Abstract. Reactive gases and aerosols are produced by terrestrial ecosystems, processed within plant canopies, and can then be emitted into the above-canopy atmosphere. Estimates of the above-canopy fluxes are needed for quantitative earth system studies and assessments of past, present and future air quality and climate. The Model of Emissions of Gases and Aerosols from Nature (MEGAN) is described and used to quantify net terrestrial biosphere emission of isoprene into the atmosphere. MEGAN is designed for both global and regional emission modeling and has global coverage with ∼1 km 2 spatial resolution. Field and laboratory investigations of the processes controlling isoprene emission are described and data available for model development and evaluation are summarized. The factors controlling isoprene emissions include biological, physical and chemical driving variables. MEGAN driving variables are derived from models and satellite and ground observations. Tropical broadleaf trees contribute almost half of the estimated global annual isoprene emission due to their relatively high emission factors and because they are often exposed to conditions that are conducive for isoprene emission. The remaining flux is primarily from shrubs which have a widespread distribution. The annual global isoprene emission estimated with MEGAN ranges from about 500 to 750 Tg isoprene (440 to 660 Tg carbon) depending on the driving variables which include temperature, solar radiation, Leaf Area Index, and plant functional type. The global annual isoprene emission estimated using the standard driving variables is ∼600 Tg isoprene. Differences in driving variables result in emission estimates that differ by more than a factor of three for specific times and locations. It is difficult to evaluate isoCorrespondence to: A. Guenther (guenther@ucar.edu) prene emission estimates using the concentration distributions simulated using chemistry and transport models, due to the substantial uncertainties in other model components, but at least some global models produce reasonable results when using isoprene emission distributions similar to MEGAN estimates. In addition, comparison with isoprene emissions estimated from satellite formaldehyde observations indicates reasonable agreement. The sensitivity of isoprene emissions to earth system changes (e.g., climate and land-use) demonstrates the potential for large future changes in emissions. Using temperature distributions simulated by global climate models for year 2100, MEGAN estimates that isoprene emissions increase by more than a factor of two. This is considerably greater than previous estimates and additional observations are needed to evaluate and improve the methods used to predict future isoprene emissions.

Biomass burning (BB) is the second largest source of trace gases and the largest source of primary fine carbonaceous particles in the global troposphere. Many recent BB studies have provided new emission factor (EF) measurements. This is especially true for non-methane organic compounds (NMOC), which influence secondary organic aerosol (SOA) and ozone formation. New EF should improve regional to global BB emissions estimates and therefore, the input for atmospheric models. In this work we present an up-to-date, comprehensive tabulation of EF for known pyrogenic species based on measurements made in smoke that has cooled to ambient temperature, but not yet undergone significant photochemical processing. All EFs are converted to one standard form (g compound emitted per kg dry biomass burned) using the carbon mass balance method and they are categorized into 14 fuel or vegetation types. Biomass burning terminology is defined to promote consistency. We compile a large number of measurements of biomass consumption per unit area for important fire types and summarize several recent estimates of global biomass consumption by the major types of biomass burning. Post emission processes are discussed to provide a context for the emission factor concept within overall atmospheric chemistry and also highlight the potential for rapid changes relative to the scale of some models or remote sensing products. Recent work shows that individual biomass fires emit significantly more gas-phase NMOC than previously thought and that including additional NMOC can improve photochemical model performance. A detailed global estimate suggests that BB emits at least 400 Tg yr⁻¹ of gas-phase NMOC, which is almost 3 times larger than most previous estimates. Selected recent results (e.g. measurements of HONO and the BB tracers HCN and CH₃CN) are highlighted and key areas requiring future research are briefly discussed

Biomass burning (BB) is the second largest source of trace gases and the largest source of primary fine carbonaceous particles in the global troposphere. Many recent BB studies have provided new emission factor (EF) measurements. This is especially true for non methane organic compounds (NMOC), which influence secondary organic aerosol (SOA) and ozone formation. New EF should improve regional to global BB emissions estimates and therefore, the input for atmospheric models. In this work we present an up-to-date, comprehensive tabulation of EF for known pyrogenic species based on measurements made in smoke that has cooled to ambient temperature, but not yet undergone significant photochemical processing. All the emission factors are converted to one standard form (g compound emitted per kg dry biomass burned) using the carbon mass balance method and they are categorized into 14 fuel or vegetation types. We compile a large number of measurements of biomass consumption per unit area for important fire types and summarize several recent estimates of global biomass consumption by the major types of biomass burning. Biomass burning terminology is defined to promote consistency. Post emission processes are discussed to provide a context for the emission factor concept within overall atmospheric chemistry and also highlight the potential for rapid changes relative to the scale of some models or remote sensing products. Recent work shows that individual biomass fires emit significantly more gas-phase NMOC than previously thought and that including additional NMOC can improve photochemical model performance. A detailed global estimate suggests that BB emits at least 400 Tg yr⁻¹ of gas-phase NMOC, which is about 4 times larger than most previous estimates. Selected recent results (e.g. measurements of HONO and the BB tracers HCN and CH₃CN) are highlighted and key areas requiring future research are briefly discussed

Abstract. In March 2006 two instrumented aircraft made the first detailed field measurements of biomass burning (BB) emissions in the Northern Hemisphere tropics as part of the MILAGRO project. The aircraft were the National Center for Atmospheric Research C-130 and a University of Montana/US Forest Service Twin Otter. The initial emissions of up to 49 trace gas or particle species were measured from 20 deforestation and crop residue fires on the Yucatan peninsula. This included two trace gases useful as indicators of BB (HCN and acetonitrile) and several rarely, or never before, measured species: OH, peroxyacetic acid, propanoic acid, hydrogen peroxide, methane sulfonic acid, and sulfuric acid. Crop residue fires emitted more organic acids and ammonia than deforestation fires, but the emissions from the main fire types were otherwise fairly similar. The Yucatan firesCorrespondence to: R. J. Yokelson (bob.yokelson@umontana.edu) emitted unusually high amounts of SO 2 and particle chloride, likely due to a strong marine influence on this peninsula. As smoke from one fire aged, the ratio O 3 / CO increased to ∼15% in <∼1 h similar to the fast net production of O 3 in BB plumes observed earlier in Africa. The rapid change in O 3 occurs at a finer spatial scale than is employed in global models and is also faster than predicted by microscale models. Fast increases in PAN, H 2 O 2 , and two organic acids were also observed. The amount of secondary organic acid is larger than the amount of known precursors. Rapid secondary formation of organic and inorganic aerosol was observed with the ratio PM 2.5 / CO more than doubling in ∼1.4±0.7 h. The OH measurements revealed high initial levels (>1×10 7 molecules/cm 3 ) that were likely caused in part by high initial HONO (∼10% of NO y ). Thus, more research is needed to understand critical post emission processes for the second-largest trace gas source on Earth. It is estimated that ∼44 Tg of biomass burned in the Yucatan in the spring Published by Copernicus Publications on behalf of the European Geosciences Union.

Abstract. In recent years evidence has emerged that the amount of isoprene emitted from a leaf is affected by the CO 2 growth environment. Many -though not all -laboratory experiments indicate that emissions increase significantly at below-ambient CO 2 concentrations and decrease when concentrations are raised to above-ambient. A small number of process-based leaf isoprene emission models can reproduce this CO 2 stimulation and inhibition. These models are briefly reviewed, and their performance in standard conditions compared with each other and to an empirical algorithm. One of the models was judged particularly useful for incorporation into a dynamic vegetation model framework, LPJ-GUESS, yielding a tool that allows the interactive effects of climate and increasing CO 2 concentration on vegetation distribution, productivity, and leaf and ecosystem isoprene emissions to be explored. The coupled vegetation dynamics-isoprene model is described and used here in a mode particularly suited for the ecosystem scale, but it can be employed at the global level as well.Annual and/or daily isoprene emissions simulated by the model were evaluated against flux measurements (or model estimates that had previously been evaluated with flux data) from a wide range of environments, and agreement between modelled and simulated values was generally good. By usCorrespondence to: A. Arneth (almut.arneth@nateko.lu.se) ing a dynamic vegetation model, effects of canopy composition, disturbance history, or trends in CO 2 concentration can be assessed. We show here for five model test sites that the suggested CO 2 -inhibition of leaf-isoprene metabolism can be large enough to offset increases in emissions due to CO 2 -stimulation of vegetation productivity and leaf area growth. When effects of climate change are considered atop the effects of atmospheric composition the interactions between the relevant processes will become even more complex. The CO 2 -isoprene inhibition may have the potential to significantly dampen the expected steep increase of ecosystem isoprene emission in a future, warmer atmosphere with higher CO 2 levels; this effect raises important questions for projections of future atmospheric chemistry, and its connection to the terrestrial vegetation and carbon cycle.

Abstract. Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3 ‰) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of fCO2 vs. fC5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2, if the fC5H6O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.

[1] Disjunct eddy covariance in conjunction with continuous in-canopy gradient measurements allowed for the first time to quantify the fine-scale source and sink distribution of some of the most abundant biogenic (isoprene, monoterpenes, methanol, acetaldehyde, and acetone) and photooxidized (MVK+MAC, acetone, acetaldehyde, acetic, and formic acid) VOCs in an old growth tropical rain forest. Our measurements revealed substantial isoprene emissions (up to 2.50 mg m À2 h À1 ) and light-dependent monoterpene emissions (up to 0.33 mg m À2 h À1 ) at the peak of the dry season (April and May 2003). Oxygenated species such as methanol, acetone, and acetaldehyde were typically emitted during daytime with net fluxes up to 0.50, 0.36, and 0.20 mg m À2 h À1 , respectively. When generalized for tropical rain forests, these fluxes would add up to a total emission of 36, 16, 19, 106, and 7.2 Tg/yr for methanol, acetaldehyde, acetone, isoprene, and monoterpenes, respectively. During nighttime we observed strong sinks for oxygenated and nitrogen-containing compounds such as methanol, acetone, acetaldehyde, MVK+MAC, and acetonitrile with deposition velocities close to the aerodynamic limit. This suggests that the canopy resistance (R c ) is very small and not the rate-limiting step for the nighttime deposition of many VOCs. Our measured mean dry deposition velocities of methanol, acetone, acetaldehyde, MVK+MAC, and acetonitrile were a factor 10-20 higher than estimated from traditional deposition models. If our measurements are generalized, this could have important implications for the redistribution of VOCs in atmospheric chemistry models. Our observations indicate that the current understanding of reactive carbon exchange can only be seen as a first-order approximation.

[1] Airborne and ground-based mixing ratio and flux measurements using eddy covariance (EC) and for the first time the mixed layer gradient (MLG) and mixed layer variance (MLV) techniques are used to assess the impact of isoprene and monoterpene emissions on atmospheric chemistry in the Amazon basin. Average noon isoprene (7.8 ± 2.3 mg/m 2 /h) and monoterpene fluxes (1.2 ± 0.5 mg/m 2 /h) compared well between ground and airborne measurements and are higher than fluxes estimated in this region during other seasons. The biogenic emission model, Model of Emissions of Gases and Aerosols from Nature (MEGAN), estimates fluxes that are within the model and measurement uncertainty and can describe the large observed variations associated with land-use change in the region north-west of Manaus. Isoprene and monoterpenes accounted for $75% of the total OH reactivity in this region and are important volatile organic compounds (VOCs) for modeling atmospheric chemistry in Amazonia. The presence of fair weather clouds (cumulus humilis) had an important impact on the vertical distribution and chemistry of VOCs through the planetary boundary layer (PBL), the cloud layer, and the free troposphere (FT). Entrainment velocities between 10:00 and 11:30 local time (LT) are calculated to be on the order of 8-10 cm/s. The ratio of methyl-vinyl-ketone (MVK) and methacrolein (MAC) (unique oxidation products of isoprene chemistry) with respect to isoprene showed a pronounced increase in the cloud layer due to entrainment and an increased oxidative capacity in broken cloud decks. A decrease of the ratio in the lower free troposphere suggests cloud venting through activated clouds. OH modeled in the planetary boundary layer using a photochemical box model is much lower than OH calculated from a mixed layer budget approach. An ambient reactive sesquiterpene mixing ratio of 1% of isoprene would be sufficient to explain most of this discrepancy. Increased OH production due to increased photolysis in the cloud layer balances the low OH values modeled for the planetary boundary layer. The intensity of segregation (I s ) of isoprene and OH, defined as a relative reduction of the reaction rate constant due to incomplete mixing, is found to be significant: up to 39 ± 7% in the $800-m-deep cloud layer. The effective reaction rate between isoprene and OH can therefore vary significantly in certain parts of the lower atmosphere.