Secondary organic aerosol (SOA) is a dominant contributor of fine particulate matter in the atmosphere, but the complexity of SOA formation chemistry hinders the accurate representation of SOA in ...models. Volatility-based SOA parameterizations have been adopted in many recent chemistry modeling studies and have shown a reasonable performance compared to observations. However, assumptions made in these empirical parameterizations can lead to substantial errors when applied to future climatic conditions as they do not include the mechanistic understanding of processes but are rather fitted to laboratory studies of SOA formation. This is particularly the case for SOA derived from isoprene epoxydiols (IEPOX SOA), for which we have a higher level of understanding of the fundamental processes than is currently parameterized in most models. We predict future SOA concentrations using an explicit mechanism and compare the predictions with the empirical parameterization based on the volatility basis set (VBS) approach. We then use the Community Earth System Model 2 (CESM2.1.0) with detailed isoprene chemistry and reactive uptake processes for the middle and end of the 21st century under four Shared Socioeconomic Pathways (SSPs): SSP1–2.6, SSP2–4.5, SSP3–7.0, and SSP5–8.5. With the explicit chemical mechanism, we find that IEPOX SOA is predicted to increase on average under all future SSP scenarios but with some variability in the results depending on regions and the scenario chosen. Isoprene emissions are the main driver of IEPOX SOA changes in the future climate, but the IEPOX SOA yield from isoprene emissions also changes by up to 50 % depending on the SSP scenario, in particular due to different sulfur emissions. We conduct sensitivity simulations with and without CO2 inhibition of isoprene emissions that is highly uncertain, which results in factor of 2 differences in the predicted IEPOX SOA global burden, especially for the high-CO2 scenarios (SSP3–7.0 and SSP5–8.5). Aerosol pH also plays a critical role in the IEPOX SOA formation rate, requiring accurate calculation of aerosol pH in chemistry models. On the other hand, isoprene SOA calculated with the VBS scheme predicts a nearly constant SOA yield from isoprene emissions across all SSP scenarios; as a result, it mostly follows isoprene emissions regardless of region and scenario. This is because the VBS scheme does not consider heterogeneous chemistry; in other words, there is no dependency on aerosol properties. The discrepancy between the explicit mechanism and VBS parameterization in this study is likely to occur for other SOA components as well, which may also have dependencies that cannot be captured by VBS parameterizations. This study highlights the need for more explicit chemistry or for parameterizations that capture the dependence on key physicochemical drivers when predicting SOA concentrations for climate studies.
Black carbon (BC) concentrations observed in 22 snowpits sampled in the northwest sector of the Greenland ice sheet in April 2014 have allowed us to identify a strong and widespread BC aerosol ...deposition event, which was dated to have accumulated in the pits from two snow storms between 27 July and 2 August 2013. This event comprises a significant portion (57 on average across all pits) of total BC deposition over 10 months (July 2013 to April 2014). Here we link this deposition event to forest fires burning in Canada during summer 2013 using modeling and remote sensing tools. Aerosols were detected by both the Cloud-Aerosol Lidar with Orthogonal Polarization (on board CALIPSO) and Moderate Resolution Imaging Spectroradiometer (Aqua) instruments during transport between Canada and Greenland. We use high-resolution regional chemical transport modeling (WRF-Chem) combined with high-resolution fire emissions (FINNv1.5) to study aerosol emissions, transport, and deposition during this event. The model captures the timing of the BC deposition event and shows that fires in Canada were the main source of deposited BC. However, the model underpredicts BC deposition compared to measurements at all sites by a factor of 2100. Underprediction of modeled BC deposition originates from uncertainties in fire emissions and model treatment of wet removal of aerosols. Improvements in model descriptions of precipitation scavenging and emissions from wildfires are needed to correctly predict deposition, which is critical for determining the climate impacts of aerosols that originate from fires.
This study quantifies future changes in tropospheric ozone (O3) using
a simple parameterisation of source–receptor relationships based on
simulations from a range of models participating in the Task ...Force on
Hemispheric Transport of Air Pollutants (TF-HTAP) experiments. Surface and
tropospheric O3 changes are calculated globally and across 16 regions
from perturbations in precursor emissions (NOx, CO, volatile organic compounds – VOCs)
and methane (CH4) abundance only, neglecting any impact from climate
change. A source attribution is provided for each source region along with an
estimate of uncertainty based on the spread of the results from the models.
Tests against model simulations using the Hadley Centre Global Environment
Model version 2 – Earth system configuration (HadGEM2-ES) confirm that the approaches
used within the parameterisation perform well for most regions. The
O3 response to changes in CH4 abundance is slightly larger in
the TF-HTAP Phase 2 than in the TF-HTAP Phase 1 assessment (2010) and provides
further evidence that controlling CH4 is important for limiting
future O3 concentrations. Different treatments of chemistry and
meteorology in models remain one of the largest uncertainties in calculating
the O3 response to perturbations in CH4 abundance and
precursor emissions, particularly over the Middle East and south Asia
regions. Emission changes for the future Evaluating the CLimate and Air Quality
ImPacts of Short-livEd Pollutants (ECLIPSE) scenarios and a subset of
preliminary Shared Socioeconomic Pathways (SSPs) indicate that surface
O3 concentrations will increase regionally by 1 to 8 ppbv in 2050.
Source attribution analysis highlights the growing importance of CH4
in the future under current legislation. A change in the global tropospheric
O3 radiative forcing of +0.07 W m−2 from 2010 to 2050 is
predicted using the ECLIPSE scenarios and SSPs, based solely on changes in
CH4 abundance and tropospheric O3 precursor emissions and
neglecting any influence of climate change. Current legislation is shown to
be inadequate in limiting the future degradation of surface ozone air quality
and enhancement of near-term climate warming. More stringent future emission
controls provide a large reduction in both surface O3 concentrations
and O3 radiative forcing. The parameterisation provides a simple tool
to highlight the different impacts and associated uncertainties of local and
hemispheric emission control strategies on both surface air quality and the
near-term climate forcing by tropospheric O3.
The Community Earth System Model (CESM1) CAM4-chem has been used to perform the Chemistry Climate Model Initiative (CCMI) reference and sensitivity simulations. In this model, the Community ...Atmospheric Model version 4 (CAM4) is fully coupled to tropospheric and stratospheric chemistry. Details and specifics of each configuration, including new developments and improvements are described. CESM1 CAM4-chem is a low-top model that reaches up to approximately 40 km and uses a horizontal resolution of 1.9° latitude and 2.5° longitude. For the specified dynamics experiments, the model is nudged to Modern-Era Retrospective Analysis for Research and Applications (MERRA) reanalysis. We summarize the performance of the three reference simulations suggested by CCMI, with a focus on the last 15 years of the simulation when most observations are available. Comparisons with selected data sets are employed to demonstrate the general performance of the model. We highlight new data sets that are suited for multi-model evaluation studies. Most important improvements of the model are the treatment of stratospheric aerosols and the corresponding adjustments for radiation and optics, the updated chemistry scheme including improved polar chemistry and stratospheric dynamics and improved dry deposition rates. These updates lead to a very good representation of tropospheric ozone within 20 % of values from available observations for most regions. In particular, the trend and magnitude of surface ozone is much improved compared to earlier versions of the model. Furthermore, stratospheric column ozone of the Southern Hemisphere in winter and spring is reasonably well represented. All experiments still underestimate CO most significantly in Northern Hemisphere spring and show a significant underestimation of hydrocarbons based on surface observations.
This study presents the distribution of tropospheric ozone and related species for South Asia using the Model for Ozone and Related chemical Tracers (MOZART-4) and Hemispheric Transport of Air ...Pollution version-2 (HTAP-v2) emission inventory. The model present-day simulated ozone (O3), carbon monoxide (CO) and nitrogen dioxide (NO2) are evaluated against surface-based, balloon-borne and satellite-based (MOPITT and OMI) observations. The model systematically overestimates surface O3 mixing ratios (range of mean bias about: 1–30 ppbv) at different ground-based measurement sites in India. Comparison between simulated and observed vertical profiles of ozone shows a positive bias from the surface up to 600 hPa and a negative bias above 600 hPa. The simulated seasonal variation in surface CO mixing ratio is consistent with the surface observations, but has a negative bias of about 50–200 ppb which can be attributed to a large part to the coarse model resolution. In contrast to the surface evaluation, the model shows a positive bias of about 15–20 × 1017 molecules/cm2 over South Asia when compared to satellite derived CO columns from the MOPITT instrument. The model also overestimates OMI retrieved tropospheric column NO2 abundance by about 100–250 × 1013 molecules/cm2. A response to 20% reduction in all anthropogenic emissions over South Asia shows a decrease in the anuual mean O3 mixing ratios by about 3–12 ppb, CO by about 10–80 ppb and NOX by about 3–6 ppb at the surface level. During summer monsoon, O3 mixing ratios at 200 hPa show a decrease of about 6–12 ppb over South Asia and about 1–4 ppb over the remote northern hemispheric western Pacific region.
•Simulations of trace gases over South Asia using MOZART-4 and HTAP-v2 emissions.•Evaluated the model results with satellite and ground based observations.•Long range transport of pollution from South Asia during summer monsoon season.
We present a 60-year record of the stable isotopes of atmospheric carbon monoxide (CO) from firn air samples collected under the framework of the North Greenland Eemian Ice Drilling (NEEM) project. ...CO concentration, δ13C, and δ18O of CO were measured by gas chromatography/isotope ratio mass spectrometry (gc-IRMS) from trapped gases in the firn. We applied LGGE-GIPSA firn air models (Witrant et al., 2011) to correlate gas age with firn air depth and then reconstructed the trend of atmospheric CO and its stable isotopic composition at high northern latitudes since 1950. The most probable firn air model scenarios show that δ13C decreased slightly from −25.8‰ in 1950 to −26.4‰ in 2000, then decreased more significantly to −27.2‰ in 2008. δ18O decreased more regularly from 9.8‰ in 1950 to 7.1‰ in 2008. Those same scenarios show CO concentration increased gradually from 1950 and peaked in the late 1970s, followed by a gradual decrease to present day values (Petrenko et al., 2012). Results from an isotope mass balance model indicate that a slight increase, followed by a large reduction, in CO derived from fossil fuel combustion has occurred since 1950. The reduction of CO emission from fossil fuel combustion after the mid-1970s is the most plausible mechanism for the drop of CO concentration during this time. Fossil fuel CO emissions decreased as a result of the implementation of catalytic converters and the relative growth of diesel engines, in spite of the global vehicle fleet size having grown several fold over the same time period.
This paper quantifies the pre-industrial (1850) to present-day (2014) effective radiative forcing (ERF) of anthropogenic emissions of NOX, volatile organic compounds (VOCs; including CO), SO2, NH3, ...black carbon, organic carbon, and concentrations of methane, N2O and ozone-depleting halocarbons, using CMIP6 models. Concentration and emission changes of reactive species can cause multiple changes in the composition of radiatively active species: tropospheric ozone, stratospheric ozone, stratospheric water vapour, secondary inorganic and organic aerosol, and methane. Where possible we break down the ERFs from each emitted species into the contributions from the composition changes. The ERFs are calculated for each of the models that participated in the AerChemMIP experiments as part of the CMIP6 project, where the relevant model output was available.
The 1850 to 2014 multi-model mean ERFs (± standard deviations) are −1.03 ± 0.37 W/sq.m for SO2 emissions, −0.25 ± 0.09 W/sq.m for organic carbon (OC), 0.15 ± 0.17 W/sq.m for black carbon (BC) and −0.07 ± 0.01 W/sq.m for NH3. For the combined aerosols (in the piClim-aer experiment) it is −1.01 ± 0.25 W/sq.m. The multi-model means for the reactive well-mixed greenhouse gases (including any effects on ozone and aerosol chemistry) are 0.67 ± 0.17 W/sq.m for methane (CH4), 0.26 ± 0.07 W/sq.m for nitrous oxide (N2O) and 0.12 ± 0.2 W/sq.m for ozone-depleting halocarbons (HC). Emissions of the ozone precursors nitrogen oxides (NOx), volatile organic compounds and both together (O3) lead to ERFs of 0.14 ± 0.13, 0.09 ± 0.14 and 0.20 ± 0.07 W/sq.m respectively. The differences in ERFs calculated for the different models reflect differences in the complexity of their aerosol and chemistry schemes, especially in the case of methane where tropospheric chemistry captures increased forcing from ozone production.
We examine the ozone production from boreal forest fires based on a case study of wildfires in Alaska and Canada in summer 2004. The model simulations were performed with the chemistry transport ...model, MOZART‐4, and were evaluated by comparison with a comprehensive set of aircraft measurements. In the analysis we use measurements and model simulations of carbon monoxide (CO) and ozone (O3) at the PICO‐NARE station located in the Azores within the pathway of North American outflow. The modeled mixing ratios were used to test the robustness of the enhancement ratio ΔO3/ΔCO (defined as the excess O3 mixing ratio normalized by the increase in CO) and the feasibility for using this ratio in estimating the O3 production from the wildfires. Modeled and observed enhancement ratios are about 0.25 ppbv/ppbv which is in the range of values found in the literature and results in a global net O3 production of 12.9 ± 2 Tg O3 during summer 2004. This matches the net O3 production calculated in the model for a region extending from Alaska to the east Atlantic (9–11 Tg O3) indicating that observations at PICO‐NARE representing photochemically well aged plumes provide a good measure of the O3 production of North American boreal fires. However, net chemical loss of fire‐related O3 dominates in regions far downwind from the fires (e.g., Europe and Asia) resulting in a global net O3 production of 6 Tg O3 during the same time period. On average, the fires increased the O3 burden (surface −300 mbar) over Alaska and Canada during summer 2004 by about 7–9% and over Europe by about 2–3%.
We present an inverse model analysis to quantify the emissions of wildfires in Alaska and Canada in the summer of 2004 using carbon monoxide (CO) data from the Measurements of Pollution in the ...Troposphere (MOPITT) remote sensing instrument together with the chemistry transport model MOZART (Model for Ozone and Related Chemical Tracers). We use data assimilation outside the region of the fires to optimally constrain the CO background level and the transport into that region. Inverse modeling is applied locally to quantify the fire emissions. Our a posteriori estimate of the wildfire emissions gives a total of 30 ± 5 Tg CO emitted during June–August 2004 which is of comparable order to the anthropogenic emissions for the continental US. The simulated CO fields have been evaluated by comparison with MOPITT and independent aircraft data.
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