scholarly journals Impact of reactive bromine chemistry in the troposphere

2004 ◽  
Vol 4 (4) ◽  
pp. 4877-4913 ◽  
Author(s):  
R. von Glasow ◽  
R. von Kuhlmann ◽  
M. G. Lawrence ◽  
U. Platt ◽  
P. J. Crutzen
Keyword(s):  
Atmospheric Chemistry ◽  
Climate Changes ◽  
Dimethyl Sulfide ◽  
Transport Model ◽  
Satellite Observations ◽  
Mixing Ratio ◽  
Chemistry Transport Model ◽  
Bromine Oxide ◽  
Mixing Ratios ◽  
Field Campaigns

Abstract. Recently several field campaigns and satellite observations found strong indications for bromine oxide (BrO) in the free troposphere. Using a global atmospheric chemistry transport model we show that BrO measurements mixing ratios of a few tenths to 2 pmol mol−1 lead to a reduction in the zonal mean O3 mixing ratio of up to 18% in widespread areas and locally even up to 40% compared to a model run without bromine chemistry. For dimethyl sulfide (DMS) the effect is even larger with up to 60% decreases. This is accompanied by dramatic changes in DMS oxidation pathways, reducing its cooling effect on climate. Changes in the HO2:OH ratio also cause changes for NOx and PAN. These results imply that a very strong sink for O3 and DMS has so far been ignored in many studies of the chemistry of the troposphere.

scholarly journals Impact of reactive bromine chemistry in the troposphere

2004 ◽  
Vol 4 (11/12) ◽  
pp. 2481-2497 ◽  
Author(s):  
R. von Glasow ◽  
R. von Kuhlmann ◽  
M. G. Lawrence ◽  
U. Platt ◽  
P. J. Crutzen
Keyword(s):  
Atmospheric Chemistry ◽  
Dimethyl Sulfide ◽  
Marine Boundary Layer ◽  
Transport Model ◽  
Sea Salt ◽  
Chemistry Transport Model ◽  
Bromine Oxide ◽  
Mixing Ratios ◽  
Sea Salt Aerosol ◽  
Field Campaigns

Abstract. Recently several field campaigns and satellite observations have found strong indications for the presence of bromine oxide (BrO) in the free troposphere. Using a global atmospheric chemistry transport model we show that BrO mixing ratios of a few tenths to 2 pmol mol-1 lead to a reduction in the zonal mean O3 mixing ratio of up to 18% in widespread areas and regionally up to 40% compared to a model run without bromine chemistry. A lower limit approach for the marine boundary layer, that does not explicitly include the release of halogens from sea salt aerosol, shows that for dimethyl sulfide (DMS) the effect is even larger, with up to 60% reduction of its tropospheric column. This is accompanied by dramatic changes in DMS oxidation pathways, reducing its cooling effect on climate. In addition there are changes in the HO2:OH ratio that also affect NOx and PAN. These results imply that potentially significant strong sinks for O3 and DMS have so far been ignored in many studies of the chemistry of the troposphere.

scholarly journals What drives the observed variability of HCN in the troposphere and lower stratosphere?

2009 ◽  
Vol 9 (21) ◽  
pp. 8531-8543 ◽  
Author(s):  
Q. Li ◽  
P. I. Palmer ◽  
H. C. Pumphrey ◽  
P. Bernath ◽  
E. Mahieu
Keyword(s):  
Atmospheric Chemistry ◽  
Lower Stratosphere ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Negative Bias ◽  
Mixing Ratio ◽  
Chemistry Transport Model ◽  
Annual Variations ◽  
Surface Emission ◽  
Chemistry Experiment

Abstract. We use the GEOS-Chem global 3-D chemistry transport model to investigate the relative importance of chemical and physical processes that determine observed variability of hydrogen cyanide (HCN) in the troposphere and lower stratosphere. Consequently, we reconcile ground-based FTIR column measurements of HCN, which show annual and semi-annual variations, with recent space-borne measurements of HCN mixing ratio in the tropical lower stratosphere, which show a large two-year variation. We find that the observed column variability over the ground-based stations is determined by a superposition of HCN from several regional burning sources, with GEOS-Chem reproducing these column data with a positive bias of 5%. GEOS-Chem reproduces the observed HCN mixing ratio from the Microwave Limb Sounder and the Atmospheric Chemistry Experiment satellite instruments with a mean negative bias of 20%, and the observed HCN variability with a mean negative bias of 7%. We show that tropical biomass burning emissions explain most of the observed HCN variations in the upper troposphere and lower stratosphere (UTLS), with the remainder due to atmospheric transport and HCN chemistry. In the mid and upper stratosphere, atmospheric dynamics progressively exerts more influence on HCN variations. The extent of temporal overlap between African and other continental burning seasons is key in establishing the apparent bienniel cycle in the UTLS. Similar analysis of other, shorter-lived trace gases have not observed the transition between annual and bienniel cycles in the UTLS probably because the signal of inter-annual variations from surface emission has been diluted before arriving at the lower stratosphere (LS), due to shorter atmospheric lifetimes.

scholarly journals A quasi chemistry-transport model mode for EMAC

2011 ◽  
Vol 4 (1) ◽  
pp. 195-206 ◽  
Author(s):  
R. Deckert ◽  
P. Jöckel ◽  
V. Grewe ◽  
K.-D. Gottschaldt ◽  
P. Hoor
Keyword(s):  
Water Vapor ◽  
Nitric Acid ◽  
Atmospheric Chemistry ◽  
Transport Model ◽  
Climate Simulation ◽  
Chemistry Transport Model ◽  
Mixing Ratios ◽  
Reference Simulation ◽  
The Difference ◽  
Chemical Water

Abstract. A quasi chemistry-transport model mode (QCTM) is presented for the numerical chemistry-climate simulation system ECHAM/MESSy Atmospheric Chemistry (EMAC). It allows for a quantification of chemical signals through suppression of any feedback between chemistry and dynamics. Noise would otherwise interfere too strongly. The signal is calculated from the difference of two QCTM simulations, a reference simulation and a sensitivity simulation. In order to avoid the feedbacks, the simulations adopt the following offline chemical fields: (a) offline mixing ratios of radiatively active substances enter the radiation scheme, (b) offline mixing ratios of nitric acid enter the scheme for re-partitioning and sedimentation from polar stratospheric clouds, (c) and offline methane oxidation is the exclusive source of chemical water-vapor tendencies. Any set of offline fields suffices to suppress the feedbacks, though may be inconsistent with the simulation setup. An adequate set of offline climatologies can be produced from a non-QCTM simulation using the setup of the reference simulation. Test simulations reveal the particular importance of adequate offline fields associated with (a). Inconsistencies from (b) are negligible when using adequate fields of nitric acid. Acceptably small inconsistencies come from (c), but should vanish for an adequate prescription of chemical water vapor tendencies. Toggling between QCTM and non-QCTM is done via namelist switches and does not require a source code re-compilation.

scholarly journals New approach to evaluate satellite derived XCO<sub>2</sub> over oceans by integrating ship and aircraft observations

2020 ◽  
Author(s):  
Astrid Müller ◽  
Hiroshi Tanimoto ◽  
Takafumi Sugita ◽  
Toshinobu Machida ◽  
Shin-ichiro Nakaoka ◽  
...  
Keyword(s):  
Carbon Cycle ◽  
Atmospheric Chemistry ◽  
Transport Model ◽  
Satellite Observations ◽  
Reference Dataset ◽  
Model Calculations ◽  
New Approach ◽  
Mixing Ratios ◽  
In Situ Data

Abstract. Satellite observations provide spatially-resolved global estimates of column-averaged mixing ratios of CO2 (XCO2) over the Earth's surface. The accuracy of these datasets can be validated against reliable standards in some areas, but other areas remain inaccessible. To date, limited reference data over oceans hinders successful uncertainty quantification or bias correction efforts, and precludes reliable conclusions about changes in the carbon cycle in some regions. Here, we propose a new approach to analyze and evaluate seasonal, interannual and latitudinal variations of XCO2 over oceans by integrating cargo-ship (SOOP, Ship Of Opportunity) and commercial aircraft (CONTRAIL, Comprehensive Observation Network for Trace gases by Airliner) observations with the aid of state-of-the art atmospheric chemistry-transport model calculations. The consistency of the in situ based column-averaged CO2 dataset (in situ XCO2) with satellite estimates was analyzed over the Western Pacific between 2014 and 2017, and its utility as reference dataset evaluated. Our results demonstrate that the new dataset accurately captures seasonal and interannual variations of CO2. Retrievals of XCO2 over the ocean from GOSAT (Greenhouse gases observing satellite: NIES v02.75, National Institute for Environmental Studies; ACOS v7.3, Atmospheric CO2 Observation from Space) and OCO-2 (Orbiting Carbon Observatory, v9r) observations show a negative bias of about 1 parts per million (ppm) in northern midlatitudes, which was attributed to measurement uncertainties of the satellite observations. The NIES retrieval had higher consistency with in situ XCO2 at midlatitudes as compared to the other retrievals. At low latitudes, it shows many fewer valid data and high scatter, such that ACOS and OCO-2 appear to provide a better representation of the carbon cycle. At different times, the seasonal cycles of all three retrievals show positive phase shifts of one month relative to the in situ data. The study indicates that even if the retrievals complement each other, remaining uncertainties limit the accurate interpretation of spatiotemporal changes in CO2 fluxes. A continuous long-term XCO2 dataset with wide latitudinal coverage based on the new approach has a great potential as a robust reference dataset for XCO2 and can help to better understand changes in the carbon cycle in response to climate change using satellite observations.

scholarly journals New approach to evaluate satellite-derived XCO<sub>2</sub> over oceans by integrating ship and aircraft observations

2021 ◽  
Vol 21 (10) ◽  
pp. 8255-8271
Author(s):  
Astrid Müller ◽  
Hiroshi Tanimoto ◽  
Takafumi Sugita ◽  
Toshinobu Machida ◽  
Shin-ichiro Nakaoka ◽  
...  
Keyword(s):  
Carbon Cycle ◽  
Atmospheric Chemistry ◽  
Transport Model ◽  
Satellite Observations ◽  
Reference Dataset ◽  
Commercial Aircraft ◽  
Model Calculations ◽  
New Approach ◽  
Mixing Ratios ◽  
Spatially Resolved

Abstract. Satellite observations provide spatially resolved global estimates of column-averaged mixing ratios of CO2 (XCO2) over the Earth's surface. The accuracy of these datasets can be validated against reliable standards in some areas, but other areas remain inaccessible. To date, limited reference data over oceans hinder successful uncertainty quantification or bias correction efforts and preclude reliable conclusions about changes in the carbon cycle in some regions. Here, we propose a new approach to analyze and evaluate seasonal, interannual, and latitudinal variations of XCO2 over oceans by integrating cargo-ship (Ship Of Opportunity – SOOP) and commercial aircraft (Comprehensive Observation Network for Trace gases by Airliner – CONTRAIL) observations with the aid of state-of-the art atmospheric chemistry-transport model calculations. The consistency of the “observation-based column-averaged CO2” dataset (obs. XCO2) with satellite estimates was analyzed over the western Pacific between 2014 and 2017, and its utility as a reference dataset evaluated. Our results demonstrate that the new dataset accurately captures seasonal and interannual variations of CO2. Retrievals of XCO2 over the ocean from GOSAT (Greenhouse Gases Observing Satellite: National Institute for Environmental Studies – NIES v02.75; Atmospheric CO2 Observation from Space – ACOS v7.3) and OCO-2 (Orbiting Carbon Observatory, v9r) observations show a negative bias of about 1 part per million (ppm) in northern midlatitudes, which was attributed to measurement uncertainties of the satellite observations. The NIES retrieval had higher consistency with obs. XCO2 at midlatitudes as compared to the other retrievals. At low latitudes, it shows many fewer valid data and high scatter, such that ACOS and OCO-2 appear to provide a better representation of the carbon cycle. At different times, the seasonal cycles of all three retrievals show positive phase shifts of 1 month relative to the observation-based data. The study indicates that even if the retrievals complement each other, remaining uncertainties limit the accurate interpretation of spatiotemporal changes in CO2 fluxes. A continuous long-term XCO2 dataset with wide latitudinal coverage based on the new approach has great potential as a robust reference dataset for XCO2 and can help to better understand changes in the carbon cycle in response to climate change using satellite observations.

scholarly journals A quasi chemistry-transport model mode for EMAC

2010 ◽  
Vol 3 (4) ◽  
pp. 2189-2220
Author(s):  
R. Deckert ◽  
P. Jöckel ◽  
V. Grewe ◽  
K.-D. Gottschaldt ◽  
P. Hoor
Keyword(s):  
Water Vapor ◽  
Nitric Acid ◽  
Atmospheric Chemistry ◽  
Transport Model ◽  
Climate Simulation ◽  
Chemistry Transport Model ◽  
Mixing Ratios ◽  
The Difference ◽  
Stratospheric Clouds ◽  
Chemical Fields

Abstract. A quasi chemistry-transport model mode (QCTM) is presented for the numerical chemistry-climate simulation system ECHAM/MESSy Atmospheric Chemistry (EMAC). It allows for a quantification of chemical signals through suppression of any feedback between chemistry and dynamics. Noise would otherwise interfere too strongly. The signal follows from the difference of two QCTM simulations, reference and sensitivity. These are fed with offline chemical fields as a substitute of the feedbacks between chemistry and dynamics: offline mixing ratios of radiatively active substances enter the radiation scheme (a), offline mixing ratios of nitric acid enter the scheme for re-partitioning and sedimentation from polar stratospheric clouds (b). Offline methane oxidation is the exclusive source of chemical water-vapor tendencies (c). Any set of offline fields suffices to suppress the feedbacks, though may be inconsistent with the simulation setup. An adequate set of offline climatologies can be produced from a non-QCTM simulation of the reference setup. Test simulations reveal the particular importance of adequate offline fields associated with (a). Inconsistencies from (b) are negligible when using adequate fields of nitric acid. Acceptably small inconsistencies come from (c), but should vanish for an adequate prescription of water vapor tendencies. Toggling between QCTM and non-QCTM is done via namelist switches and does not require a source code re-compilation.

scholarly journals Structural changes in the shallow and transition branch of the Brewer–Dobson circulation induced by El Niño

2018 ◽  
Author(s):  
Mohamadou Diallo ◽  
Paul Konopka ◽  
Michelle L. Santee ◽  
Rolf Müller ◽  
Mengchu Tao ◽  
...  
Keyword(s):  
El Niño ◽  
Structural Changes ◽  
Lower Stratosphere ◽  
Transport Model ◽  
El Nino ◽  
Southern Oscillation ◽  
Satellite Observations ◽  
Trace Gas ◽  
Residual Circulation ◽  
Mixing Ratios

Abstract. The stratospheric Brewer–Dobson circulation (BD-circulation) determines the transport and lifetime of key radiatively active trace gases and further impacts surface climate through downward coupling. Here, we quantify the variability in the lower stratospheric BD-circulation induced by the El Nino Southern Oscillation (ENSO), using satellite trace gas measurements and simulations with the Lagrangian chemistry transport model, CLaMS, driven by ERA-Interim and JRA-55 reanalyses. We show that despite discrepancies in the deseasonalised ozone (O3) mixing ratios between CLaMS simulations and satellite observations, the patterns of changes in the lower stratospheric O3 anomalies induced by ENSO agree remarkably well over the 2005–2016 period. Particularly during the most recent El Niño in 2015–2016, both satellite observations and CLaMS simulations show the largest negative tropical O3 anomaly in the record. Regression analysis of different metrics of the BD-circulation strength, including mean age of air, vertical velocity, residual circulation and age spectrum, shows clear evidence for structural changes of the BD-circulation in the lower stratosphere induced by El Niño, consistent with observed O3 anomalies. These structural changes during El Niño include a weakening of the transition branch of the BD-circulation between about 370–420 K (∼ 100–70 hPa) and equatorward of about 60° and, a strengthening of the shallow branch at the same latitudes and between about 420–500 K (∼ 70–30 hPa). The strengthening of the shallow branch induces negative tropical O3 anomalies due to enhanced tropical upwelling, while the weakening of the transition branch combined with enhanced downwelling due to the strengthening shallow branch leads to positive O3 anomalies in the extratropical upper troposphere-lower stratosphere (UTLS). Our results suggest that a shift of the ENSO basic state toward more frequent El Niño-like conditions in a warming future climate will substantially alter UTLS trace gas distributions due to these changes in the vertical structure of the stratospheric circulation.

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.

scholarly journals The influence of biogenic emissions on upper-tropospheric methanol as revealed from space

2007 ◽  
Vol 7 (24) ◽  
pp. 6119-6129 ◽  
Author(s):  
G. Dufour ◽  
S. Szopa ◽  
D. A. Hauglustaine ◽  
C. D. Boone ◽  
C. P. Rinsland ◽  
...  
Keyword(s):  
Northern Hemisphere ◽  
Biomass Burning ◽  
Transport Model ◽  
Tropospheric Chemistry ◽  
Biogenic Emissions ◽  
Chemistry Transport Model ◽  
Mixing Ratios ◽  
Oxygenated Compounds ◽  
Global Space ◽  
The Impact

Abstract. The distribution and budget of oxygenated organic compounds in the atmosphere and their impact on tropospheric chemistry are still poorly constrained. Near-global space-borne measurements of seasonally resolved upper tropospheric profiles of methanol (CH3OH) by the ACE Fourier transform spectrometer provide a unique opportunity to evaluate our understanding of this important oxygenated organic species. ACE-FTS observations from March 2004 to August 2005 period are presented. These observations reveal the pervasive imprint of surface sources on upper tropospheric methanol: mixing ratios observed in the mid and high latitudes of the Northern Hemisphere reflect the seasonal cycle of the biogenic emissions whereas the methanol cycle observed in the southern tropics is highly influenced by biomass burning emissions. The comparison with distributions simulated by the state-of-the-art global chemistry transport model, LMDz-INCA, suggests that: (i) the background methanol (high southern latitudes) is correctly represented by the model considering the measurement uncertainties; (ii) the current emissions from the continental biosphere are underestimated during spring and summer in the Northern Hemisphere leading to an underestimation of modelled upper tropospheric methanol; (iii) the seasonal variation of upper tropospheric methanol is shifted to the fall in the model suggesting either an insufficient destruction of CH3OH (due to too weak chemistry and/or deposition) in fall and winter months or an unfaithful representation of transport; (iv) the impact of tropical biomass burning emissions on upper tropospheric methanol is rather well reproduced by the model. This study illustrates the potential of these first global profile observations of oxygenated compounds in the upper troposphere to improve our understanding of their global distribution, fate and budget.

Sign in / Sign up

Export Citation Format

Share Document