Atmospheric acidity is increasingly determined by carbon dioxide and organic acids
. Among the latter, formic acid facilitates the nucleation of cloud droplets
and contributes to the acidity of ...clouds and rainwater
. At present, chemistry-climate models greatly underestimate the atmospheric burden of formic acid, because key processes related to its sources and sinks remain poorly understood
. Here we present atmospheric chamber experiments that show that formaldehyde is efficiently converted to gaseous formic acid via a multiphase pathway that involves its hydrated form, methanediol. In warm cloud droplets, methanediol undergoes fast outgassing but slow dehydration. Using a chemistry-climate model, we estimate that the gas-phase oxidation of methanediol produces up to four times more formic acid than all other known chemical sources combined. Our findings reconcile model predictions and measurements of formic acid abundance. The additional formic acid burden increases atmospheric acidity by reducing the pH of clouds and rainwater by up to 0.3. The diol mechanism presented here probably applies to other aldehydes and may help to explain the high atmospheric levels of other organic acids that affect aerosol growth and cloud evolution.
The vertical columns of formaldehyde (HCHO) retrieved from two satellite instruments, the Global Ozone Monitoring Instrument-2 (GOME-2) on Metop-A and the Ozone Monitoring Instrument (OMI) on Aura, ...are used to constrain global emissions of HCHO precursors from open fires, vegetation and human activities in the year 2010. To this end, the emissions are varied and optimized using the adjoint model technique in the IMAGESv2 global CTM (chemical transport model) on a monthly basis and at the model resolution. Given the different local overpass times of GOME-2 (09:30 LT) and OMI (13:30 LT), the simulated diurnal cycle of HCHO columns is investigated and evaluated against ground-based optical measurements at seven sites in Europe, China and Africa. The modeled diurnal cycle exhibits large variability, reflecting competition between photochemistry and emission variations, with noon or early afternoon maxima at remote locations (oceans) and in regions dominated by anthropogenic emissions, late afternoon or evening maxima over fire scenes, and midday minima in isoprene-rich regions. The agreement between simulated and ground-based columns is generally better in summer (with a clear afternoon maximum at mid-latitude sites) than in winter, and the annually averaged ratio of afternoon to morning columns is slightly higher in the model (1.126) than in the ground-based measurements (1.043). The anthropogenic VOC (volatile organic compound) sources are found to be weakly constrained by the inversions on the global scale, mainly owing to their generally minor contribution to the HCHO columns, except over strongly polluted regions, like China. The OMI-based inversion yields total flux estimates over China close to the bottom-up inventory (24.6 vs. 25.5 TgVOC yr−1 in the a priori) with, however, pronounced increases in the northeast of China and reductions in the south. Lower fluxes are estimated based on GOME-2 HCHO columns (20.6 TgVOC yr−1), in particular over the northeast, likely reflecting mismatches between the observed and the modeled diurnal cycle in this region. The resulting biogenic and pyrogenic flux estimates from both optimizations generally show a good degree of consistency. A reduction of the global annual biogenic emissions of isoprene is derived, of 9 and 13 % according to GOME-2 and OMI, respectively, compared to the a priori estimate of 363 Tg in 2010. The reduction is largest (up to 25–40 %) in the Southeastern US, in accordance with earlier studies. The GOME-2 and OMI satellite columns suggest a global pyrogenic flux decrease by 36 and 33 %, respectively, compared to the GFEDv3 (Global Fire Emissions Database) inventory. This decrease is especially pronounced over tropical forests, such as in Amazonia, Thailand and Myanmar, and is supported by comparisons with CO observations from IASI (Infrared Atmospheric Sounding Interferometer). In contrast to these flux reductions, the emissions due to harvest waste burning are strongly enhanced over the northeastern China plain in June (by ca. 70 % in June according to OMI) as well as over Indochina in March. Sensitivity inversions showed robustness of the inferred estimates, which were found to lie within 7 % of the standard inversion results at the global scale.
The advent of high-resolution spectrographs and detailed stellar atmosphere modelling has strengthened the need for accurate molecular data. Carbon-enhanced metal-poor (CEMP) stars spectra are ...interesting objects with which to study transitions from the CH molecule. We combine programs for spectral analysis of molecules and stellar-radiative transfer codes to build an extensive CH linelist, including predissociation broadening as well as newly identified levels. We show examples of strong predissociation CH lines in CEMP stars, and we stress the important role played by the CH features in the Bond-Neff feature depressing the spectra of barium stars by as much as 0.2 mag in the λ = 3000−5500 Å range. Because of the extreme thermodynamic conditions prevailing in stellar atmospheres (compared to the laboratory), molecular transitions with high energy levels can be observed. Stellar spectra can thus be used to constrain and improve molecular data.
Atmospheric aerosols impact air quality and global climate. Space based measurements are the best way to observe their spatial and temporal distributions, and can also be used to gain better ...understanding of their chemical, physical and optical properties. Aerosol composition is the key parameter affecting the refractive index, which determines how much radiation is scattered and absorbed. Composition of aerosols is unfortunately not measured by state of the art satellite remote sounders. Here we use high resolution infrared measurements for aerosol type differentiation, exploiting, in that part of spectrum, the dependency of their refractive index on wavelength. We review existing detection methods and present a unified detection method based on linear discrimination analysis. We demonstrate this method on measurements of the Infrared Atmospheric Sounding Interferometer (IASI) and five different aerosol types, namely volcanic ash, windblown sand, sulfuric acid droplets, ammonium sulfate and smoke particles. We compare these with traditional MODIS AOD measurements. The detection of the last three types is unprecedented in the infrared in nadir mode, but is very promising, especially for sulfuric acid droplets which are detected in the lower troposphere and up to 6 months after injection in the upper troposphere/lower stratosphere.
We use in situ observations from the Interagency Monitoring of PROtected Visual Environments (IMPROVE) network, the Midwest Ammonia Monitoring Project, 11 surface site campaigns as well as Infrared ...Atmospheric Sounding Interferometer (IASI) satellite measurements with the GEOS-Chem model to investigate inorganic aerosol loading and atmospheric ammonia concentrations over the United States. IASI observations suggest that current ammonia emissions are underestimated in California and in the springtime in the Midwest. In California this underestimate likely drives the underestimate in nitrate formation in the GEOS-Chem model. However in the remaining continental United States we find that the nitrate simulation is biased high (normalized mean bias > = 1.0) year-round, except in Spring (due to the underestimate in ammonia in this season). None of the uncertainties in precursor emissions, the uptake efficiency of N2O5 on aerosols, OH concentrations, the reaction rate for the formation of nitric acid, or the dry deposition velocity of nitric acid are able to explain this bias. We find that reducing nitric acid concentrations to 75% of their simulated values corrects the bias in nitrate (as well as ammonium) in the US. However the mechanism for this potential reduction is unclear and may be a combination of errors in chemistry, deposition and sub-grid near-surface gradients. This "updated" simulation reproduces PM and ammonia loading and captures the strong seasonal and spatial gradients in gas-particle partitioning across the United States. We estimate that nitrogen makes up 15−35% of inorganic fine PM mass over the US, and that this fraction is likely to increase in the coming decade, both with decreases in sulfur emissions and increases in ammonia emissions.
Atmospheric carbon monoxide (CO) distributions are controlled by anthropogenic emissions, biomass burning, transport and oxidation by reaction with the hydroxyl radical (OH). Quantifying trends in CO ...is therefore important for understanding changes related to all of these contributions. Here we present a comprehensive record of satellite observations from 2000 through 2011 of total column CO using the available measurements from nadir-viewing thermal infrared instruments: MOPITT, AIRS, TES and IASI. We examine trends for CO in the Northern and Southern Hemispheres along with regional trends for Eastern China, Eastern USA, Europe and India. We find that all the satellite observations are consistent with a modest decreasing trend similar to -1 % yr super(-1) in total column CO over the Northern Hemisphere for this time period and a less significant, but still decreasing trend in the Southern Hemisphere. Although decreasing trends in the United States and Europe have been observed from surface CO measurements, we also find a decrease in CO over E. China that, to our knowledge, has not been reported previously. Some of the interannual variability in the observations can be explained by global fire emissions, but the overall decrease needs further study to understand the implications for changes in anthropogenic emissions.
We exploit 6 years of measurements from the Infrared Atmospheric Sounding Interferometer (IASI)/MetOp‐A instrument to identify seasonal patterns and interannual variability of atmospheric NH3. This ...is achieved by analyzing the time evolution of the monthly mean NH3 columns in 12 subcontinental areas around the world, simultaneously considering measurements from IASI morning and evening overpasses. For most regions, IASI has a sufficient sensitivity throughout the years to capture the seasonal patterns of NH3 columns, and we show that each region is characterized by a well‐marked and distinctive cycle, with maxima mainly related to underlying emission processes. The largest column abundances and seasonal amplitudes throughout the years are found in southwestern Asia, with maxima twice as large as what is observed in southeastern China. The relation between emission sources and retrieved NH3 columns is emphasized at a smaller regional scale by inferring a climatology of the month of maximum columns.
Key Points
Six years of NH3 morning and evening IASI measurements are analyzed
Seasonal cycles of atmospheric NH3 are characterized for subcontinental areas
Source processes are attributed from a climatology of the month of NH3 maximum
The large-scale burning of crop residues in the North China Plain (NCP), one of the most densely populated world regions, was recently recognized to cause severe air pollution and harmful health ...effects. A reliable quantification of the magnitude of these fires is needed to assess regional air quality. Here, we use an eight-year record (2005-2012) of formaldehyde measurements from space to constrain the emissions of volatile organic compounds (VOCs) in this region. Using inverse modelling, we derive that satellite-based post-harvest burning fluxes are, on average, at least a factor of 2 higher than state-of-the-art bottom-up statistical estimates, although with significant interannual variability. Crop burning is calculated to cause important increases in surface ozone (+7%) and fine aerosol concentrations (+18%) in the North China Plain in June. The impact of crop fires is also found in satellite observations of other species, glyoxal, nitrogen dioxide and methanol, and we show that those measurements validate the magnitude of the top-down fluxes. Our study indicates that the top-down crop burning fluxes of VOCs in June exceed by almost a factor of 2 the combined emissions from other anthropogenic activities in this region, underscoring the need for targeted actions towards changes in agricultural management practices.
In this paper, we describe a new flexible and robust NH3 retrieval algorithm from measurements of the Infrared Atmospheric Sounding Interferometer (IASI). The method is based on the calculation of a ...spectral hyperspectral range index (HRI) and subsequent conversion to NH3 columns via a neural network. It is an extension of the method presented in Van Damme et al. (2014a) who used lookup tables (LUT) for the radiance‐concentration conversion. The new method inherits the advantages of the LUT‐based method while providing several significant improvements. These include the following: (1) Complete temperature and humidity vertical profiles can be accounted for. (2) Third‐party NH3 vertical profile information can be used. (3) Reported positive biases of LUT retrieval are reduced, and finally (4) a full measurement uncertainty characterization is provided. A running theme in this study, related to item (2), is the importance of the assumed vertical NH3 profile. We demonstrate the advantages of allowing variable profile shapes in the retrieval. As an example, we analyze how the retrievals change when all NH3 is assumed to be confined to the boundary layer. We analyze different averaging procedures in use for NH3 in the literature, introduced to cope with the variable measurement sensitivity and derive global averaged distributions for the year 2013. A comparison with a GEOS‐Chem modeled global distribution is also presented, showing a general good correspondence (within ±3 × 1015 molecules.cm−2) over most of the Northern Hemisphere. However, IASI finds mean columns about 1–1.5 × 1016 molecules.cm−2 (∼50–60%) lower than GEOS‐Chem for India and the North China plain.
Key Points
New IASI‐NH3 retrieval approach based on a neural network
Flexible NH3 vertical profiles ease comparison with model and in situ data
The impact of using ECMWF or GEOS‐Chem vertical profile information leads to differences in the retrieved columns up to 50‐60%
In the autumn of 2015, thousands of square kilometers of forest and peatlands in Indonesia went up in flames. Among the primary species emitted by fires, ammonia (NH3) is of special relevance for air ...quality. Here we derive daily and total NH3 emission fluxes over the affected area using satellite measurements for the years 2008–2015. The 2015 fires emitted an estimated 1.4–8.2 Tg of NH3 (with a maximum of 0.06–0.33 Tg d−1). On an annual basis, the 2015 NH3 emissions are a factor 2–3 larger than in the previous 7 years. We derive NH3 emission factors for peat soils, which are found to be 2.5–8 times lower than those used in the GFASv1.2 emission inventory but in excellent agreement with those reported in other recent studies. Finally, we estimate that 3.28 × 109 m3 peat soil was consumed during these 2015 fires, corresponding to an average burn depth of 39 cm.
Key Points
NH3 emissions in Indonesia for 2015 are 2–3 times higher than in the past 7 years
IASI‐derived ammonia emission factors for peatlands are 2.5–8 times lower than those used in GFAS
First IASI‐derived assessment of peat soil combustion
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