Biogenic isoprene emissions, dry deposition velocity, and surface ozone concentration during summer droughts, heatwaves, and normal conditions in southwestern Europe

At high concentrations, tropospheric ozone (O3) deteriorates air quality, inducing adverse effects on human and ecosystem health. Meteorological conditions are key to understanding the variability in O3 concentration, especially during extreme weather events. In addition to modifying photochemistry and atmospheric transport, droughts and heatwaves affect the state of vegetation and thus the biosphere–troposphere interactions that control atmospheric chemistry, namely biogenic emissions of precursors and gas dry deposition. A major source of uncertainty and inaccuracy in the simulation of surface O3 during droughts and heatwaves is the poor representation of such interactions. This publication aims at quantifying the isolated and combined impacts of both extremes on biogenic isoprene (C5H8) emissions, O3 dry deposition, and surface O3 in southwestern Europe. First, the sensitivity of biogenic C5H8 emissions, O3 dry deposition, and surface O3 to two specific effects of droughts, the decrease in soil moisture and in biomass, is analysed for the extremely dry summer 2012 using the biogenic emission model MEGANv2.1 and the chemistry transport model CHIMEREv2020r1. Despite a significant decrease in biogenic C5H8 emissions and O3 dry deposition velocity, characterized by a large spatial variability, the combined effect on surface O3 concentration remains limited (between +0.5 % and +3 % over the continent). The variations in simulated biogenic C5H8 emissions, O3 dry deposition, and surface O3 during the heatwaves and agricultural droughts are then analysed for summer 2012 (warm and dry), 2013 (warm), and 2014 (relatively wet and cool). We compare the results with large observational data sets, namely O3 concentrations from Air Quality (AQ) e-Reporting (2000–2016) and total columns of formaldehyde (HCHO, which is used as a proxy for biogenic emissions of volatile organic compounds) from the Ozone Monitoring Instrument (OMI) of the Aura satellite (2005–2016). Based on a cluster approach using the percentile limit anomalies indicator, we find that C5H8 emissions increase by +33 % during heatwaves compared to normal conditions, do not vary significantly during all droughts (either accompanied or not by a heatwave), and decrease by −16 % during isolated droughts. OMI data confirm an average increase in HCHO during heatwaves (between +15 % and +31 % depending on the product used) and decrease in HCHO (between −2 % and −6 %) during isolated droughts over the 2005–2016 summers. Simulated O3 dry deposition velocity decreases by −25 % during heatwaves and −35 % during all droughts. Simulated O3 concentrations increase by +7 % during heatwaves and by +3 % during all droughts. Compared to observations, CHIMERE tends to underestimate the daily maximum O3. However, similar sensitivity to droughts and heatwaves are obtained. The analysis of the AQ e-Reporting data set shows an average increase of +14 % during heatwaves and +7 % during all droughts over the 2000–2016 summers (for an average daily concentration value of 69 µg m−3 under normal conditions). This suggests that identifying the presence of combined heatwaves is fundamental to the study of droughts on surface–atmosphere interactions and O3 concentration.</p

North American Influence on Tropospheric Ozone and the Effects of Recent Emission Reductions: Constraints from ICARTT Observations

We use observations from the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) campaign over eastern North America in summer 2004, interpreted with a global 3‐D model of tropospheric chemistry (GEOS‐Chem), to improve and update estimates of North American influence on global tropospheric ozone and the effect of recent U.S. anthropogenic reductions on surface ozone pollution. We find that the 50% decrease in U.S. stationary NOx sources since 1999 has decreased mean U.S. boundary layer ozone concentrations by 6–8 ppbv in the southeast and 4–6 ppbv in the Midwest. The observed dO3/dCO molar enhancement ratio in the U.S. boundary layer during ICARTT was 0.46 mol mol−1, larger than the range of 0.3–0.4 from studies in the early 1990s, possibly reflecting the decrease in the NOx/CO emission ratio as well as an increase in the ozone production efficiency per unit NOx. North American NOx emissions during summer 2004 as constrained by the ICARTT observations (0.72 Tg N fossil fuel, 0.11 Tg N biomass burning, 0.28 Tg N lightning for 1 July to 15 August) enhanced the hemispheric tropospheric ozone burden by 12.4%, with comparable contributions from fossil fuel and lightning (5–6%), but only 1% from biomass burning emissions despite 2004 being a record fire year over Alaska and western Canada.Earth and Planetary Science

Biogenic Versus Anthropogenic Sources of CO in the United States

Aircraft observations of carbon monoxide (CO) from the ICARTT campaign over the eastern United States in summer 2004 (July 1–August 15), interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem), show that the national anthropogenic emission inventory from the U.S. Environmental Protection Agency (93 Tg CO y−1) is too high by 60% in summer. Our best estimate of the CO anthropogenic source for the ICARTT period is 6.4 Tg CO, including 4.6 Tg from direct emission and 1.8 Tg CO from oxidation of anthropogenic volatile organic compounds (VOCs). The biogenic CO source for the same period from the oxidation of isoprene and other biogenic VOCs is 8.3 Tg CO, and is independently constrained by ICARTT observations of formaldehyde (HCHO). Anthropogenic emissions of CO in the U.S. have decreased to the point that they are now lower than the biogenic source in summer.Earth and Planetary SciencesEngineering and Applied Science

Surface and lightning sources of nitrogen oxides over the United States: Magnitudes, chemical evolution, and outflow

We use observations from two aircraft during the ICARTT campaign over the eastern United States and North Atlantic during summer 2004, interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem) to test current understanding of regional sources, chemical evolution, and export of NOx. The boundary layer NOx data provide top-down verification of a 50% decrease in power plant and industry NOx emissions over the eastern United States between 1999 and 2004. Observed NOx concentrations at 8–12 km altitude were 0.55 ± 0.36 ppbv, much larger than in previous U.S. aircraft campaigns (ELCHEM, SUCCESS, SONEX) though consistent with data from the NOXAR program aboard commercial aircraft. We show that regional lightning is the dominant source of this upper tropospheric NOx and increases upper tropospheric ozone by 10 ppbv. Simulating ICARTT upper tropospheric NOx observations with GEOS-Chem requires a factor of 4 increase in modeled NOx yield per flash (to 500 mol/ flash). Observed OH concentrations were a factor of 2 lower than can be explained from current photochemical models, for reasons that are unclear. A NOy-CO correlation analysis of the fraction f of North American NOx emissions vented to the free troposphere as NOy (sum of NOx and its oxidation products) shows observed f = 16 ± 10% and modeled f = 14 ± 9%, consistent with previous studies. Export to the lower free troposphere is mostly HNO3 but at higher altitudes is mostly PAN. The model successfully simulates NOy export efficiency and speciation, supporting previous model estimates of a large U.S. anthropogenic contribution to global tropospheric ozone through PAN export

Impact of forest fires, biogenic emissions and high temperatures on the elevated Eastern Mediterranean ozone levels during the hot summer of 2007

International audienceThe hot summer of 2007 in southeast Europe has been studied using two regional atmospheric chemistry models; WRF-Chem and EMEP MSC-W. The region was struck by three heat waves and a number of forest fire episodes, greatly affecting air pollution levels. We have focused on ozone and its precursors using state-of-the-art inventories for anthropogenic, biogenic and forest fire emissions. The models have been evaluated against measurement data, and processes leading to ozone formation have been quantified. Heat wave episodes are projected to occur more frequently in a future climate, and therefore this study also makes a contribution to climate change impact research. The plume from the Greek forest fires in August 2007 is clearly seen in satellite observations of CO and NO2 columns, showing extreme levels of CO in and downwindof the fires. Model simulations reflect the location and influence of the fires relatively well, but the modelled magnitude of CO in the plume core is too low. Most likely, this is caused by underestimation of CO in the emission inventories, suggesting that the CO/NOx ratios of fire emissions should be re-assessed. Moreover, higher maximum values are seen in WRF-Chem than in EMEP MSC-W, presumably due to differences in plume rise altitudes as the first model emits a larger fraction of the fire emissions in the lowermost model layer. The model results are also in fairly good agreement with surface ozone measurements. Biogenic VOC emissions reacting with anthropogenic NOx emissions are calculated to contribute significantly to the levels of ozone in the region, but the magnitude and geographical distribution depend strongly on the model and biogenic emission module used. During the July and August heat waves, ozone levels increased substantially due to a combination of forest fire emissions and the effect of high temperatures. We found that the largest temperature impact on ozone was through the temperature dependence of the biogenic emissions, closely followed by the effect of reduced dry deposiion caused by closing of the plants' stomata at very high temperatures. The impact of high temperatures on the ozone chemistry was much lower. The results suggest that forest fire emissions, and the temperature effect on biogenic emissions and dry deposition, will potentially lead to substantial ozone increases in a warmer climate

Biomass burning influence on high-latitude tropospheric ozone and reactive nitrogen in summer 2008: a multi-model analysis based on POLMIP simulations

We have evaluated tropospheric ozone enhancement in air dominated by biomass burning emissions at high latitudes (> 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, ΔO3/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 (4.47 to 7.00 pptv ppbv−1) than GEOS5-forced models (1.87 to 3.28 pptv ppbv−1), which we show is likely linked to differences in 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 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 HOx 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

Impact of wildfires on particulate matter in the Euro-Mediterranean in 2007: sensitivity to some parameterizations of emissions in air quality models

This study examines the uncertainties on air quality modeling associated with the integration of wildfire emissions in chemistry-transport models (CTMs). To do so, aerosol concentrations during the summer of 2007, which was marked by severe fire episodes in the Euro-Mediterranean region especially in the Balkans (20–31 July, 24–30 August 2007) and Greece (24–30 August 2007), are analyzed. Through comparisons to observations from surface networks and satellite remote sensing, we evaluate the abilities of two CTMs, Polyphemus/Polair3D and CHIMERE, to simulate the impact of fires on the regional particulate matter (PM) concentrations and optical properties. During the two main fire events, fire emissions may contribute up to 90&thinsp;% of surface PM2.5 concentrations in the fire regions (Balkans and Greece), with a significant regional impact associated with long-range transport. Good general performances of the models and a clear improvement of PM2.5 and aerosol optical depth (AOD) are shown when fires are taken into account in the models with high correlation coefficients. Two sources of uncertainties are specifically analyzed in terms of surface PM2.5 concentrations and AOD using sensitivity simulations: secondary organic aerosol (SOA) formation from intermediate and semi-volatile organic compounds (I/S-VOCs) and emissions' injection heights. The analysis highlights that surface PM2.5 concentrations are highly sensitive to injection heights (with a sensitivity that can be as high as 50&thinsp;% compared to the sensitivity to I/S-VOC emissions which is lower than 30&thinsp;%). However, AOD which is vertically integrated is less sensitive to the injection heights (mostly below 20&thinsp;%) but highly sensitive to I/S-VOC emissions (with sensitivity that can be as high as 40&thinsp;%). The maximum statistical dispersion, which quantifies uncertainties related to fire emission modeling, is up to 75&thinsp;% for PM2.5 in the Balkans and Greece, and varies between 36&thinsp;% and 45&thinsp;% for AOD above fire regions. The simulated number of daily exceedance of World Health Organization (WHO) recommendations for PM2.5 over the considered region reaches 30 days in regions affected by fires and ∼10 days in fire plumes, which is slightly underestimated compared to available observations. The maximum statistical dispersion (σ) on this indicator is also large (with σ reaching 15 days), showing the need for better understanding of the transport and evolution of fire plumes in addition to fire emissions.</p

Quantifying The Causes of Differences in Tropospheric OH within Global Models

The hydroxyl radical (OH) is the primary daytime oxidant in the troposphere and provides the main loss mechanism for many pollutants and greenhouse gases, including methane (CH4). Global mean tropospheric OH differs by as much as 80% among various global models, for reasons that are not well understood. We use neural networks (NNs), trained using archived output from eight chemical transport models (CTMs) that participated in the POLARCAT Model Intercomparison Project (POLMIP), to quantify the factors responsible for differences in tropospheric OH and resulting CH4 lifetime (τCH4) between these models. Annual average τCH4, for loss by OH only, ranges from 8.0–11.6 years for the eight POLMIP CTMs. The factors driving these differences were quantified by inputting 3-D chemical fields from one CTM into the trained NN of another CTM. Across all CTMs, the largest mean differences in τCH4 (ΔτCH4) result from variations in chemical mechanisms (ΔτCH4 = 0.46 years), the photolysis frequency (J) of O3→O(1D) (0.31 years), local O3 (0.30 years), and CO (0.23 years). The ΔτCH4 due to CTM differences in NOx (NO + NO2) is relatively low (0.17 years), though large regional variation in OH between the CTMs is attributed to NOx. Differences in isoprene and J(NO2) have negligible overall effect on globally averaged tropospheric OH, though the extent of OH variations due to each factor depends on the model being examined. This study demonstrates that NNs can serve as a useful tool for quantifying why tropospheric OH varies between global models, provided essential chemical fields are archived