/p&gt;

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