Naturally driven variability in the global secondary organic aerosol over a decade

International audienceIn order to investigate the variability of the secondary organic aerosol (SOA) distributions and budget and provide a measure for the robustness of the conclusions on human induced changes of SOA, a global 3-dimensional chemistry transport model describing both the gas and the particulate phase chemistry of the troposphere has been applied. The response of the global budget of SOA to temperature and moisture changes as well as to biogenic emission changes over a decade (1984-1993) has been evaluated. The considered emissions of biogenic non-methane volatile organic compounds (VOC) are driven by temperature, light and vegetation. They vary between 756 and 810 Tg Cy-1 and are therefore about 5.5 times higher than the anthropogenic VOC emissions. All secondary aerosols (sulphuric, nitrates and organics) are computed on-line together with the aerosol associated water. Over the studied decade, the computed natural variations (8%) in the chemical SOA production from biogenic VOC oxidation equal the chemical SOA production from anthropogenic VOC oxidation. Maximum values are calculated for 1990 (warmer and drier) and minimum values for 1986 (colder and wetter). The SOA computed variability results from a 7% increase in biogenic VOC emissions from 1986 to 1990 combined with 8.5% and 6% increases in the wet and dry deposition of SOA and leads to about 11.5% increase in the SOA burden of biogenic origin. The present study also demonstrates the importance of the hydrological cycle in determining the built up and fate of SOA in the atmosphere. It also reveals the existence of significant positive and negative feedback mechanisms in the atmosphere responsible for the non linear relationship between emissions of biogenic VOC and SOA burden

Interactive chemistry in the Laboratoire de Météorologie Dynamique general circulation model: model description and impact analysis of biogenic hydrocarbons on tropospheric chemistry

We present a description and evaluation of LMDz-INCA, a global three-dimensional chemistry-climate model, pertaining to its recently developed NMHC version. In this substantially extended version of the model a comprehensive representation of the photochemistry of non-methane hydrocarbons (NMHC) and volatile organic compounds (VOC) from biogenic, anthropogenic, and biomass-burning sources has been included. The tropospheric annual mean methane (9.2 years) and methylchloroform (5.5 years) chemical lifetimes are well within the range of previous modelling studies and are in excellent agreement with estimates established by means of global observations. The model provides a reasonable simulation of the horizontal and vertical distribution and seasonal cycle of CO and key non-methane VOC, such as acetone, methanol, and formaldehyde as compared to observational data from several ground stations and aircraft campaigns. LMDz-INCA in the NMHC version reproduces tropospheric ozone concentrations fairly well throughout most of the troposphere. The model is applied in several sensitivity studies of the biosphere-atmosphere photochemical feedback. The impact of surface emissions of isoprene, acetone, and methanol is studied. These experiments show a substantial impact of isoprene on tropospheric ozone and carbon monoxide concentrations revealing an increase in surface O₃ and CO levels of up to 30 ppbv and 60 ppbv, respectively. Isoprene also appears to significantly impact the global OH distribution resulting in a decrease of the global mean tropospheric OH concentration by approximately 0.7×10⁵ molecules cm^-3 or roughly 8% and an increase in the global mean tropospheric methane lifetime by approximately seven months. A global mean ozone net radiative forcing due to the isoprene induced increase in the tropospheric ozone burden of 0.09 W m^-2 is found. The key role of isoprene photooxidation in the global tropospheric redistribution of NO_x is demonstrated. LMDz-INCA calculates an increase of PAN surface mixing ratios ranging from 75 to 750 pptv and 10 to 250 pptv during northern hemispheric summer and winter, respectively. Acetone and methanol are found to play a significant role in the upper troposphere/lower stratosphere (UT/LS) budget of peroxy radicals. Calculations with LMDz-INCA show an increase in HO_x concentrations region of 8 to 15% and 10 to 15% due to methanol and acetone biogenic surface emissions, respectively. The model has been used to estimate the global tropospheric CO budget. A global CO source of 3019 Tg CO yr^-1 is estimated. This source divides into a primary source of 1533 Tg CO yr^-1 and secondary source of 1489 Tg CO yr^-1 deriving from VOC photooxidation. Global VOC-to-CO conversion efficiencies of 90% for methane and between 20 and 45% for individual VOC are calculated by LMDz-INCA

Influence of future climate and cropland expansion on isoprene emissions and tropospheric ozone

Over the 21st century, changes in CO2 levels, climate and land use are expected to alter the global distribution of vegetation, leading to changes in trace gas emissions from plants, including, importantly, the emissions of isoprene. This, combined with changes in anthropogenic emissions, has the potential to impact tropospheric ozone levels, which above a certain level are harmful to animals and vegetation. In this study we use a biogenic emissions model following the empirical parameterisation of the MEGAN model, with vegetation distributions calculated by the Sheffield Dynamic Global Vegetation Model (SDGVM) to explore a range of potential future (2095) changes in isoprene emissions caused by changes in climate (including natural land use changes), land use, and the inhibition of isoprene emissions by CO2. From the present-day (2000) value of 467 Tg C yr−1, we find that the combined impact of these factors could cause a net decrease in isoprene emissions of 259 Tg C yr−1 (55%) with individual contributions of +78 Tg C yr−1 (climate change), −190 Tg C yr−1 (land use) and −147 Tg C yr−1 (CO2 inhibition). Using these isoprene emissions and changes in anthropogenic emissions, a series of integrations is conducted with the UM-UKCA chemistry-climate model with the aim of examining changes in ozone over the 21st century. Globally, all combined future changes cause a decrease in the tropospheric ozone burden of 27 Tg (7%) from 379 Tg in the present-day. At the surface, decreases in ozone of 6–10 ppb are calculated over the oceans and developed northern hemispheric regions, due to reduced NOx transport by PAN and reductions in NOx emissions in these areas respectively. Increases of 4–6 ppb are calculated in the continental tropics due to cropland expansion in these regions, increased CO2 inhibition of isoprene emissions, and higher temperatures due to climate change. These effects outweigh the decreases in tropical ozone caused by increased tropical isoprene emissions with climate change. Our land use change scenario consists of cropland expansion, which is most pronounced in the tropics. The tropics are also where land use change causes the greatest increases in ozone. As such there is potential for increased crop exposure to harmful levels of ozone. However, we find that these ozone increases are still not large enough to raise ozone to such damaging levels

Variability of BVOC emissions from a Mediterranean mixed forest in southern France with a focus on Quercus pubescens

International audienceWe aimed at quantifying biogenic volatile organic compound (BVOC) emissions in June from three Mediter-ranean species located at the O 3 HP site (southern France): Quercus pubescens, Acer monspessulanum and C. coggygria (for isoprene only). As Q. pubescens was shown to be the main BVOC emitter with isoprene representing ≈ 99 % of the carbon emitted as BVOC, we mainly focused on this species. C. coggygria was found to be a non-isoprene emitter (no other BVOCs were investigated). To fully understand both the canopy effect on Q. pubescens isoprene emissions and the inter-individual variability (tree to tree and within canopy), diurnal variations of isoprene were investigated from nine branches (seven branches located to the top of canopy at ≈ 4 m above ground level (a.g.l.), and two inside the canopy at ≈ 2 m a.g.l.). The Q. pubescens daily mean isoprene emission rate (ER d) fluctuated between 23 and 98 µgC g −1 DM h −1. Q. pubescens daily mean net assimilation (Pn) ranged between 5.4 and 13.8, and 2.8 and 6.4 µmol CO 2 m −2 s −1 for sunlit and shaded branches respectively. Both ER d and isoprene emission factors (Is), assessed according to Guenther et al. (1993) algorithm, varied by a factor of 4.3 among the sunlit branches. While sunlit branches ER d was clearly higher than for shaded branches, there was a non-significant variability of Is (59 to 77 µgC g −1 DM h −1). Diurnal variations of iso-prene emission rates (ERs) for sunlit branches were also investigated. ERs were detected at dawn 2 h after Pn became positive and were mostly exponentially dependent on Pn. Diurnal variations of ERs were not equally well described throughout the day by temperature (C T) and light (C L) parameters according to G93 algorithm. Temperature had more impact than photosynthetically active radiation (PAR) on the morning emissions increase, and ER was no longer correlated to C L × C T between solar noon (maximum ER) and mid-afternoon, possibly due to thermal stress of the plant. A comparison between measured and calculated emissions using two isoprene algorithms (G93 and MEGAN – Model of Emissions of Gases and Aerosols from Nature) highlighted the importance of isoprene emission factor Is value used, and some weakness in assessing isoprene emissions under Mediterranean climate conditions (drought) with current iso-prene models

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

Concentrations and fluxes of isoprene and oxygenated VOCs at a French Mediterranean oak forest

The CANOPEE project aims to better understand the biosphere–atmosphere exchanges of biogenic volatile organic compounds (BVOCs) in the case of Mediterranean ecosystems and the impact of in-canopy processes on the atmospheric chemical composition above the canopy. Based on an intensive field campaign, the objective of our work was to determine the chemical composition of the air inside a canopy as well as the net fluxes of reactive species between the canopy and the boundary layer. Measurements were carried out during spring 2012 at the field site of the Oak Observatory of the Observatoire de Haute Provence (O3HP) located in the southeast of France. The site is a forest ecosystem dominated by downy oak, Quercus pubescens Willd., a typical Mediterranean species which features large isoprene emission rates. Mixing ratios of isoprene, its degradation products methylvinylketone (MVK) and methacrolein (MACR) and several other oxygenated VOC (OxVOC) were measured above the canopy using an online proton transfer reaction mass spectrometer (PTR-MS), and fluxes were calculated by the disjunct eddy covariance approach. The O3HP site was found to be a very significant source of isoprene emissions, with daily maximum ambient concentrations ranging between 2–16 ppbv inside and 2–5 ppbv just above the top of the forest canopy. Significant isoprene fluxes were observed only during daytime, following diurnal cycles with midday net emission fluxes from the canopy ranging between 2.0 and 9.7 mg m−2 h1. Net isoprene normalized flux (at 30 °C, 1000 μmol quanta m−2 s−1) was estimated at 7.4 mg m−2 h−1. Evidence of direct emission of methanol was also found exhibiting maximum daytime fluxes ranging between 0.2 and 0.6 mg m−2 h−1, whereas flux values for monoterpenes and others OxVOC such as acetone and acetaldehyde were below the detection limit. The MVK+MACR-to-isoprene ratio provided useful information on the oxidation of isoprene, and is in agreement with recent findings proposing weak production yields of MVK and MACR, in remote forest regions where the NOx concentrations are low. In-canopy chemical oxidation of isoprene was found to be weak and did not seem to have a significant impact on isoprene concentrations and fluxes above the canopy

Isoprene chemistry in pristine and polluted Amazon environments : Eulerian and Lagrangian model frameworks and the strong bearing they have on our understanding of surface ozone and predictions of rainforest exposure to this priority pollutant

This study explores our ability to simulate the atmospheric chemistry stemming from isoprene emissions in pristine and polluted regions of the Amazon basin. We confront two atmospheric chemistry models – a global, Eulerian chemistry-climate model (UM-UKCA) and a trajectory-based Lagrangian model (CiTTyCAT) – with recent airborne measurements of atmospheric composition above the Amazon made during the SAMBBA campaign of 2012. The simulations with the two models prove relatively insensitive to the chemical mechanism employed; we explore one based on the Mainz Isoprene Mechanism, and an updated one that includes changes to the chemistry of first generation isoprene nitrates (ISON) and the regeneration of hydroxyl radicals via the formation of hydroperoxy-aldehydes (HPALDS) from hydroperoxy radicals (ISO2). In the Lagrangian model, the impact of increasing the spatial resolution of trace gas emissions employed from 3.75° × 2.5° to 0.1° × 0.1° varies from one flight to another, and from one chemical species to another. What consistently proves highly influential on our simulations, however, is the model framework itself – how the treatment of transport, and consequently mixing, differs between the two models. The lack of explicit mixing in the Lagrangian model yields variability in atmospheric composition more reminiscent of that exhibited by the measurements. In contrast, the combination of explicit (and implicit) mixing in the Eulerian model removes much of this variability but yields better agreement with the measurements overall. We therefore explore a simple treatment of mixing in the Lagrangian model that, drawing on output from the Eulerian model, offers a compromise between the two models. We use this Lagrangian/Eulerian combination, in addition to the separate Eulerian and Lagrangian models, to simulate ozone at a site in the boundary layer downwind of Manaus, Brazil. The Lagrangian/Eulerian combination predicts a value for an AOT40-like accumulated exposure metric of around 1000 ppbv h, compared to just 20 ppbv h with the Eulerian model. The model framework therefore has considerable bearing on our understanding of the frequency at which, and the duration for which, the rainforest is exposed to damaging ground-level ozone concentrations

Impact of leaf surface and in-canopy air chemistry on the ecosystem/atmosphere exchange of atmospheric pollutants

Chemical processes occurring on leaf surface and in air inside vegetation canopies play significant and sometimes dominant roles on pollutant dry deposition budgets. Yet, these processes are seldom explicitly treated in dry deposition parameterizations/models. This report briefly summarizes the current knowledge, outstanding issues, and recommendations for pollutant leaf surface exchange including ammonia (NH3), ozone (O3) and nitrogen oxides (NOx = NO + NO2), acidifying pollutants, volatile organic compounds (VOCs), and atmospheric aerosols

Impact of future land-cover changes on HNO₃ and O₃ surface dry deposition

International audienceDry deposition is a key component of surface–atmosphere exchange of compounds, acting as a sink for several chemical species. Meteorological factors, chemical properties of the trace gas considered and land surface properties are strong drivers of dry deposition efficiency and variability. Under both climatic and anthropogenic pressure, the vegetation distribution over the Earth has been changing a lot over the past centuries and could be significantly altered in the future. In this study, we perform a modeling investigation of the potential impact of land-cover changes between the present day (2006) and the future (2050) on dry deposition velocities at the surface, with special interest for ozone (O3) and nitric acid (HNO3), two compounds which are characterized by very different physicochemical properties. The 3-D chemistry-transport model LMDz-INCA is used, considering changes in vegetation distribution based on the three future projections, RCPs 2.6, 4.5 and 8.5, and present-day (2007) meteorology. The 2050 RCP 8.5 vegetation distribution leads to a rise of up to 7 % (+0.02 cm s−1) in the surface deposition velocity calculated for ozone (Vd,O3) and a decrease of −0.06 cm s−1 in the surface deposition velocity calculated for nitric acid (Vd,HNO3) relative to the present-day values in tropical Africa and up to +18 and −15 %, respectively, in Australia. When taking into account the RCP 4.5 scenario, which shows dramatic land-cover change in Eurasia, Vd,HNO3 increases by up to 20 % (annual-mean value) and reduces Vd,O3 by the same magnitude in this region. When analyzing the impact of surface dry deposition change on atmospheric chemical composition, our model calculates that the effect is lower than 1 ppb on annual-mean surface ozone concentration for both the RCP 8.5 and RCP 2.6 scenarios. The impact on HNO3 surface concentrations is more disparate between the two scenarios regarding the spatial repartition of effects. In the case of the RCP 4.5 scenario, a significant increase of the surface O3 concentration reaching locally by up to 5 ppb (+5 %) is calculated on average during the June–August period. This scenario also induces an increase of HNO3 deposited flux exceeding locally 10 % for monthly values. Comparing the impact of land-cover change to the impact of climate change, considering a 0.93 °C increase of global temperature, on dry deposition velocities, we estimate that the strongest increase over lands occurs in the Northern Hemisphere during winter, especially in Eurasia, by +50 % (+0.07 cm s−1) for Vd,O3 and +100 % (+0.9 cm s−1) for Vd,HNO3. However, different regions are affected by both changes, with climate change impact on deposition characterized by a latitudinal gradient, while the land-cover change impact is much more heterogeneous depending on vegetation distribution modification described in the future RCP scenarios. The impact of long-term land-cover changes on dry deposition is shown to be significant and to differ strongly from one scenario to another. It should therefore be considered in biosphere–atmospheric chemistry interaction studies in order to have a fully consistent picture