WP6 : Flux and Atmospheric Fate of Volatile Compounds Formed by the Continental Surfaces

Abdelwahid Mellouki (CNRS-ICARE), Christophe Guimbaud (University-LPC2E), Fatima Laggoun-Défarge
(CNRS-ISTO)

Currently, to determine the impact of industrial activities considered to be polluting and responsible for apart of global change, it is vital to qualitatively and quantitatively understand the role of “natural”emissions. For this, VOLTAIRE has chosen to gather various experts so as to contribute greater robustness to coupled models. The basic idea is to simultaneously study different environments having a strong impact on carbon, nitrogen and halogens cycles. These are (Figure 1) :

  1. Peatlands and cultivated areas, then to study in the troposphere the fate of these compounds (photo-oxidation, aerosols)
  2. Volcanoes with a particular emphasis on their role in the composition of tropospheric halogens.
Figure 1. VOCs exchange from biogenic and anthropogenic continental surfaces to atmosphere (links with WP5 and WP7)

Peatlands. Sphagnum bogs will be studied on the global scale, in order to compare the impact of global changes on the carbon sink/source balance in temperate and subarctic regions. Eighty percent of these bogs are found at high latitudes of the northern hemisphere, precisely where the greatest warming is expected for the coming decades (IPCC 2007 b, c). With such a scenario, their carbon sink function could be reversed. Hence, it has become vital to consider the possible destocking of C by these environments in long-term climate predictions. VOLTAIRE will conduct these studies :

  1. as part of a national network of the SNO “Tourbières” (Peatlands) which alone will allow the necessary comparison between several sites chosen for their biogeographic and climatic diversity and their degree of anthropization ;
  2. as part of international projects for studying the vulnerability to climate change of subarctic peatland complexes, like “Mukhrino” in western Siberia and under natural and simulated conditions. The forcing factors will be temperature, by installation of experimental arrangements for the warming of the air and the soil, and hydrology by manipulation of the groundwater level or interception of rainfall.

Cultivated areas. N2O emissions will be studied on instrumented field sites being exploited that have representative soil that is more or less hydromorphic and potentially a strong emitter of N2O as well as control plots characterized by soil rich in clay (Beauce).
N2O isotopes will help to understand the microbial processes at play (denitrification/nitrification). Measurements of gas emissions (with isotope characterization) will be done at either the plant or site scale (chamber method) or at the plot/landscape scale (measurements on masts by the micrometeorological method, for example, turbulent eddy correlation, which will be initiated as part of VOLTAIRE). On the basis of our observations, we will be able to propose new functions representing the process at work and integrate them into biogeochemical models. We will rely on the CERES-NOE model, which allows simulating gas emissions by soil or the “Virtual Soil” modeling platform developed by the INRA. For the medium-term, we will integrate these data into coupled atmospheric chemistry-meteorology models.

The atmospheric degradation of unsaturated VOCs of biogenic or anthropogenic origin will be studied, specifying the nature of the degradation products of aerosol precursor species, by determining their formation rate and their chemical composition. The processes of nucleation, from chemical evolution and aging of SOAs (Secondary Organic Aerosols) to the formation of condensation nuclei will be studied. Research will be conducted on the impact of the chemistry of unsaturated volatile organic compounds onthe radical budget in the troposphere. Moreover, studies of the heterogeneous reactivity of volatile species on aerosols in suspension or representative continental surfaces will be conducted in order to better understand the process of atmospheric recycling, as well as the process of heterogeneous photocatalysis, making use of the experience acquired at ICARE in the field of photocatalytic remediation. The large natural radiation chamber, HELIOS (3rd in size in Europe and 1st in France) being built at Orléans will reproduce the conditions under which species are oxidized in the atmosphere.

Volcanic halogenated compounds will be studied to obtain the most exhaustive overview of halogenated compound emissions of natural origin: from their emissions to their atmospheric fate. A program of detailed studies of the processes of photochemistry, wash-out and transport of these compounds of volcanic origin in the troposphere has begun with the aid of the C-CATT-BRAMS mesoscale chemistry-meteorology coupled model (Freitas et al., 2009). We will focus on minor eruptions and passive emissions whose global scale effect is probably greater than that of less frequent major eruptions, in order to study the impact of these halogen emissions on the atmospheric chemistry at local and regional scales.

To do this, realistic emission fluxes, in agreement with experiments in autoclaves (artificial magma) and on site (volcanoes to be defined) done at ISTO, as well as specific reactions involving the source gases HBr and HCl in gas phase and heterogeneous in sulfate aerosols will be implemented in the model. These projects, conducted in collaboration with the CNRM-GAME, will partially rely on the Equipex PLANEX project for an analysis of the HCl and HBr emitted. The possible transport of these halogenated compounds and their transformation in the stratosphere will be considered in the WP7 projects in close interaction with this group.

Results of WP 6 (2011-2014)

Emissions of greenhouse gases (CO2, CH4, N2O) by continental surfaces from sphagnum peatlands and croplands. This work was performed in continuity of WP5 in order to study the spatial and temporal variability of the emissions of GHGs. Measurements are performed on the sites of the Service National d’Observation Tourbières (label INSU-SIC) and the Observatoire Spatialisé Orléanais des Sols (OS2) located in Villebon (Beauce Chartraine-faux Perche) composed of various types of soils, land use, and crops:

– Measurements of seasonal and daily cycles of CO2 exchange and of CH4 emissions from peatlands to atmosphere were made on the sites of the SNO “tourbières”. Temperature (ground and air) is a major factor controlling CO2 and CH4 emissions from the respiration process. The delay between daily variations of the CO2 emission and soil temperature has been systematically monitored on the 4 sites of the SNO “tourbières”, so as to ultimately develop empirical and mechanistic models of CO2 emissions;
– N2O flux measurements campaigns on the OS² site and on the experimental site of the European project INGOS in Scotland have been performed for a better understanding of the spatial variability of N2O emissions and for testing the efficiency of the SPIRIT instrument (developed at LPC2E) for local GHGs flux measurements. As a result, the introduction of a stochastic approach in the Nitrous Oxide Emissions model enabled to simulate the distribution of N2O emissions at different intra-parcel scales.

Foreseen developments are (i) to upscale field observations at the land level by the installation of eddy covariance flux towers for peatland and cropland sites (equipement will be purchased via regional and national (CPER) funds, within the framework of the regional PIVOTS project) ; (ii) collaborations with IPSL-LSCE (Bertrand Guenet, Philippe Ciais) and LGGE Grenoble (Gerhard Krinner, Chloé Langeron) to integrate the peat GHG production and transport model developed at ISTO into the emission surface ORCHIDEE model for a future coupling with atmospheric chemistry and climate (LMDz) models.

Emissions of volcanic gases and their atmospheric reactivity. The objective is to understand better the fate and impact of volcanic emissions in the troposphere at the local and regional scales. The approach adopted consists in (i) laboratory studies of volatiles behaviour in magmas, and (ii) modelling of volcanic plumes using either a regional atmospheric model CCATT-BRAMS using information from measurements campaign, box model and laboratory studies, or at a global scale:

– Laboratory studies have focused on halogens and sulfur, since their behaviours are the least well known. Prior to this we have consolidated our data base of pre-eruptive conditions of case studies (Santorini, Etna, Vesuvius, Stromboli, etc.) which give the starting conditions of magmatic degassing. Laboratory work was then dedicated at defining the fluid/melt partition of halogens (Br in particular) and sulfur in various melt compositions. A general equation for calculating Br fluid/melt partition for basalt to rhyolite magma compositions was proposed (such data were so far available only for SiO2 rich magmas, and applied by default to all categories). This will enable to calculate rigorously the gas source composition needed to run models of gas atmosphere mixing at the local scale, which in turn serve as input parameters to regional models such as CCATT-BRAMS;

– The CCATT-BRAMS model was adapted to include the specific reactions taking place in volcanic plumes at a regional scale. Simulations on Ambrym volcano (responsible for about 20% of the global SO2 emissions) show that the salient features of volcanic plume chemistry (e.g. SO2 and BrO) are well captured. The impact of this degassing episode on the oxidizing power of the troposphere as well as on the bromine loading in the upper troposphere were assessed;

– The modeling of key points of volcanic plume chemistry was improved. Regional or global models use a fixed reactive uptake coefficient to quantify the reactive uptake of HOBr onto sulfate aerosol in volcanic plumes. Our results show that this approach can lead to strong inaccuracies and allow a novel HOBr kinetic parameterization (Roberts et al., 2014a). In parallel, in-situ real time measurements (SO2, H2S, H2O, CO2, HCl) were performed at Mt Etna (paper in prep.) with miniature electrochemical gas sensors (Roberts et al. 2014b) alongside the LOAC aerosol particle counter (developed at LPC2E). Box model sensitivity simulations were also performed in order to identify the keys processes and uncertainties in the chemistry of the volcanic plumes (Roberts et al., 2014c). Large scale modelling of mid-term (up to a decade) volcanic effects on climate were done in collaboration with S. Bekki (LATMOS) on the specific case of Santorini Minoan eruption. They demonstrate the important role of Br for stratospheric chemistry, even in the case of sulfur poor eruptions (Cadoux et al., subjudice). The Minoan event could have generated a ten year lasting ozone hole similar in magnitude to that observed prior to the banishment of CFC gases.

Future work will be dedicated to incorporate all these findings into the CCATT-BRAMS model, and redo the simulation of Ambrym volcano degassing (and extend it to different periods). The new laboratory data on Br behaviour will be used to refine the gas source compositions (which depend on the type of volcanic source, i.e. basaltic, andesitic or rhyolitic volcano) which are needed to run atmospheric dispersion models. Progress in constraining volcanic halogen fluxes at the global scale will be done by applying these laboratory results and improved models on new field constraints on volcanic gases gathered along volcanic arc segments selected among the most productive one (South America and Indonesia). Field data acquisition will be done within the framework of a field trip co-sponsored by the Royal Geological Society and Land Rover company, led by Y. Moussallam, who will be hired starting next September by the Labex to achieve the global estimate. Biogenic volatile organic compounds atmospheric chemistry. The research activities aim at investigating the atmospheric chemistry of biogenic volatile organic compounds with respect to the HOx radicals budget and secondary organic aerosols formation:

– The newly built atmospheric simulation chamber (HELIOS) has been used to study the chemistry of a number of BVOCs (α-carene, β-carene and isoprene) under real atmospheric conditions. Kinetic parameters as well as gas phase products and aerosols formation yields have been determined. The SPIRIT instrument has been successfully tested and showed high capabilities for measurements of CO and HCHO.

– Kinetic studies of the atmospherically relevant reactions of the Criegee biradicals with SO2, NO2, O3 and H2O are being conducted. These reactions are a matter of current concern because of their extremely important role in the formation of atmospheric aerosols and influence on the atmospheric oxidative capacity. For these studies a new experimental setup has been developed. It consists of a newly designed atmospheric pressure flow tube reactor coupled to the chemical ionisation mass
spectrometer (SAMU) for the OH and H2SO4 measurements. The new setup is currently used for the studies of the reactions of the Criegee biradicals produced in the reaction of (CH3)2C=C(CH3)2 with O3. The results have been obtained on the reaction rate constants of this intermediate with SO2, NO2, O3 and H2O.

In the near future, experiments will be extended a variety of other important BVOCs in HELIOS and campaigns will be held with other French groups (Lyon and Bordeaux) in the framework of the two new projects CRASA (INSU) and COGNAC (ANR).

Results of WP 6 (2015-2018)

As a follow up of previous activities, the main topics addressed are emissions of greenhouse gases (GHGs) from peatlands and croplands and volatile species from volcanism, and atmospheric reactivity of (in)organic volatiles.

Emissions of GHGs from peatlands and croplands: Seasonal and daily cycles of CO2 exchange and CH4 emissions are monitored at the m2 scale on the 4 sites of the SNO Tourbières and on mesocosms extracted in la Guette peatland (LG) to set controlling factors of GHG fluxes. Thus, empirical and mechanistic models for production-exchange of GHG were developed (D’Angelo et al., 2016, AFM; Leroy et al., 2017, SBB). Following this, Carbon balance is investigated in la Guette peatland before and after water table restoration initiated by the installation of a dam upstream the peatland in the frame FEDER-EU, Région CVL :  CARBIODIV (2013-16) and CAREX (2017-21) projects. Gap filing for missing data at different scales (spatial and temporal) could be achieved to estimated C balance for peatlands of the SNO tourbières. First results had underlined that la Guette peatland operates as a source of C to the atmosphere before water table restoration (220 gC.m-2.year-1) (d’Angelo et al., submitted 2018) (Figure 2).

Figure 2. La Guette peatland : Carbon exchange and balance before water table restauration; fluxes are given in gC.m2.year-1

With regard to the flow and balance of dissolved organic carbon (DOC) at the ecosystem level, the improvement of the hydrological model (Binet et al., 2013, JH) and the incorporation of a biogeochemistry module to represent DOC dynamics in the peatland led to results highlighting the effect of hydrological conditions (rewetted area vs. drained area) in the control of DOC dynamics in this rehabilitated Sphagnum-dominated peatland (Bernard-Jannin et al., 2017, HESSD). To improve C balance investigation, ecosystem level observations in the frame of the French Peatland Observation Service (SNO Tourbières, CNRS/INSU) are studied since 2017 by the installation of an eddy covariance flux station on la Guette peatland supported by the project PIVOTS Région CVL (ARD2020, FEDER, CPER) (Figure 3).

Figure 3. La Guette peatland eddy covariance flux tower and automatic chambers set at the footprint of the flux tower

To carry on previous modelling studies (Qiu et al., 2018, GMD), the field and experiment observations (GHG fluxes) obtained and the peat GHG production-transport model developed at OSUC will be used in the emission surface ORCHIDEE model for a future coupling with atmospheric chemistry and climate (LMDz) models. This will be performed during the future Labex VOLTAIRE projects (research topic 3) in continuation of WP5 and WP6 where the modeling work, included DOC dynamics, is carried out in coll. with the LSCE, Gif / Yvette (B. Guenet, P. Peylin, and P. Ciais). Ecosystem level observations are studied by the installation of an eddy covariance flux station on LG. Observations data and the peat GHGs model are used in the emission surface ORCHIDEE model for a future coupling with atmospheric chemistry and climate (LMDz) models (Coll. IPSL-LSCE).

N2O fluxes monitored at different scales (chambers and/or micro-meteorology, with the SPIRIT-INRA) on croplands (OS2 site in Beauce-Chartraine, mainly, where the location is shown in Figure 4,

Figure 4. Location and description of the OS2 site in Beauce-Chartraine

and CEH-Scotland site of the EU project INGOS once) improved the understanding and modelling of the spatial variability of N2O fluxes at the intra-plot (Grossel et al., 2014, EM) or landscape scale (Grossel et al., 2016, AEE, Bureau et al., 2017, AEE) as shown in  Figure 5.

Figure 5. Investigation of the spatial variability of N2O emissions at different scale on the OS2 site in Beauce-Chartraine

In the frame of future Labex VOLTAIRE projects (research topic 2), indirect emissions of N2O will be investigated in more details such as N2O released by N or N2O transport from water streams (Figure 6).

Figure 6. : Investigation of N2O indirect emissions on the OS2 site in Beauce-Chartraine and related explanations.

In addition, research topic 3 in interaction with labex CAPRYSSES, will investigate mitigation processes of GHG emissions from croplands by preparation and amendment of suitable hydrochars, where a PRC program has been deposited in June 2018 in coll. between Orléans (CNRS and INRA) and Chinese partners: Shandong Univ., Qingdao, China)

Emissions and atmospheric degradation of biogenic or anthropogenic VOCsThe development of the HELIOS platform (the largest outdoor solar irradiation atmospheric simulation chamber in France and 3rd in Europe) dedicated to the investigation of the atmospheric processes under realistic conditions has been accomplished (Figure 7).

Figure 7. HELIOS platform, the largest outdoor solar irradiation atmospheric simulation chamber in France and 3rd in Europe.

It has been used to study the atmospheric fate of a series of biogenic VOCs in collaboration with national and international partners (Europe, US and China) within regional, national and international research programs (ANR (COGNAC: 2014-2018), ANR-RGC/Hong-Kong (SEAM : 2017-2021), CNRS-INSU, EU-FP7 (Marie-Curie/IRSES: 2012-2016), H2020 (Marie-Curie/RISE: 2016-2020), H2020 (Eurochamp: 2016-2020)). Both Marie Curie projects have been coordinated by CNRS-ICARE.

Fundamental data have been obtained for the ozonolysis of biogenic VOCs (Isoprène, α-pinène, limonène, carène,..) which enabled to make significant conclusions about the kinetics and mechanisms (Mellouki et al. 2015, ACS, Kukui et al. 2015, JPC; Zogka et al. 2016, JPC; Zhou et al. 2017, JPC; Ren et al., 2017, FD; He et al., 2018, STE) such as those leading to the formation of sulphuric acid and atmospheric aerosols. In addition, HELIOS has been used to investigate the photolysis of oxygenated VOCs under solar light conditions in collaboration with Colorado State University to determine the photolysis rates and the radical budget. These data are of tremendous importance for the understanding of the atmospheric oxidative capacity and the radical chemistry (Ren et al. 2018, JES).

Within labex Voltaire I and II projects,  an airborne CRDS instrument is under development for aircraft adaptation to measure atmospheric NO3 and N2O5 concentrations (Figure 8) to get a better understanding on the VOC night oxidation. This is an international project in Coll. with NOAA-Boulder, CSU-Fort Collins (USA), LATMOS-IPSL (Paris) and CNRS-ICARE-LPC2E (Orléans) where preliminary measurements of NO3 and N2O5 by CRDS have been performed for the first time in France near Paris.

Figure 8. Airborne instrument development to measure atmospheric NO3 and N2O5 concentrations

Emissions of volcanic gases and their atmospheric reactivity (halogens)

The objective is to assess the budget of halogens, and sulfur compounds among other volatiles to understand the impact of volcanic gases on ozone destruction, sulfate aerosols and clouds formation and thus on climate (Figure 9).

Figure 9. A sketch explaining the various volatiles emitted from volcanoes and their interactions with the atmosphere

Emissions of volcanic gases were quantified in-situ: a new low-cost approach to measure volcanic HCl (Roberts et al., 2017, BV) was developed using miniature gas sensors (Roberts et al., 2014a, JVGR), with size-resolved volcanic aerosol measured by LOAC OPC (Vignelles et al., 2016, EPSL; Roberts et al., 2018b,c GCA, G). Volcanic gas fluxes were studied by remote sensing FTIR-imager (Figure 10).

Figure 10. Volcanic gas emissions studied by remote sensing FTIR-imager, showing that previous measurements of SO2 found in literature by UV underestimated SO2 concentration by a factor 4 to 6 in volcanic plumes of high contents of ashes and sulfate aerosols

Atmospheric processing of halogens in the young plume was simulated by numerical box model, with a new parameterization proposed for their heterogeneous reactions (Roberts et al., 2014b,c, ACP). The halogen-mediated destruction of ozone in the plume was quantified (Roberts, 2018). Impacts of the aged, dispersing plume were investigated by regional-scale modelling (Jourdain et al., 2016, ACP). A LPC2E-ICARE collaboration has started to model the chemistry of hot volcanic gases very near-to-source, in interaction with labex Caprysses. This collaboration will bring key improvements to understand the overall chemistry of gases and particles on volcanic plumes and beyond by combination of field measurements and multiscale models (Figure 11) which will be also developed within Voltaire II project.

Figure 11. Volcanic and biomass burning gas emissions : high temperature and pressure chemistry field measurements and multiscale models approach

As significant results, the behaviour of bromine in a variety of silicate melts over a range of pressure and temperature has been determined, and applied to well know volcanoes (Cadoux et al., 2018, EPSL, Figure 12).

Figure 12.(a) Triangular plot of S–Cl–Br*300 compositions of volcanic gas samples from selected mafic arc volcanoes. All data refer to near-vent in-situ measurements with filter packs, and are thus representative of gas species SO2, HCl and HBr (the main S and halogen reservoirs in near-vent plumes; Aiuppa et al., 2005). Volcanic gas data sources: Reunion Island (Indian Ocean): Allard et al.(2011); Nyiragongo (Congo): Bobrowski et al.(2015); Hawaii (Pacific Ocean): Mather et al.(2012); Etna (Sicily): Aiuppa et al.(2005), Aiuppa(2009), Aiuppa (unpublished results); Stromboli (Aeolian Islands): Aiuppa(2009); Masaya (Nicaragua): Witt et al.(2008); Mount Asama (Japan): Aiuppa(2009), Aiuppa (unpublished results); Myike-jima (Japan): Aiuppa(2009), Aiuppa (unpublished results); Gorely (Kamchatka, Russia): Aiuppa et al.(2012); Villarrica (Chile): Sawyer et al.(2011). For comparison, the model-derived compositions of gas initially coexisting with an Etna-like primitive melt (S: 0.27wt%, Cl: 0.18wt%, and Br: 5.1ppm) are shown by the thick solid green curve. Dashed green lines are examples of Etna-like melt model trends obtained using same initial S and Cl contents (S: 0.27wt%, Cl: 0.18wt%) but slightly different initial Br contents (of respectively 3 and 6.1ppm), within the range observed in glass inclusions (see TableA.2). The initial Br contents for the 3 Etna runs are labelledin the plot. Model lines are obtained using the Rayleigh-type open-system equations described in the text. Extent of degassing along both model lines varies from top (“early gas”) to bottom (“late gas”) (R values for specific points are shown in italics). See text for discussion. (b) The glass inclusion compositions from Etna and Stromboli (data from TableA.2) are displayed against the model-derived compositions, ranging from S-rich “early melts” to halogen-enriched (relative to S) “late melts”. The melt model line (solid red curve) is derived from the same Etna-like primitive melt composition given above (S: 0.27wt%, Cl: 0.18 wt%, and Br: 5.1ppm). Dashed red lines are examples of Etna-like melt model trends obtained using same initial S and Cl contents (S: 0.27wt%, Cl: 0.18wt%) but slightly different initial Br contents (of respectively 3 and 6.1ppm), within the range observed in glass inclusions (see TableA.2). The initial Br contents for the 3 Etna runs are labelledin the plot. The melt model trend initialized at conditions representative of a Stromboli’s primitive melt (S: 0.2wt%, Cl: 0.17wt%, and Br: 4.8ppm; see TableA.2) is depicted by the orange solid line. Rvalues for specific points are shown in italics.

The recent volcanic emissions of Kilauea volcano, Hawaii, have been carefully analysed, combining detailed FTIR, melt inclusion analyses and thermophysical modelling to show that the redox state of volcanic gases losses its magma imprint during its expansion-driven cooling into the open atmosphere (Oppenheimer et al., 2018, Nat. Geo.) with profound implications for the use of gas as a monitoring tool or for our understanding of the chemical evolution of Earth’s early atmosphere (Figure 13).

Figure 13. Computed equilibrium temperature and fO2 for spectrosccopic measurements of gas emissions from Kīlauea’s lava lake. The dataset is classified into mild-degassing (12:14 to 13:14 h local time) and vigorous degassing (15:16 to 15:23 h) regimes on 5 March 2013. Also shown are NNO and QFM buffers; the solidus temperature of Kīlauea basalt; ranges of CO2/CO and SO2/H2S, temperature–fO2 calculations for ‘type I’ and ‘type II’ gases (Kīlauea Summit and East Rift Zone emissions, respectively) and associated empirical fit9; and reported fO2 at 1,200 °C for 2008 and 2010 matrix glasses for ejecta from the Overlook Vent (mean and range shown)30. Note that, below the solidus, our analyses for ‘vigorous degassing’ are more oxidized than ‘type II’ gases at equivalent equilibrium temperatures. The white and black dotted line with arrow shows temperature – fO2 calculations for closed-system, gas-only cooling starting with our measured gas composition at 1,150 °C (open triangle), showing a close fit to the dataset (From Oppenheimer et al., 2018, Nat Geo).

References from 2015 to 2018

2018

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2017

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Bureau J., A. Grossel, B. Loubet, P. Laville, R. Massad, E. Haas, K. Butterbach-Bahl, C. Guimbaud, C. Hénault (2017). Evaluation of new flux attribution methods for mapping N2O emissions at the landscape scale, Agriculture, Ecosystems and Environment, 247, 9-22, DOI: 10.1016/j.agee.2017.06.012.

Catoire, V., C. Robert, M. Chartier, P. Jacquet, C. Guimbaud, G. Krysztofiak (2017). The SPIRIT airborne instrument: a three-channel infrared absorption spectrometer with quantum cascade lasers for in-situ atmospheric trace-gas measurements, Applied Physics B, 123:244, DOI: 10.1007/s00340-017-6820-x.

Diallo, M., F. Ploeger, P. Konopka, B. Legras, M. Riese, R. Müller, H. Garny, E. Ray, T. Birner, G. Berthet, F. Jégou (2017). Significant contributions of volcanic aerosols to decadal changes in the stratospheric circulation, Geophys. Res. Lett., 44, DOI: 10.1002/2017GL074662.

Duruisseau F., N. Huret, A. Andral, C. Camy-Peyret, Assessment of the ERA-Interim reanalysis data using balloons operating at high altitude in the stratosphere, J. Atmos. Sci., 2017.

Jiang, Z. H., B. Grosselin, V. Daële, A. Mellouki, Y. Mu (2017). Seasonal and diurnal variations of BTEX compounds in the semi-urban environment of Orleans, France, Science of the Total Environment, 574, 1659-1664, DOI: 10.1016/j.scitotenv.2016.08.214.

Leroy, F., S. Gogo, C. Guimbaud, L. Bernard-Jannin, Z. Hu, F. Laggoun-Défarge (2017). Vegetation composition controls temperature sensitivity of CO2 and CH4 emissions and DOC concentration in peatlands, Soil Biology and Biochemistry, 107, 164–167, DOI: 10.1016/j.soilbio.2017.01.005

Ren Y., Grosselin B., Daële V., Mellouki A. (2017). Investigation of the reaction of ozone with isoprene, methacrolein and methyl vinyl ketone using the HELIOS chamber, Faraday discussions, DOI: 10.1039/c7fd00014f.

Ricaud, P., R. Zbinden, V. Catoire, V. Brocchi, F. Dulac, …, P. Jacquet, S. Chevrier, C. Robert, …, G. Krysztofiak, et al. (2017). The GLAM airborne campaign across the Mediterranean basin, Bulletin of the American Meteorological Society, DOI: 10.1175/BAMS-D-16-0226.1.

Roberts T.J., Giudice G., Liuzzo M., Aiuppa A.,  Coltelli M., Vignelles D., Salerno G., Couté B., Chartier M., Baron, R. Saffell J. R., Scaillet B. (2017). Validation of a novel Multi-Gas sensor for volcanic HCl alongside H2S and SO2 at Mt Etna, Bulletin of Volcanology, 79, 36, DOI: 10.1007/s00445-017-1114-z.

Roberts, T.J. (2018). Ozone depletion in Tropospheric Volcanic Plumes: From Halogen-Poor to Halogen-Rich Emissions, Geosciences, 8, 2, 68, DOI: 10.3390/geosciences8020068.

Roberts T.J., Vignelles D., Liuzzo M., Giudice G., Aiuppa A., Coltelli M., Salerno G., Chartier M., Couté B., Berthet G., Lurton T., Dulac F., Renard J.-B. (2018). The primary volcanic aerosol emission from Mt Etna: size-resolved particles with SO2 and role in plume reactive halogen chemistry, Geochimica et Cosmochimica Acta, 222, 74-93.

Zhou L., A.R. Ravishankara, S. Brown, M. Idir, K. Zarzana, V. Daële, A. Mellouki (2017). Kinetics of the Reactions of NO3 Radical with Methacrylate Esters, The journal of physical chemistry, DOI: 10.1021/acs.jpca.7b02332.

2016

Bernard F., M. Cazaunau, B. Grosselin, B. Zhou, J. Zheng, P. Liang, Y. Zhang, X. Ye, V. Daële, Y. Mu, R. Zhang, J. Chen, A. Mellouki (2016), Measurements of nitrous acid (HONO) in urban area of Shanghai, China. Environmental Science and Pollution Research, Volume 23, Issue 6, 2016. DOI : 10.1007/s11356-015-5797-4

Chane Ming, F., Vignelles, D., Jégou, F., Berthet, G., Renard, J.-B., Gheusi, F., Kuleshov, Y (2016). Gravity-wave effects on tracer gases and stratospheric aerosol concentrations during the 2013 ChArMEx campaign, Atmos. Chem. Phys., 16, 8023–8042, 2016, doi:10.519/acp-16-8023-2016.

D’Angelo B., Gogo S., Laggoun-Défarge F., Le Moing F., Jégou F., Guimbaud C. (2016). Soil temperature synchronisation improves representation of diel variability of ecosystem respiration in Sphagnum peatlands. Agricultural and Forest Meteorology, 223:95-102. doi: 10.1016/j.agrformet.2016.03.021

Errami M., G. El Dib, M. Cazaunau, E. Roth, R. Salghi, A. Mellouki, A. Chakir (2016), Atmospheric degradation of pyridine: UV absorption spectrum and reaction with OH radicals and O3, Chemical Physics Letters, Volume 662.

Grossel  A., B. Nicoullaud, H. Bourennane, M. Lacoste, C. Guimbaud, C. Robert, C. Hénault (2016). The effect of tile-drainage on nitrous oxide emissions from soils and drainage streams in a cropped landscape in Central France, Agriculture, Ecosystems and Environment, 230, 251-260. doi:10.1016/j.agee.2016.06.015

Guimbaud C., C. Noel, M. Chartier, V. Catoire, M. Blessing, J.C. Gourry, C. Robert (2016), A quantum cascade laser infrared spectrometer for CO2 stable isotope analysis: field implementation at a hydrocarbon contaminated site under bio-remediation, Journal of Environmental Science., 40:60-74. doi: 10.1016/j.jes.2015.11.015.

Jimenez E., S. Gonzalez, M. Cazaunau, H. Chen, B. Ballestros, V. Daële, J. Albadejo, A. Mellouki (2016), Atmospheric Degradation Initiated by OH radicals of the Potential Foam Expansion Agent, CF3(CF2)2CH=CH2 (HFC-1447fz): Kinetics and Formation of Gaseous Products and Secondary Organic Aerosols, Environmental Science and Technology, Volume 50, Issue 3, 2016, DOI : 10.1021/acs.est.5b04379

Jourdain L., Roberts T. J., Pirre M., Josse B. (2016). Modeling the reactive halogen plume from Ambrym volcano and its impact on the troposphere with the CCATT-BRAMS mesoscale model. Atmospheric Chemistry and Physics, 16, 1–27, doi:10.5194/acp-16-1-2016.

Noel C., Gourry J.-C., Deparis J., Blessing M., Ignatiadis I., Guimbaud C. (2016). Combining Geoelectrical Measurements and CO 2 Analyses to Monitor the Enhanced Bioremediation of Hydrocarbon-Contaminated Soils: A Field Implementation. Applied and Environmental Soil Science, 2016:1480976. doi: 10.1155/2016/1480976

Noel C., J.C. Gourry, J. Deparis, I. Ignatiadis, F. Battaglia-Brunet, C. Guimbaud, Suitable real time monitoring of the aerobic biodegradation of toluene in contaminated sand by Spectral Induced Polarization measurements and CO2 analyses, Near Surface Geophysics, 14 (3), 263-273, doi: 10.3997/1873-0604.2016007, 2016.

Renard J.-B., Dulac F., Berthet G., Lurton T., Vignelles D., Jégou F., Tonnelier T., Jeannot M., Couté B., Akiki R., Verdier N., Mallet M., Gensdarmes F., … Duverger V., … Roberts T., … et al. (2016). LOAC: a small aerosol optical counter/sizer for ground-based and balloon measurements of the size distribution and nature of atmospheric particles – Part 1: Principle of measurements and instrument evaluation. Atmospheric Measurement Techniques, 9(4):1721-1742. doi: 10.5194/amt-9-1721-2016

Renard J.-B., Dulac F., Berthet G., Lurton T., Vignelles D., Jégou F., Tonnelier T., Jeannot M., Couté B., Akiki R., Verdier N., Mallet M., Gensdarmes F., … Duverger, … Roberts T., et al. (2016). LOAC: a small aerosol optical counter/sizer for ground-based and balloon measurements of the size distribution and nature of atmospheric particles – Part 2. Atmospheric Measurement Techniques, 9, 3673-3686, doi:10.5194/amt-9-3673-2016.

Roberts T. J., Dutsch M., Hole L. R., Voss P. (2016). Controlled meteorological (CMET) balloon profiling of the Arctic atmospheric boundary layer around Spitsbergen compared to ERA-I and Arctic System Reanalyses, Atmospheric Chemistry and Physics, 16, 12383-12396. doi:10.5194/acp-16-12383-2016

Thiéblemont R., K. Matthes, Y. J. Orsolini, A. Hauchecorne and N. Huret (2016). Poleward Transport Variability in the Northern Hemisphere during Final Stratospheric Warmings simulated by CESM(WACCM), J. Geophys Res., 121 (18), pp.10394-10410, doi:2016JD025358R.

Vignelles D., Roberts T.J., Carboni E., Ilyinskaya E., Pfeffer M., Dagsson Waldhauserova P., Schmidt A., Berthet G., Jegou F., Renard J.-B., Ólafsson H., Bergsson B., Yeo R., Fannar Reynisson N., Grainger R.G., Galle B., Conde V., Arellano S., Lurton T., Coute B., Duverger V. (2016). Balloon-borne measurement of the aerosol size distribution from an Icelandic flood basalt eruption, Earth and Planetary Science Letters, 453, 252–259.

Zogka A., A. Mellouki, M. Romanias, Y. Bedjanian, M. Idir, B. Grosselin, V. Daële, Atmospheric Chemistry of 1-Methoxy 2-Propyl Acetate: UV Absorption Cross Sections, Rate Coefficients and Products of its Reactions with OH Radicals and Cl Atoms. The Journal of Physical Chemistry A, Volume 120, Issue 45, 2016. DOI: 10.1021/acs.jpca.6b08757

Zou Y., Z. Hu, J. Zhang, H. Xie, C. Guimbaud, Y. Fang. (2016). Effects of pH on nitrogen transformations in media-based aquaponics, Bioresource Technology, 210, 81-87. doi:10.1016/j.biortech.2015.12.079

2015

Krysztofiak G., Yao Veng Té, V. Catoire, G. Berthet, Geoffrey C. Toon,F. Jégou, P. Jeseck, C. Robert (2015). Carbonyl sulfide (OCS) variability with latitude in the atmosphere. Atmosphere-Ocean, 89-101, doi: 10.1080/07055900.2013.876609, <10.1080/07055900.2013.876609>.

Mellouki A., T. Wallington, J. Chen. Atmospheric chemistry of oxygenated volatile organic compounds (OVOCs): Impacts on air quality and climate. Chemical Reviews, American Chemical Society, 115,10, 3984-4014 (2015) DOI : 10.1021/cr500549n

Butkovskaya N.I., A. Kukui, G. Le Bras, M.T. Rayez, J.C. Rayez. Pressure Dependence of Butyl Nitrate Formation in the Reaction of Butylperoxy Radicals with Nitrogen Oxide, Journal of Physical Chemistry A, American Chemical Society, 2015, 119 (19), pp.4408-4417

References cited on the document, before 2015

Roberts T.J., J.R. Saffell, Clive Oppenheimer, T. Lurton. Electrochemical sensors applied to pollution monitoring: Measurement error and gas ratio bias — A volcano plume case study. Journal of Volcanology and Geothermal Research, Elsevier, 2014a, 281, pp.85-96. <10.1016/j.jvolgeores.2014.02.023>

Roberts T.J., R.S. Martin, L. Jourdain. Reactive bromine chemistry in Mount Etna’s volcanic plume: the influence of total Br, high-temperature processing, aerosol loading and plume–air mixing. Atmospheric Chemistry and Physics, European Geosciences Union (EGU), 2014b, 14, pp.11201-11219

Roberts T.J., L. Jourdain, P. T. Griffiths, M. Pirre. Re-evaluating the reactive uptake of HOBr in the troposphere with implications for the marine boundary layer and volcanic plumes. Atmospheric Chemistry and Physics, European Geosciences Union (EGU), 2014c, 14, pp.11185-11199

Binet S., S. Gogo, F. Laggoun-Défarge, A water-table dependent reservoir model to investigate the effect of drought and vascular plant invasion on peatland hydrology, Journal of Hydrology, Elsevier(2013) 499, pp.132-139