Abstract. The Model of Emissions of Gases and Aerosols from Nature (MEGANv2.1) together with the ModernEra Retrospective Analysis for Research and Applications (MERRA) meteorological fields were used to create a global emission data set of biogenic volatile organic compounds (BVOC) available on a monthly basis for the time period of 1980-2010. This data set, developed under the Monitoring Atmospheric Composition and Climate project (MACC), is called MEGAN-MACC. The model estimated mean annual total BVOC emission of 760 Tg (C) yr −1 consisting of isoprene (70 %), monoterpenes (11 %), methanol (6 %), acetone (3 %), sesquiterpenes (2.5 %) and other BVOC species each contributing less than 2 %.Several sensitivity model runs were performed to study the impact of different model input and model settings on isoprene estimates and resulted in differences of up to ±17 % of the reference isoprene total. A greater impact was observed for a sensitivity run applying parameterization of soil moisture deficit that led to a 50 % reduction of isoprene emissions on a global scale, most significantly in specific regions of Africa, South America and Australia.MEGAN-MACC estimates are comparable to results of previous studies. More detailed comparison with other isoprene inventories indicated significant spatial and temporal differences between the data sets especially for Australia, Southeast Asia and South America. MEGAN-MACC estimates of isoprene, α-pinene and group of monoterpenes showed a reasonable agreement with surface flux measurements at sites located in tropical forests in the Amazon and Malaysia. The model was able to capture the seasonal variation of isoprene emissions in the Amazon forest.

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The Leuven isoprene mechanism, proposed earlier to aid in rationalizing the unexpectedly high hydroxyl radical (OH) concentrations in isoprene-rich, low-nitric-oxide (NO) regions ( Peeters ; et al. Phys. Chem. Chem. Phys . 2009 , 11 , 5935 ), is presented in an upgraded and extended version, LIM1. The kinetics of the crucial reactions in the proposed isoprene-peroxy radical interconversion and isomerization pathways are re-evaluated theoretically, on the basis of energy barriers computed at the much higher CCSD(T)/aug-cc-pVTZ//QCISD/6-311G(d,p) level of theory, and using multiconformer partition functions obtained at the M06-2X/6-311++G(3df,2p) level that, different from the B3LYP level used in our earlier work, accounts for the crucial London dispersion effects in the H-bonded systems involved. The steady-state fraction of the specific Z-δ-OH-peroxy radical isomers/conformers that can isomerize by a 1,6-H shift is shown to be largely governed by hydrogen-bond strengths, whereas their isomerization itself is found to occur quasi-exclusively by hydrogen atom tunneling. The isomer-specific Z-δ-OH-peroxy 1,6-H-shift rate coefficients are predicted to be of the order of 1 s(-1) at 298 K, but the experimentally accessible bulk rate coefficients, which have to be clearly distinguished from the former, are 2 orders of magnitude lower due to the very low Z-δ-OH-peroxy steady-state fractions that are only around or below 0.01 at low to moderate NO and depend on the peroxy lifetime. Two pathways subsequent to the peroxy radical 1,6-H shift are identified, the earlier predicted route yielding the photolabile hydroperoxy-methylbutenals (HPALDs), and a second, about equally important path, to dihydroperoxy-carbonyl peroxy radicals (di-HPCARP). Taking this into account, our predicted bulk peroxy isomerization rate coefficients are about a factor 1.8 higher than the available experimental results for HPALD production ( Crounse ; et al. Phys. Chem. Chem. Phys. 2011 , 13 , 13607 ), which is within the respective uncertainty margins. We also show that the experimental temperature dependence of the HPALD production rates as well as the observed kinetic isotope effect for per-deuterated isoprene support quantitatively our theoretical peroxy interconversion rates. Global modeling implementing LIM1 indicates that on average about 28% of the isoprene peroxys react via the 1,6-H-shift isomerization route, representing 100-150 Tg carbon per year. The fast photolysis of HPALDs we proposed earlier as primary OH regeneration mechanism ( Peeters and Muller . Phys. Chem. Chem. Phys . 2010 , 12 , 14227 ) found already experimental confirmation ( Wolfe ; et al. Phys. Chem. Chem. Phys. 2012 , 14 , 7276 ); based on further theoretical work in progress, reaction schemes are presented of the oxy coproduct radicals from HPALD photolysis and of the di-HPCARP radicals from the second pathway following peroxy isomerization that are both expected to initiate considerable additional OH recycling.

Spaceborne NO2 column observations from two high‐resolution instruments, Tropospheric Monitoring Instrument (TROPOMI) on board Sentinel‐5 Precursor and Ozone Monitoring Instrument (OMI) on Aura, reveal unprecedented NO2 decreases over China, South Korea, western Europe, and the United States as a result of public health measures enforced to contain the coronavirus disease outbreak (Covid‐19) in January–April 2020. The average NO2 column drop over all Chinese cities amounts to −40% relative to the same period in 2019 and reaches up to a factor of ~2 at heavily hit cities, for example, Wuhan, Jinan, while the decreases in western Europe and the United States are also significant (−20% to −38%). In contrast with this, although Iran is also strongly affected by the disease, the observations do not show evidence of lower emissions, reflecting more limited health measures.

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A consistent body of experimental evidence from work of other groups is presented in support of the novel, theoretically based, isoprene oxidation mechanism we recently proposed to rationalize the unexpectedly high OH concentrations observed over areas with high isoprene emissions. Some explicit or implicit criticisms on the new mechanism are addressed. A particular photochemical mechanism is newly proposed for the OH-regenerating photolysis of the crucial hydroperoxy-methyl-butenals (HPALDs), formed by isomerisation of the initial isoprene hydroxy-peroxy radicals, that rationalizes a quantum yield close to 1. A similar photolysis mechanism of the resulting photolabile peroxy-acid-aldehydes (PACALDs) is shown to generate ample additional OH. Global modeling demonstrates the major importance of the new chemistry for the oxidizing capacity of the atmosphere over continents. The globally averaged yield of the HPALDs in the oxidation of isoprene by OH is estimated to be of the order of 0.6. The isomerisation reactions of isoprene peroxy radicals are found to result in modelled [OH] increases in the planetary boundary layer by up to a factor of 3, in agreement with the reported observations as in the Amazon basin.

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Abstract. We use ground-based observations of CO mixing ratios and vertical column abundances together with tropospheric NO 2 columns from the GOME satellite instrument as constraints for improving the global annual emission estimates of CO and NO x for the year 1997. The agreement between concentrations calculated by the global 3-dimensional CTM IMAGES and the observations is optimized using the adjoint modelling technique, which allows to invert for CO and NO x fluxes simultaneously, taking their chemical interactions into account. Our analysis quantifies a total of 39 flux parameters, comprising anthropogenic and biomass burning sources over large continental regions, soil and lightning emissions of NO x , biogenic emissions of CO and nonmethane hydrocarbons, as well as the deposition velocities of both CO and NO x . Comparison between observed, prior and optimized CO mixing ratios at NOAA/CMDL sites shows that the inversion performs well at the northern mid-and high latitudes, and that it is less efficient in the Southern Hemisphere, as expected due to the scarsity of measurements over this part of the globe. The inversion, moreover, brings the model much closer to the measured NO 2 columns over all regions. Sensitivity tests show that anthropogenic sources exhibit weak sensitivity to changes of the a priori errors associated to the bottom-up inventory, whereas biomass burning sources are subject to a strong variability. Our best estimate for the 1997 global top-down CO source amounts to 2760 Tg CO. Anthropogenic emissions increase by 28%, in agreement with previous inverse modelling studies, suggesting that the present bottom-up inventories underestimate the anthropogenic CO emissions in the Northern Hemisphere. The magnitude of the optimized NO x global source decreases by 14% with respect to the prior, and amounts to 42.1 Tg N, out of which 22.8 Tg N are due to anthropogenic sources. The NO x emissions increase over Tropical regions, whereasCorrespondence to: J.-F. Müller (jfm@aeronomie.be) they decrease over Europe and Asia. Our inversion results have been evaluated against independent observations from aircraft campaigns. This comparison shows that the optimization of CO emissions constrained by both CO and NO 2 observations leads to a better agreement between modelled and observed values, especially in the Tropics and the Southern Hemisphere, compared to the case where only CO observations are used. A posteriori estimation of errors on the control parameters shows that a significant error reduction is achieved for the majority of the anthropogenic source parameters, whereas biomass burning emissions are still subject to large errors after optimization. Nonetheless, the constraints provided by the GOME measurements allow to reduce the uncertainties on savanna burning emissions of both CO and NO x , suggesting thus that the incorporation of these data in the inversion yields more robust results for carbon monoxide.