scholarly journals Tropospheric bromine chemistry: implications for present and pre-industrial ozone and mercury

2012 ◽  
Vol 12 (4) ◽  
pp. 9665-9715 ◽  
Author(s):  
J. P. Parrella ◽  
D. J. Jacob ◽  
Q. Liang ◽  
Y. Zhang ◽  
L. J. Mickley ◽  
...  

Abstract. We present a new model for the global tropospheric chemistry of inorganic bromine (Bry) coupled to oxidant-aerosol chemistry in the GEOS-Chem chemical transport model (CTM). Sources of tropospheric Bry include debromination of sea-salt aerosol, photolysis and oxidation of short-lived bromocarbons, and transport from the stratosphere. Comparison to a GOME-2 satellite climatology of tropospheric BrO columns shows that the model can reproduce the observed increase of BrO with latitude, the northern mid-latitudes maximum in winter, and the Arctic maximum in spring. This successful simulation is contingent on the HOBr + HBr reaction taking place in aqueous aerosols and ice clouds. Bromine chemistry in the model decreases tropospheric ozone concentrations by <1−8 nmol mol−1 (6.5% globally), with the largest effects in the northern extratropics in spring. The global mean tropospheric OH concentration decreases by 4%. Inclusion of bromine chemistry improves the ability of global models (GEOS-Chem and p-TOMCAT) to simulate observed 19th-century ozone and its seasonality. Bromine effects on tropospheric ozone are comparable in the present-day and pre-industrial atmospheres so that estimates of anthropogenic radiative forcing are minimally affected. Br atom concentrations are 40% higher in the pre-industrial atmosphere due to lower ozone, which would decrease by a factor of 2 the atmospheric lifetime of elemental mercury against oxidation by Br. This suggests that historical anthropogenic mercury emissions may have mostly deposited to northern mid-latitudes, enriching the corresponding surface reservoirs. The persistent rise in background surface ozone at northern mid-latitudes during the past decades could possibly contribute to the observations of elevated mercury in subsurface waters of the North Atlantic.

2012 ◽  
Vol 12 (15) ◽  
pp. 6723-6740 ◽  
Author(s):  
J. P. Parrella ◽  
D. J. Jacob ◽  
Q. Liang ◽  
Y. Zhang ◽  
L. J. Mickley ◽  
...  

Abstract. We present a new model for the global tropospheric chemistry of inorganic bromine (Bry) coupled to oxidant-aerosol chemistry in the GEOS-Chem chemical transport model (CTM). Sources of tropospheric Bry include debromination of sea-salt aerosol, photolysis and oxidation of short-lived bromocarbons, and transport from the stratosphere. Comparison to a GOME-2 satellite climatology of tropospheric BrO columns shows that the model can reproduce the observed increase of BrO with latitude, the northern mid-latitudes maximum in winter, and the Arctic maximum in spring. This successful simulation is contingent on the HOBr + HBr reaction taking place in aqueous aerosols and ice clouds. Bromine chemistry in the model decreases tropospheric ozone mixing ratios by <1–8 nmol mol−1 (6.5% globally), with the largest effects in the northern extratropics in spring. The global mean tropospheric OH concentration decreases by 4%. Inclusion of bromine chemistry improves the ability of global models (GEOS-Chem and p-TOMCAT) to simulate observed 19th-century ozone and its seasonality. Bromine effects on tropospheric ozone are comparable in the present-day and pre-industrial atmospheres so that estimates of anthropogenic radiative forcing are minimally affected. Br atom concentrations are 40% higher in the pre-industrial atmosphere due to lower ozone, which would decrease by a factor of 2 the atmospheric lifetime of elemental mercury against oxidation by Br. This suggests that historical anthropogenic mercury emissions may have mostly deposited to northern mid-latitudes, enriching the corresponding surface reservoirs. The persistent rise in background surface ozone at northern mid-latitudes during the past decades could possibly contribute to the observations of elevated mercury in subsurface waters of the North Atlantic.


2013 ◽  
Vol 13 (8) ◽  
pp. 21125-21157 ◽  
Author(s):  
M. M. Fry ◽  
M. D. Schwarzkopf ◽  
Z. Adelman ◽  
J. J. West

Abstract. Non-methane volatile organic compounds (NMVOCs) influence air quality and global climate change through their effects on secondary air pollutants and climate forcers. Here we simulate the air quality and radiative forcing (RF) impacts of changes in ozone, methane, and sulfate from halving anthropogenic NMVOC emissions globally and from 10 regions individually, using a global chemical transport model and a standalone radiative transfer model. Halving global NMVOC emissions decreases global annual average tropospheric methane and ozone by 36.6 ppbv and 3.3 Tg, respectively, and surface ozone by 0.67 ppbv. All regional reductions slow the production of PAN, resulting in regional to intercontinental PAN decreases and regional NOx increases. These NOx increases drive tropospheric ozone increases nearby or downwind of source regions in the Southern Hemisphere (South America, Southeast Asia, Africa, and Australia). Some regions' NMVOC emissions contribute importantly to air pollution in other regions, such as East Asia, Middle East, and Europe, whose impact on US surface ozone is 43%, 34%, and 34% of North America's impact. Global and regional NMVOC reductions produce widespread negative net RFs (cooling) across both hemispheres from tropospheric ozone and methane decreases, and regional warming and cooling from changes in tropospheric ozone and sulfate (via several oxidation pathways). The total global net RF for NMVOCs is estimated as 0.0277 W m−2 (~1.8% of CO2 RF since the preindustrial). The 100 yr and 20 yr global warming potentials (GWP100, GWP20) are 2.36 and 5.83 for the global reduction, and 0.079 to 6.05 and −1.13 to 18.9 among the 10 regions. The NMVOC RF and GWP estimates are generally lower than previously modeled estimates, due to differences among models in ozone, methane, and sulfate sensitivities, and the climate forcings included in each estimate. Accounting for a~fuller set of RF contributions may change the relative magnitude of each region's impacts. The large variability in the RF and GWP of NMVOCs among regions suggest that regionally-specific metrics may be necessary to include NMVOCs in multi-gas climate trading schemes.


2014 ◽  
Vol 14 (2) ◽  
pp. 523-535 ◽  
Author(s):  
M. M. Fry ◽  
M. D. Schwarzkopf ◽  
Z. Adelman ◽  
J. J. West

Abstract. Non-methane volatile organic compounds (NMVOCs) influence air quality and global climate change through their effects on secondary air pollutants and climate forcers. Here we simulate the air quality and radiative forcing (RF) impacts of changes in ozone, methane, and sulfate from halving anthropogenic NMVOC emissions globally and from 10 regions individually, using a global chemical transport model and a standalone radiative transfer model. Halving global NMVOC emissions decreases global annual average tropospheric methane and ozone by 36.6 ppbv and 3.3 Tg, respectively, and surface ozone by 0.67 ppbv. All regional reductions slow the production of peroxyacetyl nitrate (PAN), resulting in regional to intercontinental PAN decreases and regional NOx increases. These NOx increases drive tropospheric ozone increases nearby or downwind of source regions in the Southern Hemisphere (South America, Southeast Asia, Africa, and Australia). Some regions' NMVOC emissions contribute importantly to air pollution in other regions, such as East Asia, the Middle East, and Europe, whose impact on US surface ozone is 43%, 34%, and 34% of North America's impact. Global and regional NMVOC reductions produce widespread negative net RFs (cooling) across both hemispheres from tropospheric ozone and methane decreases, and regional warming and cooling from changes in tropospheric ozone and sulfate (via several oxidation pathways). The 100 yr and 20 yr global warming potentials (GWP100, GWP20) are 2.36 and 5.83 for the global reduction, and 0.079 to 6.05 and −1.13 to 18.9 among the 10 regions. The NMVOC RF and GWP estimates are generally lower than previously modeled estimates, due to the greater NMVOC/NOx emissions ratios simulated, which result in less sensitivity to NMVOC emissions changes and smaller global O3 burden responses, in addition to differences in the representation of NMVOCs and oxidation chemistry among models. Accounting for a fuller set of RF contributions may change the relative magnitude of each region's impacts. The large variability in the RF and GWP of NMVOCs among regions suggest that regionally specific metrics may be necessary to include NMVOCs in multi-gas climate trading schemes.


2017 ◽  
Author(s):  
Ben Newsome ◽  
Mat Evans

Abstract. Chemical rate constants determine the composition of the atmosphere and how this composition has changed over time. They are central to our understanding of climate change and air quality degradation. Atmospheric chemistry models, whether online or offline, box, regional or global use these rate constants. Expert panels synthesise laboratory measurements, making recommendations for the rate constants that should be used. This results in very similar or identical rate constants being used by all models. The inherent uncertainties in these recommendations are, in general, therefore ignored. We explore the impact of these uncertainties on the composition of the troposphere using the GEOS-Chem chemistry transport model. Based on the JPL and IUPAC evaluations we assess 50 mainly inorganic rate constants and 10 photolysis rates, through simulations where we increase the rate of the reactions to the 1σ upper value recommended by the expert panels. We assess the impact on 4 standard metrics: annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime. Uncertainty in the rate constants for NO2 + OH    M →  HNO3, OH + CH4 → CH3O2 + H2O and O3 + NO → NO2 + O2 are the three largest source of uncertainty in these metrics. We investigate two methods of assessing these uncertainties, addition in quadrature and a Monte Carlo approach, and conclude they give similar outcomes. Combining the uncertainties across the 60 reactions, gives overall uncertainties on the annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime of 11, 12, 17 and 17 % respectively. These are larger than the spread between models in recent model inter-comparisons. Remote regions such as the tropics, poles, and upper troposphere are most uncertain. This chemical uncertainty is sufficiently large to suggest that rate constant uncertainty should be considered when model results disagree with measurement. Calculations for the pre-industrial allow a tropospheric ozone radiative forcing to be calculated of 0.412 ± 0.062 Wm−2. This uncertainty (15 %) is comparable to the inter-model spread in ozone radiative forcing found in previous model-model inter-comparison studies where the rate constants used in the models are all identical or very similar. Thus the uncertainty of tropospheric ozone radiative forcing should expanded to include this additional source of uncertainty. These rate constant uncertainties are significant and suggest that refinement of supposedly well known chemical rate constants should be considered alongside other improvements to enhance our understanding of atmospheric processes.


2017 ◽  
Vol 17 (23) ◽  
pp. 14661-14674 ◽  
Author(s):  
Yaoxian Huang ◽  
Shiliang Wu ◽  
Louisa J. Kramer ◽  
Detlev Helmig ◽  
Richard E. Honrath

Abstract. Recent studies have shown significant challenges for atmospheric models to simulate tropospheric ozone (O3) and its precursors in the Arctic. In this study, ground-based data were combined with a global 3-D chemical transport model (GEOS-Chem) to examine the abundance and seasonal variations of O3 and its precursors at Summit, Greenland (72.34° N, 38.29° W; 3212 m a.s.l.). Model simulations for atmospheric nitrogen oxides (NOx), peroxyacetyl nitrate (PAN), ethane (C2H6), propane (C3H8), carbon monoxide (CO), and O3 for the period July 2008–June 2010 were compared with observations. The model performed well in simulating certain species (such as CO and C3H8), but some significant discrepancies were identified for other species and further investigated. The model generally underestimated NOx and PAN (by  ∼  50 and 30 %, respectively) for March–June. Likely contributing factors to the low bias include missing NOx and PAN emissions from snowpack chemistry in the model. At the same time, the model overestimated NOx mixing ratios by more than a factor of 2 in wintertime, with episodic NOx mixing ratios up to 15 times higher than the typical NOx levels at Summit. Further investigation showed that these simulated episodic NOx spikes were always associated with transport events from Europe, but the exact cause remained unclear. The model systematically overestimated C2H6 mixing ratios by approximately 20 % relative to observations. This discrepancy can be resolved by decreasing anthropogenic C2H6 emissions over Asia and the US by  ∼ 20 %, from 5.4 to 4.4 Tg year−1. GEOS-Chem was able to reproduce the seasonal variability of O3 and its spring maximum. However, compared with observations, it underestimated surface O3 by approximately 13 % (6.5 ppbv) from April to July. This low bias appeared to be driven by several factors including missing snowpack emissions of NOx and nitrous acid in the model, the weak simulated stratosphere-to-troposphere exchange flux of O3 over the summit, and the coarse model resolution.


2014 ◽  
Vol 14 (17) ◽  
pp. 24573-24621 ◽  
Author(s):  
S. R. Arnold ◽  
L. K. Emmons ◽  
S. A. Monks ◽  
K. S. Law ◽  
D. A. Ridley ◽  
...  

Abstract. We have evaluated tropospheric ozone enhancement in air dominated by biomass burning emissions at high laititudes (> 50˚ N) in July 2008, using 10 global chemical transport model simulations from the POLMIP multi-model comparison exercise. In model air masses dominated by fire emissions, Δ O3/ΔCO values ranged between 0.039 and 0.196 ppbv ppbv−1 (mean: 0.113 ppbv ppbv−1) in freshly fire-influenced air, and between 0.140 and 0.261 ppbv ppbv−1 (mean: 0.193 ppbv) in more aged fire-influenced air. These values are in broad agreement with the range of observational estimates from the literature. Model ΔPAN/ΔCO enhancement ratios show distinct groupings according to the meteorological data used to drive the models. ECMWF-forced models produce larger ΔPAN/ΔCO values (4.44–6.28 pptv ppbv−1) than GEOS5-forced models (2.02–3.02 pptv ppbv−1), which we show is likely linked to differences efficiency of vertical transport during poleward export from mid-latitude source regions. Simulations of a large plume of biomass burning and anthropogenic emissions exported from Asia towards the Arctic using a Lagrangian chemical transport model show that 4 day net ozone change in the plume is sensitive to differences in plume chemical composition and plume vertical position among the POLMIP models. In particular, Arctic ozone evolution in the plume is highly sensitive to initial concentrations of PAN, as well as oxygenated VOCs (acetone, acetaldehyde), due to their role in producing the peroxyacetyl radical PAN precursor. Vertical displacement is also important due to its effects on the stability of PAN, and subsequent effect on NOx abundance. In plumes where net ozone production is limited, we find that the lifetime of ozone in the plume is sensitive to hydrogen peroxide loading, due to the production of HO2 from peroxide photolysis, and the key role of HO2 + O3 in controlling ozone loss. Overall, our results suggest that emissions from biomass burning lead to large-scale photochemical enhancement in high latitude tropospheric ozone during summer.


2013 ◽  
Vol 13 (8) ◽  
pp. 21455-21505
Author(s):  
E. Emili ◽  
B. Barret ◽  
S. Massart ◽  
E. Le Flochmoen ◽  
A. Piacentini ◽  
...  

Abstract. Accurate and temporally resolved fields of free-troposphere ozone are of major importance to quantify the intercontinental transport of pollution and the ozone radiative forcing. In this study we examine the impact of assimilating ozone observations from the Microwave Limb Sounder (MLS) and the Infrared Atmospheric Sounding Interferometer (IASI) in a global chemical transport model (MOdèle de Chimie Atmosphérique à Grande Échelle, MOCAGE). The assimilation of the two instruments is performed by means of a variational algorithm (4-D-VAR) and allows to constrain stratospheric and tropospheric ozone simultaneously. The analysis is first computed for the months of August and November 2008 and validated against ozone-sondes measurements to verify the presence of observations and model biases. It is found that the IASI Tropospheric Ozone Column (TOC, 1000–225 hPa) should be bias-corrected prior to assimilation and MLS lowermost level (215 hPa) excluded from the analysis. Furthermore, a longer analysis of 6 months (July–August 2008) showed that the combined assimilation of MLS and IASI is able to globally reduce the uncertainty (Root Mean Square Error, RMSE) of the modeled ozone columns from 30% to 15% in the Upper-Troposphere/Lower-Stratosphere (UTLS, 70–225 hPa) and from 25% to 20% in the free troposphere. The positive effect of assimilating IASI tropospheric observations is very significant at low latitudes (30° S–30° N), whereas it is not demonstrated at higher latitudes. Results are confirmed by a comparison with additional ozone datasets like the Measurements of OZone and wAter vapour by aIrbus in-service airCraft (MOZAIC) data, the Ozone Monitoring Instrument (OMI) total ozone columns and several high-altitude surface measurements. Finally, the analysis is found to be little sensitive to the assimilation parameters and the model chemical scheme, due to the high frequency of satellite observations compared to the average life-time of free-troposphere/low-stratosphere ozone.


2016 ◽  
Vol 16 (3) ◽  
pp. 1511-1530 ◽  
Author(s):  
V. Shah ◽  
L. Jaeglé ◽  
L. E. Gratz ◽  
J. L. Ambrose ◽  
D. A. Jaffe ◽  
...  

Abstract. We collected mercury observations as part of the Nitrogen, Oxidants, Mercury, and Aerosol Distributions, Sources, and Sinks (NOMADSS) aircraft campaign over the southeastern US between 1 June and 15 July 2013. We use the GEOS-Chem chemical transport model to interpret these observations and place new constraints on bromine radical initiated mercury oxidation chemistry in the free troposphere. We find that the model reproduces the observed mean concentration of total atmospheric mercury (THg) (observations: 1.49 ± 0.16 ng m−3, model: 1.51 ± 0.08 ng m−3), as well as the vertical profile of THg. The majority (65 %) of observations of oxidized mercury (Hg(II)) were below the instrument's detection limit (detection limit per flight: 58–228 pg m−3), consistent with model-calculated Hg(II) concentrations of 0–196 pg m−3. However, for observations above the detection limit we find that modeled Hg(II) concentrations are a factor of 3 too low (observations: 212 ± 112 pg m−3, model: 67 ± 44 pg m−3). The highest Hg(II) concentrations, 300–680 pg m−3, were observed in dry (RH  <  35 %) and clean air masses during two flights over Texas at 5–7 km altitude and off the North Carolina coast at 1–3 km. The GEOS-Chem model, back trajectories and observed chemical tracers for these air masses indicate subsidence and transport from the upper and middle troposphere of the subtropical anticyclones, where fast oxidation of elemental mercury (Hg(0)) to Hg(II) and lack of Hg(II) removal lead to efficient accumulation of Hg(II). We hypothesize that the most likely explanation for the model bias is a systematic underestimate of the Hg(0) + Br reaction rate. We find that sensitivity simulations with tripled bromine radical concentrations or a faster oxidation rate constant for Hg(0) + Br, result in 1.5–2 times higher modeled Hg(II) concentrations and improved agreement with the observations. The modeled tropospheric lifetime of Hg(0) against oxidation to Hg(II) decreases from 5 months in the base simulation to 2.8–1.2 months in our sensitivity simulations. In order to maintain the modeled global burden of THg, we need to increase the in-cloud reduction of Hg(II), thus leading to faster chemical cycling between Hg(0) and Hg(II). Observations and model results for the NOMADSS campaign suggest that the subtropical anticyclones are significant global sources of Hg(II).


2013 ◽  
Vol 13 (8) ◽  
pp. 21427-21453
Author(s):  
H. Zhang ◽  
S. Wu ◽  
Y. Wang

Abstract. The stratospheric ozone has decreased greatly since 1980 due to ozone depleting substances (ODSs). As a result of the implementation of the Montreal Protocol and its amendments and adjustments, stratospheric ozone is expected to recover towards its pre-1980 level in the coming decades. We examine the implications of stratospheric ozone recovery for the tropospheric chemistry and ozone air quality with a global chemical transport model (GEOS-Chem). Significant decreases in surface ozone photolysis rates due to stratospheric ozone recovery are simulated. Increases in ozone lifetime by up to 7% are calculated in the troposphere. The global average OH decreases by 1.74% and the global burden of tropospheric ozone increases by 0.78%. The perturbations to tropospheirc ozone and surface ozone show large seasonal and spatial variations. General increases in surface ozone are calculated for each season, with increases by up to 5% for some regions.


2020 ◽  
Author(s):  
Florence Goutail ◽  
Jean-Pierre Pommereau ◽  
Andrea Pazmino ◽  
Franck Lefevre ◽  
Cathy Clerbaux ◽  
...  

&lt;p&gt;The amplitude of ozone depletion in the Arctic is monitored every year since 1990 by comparison between total ozone measurements of SAOZ / NDACC UV-Vis spectrometers deployed in the Arctic and 3-D chemical transport model simulations in which ozone is considered as a passive tracer.&lt;/p&gt;&lt;p&gt;When SAOZ measurements are missing for various reasons, lack of sunlight, station closed or instrument failure, they are replaced since 2017 by IASI/Metop overpasses above the station. These measurements in the thermal Infrared are available all year around, at all latitudes even in the polar night. IASI data have been compared to SAOZ and to 3-D CTM REPROBUS and the agreement is better than 3% at the latitude of the polar circle.&lt;/p&gt;&lt;p&gt;The method allows determining the evolution of the daily rate of the ozone destruction and the amplitude of the cumulative loss at the end of the winter. The amplitude of the destruction varies between 0-10% in relatively warm and short vortex duration years up to 25-39% in colder and longer ones.&lt;/p&gt;&lt;p&gt;Since a strong and large vortex centred at the North Pole, PSCs and activated chlorine are still present at all levels in the lower stratosphere on January 9, 2020, there is a good probability that a significant O&lt;sub&gt;3&lt;/sub&gt; loss may happen in 2020. But since, as shown by the unprecedented depletion of 39% in 2010/11, the loss depends on the vortex duration, strength and possible re-noxification, it is difficult to predict in advance the amplitude of the cumulative loss at the end of the winter.&lt;/p&gt;&lt;p&gt;Shown in this presentation will be the evolution of ozone loss and re-noxification in the Arctic vortex during the winter 2019/20 compared to previous winters and REPROBUS and SLIMCAT CTM simulations.&lt;/p&gt;


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