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.

Our changing atmosphere: evidence based on long-term infrared solar observations at the Jungfraujoch since 1950.

The Institute of Astrophysics of the University of Liège has been present at the High Altitude Research Station Jungfraujoch, Switzerland, since the late 1940s, to perform spectrometric solar observations under dry and weakly polluted high-mountain conditions. Several solar atlases of photometric quality, extending altogether from the near-ultra-violet to the middle-infrared, were produced between 1956 and 1994, first with grating spectrometers then with Fourier transform instruments. During the early 1970s, scientific concerns emerged about atmospheric composition changes likely to set in as a consequence of the growing usage of nitrogen-containing agricultural fertilisers and the industrial production of chlorine-bearing compounds such as the chlorofluorocarbons and hydro-chlorofluorocarbons. Resulting releases to the atmosphere with ensuing photolysis in the stratosphere and catalytic depletion of the protective ozone layer prompted a worldwide consortium of chemical manufacturing companies to solicit the Liège group to help in clarifying these concerns by undertaking specific observations with its existing Jungfraujoch instrumentation. The following pages evoke the main steps that led from quasi full sun-oriented studies to priority investigations of the Earth's atmosphere, in support of both the Montreal and the Kyoto Protocols.

BARCOS, an automation and remote control system for atmospheric observations with a Bruker interferometer.

In order to make long-term monitoring of the atmospheric composition using commercial Bruker Fourier transform spectrometers more cost effective, a system called BARCOS has been developed. The system enables one to perform the operation of the spectrometric atmospheric observations in a remotely controlled or autonomous way, without human presence at the measuring site. Several observation geometries are foreseen, including solar and lunar absorption spectrometry. BARCOS is built using existing commercial hardware and software components, including the Bruker software for the operation of the spectrometer (OPUS) and runs in a personal computer (Microsoft) environment. It includes a small meteorological station. It is a flexible system, allowing manual interventions at any time. To run BARCOS effectively, the only prerequisite is that internet access is available at the site of operation. This article describes the BARCOS system hardware and software configurations.

The Orbiting Carbon Observatory (OCO-2) tracks 2-3 peta-gram increase in carbon release to the atmosphere during the 2014-2016 El Niño.

The powerful El Niño event of 2015-2016 - the third most intense since the 1950s - has exerted a large impact on the Earth's natural climate system. The column-averaged CO2 dry-air mole fraction (XCO2) observations from satellites and ground-based networks are analyzed together with in situ observations for the period of September 2014 to October 2016. From the differences between satellite (OCO-2) observations and simulations using an atmospheric chemistry-transport model, we estimate that, relative to the mean annual fluxes for 2014, the most recent El Niño has contributed to an excess CO2 emission from the Earth's surface (land + ocean) to the atmosphere in the range of 2.4 ± 0.2 PgC (1 Pg = 1015 g) over the period of July 2015 to June 2016. The excess CO2 flux is resulted primarily from reduction in vegetation uptake due to drought, and to a lesser degree from increased biomass burning. It is about the half of the CO2 flux anomaly (range: 4.4-6.7 PgC) estimated for the 1997/1998 El Niño. The annual total sink is estimated to be 3.9 ± 0.2 PgC for the assumed fossil fuel emission of 10.1 PgC. The major uncertainty in attribution arise from error in anthropogenic emission trends, satellite data and atmospheric transport.

Importance of secondary sources in the atmospheric budgets of formic and acetic acids.

We present a detailed budget of formic and acetic acids, two of the most abundant trace gases in the atmosphere. Our bottom-up estimate of the global source of formic and acetic acids are ∼1200 and ∼1400Gmolyr-1, dominated by photochemical oxidation of biogenic volatile organic compounds, in particular isoprene. Their sinks are dominated by wet and dry deposition. We use the GEOS-Chem chemical transport model to evaluate this budget against an extensive suite of measurements from ground, ship and satellite-based Fourier transform spectrometers, as well as from several aircraft campaigns over North America. The model captures the seasonality of formic and acetic acids well but generally underestimates their concentration, particularly in the Northern midlatitudes. We infer that the source of both carboxylic acids may be up to 50% greater than our estimate and report evidence for a long-lived missing secondary source of carboxylic acids that may be associated with the aging of organic aerosols. Vertical profiles of formic acid in the upper troposphere support a negative temperature dependence of the reaction between formic acid and the hydroxyl radical as suggested by several theoretical studies.

An instrumented station for the survey of ozone and climate change in the southern tropics.

The assessment of changes induced by human activities on Earth atmospheric composition and thus on global climate requires a long-term and regular survey of the stratospheric and tropospheric atmospheric layers. The objective of this paper is to describe the atmospheric observations performed continuously at Reunion Island (55.5 degrees east, 20.8 degrees south) for 15 years. The various instruments contributing to the systematic observations are described as well as the measured parameters, the accuracy and the database. The LiDAR systems give profiles of temperature, aerosols and ozone in the troposphere and stratosphere, probes give profiles of temperature, ozone and relative humidity, radiometers and spectrometers give stratospheric and tropospheric integrated columns of a variety of atmospheric trace gases. Data are included in international networks, and used for satellite validation. Moreover, some scientific activities for which this station offers exceptional opportunities are highlighted, especially air mass exchanges nearby dynamical barriers: (1) On the vertical scale through the tropical tropopause layer (stratosphere-troposphere exchange). (2) On the quasi-horizontal scale across the southern subtropical barrier separating the tropical stratospheric reservoir from mid- and high latitudes.

Phase noise elimination in interferometric experiments by sawtooth phase modulation.

A technique has been developed for eliminating the phase sensitivity in interferometric measurements. It is based on sawtooth phase modulation of the signal and double phase sensitive detection. It overcomes the restrictions due to background transmission that have been recognized by us in a previously proposed method based on rms detection. This paper focuses on its use in time resolved stimulated Raman gain measurements.

Determination of the aerosol size distribution by analytic inversion of the extinction spectrum in the complex anomalous diffraction approximation.

A new derivation is presented for the analytical inversion of aerosol spectral extinction data to size distributions. It is based on the complex analytic extension of the anomalous diffraction approximation (ADA). We derive inverse formulas that are applicable to homogeneous nonabsorbing and absorbing spherical particles. Our method simplifies, generalizes, and unifies a number of results obtained previously in the literature. In particular, we clarify the connection between the ADA transform and the Fourier and Laplace transforms. Also, the effect of the particle refractive-index dispersion on the inversion is examined. It is shown that, when Lorentz's model is used for this dispersion, the continuous ADA inverse transform is mathematically well posed, whereas with a constant refractive index it is ill posed. Further, a condition is given, in terms of Lorentz parameters, for which the continuous inverse operator does not amplify the error.