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Forest self-reliance Measurements taken by aircraft flying over the Amazon rain forest reveal unexpectedly high concentrations of hydroxyl radicals in the lower atmosphere. Hydroxyl is the primary atmospheric oxidant, and it was conventional wisdom that large forest emissions of hydrocarbons strongly reduce the atmospheric oxidation capacity. The new data suggest that this is not the case, and that the pristine forest can 'manage' its atmospheric sustainability remarkably well. A possible mechanism is suggested: hydroxyl radicals may be recycling via the natural oxidation of volatile organic compounds, mainly isoprene. In the absence of external influences, the forest seems able to maintain a benign atmosphere. But where deforestation and anthropogenic emissions of NO intervene, photochemical air pollution remains likely. Aircraft measurements of atmospheric trace gases performed over the pristine Amazon forest find unexpectedly high hydroxyl radical concentrations. On the basis of a model study and the results of laboratory experiments, it is proposed that natural volatile organic compounds oxidation, notably of isoprene, recycles hydroxyl radical efficiently through reactions of organic peroxy radicals, which may be able to explain the high hydroxyl radical levels observed. Terrestrial vegetation, especially tropical rain forest, releases vast quantities of volatile organic compounds (VOCs) to the atmosphere 1 , 2 , 3 , which are removed by oxidation reactions and deposition of reaction products 4 , 5 , 6 . The oxidation is mainly initiated by hydroxyl radicals (OH), primarily formed through the photodissociation of ozone 4 . Previously it was thought that, in unpolluted air, biogenic VOCs deplete OH and reduce the atmospheric oxidation capacity 5 , 6 , 7 , 8 , 9 , 10 . Conversely, in polluted air VOC oxidation leads to noxious oxidant build-up by the catalytic action of nitrogen oxides 5 , 6 , 7 , 8 , 9 , 10 (NO x = NO + NO 2 ). Here we report aircraft measurements of atmospheric trace gases performed over the pristine Amazon forest. Our data reveal unexpectedly high OH concentrations. We propose that natural VOC oxidation, notably of isoprene, recycles OH efficiently in low-NO x air through reactions of organic peroxy radicals. Computations with an atmospheric chemistry model and the results of laboratory experiments suggest that an OH recycling efficiency of 40–80 per cent in isoprene oxidation may be able to explain the high OH levels we observed in the field. Although further laboratory studies are necessary to explore the chemical mechanism responsible for OH recycling in more detail, our results demonstrate that the biosphere maintains a remarkable balance with the atmospheric environment.

The hydroxyl radical is a key oxidant in the Earth’s atmosphere. The inclusion in an atmospheric chemistry model of a detailed mechanism of isoprene oxidation, involving the buffering of hydroxyl radical concentrations, improves agreement between model simulations of hydroxyl radical levels and observations. The hydroxyl radical is a key oxidant in the Earth’s atmosphere. This short-lived highly reactive molecule plays an important role in the degradation of volatile organic compounds, leading to the production of ozone and the formation and growth of aerosol particles 1 , 2 , 3 . In this way, hydroxyl radicals influence air quality and regional climate. Measurements over tropical forests suggest that hydroxyl radicals are recycled following reaction with the volatile organic compound isoprene 4 , 5 , but the chemistry underpinning this observation is uncertain. Here, we propose a detailed chemical mechanism for the oxidation of isoprene by hydroxyl radicals. The photo-oxidation of unsaturated hydroperoxy-aldehydes—a product of isoprene oxidation—is a central part of the mechanism; their photolysis initiates a hydroxyl radical production cascade that is limited by the reaction of hydroperoxy-aldehydes with the hydroxyl radical itself. We incorporate this mechanism into a global atmospheric chemistry model and find that measurements of hydroxyl radical concentrations over a pristine region of the Amazon, and in moderately polluted conditions, are captured well. On the basis of this agreement, we suggest that isoprene oxidation can buffer hydroxyl radical concentrations, by serving as both a sink and source for these radicals.

Recent experimental findings indicate that secondary organic aerosol (SOA) represents an important and, under many circumstances, the major fraction of the organic aerosol burden. Here, we use a global 3-D model (IMPACT) to test the results of different mechanisms for the production of SOA. The basic mechanism includes SOA formation from organic nitrates and peroxides produced from an explicit chemical formulation, using partition coefficients based on thermodynamic principles together with assumptions for the rate of formation of low-volatility oligomers. We also include the formation of low-volatility SOA from the reaction of glyoxal and methylglyoxal on aqueous aerosols and cloud droplets as well as from the reaction of epoxides on aqueous aerosols. A model simulation including these SOA formation mechanisms gives an annual global SOA production of 120.5 Tg. The global production of SOA is decreased substantially to 90.8 Tg yr−1 if the HOx regeneration mechanism proposed by Peeters et al. (2009) is used. Model predictions with and without this HOx (OH and HO2 regeneration scheme are compared with multiple surface observation datasets, namely: the Interagency Monitoring of Protected Visual Environments (IMPROVE) for the United States, the European Monitoring and Evaluation Programme (EMEP), and aerosol mass spectrometry (AMS) data measured in both the Northern Hemisphere and tropical forest regions. All model simulations show reasonable agreement with the organic carbon mass observed in the IMPROVE network and the AMS dataset, however observations in Europe are significantly underestimated, which may be caused by an underestimation of primary organic aerosol emissions (POA) in winter and of emissions and/or SOA production in the summer. The modeled organic aerosol concentrations tend to be higher by roughly a factor of three when compared with measurements at three tropical forest sites. This overestimate suggests that more measurements and model studies are needed to examine the formation of organic aerosols in the tropics. The modeled organic carbon (OC) in the free troposphere is in agreement with measurements in the ITCT-2K4 aircraft campaign over North America and in pollution layers off Asia during the INTEX-B campaign, although the model underestimates OC in the free troposphere in comparison with the ACE-Asia campaign off the coast of Japan.

A biogenic emission scheme based on the Model of Emissions of Gases and Aerosols from Nature (MEGAN) version 2.1 (Guenther et al., 2012) has been integrated into the ECHAM6-HAMMOZ chemistry climate model in order to calculate the emissions from terrestrial vegetation of 32 compounds. The estimated annual global total for the reference simulation is 634TgCyr-1 (simulation period 2000-2012). Isoprene is the main contributor to the average emission total, accounting for 66% (417TgCyr-1), followed by several monoterpenes (12%), methanol (7%), acetone (3.6%), and ethene (3.6%). Regionally, most of the high annual emissions are found to be associated with tropical regions and tropical vegetation types. In order to evaluate the implementation of the biogenic model in ECHAM-HAMMOZ, global and regional biogenic volatile organic compound (BVOC) emissions of the reference simulation were compared to previous published experiment results with MEGAN. Several sensitivity simulations were performed to study the impact of different model input and parameters related to the vegetation cover and the ECHAM6 climate. BVOC emissions obtained here are within the range of previous published estimates. The large range of emission estimates can be attributed to the use of different input data and empirical coefficients within different setups of MEGAN. The biogenic model shows a high sensitivity to the changes in plant functional type (PFT) distributions and associated emission factors for most of the compounds. The global emission impact for isoprene is about -9%, but reaches +75% for α-pinene when switching from global emission factor maps to PFT-specific emission factor distributions. The highest sensitivity of isoprene emissions is calculated when considering soil moisture impact, with a global decrease of 12.5% when the soil moisture activity factor is included in the model parameterization. Nudging ECHAM6 climate towards ERA-Interim reanalysis has an impact on the biogenic emissions, slightly lowering the global total emissions and their interannual variability.

Measurements of OH and HO2 radicals were conducted in a pine-dominated forest in southern Finland during the HUMPPA-COPEC-2010 (Hyytiälä United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) field campaign in summer 2010. Simultaneous side-by-side measurements of hydroxyl radicals were conducted with two instruments using chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF), indicating small systematic disagreement, OHLIF / OHCIMS = (1.31 ± 0.14). Subsequently, the LIF instrument was moved to the top of a 20 m tower, just above the canopy, to investigate the radical chemistry at the ecosystem–atmosphere interface. Comprehensive measurements including observations of many volatile organic compounds (VOCs) and the total OH reactivity were conducted and analysed using steady-state calculations as well as an observationally constrained box model. Production rates of OH calculated from measured OH precursors are consistent with those derived from the steady-state assumption and measured total OH loss under conditions of moderate OH reactivity. The primary photolytic sources of OH contribute up to one-third to the total OH production. OH recycling, which occurs mainly by HO2 reacting with NO and O3, dominates the total hydroxyl radical production in this boreal forest. Box model simulations agree with measurements for hydroxyl radicals (OHmod. / OHobs. = 1.00 ± 0.16), while HO2 mixing ratios are significantly under-predicted (HO2mod. / HO2obs. = 0.3 ± 0.2), and simulated OH reactivity does not match the observed OH reactivity. The simultaneous under-prediction of HO2 and OH reactivity in periods in which OH concentrations were simulated realistically suggests that the missing OH reactivity is an unaccounted-for source of HO2. Detailed analysis of the HOx production, loss, and recycling pathways suggests that in periods of high total OH reactivity there are additional recycling processes forming OH directly, not via reaction of HO2 with NO or O3, or unaccounted-for primary HOx sources. Under conditions of moderate observed OH reactivity and high actinic flux, an additional RO2 source of approximately 1 × 106 molec cm−3 s−1 would be required to close the radical budget. Nevertheless, a major fraction of the OH recycling occurs via the reaction of HO2 with NO and O3 in this terpene-dominated environment.

We present version 3.0 of the atmospheric chemistry box model CAABA/MECCA. In addition to a complete update of the rate coefficients to the most recent recommendations, a number of new features have been added: chemistry in multiple aerosol size bins; automatic multiple simulations reaching steady-state conditions; Monte-Carlo simulations with randomly varied rate coefficients within their experimental uncertainties; calculations along Lagrangian trajectories; mercury chemistry; more detailed isoprene chemistry; tagging of isotopically labeled species. Further changes have been implemented to make the code more user-friendly and to facilitate the analysis of the model results. Like earlier versions, CAABA/MECCA-3.0 is a community model published under the GNU General Public License.

In the OOMPH (Ocean Organics Modifying Particles in both Hemispheres) project a ship measurement cruise took place in the late austral summer from 01 to 23 March 2007. The French research vessel Marion Dufresne sailed from Punta Arenas, Chile (70.85° W, 53.12° S), to Réunion island (55.36° E, 21.06° S) across the South Atlantic Ocean. In situ measurements of hydrogen peroxide, methylhydroperoxide and ozone were performed and are compared to simulations with the atmospheric chemistry global circulation model EMAC (ECHAM/MESSy Atmospheric Chemistry). The model generally reproduces the measured trace gas levels, but it underestimates hydrogen peroxide mixing ratios at high wind speeds, indicating too-strong dry deposition to the ocean surface. An interesting feature during the cruise is a strong increase of hydrogen peroxide, methylhydroperoxide and ozone shortly after midnight off the west coast of Africa due to an increase in the boundary layer height, leading to downward transport from the free troposphere, which is qualitatively reproduced by the model.

As a major source region of the hydroxyl radical OH, the Tropics largely control the oxidation capacity of the atmosphere on a global scale. However, emissions of hydrocarbons from the tropical rainforest that react rapidly with OH can potentially deplete the amount of OH and thereby reduce the oxidation capacity. The airborne GABRIEL field campaign in equatorial South America (Suriname) in October 2005 investigated the influence of the tropical rainforest on the HOx budget (HOx = OH + HO2). The first observations of OH and HO2 over a tropical rainforest are compared to steady state concentrations calculated with the atmospheric chemistry box model MECCA. The important precursors and sinks for HOx chemistry, measured during the campaign, are used as constraining parameters for the simulation of OH and HO2. Significant underestimations of HOx are found by the model over land during the afternoon, with mean ratios of observation to model of 12.2 ± 3.5 and 4.1 ± 1.4 for OH and HO2, respectively. The discrepancy between measurements and simulation results is correlated to the abundance of isoprene. While for low isoprene mixing ratios (above ocean or at altitudes >3 km), observation and simulation agree fairly well, for mixing ratios >200 pptV (<3 km over the rainforest) the model tends to underestimate the HOx observations as a function of isoprene. Box model simulations have been performed with the condensed chemical mechanism of MECCA and with the detailed isoprene reaction scheme of MCM, resulting in similar results for HOx concentrations. Simulations with constrained HO2 concentrations show that the conversion from HO2 to OH in the model is too low. However, by neglecting the isoprene chemistry in the model, observations and simulations agree much better. An OH source similar to the strength of the OH sink via isoprene chemistry is needed in the model to resolve the discrepancy. A possible explanation is that the oxidation of isoprene by OH not only dominates the removal of OH but also produces it in a similar amount. Several additional reactions which directly produce OH have been implemented into the box model, suggesting that upper limits in producing OH are still not able to reproduce the observations (improvement by factors of ≈2.4 and ≈2 for OH and HO2, respectively). We determine that OH has to be recycled to 94% instead of the simulated 38% to match the observations, which is most likely to happen in the isoprene degradation process, otherwise additional sources are required.

The self-cleaning or oxidation capacity of the atmosphere is principally controlled by hydroxyl (OH) radicals in the troposphere. Hydroxyl has primary (P) and secondary (S) sources, the former mainly through the photodissociation of ozone, the latter through OH recycling in radical reaction chains. We used the recent Mainz Organics Mechanism (MOM) to advance volatile organic carbon (VOC) chemistry in the general circulation model EMAC (ECHAM/MESSy Atmospheric Chemistry) and show that S is larger than previously assumed. By including emissions of a large number of primary VOC, and accounting for their complete breakdown and intermediate products, MOM is mass-conserving and calculates substantially higher OH reactivity from VOC oxidation compared to predecessor models. Whereas previously P and S were found to be of similar magnitude, the present work indicates that S may be twice as large, mostly due to OH recycling in the free troposphere. Further, we find that nighttime OH formation may be significant in the polluted subtropical boundary layer in summer. With a mean OH recycling probability of about 67 %, global OH is buffered and not sensitive to perturbations by natural or anthropogenic emission changes. Complementary primary and secondary OH formation mechanisms in pristine and polluted environments in the continental and marine troposphere, connected through long-range transport of O3, can maintain stable global OH levels.

This paper describes the background, instrumentation, goals, and the regional influences on the HUMPPA-COPEC intensive field measurement campaign, conducted at the Boreal forest research station SMEAR II (Station for Measuring Ecosystem-Atmosphere Relation) in Hyytiälä, Finland from 12 July–12 August 2010. The prevailing meteorological conditions during the campaign are examined and contrasted with those of the past six years. Back trajectory analyses show that meteorological conditions at the site in 2010 were characterized by a higher proportion of southerly flow than in the other years studied. As a result the summer of 2010 was anomalously warm and high in ozone making the campaign relevant for the analysis of possible future climates. A comprehensive land use analysis, provided on both 5 and 50 km scales, shows that the main vegetation types surrounding the site on both the regional and local scales are: coniferous forest (Scots pine and/or Norway spruce); mixed forest (Birch and conifers); and woodland scrub (e.g. Willows, Aspen); indicating that the campaign results can be taken as representative of the Boreal forest ecosystem. In addition to the influence of biogenic emissions, the measurement site was occasionally impacted by sources other than vegetation. Specific tracers have been used here to identify the time periods when such sources have impacted the site namely: biomass burning (acetonitrile and CO), urban anthropogenic pollution (pentane and SO2) and the nearby Korkeakoski sawmill (enantiomeric ratio of chiral monoterpenes). None of these sources dominated the study period, allowing the Boreal forest summertime emissions to be assessed and contrasted with various other source signatures.