Ubiquitous atmospheric production of organic acids mediated by cloud droplets.

Atmospheric acidity is increasingly determined by carbon dioxide and organic acids1-3. Among the latter, formic acid facilitates the nucleation of cloud droplets4 and contributes to the acidity of clouds and rainwater1,5. At present, chemistry-climate models greatly underestimate the atmospheric burden of formic acid, because key processes related to its sources and sinks remain poorly understood2,6-9. 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.

Record high levels of atmospheric ammonia over India: Spatial and temporal analyses.

Atmospheric ammonia (NH3) is an alkaline gas and a prominent constituent of the nitrogen cycle that adversely affects ecosystems at higher concentrations. It is a pollutant, which influences all three spheres such as haze formation in the atmosphere, soil acidification in the lithosphere, and eutrophication in water bodies. Atmospheric NH3 reacts with sulfur (SOx) and nitrogen (NOx) oxides to form aerosols, which eventually affect human health and climate. Here, we present the seasonal and inter-annual variability of atmospheric NH3 over India in 2008-2016 using the IASI (Infrared Atmospheric Sounding Interferometer) satellite observations. We find that Indo-Gangetic Plains (IGP) is one of the largest and rapidly growing NH3 hotspots of the world, with a growth rate of +1.2% yr-1 in summer (June-August: Kharif season), due to intense agricultural activities and presence of many fertilizer industries there. However, our analyses show insignificant decreasing trends in annual NH3 of about -0.8% yr-1 in all India, about -0.4% yr-1 in IGP, and -1.0% yr-1 in the rest of India. Ammonia is positively correlated with total fertilizer consumption (r = 0.75) and temperature (r = 0.5) since high temperature favors volatilization, and is anti-correlated with total precipitation (r = from -0.2, but -0.8 in the Rabi season: October-February) as wet deposition helps removal of atmospheric NH3. This study, henceforth, suggests the need for better fertilization practices and viable strategies to curb emissions, to alleviate the adverse health effects and negative impacts on the ecosystem in the region. On the other hand, the overall decreasing trend in atmospheric NH3 over India shows the positive actions, and commitment to the national missions and action plans to reduce atmospheric pollution and changes in climate.

Atmospheric ammonia (NH3) emanations from Lake Natron's saline mudflats.

In a recent global analysis of satellite-derived atmospheric NH3 data, a hotspot was observed in the vicinity of Lake Natron, Tanzania. The lake is in the centre of an endorheic (limited drainage) basin and has shallow, saline-alkaline waters. Its remote location and the absence of nearby large anthropogenic sources suggest that the observed NH3 is mainly of natural origin. Here we explore 10 years of IASI NH3 satellite data and other publicly available datasets over the area to characterize the natural NH3 emissions in this unique ecosystem. Temporal analysis reveals that the emissions are episodic and linked with the lake's surface area. The largest NH3 column loadings generally occur at the end of the dry season in September-November over Lake Natron's largest mudflat, that is exposed with receding water levels. The timing is different from the agricultural dominated NH3 emissions in the wider Natron area, which peak early in the year, after the first wet season. The likely source of NH3 at Lake Natron is decomposition of organic material, either from rivers and springs or produced in the lake (plankton, bird excreta). High temperatures and alkalinity are known to promote NH3 losses from soda lakes. We formulate six processes that may explain why the largest losses are observed specifically over concentrated brines and/or exposed sediments. As a by-product, we also show that hyperspectral infrared sounders such as IASI are capable of mapping different types of evaporative minerals such as trona and thermonatrite.

Substantial Underestimation of Post-Harvest Burning Emissions in the North China Plain Revealed by Multi-Species Space Observations.

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.

Tropospheric methanol observations from space: retrieval evaluation and constraints on the seasonality of biogenic emissions.

Methanol retrievals from nadir-viewing space-based sensors offer powerful new information for quantifying methanol emissions on a global scale. Here we apply an ensemble of aircraft observations over North America to evaluate new methanol measurements from the Tropospheric Emission Spectrometer (TES) on the Aura satellite, and combine the TES data with observations from the Infrared Atmospheric Sounding Interferometer (IASI) on the MetOp-A satellite to investigate the seasonality of methanol emissions from northern midlatitude ecosystems. Using the GEOS-Chem chemical transport model as an intercomparison platform, we find that the TES retrieval performs well when the degrees of freedom for signal (DOFS) are above 0.5, in which case the model:TES regressions are generally consistent with the model:aircraft comparisons. Including retrievals with DOFS below 0.5 degrades the comparisons, as these are excessively influenced by the a priori. The comparisons suggest DOFS >0.5 as a minimum threshold for interpreting retrievals of trace gases with a weak tropospheric signal. We analyze one full year of satellite observations and find that GEOS-Chem, driven with MEGANv2.1 biogenic emissions, underestimates observed methanol concentrations throughout the midlatitudes in springtime, with the timing of the seasonal peak in model emissions 1-2 months too late. We attribute this discrepancy to an underestimate of emissions from new leaves in MEGAN, and apply the satellite data to better quantify the seasonal change in methanol emissions for midlatitude ecosystems. The derived parameters (relative emission factors of 11.0, 0.26, 0.12 and 3.0 for new, growing, mature, and old leaves, respectively, plus a leaf area index activity factor of 0.5 for expanding canopies with leaf area index <1.2) provide a more realistic simulation of seasonal methanol concentrations in midlatitudes on the basis of both the IASI and TES measurements.

Direct estimate of methane radiative forcing by use of nadir spectral radiances.

Direct determination of the radiative forcing of trace gases will be made possible by use of the next generation of nadir-looking spaceborne instruments that provide measurements of atmospheric radiances in the infrared spectral range with improved spectral and spatial resolution. An inversion statistical method has thus been developed and applied to the direct determination of the radiative forcing of methane, based on such instruments as the Fourier-transform Interferometric Monitor for Greenhouse Gases launched onboard the Japanese Advanced Earth Observing Satellite in 1996 and the Infrared Atmospheric Sounding Interferometer planned for the European polar platform Meteorological Operational Satellite in 2000. The method is based on simple statistical laws that directly relate the measured radiances to the radiative forcing by use of an a priori selection of appropriate spectral intervals and global modeling of methane spatial variations. This procedure avoids the use of an indirect determination based on an inversion process that requires precise knowledge of the methane vertical profiles throughout the troposphere. The overall accuracy and precision of this new algorithm are studied, and interfering gases and instrumental characteristics are taken into account. It is shown that radiative forcing can be determined at high horizontal spatial resolution with a precision better than 7% in cloud-free conditions and with well-known surface properties.