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Formic acid contributes significantly to acid rain in remote environments1, 2. Direct sources of formic acid include human activities, biomass burning and plant leaves. Aside from these direct sources, sunlight-induced oxidation of non-methane hydrocarbons (largely of biogenic origin) is probably the largest source3, 4. However, model simulations substantially underpredict atmospheric formic acid levels5, 6, 7, indicating that not all sources have been included in the models. Here, we use satellite measurements of formic acid concentrations to constrain model simulations of the global formic acid budget. According to our simulations, 100–120 Tg of formic acid is produced annually, which is two to three times more than that estimated from known sources. We show that 90% of the formic acid produced is biogenic in origin, and largely sourced from tropical and boreal forests. We suggest that terpenoids—volatile organic compounds released by plants—are the predominant precursors. Model comparisons with independent observations of formic acid strengthen our conclusions, and provide indirect validation for the satellite measurements. Finally, we show that the larger formic acid emissions have a substantial impact on rainwater acidity, especially over boreal forests in the summer, where formic acid reduces pH by 0.25–0.5.

Air quality, ecosystem exposure to nitrogen deposition, and climate change are intimately coupled problems: we assess changes in the global atmospheric environment between 2000 and 2030 using 26 state-of-the-art global atmospheric chemistry models and three different emissions scenarios. The first (CLE) scenario reflects implementation of current air quality legislation around the world, while the second (MFR) represents a more optimistic case in which all currently feasible technologies are applied to achieve maximum emission reductions. We contrast these scenarios with the more pessimistic IPCC SRES A2 scenario. Ensemble simulations for the year 2000 are consistent among models and show a reasonable agreement with surface ozone, wet deposition, and NO2 satellite observations. Large parts of the world are currently exposed to high ozone concentrations and high deposition of nitrogen to ecosystems. By 2030, global surface ozone is calculated to increase globally by 1.5 +/- 1.2 ppb (CLE) and 4.3 +/- 2.2 ppb (A2), using the ensemble mean model results and associated +/- 1 sigma standard deviations. Only the progressive MFR scenario will reduce ozone, by -2.3 +/- 1.1 ppb. Climate change is expected to modify surface ozone by -0.8 +/- 0.6 ppb, with larger decreases over sea than over land. Radiative forcing by ozone increases by 63 +/- 15 and 155 +/- 37 mW m(-2) for CLE and A2, respectively, and decreases by -45 +/- 15 mW m(-2) for MFR. We compute that at present 10.1% of the global natural terrestrial ecosystems are exposed to nitrogen deposition above a critical load of 1 g N m(-2) yr(-1). These percentages increase by 2030 to 15.8% (CLE), 10.5% (MFR), and 25% (A2). This study shows the importance of enforcing current worldwide air quality legislation and the major benefits of going further. Nonattainment of these air quality policy objectives, such as expressed by the SRES-A2 scenario, would further degrade the global atmospheric environment.

Total column amounts of CO, CH4, CO2 and N2O retrieved from SCIAMACHY nadir observations in its near-infrared channels have been compared to data from a ground-based quasi-global network of Fourier-transform infrared (FTIR) spectrometers. The SCIAMACHY data considered here have been produced by three different retrieval algorithms, WFM-DOAS (version 0.5 for CO and CH4 and version 0.4 for CO2 and N2O), IMAP-DOAS (version 1.1 and 0.9 (for CO)) and IMLM (version 6.3) and cover the January to December 2003 time period. Comparisons have been made for individual data, as well as for monthly averages. To maximize the number of reliable coincidences that satisfy the temporal and spatial collocation criteria, the SCIAMACHY data have been compared with a temporal 3rd order polynomial interpolation of the ground-based data. Particular attention has been given to the question whether SCIAMACHY observes correctly the seasonal and latitudinal variability of the target species. The present results indicate that the individual SCIAMACHY data obtained with the actual versions of the algorithms have been significantly improved, but that the quality requirements, for estimating emissions on regional scales, are not yet met. Nevertheless, possible directions for further algorithm upgrades have been identified which should result in more reliable data products in a near future.

Global tropospheric ozone distributions, budgets, and radiative forcings from an ensemble of 26 state-of-the-art atmospheric chemistry models have been intercompared and synthesized as part of a wider study into both the air quality and climate roles of ozone. Results from three 2030 emissions scenarios, broadly representing "optimistic,'' "likely,'' and "pessimistic'' options, are compared to a base year 2000 simulation. This base case realistically represents the current global distribution of tropospheric ozone. A further set of simulations considers the influence of climate change over the same time period by forcing the central emissions scenario with a surface warming of around 0.7K. The use of a large multimodel ensemble allows us to identify key areas of uncertainty and improves the robustness of the results. Ensemble mean changes in tropospheric ozone burden between 2000 and 2030 for the 3 scenarios range from a 5% decrease, through a 6% increase, to a 15% increase. The intermodel uncertainty (+/-1 standard deviation) associated with these values is about +/-25%. Model outliers have no significant influence on the ensemble mean results. Combining ozone and methane changes, the three scenarios produce radiative forcings of -50, 180, and 300 mW m(-2), compared to a CO2 forcing over the same time period of 800-1100 mW m(-2). These values indicate the importance of air pollution emissions in short-to medium-term climate forcing and the potential for stringent/lax control measures to improve/worsen future climate forcing. The model sensitivity of ozone to imposed climate change varies between models but modulates zonal mean mixing ratios by +/-5 ppbv via a variety of feedback mechanisms, in particular those involving water vapor and stratosphere-troposphere exchange. This level of climate change also reduces the methane lifetime by around 4%. The ensemble mean year 2000 tropospheric ozone budget indicates chemical production, chemical destruction, dry deposition

The metallization procedure, proposed recently for signal improvement in organic secondary ion mass spectrometry (SIMS) (Delcorte, A.; Médard, N.; Bertrand, P. Anal.Chem. 2002, 74, 4955)., has been thoroughly tested for a set of kilodalton molecules bearing various functional groups: Irganox 1010, polystyrene, polyalanine, and copper phthalocyanine. In addition to gold, we evaluate the effect of silver evaporation as a sample treatment prior to static SIMS analysis. Ion yields, damage cross sections, and emission efficiencies are compared for Ag- and Au-metallized molecular films, pristine coatings on silicon, and submonolayers of the same molecules adsorbed on silver and gold. The results are sample-dependent but as an example, the yield enhancement calculated for metallized Irganox films with respect to untreated coatings is larger than 2 orders of magnitude for the quasimolecular ion and a factor of 1-10 for characteristic fragments. Insights into the emission processes of quasimolecular ions from metallized surfaces are deduced from kinetic energy distribution measurements. The advantage of the method for imaging SIMS applications is illustrated by the study of a nonuniform coating of polystyrene oligomers on a 100-microm polypropylene film. The evaporated metal eliminates sample charging and allows us to obtain enhanced quality images of characteristic fragment ions as well as reasonably contrasted chemical mappings for cationized PS oligomers and large PP chain segments. Finally, we report on the benefit of using metal evaporation as a sample preparation procedure for laser ablation mass spectrometry. Our results show that the fingerprint spectra of Au-covered polystyrene, polypropylene, and Irganox films can be readily obtained under 337-nm irradiation, a wavelength for which the absorption of polyolefins is low. This is probably because the gold clusters embedded in the sample surface absorb and transfer the photon energy to the surrounding organic medium.

Radiative forcing due to changes in ozone is expected for the 21st century. An assessment on changes in the tropospheric oxidative state through a model intercomparison ("OxComp'') was conducted for the IPCC Third Assessment Report (IPCC-TAR). OxComp estimated tropospheric changes in ozone and other oxidants during the 21st century based on the "SRES'' A2p emission scenario. In this study we analyze the results of 11 chemical transport models (CTMs) that participated in OxComp and use them as input for detailed radiative forcing calculations. We also address future ozone recovery in the lower stratosphere and its impact on radiative forcing by applying two models that calculate both tropospheric and stratospheric changes. The results of OxComp suggest an increase in global-mean tropospheric ozone between 11.4 and 20.5 DU for the 21st century, representing the model uncertainty range for the A2p scenario. As the A2p scenario constitutes the worst case proposed in IPCC-TAR we consider these results as an upper estimate. The radiative transfer model yields a positive radiative forcing ranging from 0.40 to 0.78 W m(-2) on a global and annual average. The lower stratosphere contributes an additional 7.5-9.3 DU to the calculated increase in the ozone column, increasing radiative forcing by 0.15-0.17 W m(-2). The modeled radiative forcing depends on the height distribution and geographical pattern of predicted ozone changes and shows a distinct seasonal variation. Despite the large variations between the 11 participating models, the calculated range for normalized radiative forcing is within 25%, indicating the ability to scale radiative forcing to global-mean ozone column change.

Ozone is an air quality problem today for much of the world's population. Regions can exceed the ozone air quality standards (AQS) through a combination of local emissions, meteorology favoring pollution episodes, and the clean-air baseline levels of ozone upon which pollution builds. The IPCC 2001 assessment studied a range of global emission scenarios and found that all but one projects increases in global tropospheric ozone during the 21st century. By 2030, near-surface increases over much of the northern hemisphere are estimated to be about 5 ppb (+2 to +7 ppb over the range of scenarios). By 2100 the two more extreme scenarios project baseline ozone increases of >20 ppb, while the other four scenarios give changes of -4 to +10 ppb. Even modest increases in the background abundance of tropospheric ozone might defeat current AQS strategies. The larger increases, however, would gravely threaten both urban and rural air quality over most of the northern hemisphere.