Articles | Volume 19, issue 6
https://doi.org/10.5194/acp-19-3779-2019
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-19-3779-2019
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
25 Mar 2019
Research article |
| 25 Mar 2019
| 25 Mar 2019
Seasonality in the Δ33S measured in urban aerosols highlights an additional oxidation pathway for atmospheric SO2
David Au Yang
CORRESPONDING AUTHOR
Laboratoire de Géochimie des Isotopes Stables, Institut de
Physique du Globe de Paris, Université Paris Diderot, CNRS UMR 7154,
Sorbonne Paris-Cité, 1 rue de Jussieu, 75005 Paris, France
GEOTOP/Université du Québec à Montreal, Montreal H3C
3P8, Canada
Pierre Cartigny
Laboratoire de Géochimie des Isotopes Stables, Institut de
Physique du Globe de Paris, Université Paris Diderot, CNRS UMR 7154,
Sorbonne Paris-Cité, 1 rue de Jussieu, 75005 Paris, France
Karine Desboeufs
Laboratoire Interuniversitaire des Systèmes Atmosphériques
(LISA), UMR7583 CNRS, Université Paris 7 Denis Diderot, Université
Paris-Est Créteil, Institut Pierre-Simon Laplace, Créteil, 94010,
France
David Widory
GEOTOP/Université du Québec à Montreal, Montreal H3C
3P8, Canada
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Isabelle Genot, David Au Yang, Erwan Martin, Pierre Cartigny, Erwann Legendre, and Marc De Rafelis
Atmos. Chem. Phys., 20, 4255–4273, https://doi.org/10.5194/acp-20-4255-2020, https://doi.org/10.5194/acp-20-4255-2020, 2020
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Given their critical impact on radiative forcing, sulfate aerosols have been extensively studied using their isotope signatures (δ34S, ∆33S, ∆36S, δ18O, and ∆17O). A striking observation is that ∆33S > 0 ‰, implying a missing reservoir in the sulfur cycle. Here, we measured ∆33S < 0 ‰ in black crust sulfates (i.e., formed on carbonate walls) that must therefore result from distinct chemical pathway(s) compared to sulfate aerosols, and they may well represent this complementary reservoir.
Karine Desboeufs, Paola Formenti, Raquel Torres-Sánchez, Kerstin Schepanski, Jean-Pierre Chaboureau, Hendrik Andersen, Jan Cermak, Stefanie Feuerstein, Benoit Laurent, Danitza Klopper, Andreas Namwoonde, Mathieu Cazaunau, Servanne Chevaillier, Anaïs Feron, Cécile Mirande-Bret, Sylvain Triquet, and Stuart J. Piketh
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This study investigates the fractional solubility of iron (Fe) in dust particles along the coast of Namibia, a critical region for the atmospheric Fe supply of the South Atlantic Ocean. Our results suggest a possible two-way interplay whereby marine biogenic emissions from the coastal marine ecosystems into the atmosphere would increase the solubility of Fe-bearing dust by photo-reduction processes. The subsequent deposition of soluble Fe could act to further enhance marine biogenic emissions.
Thomas Audoux, Benoit Laurent, Karine Desboeufs, Gael Noyalet, Franck Maisonneuve, Olivier Lauret, and Servanne Chevaillier
Atmos. Chem. Phys., 23, 13485–13503, https://doi.org/10.5194/acp-23-13485-2023, https://doi.org/10.5194/acp-23-13485-2023, 2023
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In the Paris region, a campaign was conducted to study wet deposition of aerosol particles during rainfall events. Simultaneous measurements of aerosol and wet deposition allowed us to discuss their transfer from the atmosphere to rain. Chemical evolution within events revealed meteorology, atmospheric conditions and local vs. long range sources as key factors. This study highlights the variability of wet deposition and the need to consider event-specific factors to understand its mechanisms.
Karine Desboeufs, Franck Fu, Matthieu Bressac, Antonio Tovar-Sánchez, Sylvain Triquet, Jean-François Doussin, Chiara Giorio, Patrick Chazette, Julie Disnaquet, Anaïs Feron, Paola Formenti, Franck Maisonneuve, Araceli Rodríguez-Romero, Pascal Zapf, François Dulac, and Cécile Guieu
Atmos. Chem. Phys., 22, 2309–2332, https://doi.org/10.5194/acp-22-2309-2022, https://doi.org/10.5194/acp-22-2309-2022, 2022
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This article reports the first concurrent sampling of wet deposition samples and surface seawater and was performed during the PEACETIME cruise in the remote Mediterranean (May–June 2017). Through the chemical composition of trace metals (TMs) in these samples, it emphasizes the decrease of atmospheric metal pollution in this area during the last few decades and the critical role of wet deposition as source of TMs for Mediterranean surface seawater, especially for intense dust deposition events.
Matthieu Bressac, Thibaut Wagener, Nathalie Leblond, Antonio Tovar-Sánchez, Céline Ridame, Vincent Taillandier, Samuel Albani, Sophie Guasco, Aurélie Dufour, Stéphanie H. M. Jacquet, François Dulac, Karine Desboeufs, and Cécile Guieu
Biogeosciences, 18, 6435–6453, https://doi.org/10.5194/bg-18-6435-2021, https://doi.org/10.5194/bg-18-6435-2021, 2021
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Phytoplankton growth is limited by the availability of iron in about 50 % of the ocean. Atmospheric deposition of desert dust represents a key source of iron. Here, we present direct observations of dust deposition in the Mediterranean Sea. A key finding is that the input of iron from dust primarily occurred in the deep ocean, while previous studies mainly focused on the ocean surface. This new insight will enable us to better represent controls on global marine productivity in models.
Elvira Pulido-Villena, Karine Desboeufs, Kahina Djaoudi, France Van Wambeke, Stéphanie Barrillon, Andrea Doglioli, Anne Petrenko, Vincent Taillandier, Franck Fu, Tiphanie Gaillard, Sophie Guasco, Sandra Nunige, Sylvain Triquet, and Cécile Guieu
Biogeosciences, 18, 5871–5889, https://doi.org/10.5194/bg-18-5871-2021, https://doi.org/10.5194/bg-18-5871-2021, 2021
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We report on phosphorus dynamics in the surface layer of the Mediterranean Sea. Highly sensitive phosphate measurements revealed vertical gradients above the phosphacline. The relative contribution of diapycnal fluxes to total external supply of phosphate to the mixed layer decreased towards the east, where atmospheric deposition dominated. Taken together, external sources of phosphate contributed little to total supply, which was mainly sustained by enzymatic hydrolysis of organic phosphorus.
France Van Wambeke, Vincent Taillandier, Karine Desboeufs, Elvira Pulido-Villena, Julie Dinasquet, Anja Engel, Emilio Marañón, Céline Ridame, and Cécile Guieu
Biogeosciences, 18, 5699–5717, https://doi.org/10.5194/bg-18-5699-2021, https://doi.org/10.5194/bg-18-5699-2021, 2021
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Simultaneous in situ measurements of (dry and wet) atmospheric deposition and biogeochemical stocks and fluxes in the sunlit waters of the open Mediterranean Sea revealed complex physical and biological processes occurring within the mixed layer. Nitrogen (N) budgets were computed to compare the sources and sinks of N in the mixed layer. The transitory effect observed after a wet dust deposition impacted the microbial food web down to the deep chlorophyll maximum.
Evelyn Freney, Karine Sellegri, Alessia Nicosia, Leah R. Williams, Matteo Rinaldi, Jonathan T. Trueblood, André S. H. Prévôt, Melilotus Thyssen, Gérald Grégori, Nils Haëntjens, Julie Dinasquet, Ingrid Obernosterer, France Van Wambeke, Anja Engel, Birthe Zäncker, Karine Desboeufs, Eija Asmi, Hilkka Timonen, and Cécile Guieu
Atmos. Chem. Phys., 21, 10625–10641, https://doi.org/10.5194/acp-21-10625-2021, https://doi.org/10.5194/acp-21-10625-2021, 2021
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In this work, we present observations of the organic aerosol content in primary sea spray aerosols (SSAs) continuously generated along a 5-week cruise in the Mediterranean. This information is combined with seawater biogeochemical properties also measured continuously along the ship track to develop a number of parametrizations that can be used in models to determine SSA organic content in oligotrophic waters that represent 60 % of the oceans from commonly measured seawater variables.
Matthieu Roy-Barman, Lorna Foliot, Eric Douville, Nathalie Leblond, Fréderic Gazeau, Matthieu Bressac, Thibaut Wagener, Céline Ridame, Karine Desboeufs, and Cécile Guieu
Biogeosciences, 18, 2663–2678, https://doi.org/10.5194/bg-18-2663-2021, https://doi.org/10.5194/bg-18-2663-2021, 2021
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The release of insoluble elements such as aluminum (Al), iron (Fe), rare earth elements (REEs), thorium (Th) and protactinium (Pa) when Saharan dust falls over the Mediterranean Sea was studied during tank experiments under present and future climate conditions. Each element exhibited different dissolution kinetics and dissolution fractions (always lower than a few percent). Changes in temperature and/or pH under greenhouse conditions lead to a lower Th release and a higher light REE release.
Kahina Djaoudi, France Van Wambeke, Aude Barani, Nagib Bhairy, Servanne Chevaillier, Karine Desboeufs, Sandra Nunige, Mohamed Labiadh, Thierry Henry des Tureaux, Dominique Lefèvre, Amel Nouara, Christos Panagiotopoulos, Marc Tedetti, and Elvira Pulido-Villena
Biogeosciences, 17, 6271–6285, https://doi.org/10.5194/bg-17-6271-2020, https://doi.org/10.5194/bg-17-6271-2020, 2020
Cécile Guieu, Fabrizio D'Ortenzio, François Dulac, Vincent Taillandier, Andrea Doglioli, Anne Petrenko, Stéphanie Barrillon, Marc Mallet, Pierre Nabat, and Karine Desboeufs
Biogeosciences, 17, 5563–5585, https://doi.org/10.5194/bg-17-5563-2020, https://doi.org/10.5194/bg-17-5563-2020, 2020
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We describe here the objectives and strategy of the PEACETIME project and cruise, dedicated to dust deposition and its impacts in the Mediterranean Sea. Our strategy to go a step further forward than in previous approaches in understanding these impacts by catching a real deposition event at sea is detailed. We summarize the work performed at sea, the type of data acquired and their valorization in the papers published in the special issue.
Antonio Tovar-Sánchez, Araceli Rodríguez-Romero, Anja Engel, Birthe Zäncker, Franck Fu, Emilio Marañón, María Pérez-Lorenzo, Matthieu Bressac, Thibaut Wagener, Sylvain Triquet, Guillaume Siour, Karine Desboeufs, and Cécile Guieu
Biogeosciences, 17, 2349–2364, https://doi.org/10.5194/bg-17-2349-2020, https://doi.org/10.5194/bg-17-2349-2020, 2020
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Residence times of particulate metals derived from aerosol deposition in the Sea Surface Microlayer of the Mediterranean Sea ranged from a couple of minutes (e.g., for Fe) to a few hours (e.g., for Cu). Microbial activity seems to play an important role in in this process and in the concentration and distribution of metals between diferent water layers.
Laurent Menut, Guillaume Siour, Bertrand Bessagnet, Florian Couvidat, Emilie Journet, Yves Balkanski, and Karine Desboeufs
Geosci. Model Dev., 13, 2051–2071, https://doi.org/10.5194/gmd-13-2051-2020, https://doi.org/10.5194/gmd-13-2051-2020, 2020
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Modelling of mineral dust is often done using one single mean species. In this study, differentiated mineral species with their chemical composition are implemented in the CHIMERE regional chemistry-transport model by using global databases. Simulations are carried out to quantify the realism and gain of such mineralogy.
Isabelle Genot, David Au Yang, Erwan Martin, Pierre Cartigny, Erwann Legendre, and Marc De Rafelis
Atmos. Chem. Phys., 20, 4255–4273, https://doi.org/10.5194/acp-20-4255-2020, https://doi.org/10.5194/acp-20-4255-2020, 2020
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Given their critical impact on radiative forcing, sulfate aerosols have been extensively studied using their isotope signatures (δ34S, ∆33S, ∆36S, δ18O, and ∆17O). A striking observation is that ∆33S > 0 ‰, implying a missing reservoir in the sulfur cycle. Here, we measured ∆33S < 0 ‰ in black crust sulfates (i.e., formed on carbonate walls) that must therefore result from distinct chemical pathway(s) compared to sulfate aerosols, and they may well represent this complementary reservoir.
Patrick Chazette, Cyrille Flamant, Julien Totems, Marco Gaetani, Gwendoline Smith, Alexandre Baron, Xavier Landsheere, Karine Desboeufs, Jean-François Doussin, and Paola Formenti
Atmos. Chem. Phys., 19, 14979–15005, https://doi.org/10.5194/acp-19-14979-2019, https://doi.org/10.5194/acp-19-14979-2019, 2019
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Evolution of the vertical distribution and optical properties of aerosols in the free troposphere is analysed for the first time over the Namibian coast, a region where uncertainties on aerosol–cloud coupling in climate simulations are significant. The high variability of atmospheric aerosol composition is highlighted using a combination of ground-based, airborne and space-borne lidar. Aerosols are mainly transported from Angola, but part of the highest aerosol layer may come from South America.
Marc D. Mallet, Barbara D'Anna, Aurélie Même, Maria Chiara Bove, Federico Cassola, Giandomenico Pace, Karine Desboeufs, Claudia Di Biagio, Jean-Francois Doussin, Michel Maille, Dario Massabò, Jean Sciare, Pascal Zapf, Alcide Giorgio di Sarra, and Paola Formenti
Atmos. Chem. Phys., 19, 11123–11142, https://doi.org/10.5194/acp-19-11123-2019, https://doi.org/10.5194/acp-19-11123-2019, 2019
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We present findings from a summertime field campaign at the remote island of Lampedusa in the central Mediterranean Sea. We show that the aerosol loading is similar to coastal sites around the Mediterranean. We observe higher loadings of sulfate and aged organic aerosol from air masses transported over the central and eastern Mediterranean in comparison to those from the western Mediterranean. These results highlight the rarity of pristine air masses, even in remote marine environments.
Paola Formenti, Stuart John Piketh, Andreas Namwoonde, Danitza Klopper, Roelof Burger, Mathieu Cazaunau, Anaïs Feron, Cécile Gaimoz, Stephen Broccardo, Nicola Walton, Karine Desboeufs, Guillaume Siour, Mattheus Hanghome, Samuel Mafwila, Edosa Omoregie, Wolfgang Junkermann, and Willy Maenhaut
Atmos. Chem. Phys., 18, 17003–17016, https://doi.org/10.5194/acp-18-17003-2018, https://doi.org/10.5194/acp-18-17003-2018, 2018
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Three-years of continuous measurements at the Henties Bay Aerosol Observatory (HBAO; 22°S, 14°05’E), Namibia, show that during the austral wintertime, long- and medium-range transport of pollution from biomass and fossil fuel burning give rise to peaks of light-absorbing black carbon aerosols into the marine boundary layer ahead of the main biomass burning season. This could affect the cloud properties.
Karine Desboeufs, Elisabeth Bon Nguyen, Servanne Chevaillier, Sylvain Triquet, and François Dulac
Atmos. Chem. Phys., 18, 14477–14492, https://doi.org/10.5194/acp-18-14477-2018, https://doi.org/10.5194/acp-18-14477-2018, 2018
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Atmospheric deposition is known to be a major source of nutrients for the marine biosphere in the Mediterranean Sea. The study of the origin of nutrients and trace metals in Corsica presented here shows that the dust events were the major sources of Si and Fe. Conversely, combustion sources predominated the inputs of N, P, and trace metals. This work showed the importance of considering background anthropogenic deposition for estimating the impact of atmospheric forcing on marine biota.
Yinghe Fu, Karine Desboeufs, Julie Vincent, Elisabeth Bon Nguyen, Benoit Laurent, Remi Losno, and François Dulac
Atmos. Meas. Tech., 10, 4389–4401, https://doi.org/10.5194/amt-10-4389-2017, https://doi.org/10.5194/amt-10-4389-2017, 2017
Julie Vincent, Benoit Laurent, Rémi Losno, Elisabeth Bon Nguyen, Pierre Roullet, Stéphane Sauvage, Servanne Chevaillier, Patrice Coddeville, Noura Ouboulmane, Alcide Giorgio di Sarra, Antonio Tovar-Sánchez, Damiano Sferlazzo, Ana Massanet, Sylvain Triquet, Rafael Morales Baquero, Michel Fornier, Cyril Coursier, Karine Desboeufs, François Dulac, and Gilles Bergametti
Atmos. Chem. Phys., 16, 8749–8766, https://doi.org/10.5194/acp-16-8749-2016, https://doi.org/10.5194/acp-16-8749-2016, 2016
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To investigate dust deposition dynamics at the regional scale, five automatic deposition collectors named CARAGA have been deployed in the western Mediterranean basin (Lampedusa, Majorca, Corsica, Frioul and Le Casset) during 1 to 3 years depending on the station. Complementary observations provided by both satellite and air mass trajectories are used to identify the dust provenance areas and the transport pathways from the Sahara to the stations for the studied period.
M. Mallet, F. Dulac, P. Formenti, P. Nabat, J. Sciare, G. Roberts, J. Pelon, G. Ancellet, D. Tanré, F. Parol, C. Denjean, G. Brogniez, A. di Sarra, L. Alados-Arboledas, J. Arndt, F. Auriol, L. Blarel, T. Bourrianne, P. Chazette, S. Chevaillier, M. Claeys, B. D'Anna, Y. Derimian, K. Desboeufs, T. Di Iorio, J.-F. Doussin, P. Durand, A. Féron, E. Freney, C. Gaimoz, P. Goloub, J. L. Gómez-Amo, M. J. Granados-Muñoz, N. Grand, E. Hamonou, I. Jankowiak, M. Jeannot, J.-F. Léon, M. Maillé, S. Mailler, D. Meloni, L. Menut, G. Momboisse, J. Nicolas, T. Podvin, V. Pont, G. Rea, J.-B. Renard, L. Roblou, K. Schepanski, A. Schwarzenboeck, K. Sellegri, M. Sicard, F. Solmon, S. Somot, B Torres, J. Totems, S. Triquet, N. Verdier, C. Verwaerde, F. Waquet, J. Wenger, and P. Zapf
Atmos. Chem. Phys., 16, 455–504, https://doi.org/10.5194/acp-16-455-2016, https://doi.org/10.5194/acp-16-455-2016, 2016
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The aim of this article is to present an experimental campaign over the Mediterranean focused on aerosol-radiation measurements and modeling. Results indicate an important atmospheric loading associated with a moderate absorbing ability of mineral dust. Observations suggest a complex vertical structure and size distributions characterized by large aerosols within dust plumes. The radiative effect is highly variable, with negative forcing over the Mediterranean and positive over northern Africa.
Y. Zhang, N. Mahowald, R. A. Scanza, E. Journet, K. Desboeufs, S. Albani, J. F. Kok, G. Zhuang, Y. Chen, D. D. Cohen, A. Paytan, M. D. Patey, E. P. Achterberg, J. P. Engelbrecht, and K. W. Fomba
Biogeosciences, 12, 5771–5792, https://doi.org/10.5194/bg-12-5771-2015, https://doi.org/10.5194/bg-12-5771-2015, 2015
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A new technique to determine a size-fractionated global soil elemental emission inventory based on a global soil and mineralogical data set is introduced. Spatial variability of mineral dust elemental fractions (8 elements, e.g., Ca, Fe, Al) is identified on a global scale, particularly for Ca. The Ca/Al ratio ranged between 0.1 and 5.0 and is confirmed as an indicator of dust source regions by a global dust model. Total and soluble dust element fluxes into different ocean basins are estimated.
C. Guieu, C. Ridame, E. Pulido-Villena, M. Bressac, K. Desboeufs, and F. Dulac
Biogeosciences, 11, 5621–5635, https://doi.org/10.5194/bg-11-5621-2014, https://doi.org/10.5194/bg-11-5621-2014, 2014
K. Desboeufs, N. Leblond, T. Wagener, E. Bon Nguyen, and C. Guieu
Biogeosciences, 11, 5581–5594, https://doi.org/10.5194/bg-11-5581-2014, https://doi.org/10.5194/bg-11-5581-2014, 2014
P. Formenti, S. Caquineau, K. Desboeufs, A. Klaver, S. Chevaillier, E. Journet, and J. L. Rajot
Atmos. Chem. Phys., 14, 10663–10686, https://doi.org/10.5194/acp-14-10663-2014, https://doi.org/10.5194/acp-14-10663-2014, 2014
M. Bressac, C. Guieu, D. Doxaran, F. Bourrin, K. Desboeufs, N. Leblond, and C. Ridame
Biogeosciences, 11, 1007–1020, https://doi.org/10.5194/bg-11-1007-2014, https://doi.org/10.5194/bg-11-1007-2014, 2014
R. Paris and K. V. Desboeufs
Atmos. Chem. Phys., 13, 4895–4905, https://doi.org/10.5194/acp-13-4895-2013, https://doi.org/10.5194/acp-13-4895-2013, 2013
Related subject area
Subject: Isotopes | Research Activity: Field Measurements | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
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Deposition, recycling, and archival of nitrate stable isotopes between the air–snow interface: comparison between Dronning Maud Land and Dome C, Antarctica
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A very limited role of tropospheric chlorine as a sink of the greenhouse gas methane
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Stable sulfur isotope measurements to trace the fate of SO2 in the Athabasca oil sands region
Triple oxygen isotopes indicate urbanization affects sources of nitrate in wet and dry atmospheric deposition
Isotopic constraints on heterogeneous sulfate production in Beijing haze
Estimation of the fossil fuel component in atmospheric CO2 based on radiocarbon measurements at the Beromünster tall tower, Switzerland
Constraining N2O emissions since 1940 using firn air isotope measurements in both hemispheres
Seasonal variations of triple oxygen isotopic compositions of atmospheric sulfate, nitrate, and ozone at Dumont d'Urville, coastal Antarctica
Carbon isotopic signature of coal-derived methane emissions to the atmosphere: from coalification to alteration
Isotopic composition for source identification of mercury in atmospheric fine particles
Isotopic constraints on the role of hypohalous acids in sulfate aerosol formation in the remote marine boundary layer
In situ observations of the isotopic composition of methane at the Cabauw tall tower site
Oxygen isotope mass balance of atmospheric nitrate at Dome C, East Antarctica, during the OPALE campaign
Isotopic effects of nitrate photochemistry in snow: a field study at Dome C, Antarctica
Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto
WAIS Divide ice core suggests sustained changes in the atmospheric formation pathways of sulfate and nitrate since the 19th century in the extratropical Southern Hemisphere
Stable carbon isotope ratios of toluene in the boundary layer and the lower free troposphere
Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning
Can the carbon isotopic composition of methane be reconstructed from multi-site firn air measurements?
Air–snow transfer of nitrate on the East Antarctic Plateau – Part 1: Isotopic evidence for a photolytically driven dynamic equilibrium in summer
Chemical characterization and stable carbon isotopic composition of particulate Polycyclic Aromatic Hydrocarbons issued from combustion of 10 Mediterranean woods
Quantification of the carbonaceous matter origin in submicron marine aerosol by 13C and 14C isotope analysis
Temporal and spatial variability of the stable isotopic composition of atmospheric molecular hydrogen: observations at six EUROHYDROS stations
Continuous isotopic composition measurements of tropospheric CO2 at Jungfraujoch (3580 m a.s.l.), Switzerland: real-time observation of regional pollution events
Anthropogenic imprints on nitrogen and oxygen isotopic composition of precipitation nitrate in a nitrogen-polluted city in southern China
Analysis of 13C and 18O isotope data of CO2 in CARIBIC aircraft samples as tracers of upper troposphere/lower stratosphere mixing and the global carbon cycle
Tracing the fate of atmospheric nitrate deposited onto a forest ecosystem in Eastern Asia using Δ17O
Photolysis imprint in the nitrate stable isotope signal in snow and atmosphere of East Antarctica and implications for reactive nitrogen cycling
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Jessica M. Burger, Emily Joyce, Meredith G. Hastings, Kurt A. M. Spence, and Katye E. Altieri
Atmos. Chem. Phys., 23, 5605–5622, https://doi.org/10.5194/acp-23-5605-2023, https://doi.org/10.5194/acp-23-5605-2023, 2023
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A seasonal analysis of the nitrogen isotopes of atmospheric nitrate over the remote Southern Ocean reveals that similar natural NOx sources dominate in spring and summer, while winter is representative of background-level conditions. The oxygen isotopes suggest that similar oxidation pathways involving more ozone occur in spring and winter, while the hydroxyl radical is the main oxidant in summer. This work helps to constrain NOx cycling and oxidant budgets in a data-sparse remote marine region.
Claire Bekker, Wendell W. Walters, Lee T. Murray, and Meredith G. Hastings
Atmos. Chem. Phys., 23, 4185–4201, https://doi.org/10.5194/acp-23-4185-2023, https://doi.org/10.5194/acp-23-4185-2023, 2023
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Nitrate is a critical component of the atmosphere that degrades air quality and ecosystem health. We have investigated the nitrogen isotope compositions of nitrate from deposition samples collected across the northeastern United States. Spatiotemporal variability in the nitrogen isotope compositions was found to track with nitrate formation chemistry. Our results highlight that nitrogen isotope compositions may be a robust tool for improving model representation of nitrate chemistry.
Heejeong Kim, Wendell W. Walters, Claire Bekker, Lee T. Murray, and Meredith G. Hastings
Atmos. Chem. Phys., 23, 4203–4219, https://doi.org/10.5194/acp-23-4203-2023, https://doi.org/10.5194/acp-23-4203-2023, 2023
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Atmospheric nitrate has an important impact on human and ecosystem health. We evaluated atmospheric nitrate formation pathways in the northeastern US utilizing oxygen isotope compositions, which indicated a significant difference between the phases of nitrate (i.e., gas vs. particle). Comparing the observations with model simulations indicated that N2O5 hydrolysis chemistry was overpredicted. Our study has important implications for improving atmospheric chemistry model representation.
Pete D. Akers, Joël Savarino, Nicolas Caillon, Olivier Magand, and Emmanuel Le Meur
Atmos. Chem. Phys., 22, 15637–15657, https://doi.org/10.5194/acp-22-15637-2022, https://doi.org/10.5194/acp-22-15637-2022, 2022
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Nitrate isotopes in Antarctic ice do not preserve the seasonal isotopic cycles of the atmosphere, which limits their use to study the past. We studied nitrate along an 850 km Antarctic transect to learn how these cycles are changed by sunlight-driven chemistry in the snow. Our findings suggest that the snow accumulation rate and other environmental signals can be extracted from nitrate with the right sampling and analytical approaches.
Bryce F. J. Kelly, Xinyi Lu, Stephen J. Harris, Bruno G. Neininger, Jorg M. Hacker, Stefan Schwietzke, Rebecca E. Fisher, James L. France, Euan G. Nisbet, David Lowry, Carina van der Veen, Malika Menoud, and Thomas Röckmann
Atmos. Chem. Phys., 22, 15527–15558, https://doi.org/10.5194/acp-22-15527-2022, https://doi.org/10.5194/acp-22-15527-2022, 2022
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This study explores using the composition of methane of in-flight atmospheric air samples for greenhouse gas inventory verification. The air samples were collected above one of the largest coal seam gas production regions in the world. Adjacent to these gas fields are coal mines, Australia's largest cattle feedlot, and over 1 million grazing cattle. The results are also used to identify methane mitigation opportunities.
Malika Menoud, Carina van der Veen, Jaroslaw Necki, Jakub Bartyzel, Barbara Szénási, Mila Stanisavljević, Isabelle Pison, Philippe Bousquet, and Thomas Röckmann
Atmos. Chem. Phys., 21, 13167–13185, https://doi.org/10.5194/acp-21-13167-2021, https://doi.org/10.5194/acp-21-13167-2021, 2021
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Using measurements of methane isotopes in ambient air and a 3D atmospheric transport model, in Krakow, Poland, we mainly detected fossil-fuel-related sources, coming from coal mining in Silesia and from the use of natural gas in the city. Emission inventories report large emissions from coal mine activity in Silesia, which is in agreement with our measurements. However, methane sources in the urban area of Krakow related to the use of fossil fuels might be underestimated in the inventories.
Xinyi Lu, Stephen J. Harris, Rebecca E. Fisher, James L. France, Euan G. Nisbet, David Lowry, Thomas Röckmann, Carina van der Veen, Malika Menoud, Stefan Schwietzke, and Bryce F. J. Kelly
Atmos. Chem. Phys., 21, 10527–10555, https://doi.org/10.5194/acp-21-10527-2021, https://doi.org/10.5194/acp-21-10527-2021, 2021
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Many coal seam gas (CSG) facilities in the Surat Basin, Australia, are adjacent to other sources of methane, including agricultural, urban, and natural seeps. This makes it challenging to estimate the amount of methane being emitted into the atmosphere from CSG facilities. This research demonstrates that measurements of the carbon and hydrogen stable isotopic composition of methane can distinguish between and apportion methane emissions from CSG facilities, cattle, and many other sources.
Sarah Albertin, Joël Savarino, Slimane Bekki, Albane Barbero, and Nicolas Caillon
Atmos. Chem. Phys., 21, 10477–10497, https://doi.org/10.5194/acp-21-10477-2021, https://doi.org/10.5194/acp-21-10477-2021, 2021
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We report an efficient method to collect atmospheric NO2 adapted for multi-isotopic analysis and present the first NO2 triple oxygen and double nitrogen isotope measurements. Atmospheric samplings carried out in Grenoble, France, highlight the NO2 isotopic signature sensitivity to the local NOx emissions and chemical regimes. These preliminary results are very promising for using the combination of Δ17O and δ15N of NO2 as a probe of the atmospheric NOx emissions and chemistry.
Ana Moreno, Miguel Iglesias, Cesar Azorin-Molina, Carlos Pérez-Mejías, Miguel Bartolomé, Carlos Sancho, Heather Stoll, Isabel Cacho, Jaime Frigola, Cinta Osácar, Arsenio Muñoz, Antonio Delgado-Huertas, Ileana Bladé, and Françoise Vimeux
Atmos. Chem. Phys., 21, 10159–10177, https://doi.org/10.5194/acp-21-10159-2021, https://doi.org/10.5194/acp-21-10159-2021, 2021
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We present a large and unique dataset of the rainfall isotopic composition at seven sites from northern Iberia to characterize their variability at daily and monthly timescales and to assess the role of climate and geographic factors in the modulation of δ18O values. We found that the origin, moisture uptake along the trajectory and type of precipitation play a key role. These results will help to improve the interpretation of δ18O paleorecords from lacustrine carbonates or speleothems.
Kun Wang, Shohei Hattori, Mang Lin, Sakiko Ishino, Becky Alexander, Kazuki Kamezaki, Naohiro Yoshida, and Shichang Kang
Atmos. Chem. Phys., 21, 8357–8376, https://doi.org/10.5194/acp-21-8357-2021, https://doi.org/10.5194/acp-21-8357-2021, 2021
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Sulfate aerosols play an important climatic role and exert adverse effects on the ecological environment and human health. In this study, we present the triple oxygen isotopic composition of sulfate from the Mt. Everest region, southern Tibetan Plateau, and decipher the formation mechanisms of atmospheric sulfate in this pristine environment. The results indicate the important role of the S(IV) + O3 pathway in atmospheric sulfate formation promoted by conditions of high cloud water pH.
Pete D. Akers, Ben G. Kopec, Kyle S. Mattingly, Eric S. Klein, Douglas Causey, and Jeffrey M. Welker
Atmos. Chem. Phys., 20, 13929–13955, https://doi.org/10.5194/acp-20-13929-2020, https://doi.org/10.5194/acp-20-13929-2020, 2020
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Water vapor isotopes recorded for 2 years in coastal northern Greenland largely reflect changes in sea ice cover, with distinct values when Baffin Bay is ice covered in winter vs. open in summer. Resulting changes in moisture transport, surface winds, and air temperature also modify the isotopes. Local glacial ice may thus preserve past changes in the Baffin Bay sea ice extent, and this will help us better understand how the Arctic environment and water cycle responds to global climate change.
Ben Yu, Lin Yang, Linlin Wang, Hongwei Liu, Cailing Xiao, Yong Liang, Qian Liu, Yongguang Yin, Ligang Hu, Jianbo Shi, and Guibin Jiang
Atmos. Chem. Phys., 20, 9713–9723, https://doi.org/10.5194/acp-20-9713-2020, https://doi.org/10.5194/acp-20-9713-2020, 2020
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We found that Br atoms in the marine boundary layer are the most probable oxidizer that transform gaseous elemental mercury into gaseous oxidized mercury, according to the mercury isotopes in the total gaseous mercury. On the other hand, Br or Cl atoms are not the primary oxidizers that produced oxidized mercury on particles. This study showed that mercury isotopes can provide new evidence that help us to fully understand the transformations of atmospheric mercury.
Longfei Yu, Eliza Harris, Stephan Henne, Sarah Eggleston, Martin Steinbacher, Lukas Emmenegger, Christoph Zellweger, and Joachim Mohn
Atmos. Chem. Phys., 20, 6495–6519, https://doi.org/10.5194/acp-20-6495-2020, https://doi.org/10.5194/acp-20-6495-2020, 2020
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We observed the isotopic composition of nitrous oxide in the unpolluted air at Jungfraujoch for 5 years. Our results indicate a clear seasonal pattern in the isotopic composition, corresponding with that in atmospheric nitrous oxide levels. This is most likely due to temporal variations in both emission processes and air mass sources for Jungfraujoch. Our findings are of importance to global nitrous oxide modelling and to better understanding of long-term trends in atmospheric nitrous oxide.
V. Holly L. Winton, Alison Ming, Nicolas Caillon, Lisa Hauge, Anna E. Jones, Joel Savarino, Xin Yang, and Markus M. Frey
Atmos. Chem. Phys., 20, 5861–5885, https://doi.org/10.5194/acp-20-5861-2020, https://doi.org/10.5194/acp-20-5861-2020, 2020
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The transfer of the nitrogen stable isotopic composition in nitrate between the air and snow at low accumulation sites in Antarctica leaves an UV imprint in the snow. Quantifying how nitrate isotope values change allows us to interpret longer ice core records. Based on nitrate observations and modelling at Kohnen, East Antarctica, the dominant factors controlling the nitrate isotope signature in deep snow layers are the depth of light penetration into the snowpack and the snow accumulation rate.
Isabelle Genot, David Au Yang, Erwan Martin, Pierre Cartigny, Erwann Legendre, and Marc De Rafelis
Atmos. Chem. Phys., 20, 4255–4273, https://doi.org/10.5194/acp-20-4255-2020, https://doi.org/10.5194/acp-20-4255-2020, 2020
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Given their critical impact on radiative forcing, sulfate aerosols have been extensively studied using their isotope signatures (δ34S, ∆33S, ∆36S, δ18O, and ∆17O). A striking observation is that ∆33S > 0 ‰, implying a missing reservoir in the sulfur cycle. Here, we measured ∆33S < 0 ‰ in black crust sulfates (i.e., formed on carbonate walls) that must therefore result from distinct chemical pathway(s) compared to sulfate aerosols, and they may well represent this complementary reservoir.
Angelina Wenger, Katherine Pugsley, Simon O'Doherty, Matt Rigby, Alistair J. Manning, Mark F. Lunt, and Emily D. White
Atmos. Chem. Phys., 19, 14057–14070, https://doi.org/10.5194/acp-19-14057-2019, https://doi.org/10.5194/acp-19-14057-2019, 2019
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We present 14CO2 observations at a background site in Ireland and a tall tower site in the UK. These data have been used to calculate the contribution of fossil fuel sources to atmospheric CO2 mole fractions from the UK and Ireland. 14CO2 emissions from nuclear industry sites in the UK cause a higher uncertainty in the results compared to observations in other locations. The observed ffCO2 at the site was not significantly different from simulated values based on the bottom-up inventory.
Isaac J. Vimont, Jocelyn C. Turnbull, Vasilii V. Petrenko, Philip F. Place, Colm Sweeney, Natasha Miles, Scott Richardson, Bruce H. Vaughn, and James W. C. White
Atmos. Chem. Phys., 19, 8547–8562, https://doi.org/10.5194/acp-19-8547-2019, https://doi.org/10.5194/acp-19-8547-2019, 2019
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Stable isotopes of Carbon Monoxide (CO) and radiocarbon carbon dioxide were measured over three summers at Indianapolis, Indiana, US, and for 1 year at a site thought to be strongly influenced by CO from oxidized volatile organic compounds (VOCs) in South Carolina, US. The Indianapolis results were used to provide an estimate of the carbon and oxygen isotopic signatures of CO produced from oxidized VOCs. This updated estimate agrees well with the data from South Carolina during the summer.
Martine M. Savard, Amanda S. Cole, Robert Vet, and Anna Smirnoff
Atmos. Chem. Phys., 18, 10373–10389, https://doi.org/10.5194/acp-18-10373-2018, https://doi.org/10.5194/acp-18-10373-2018, 2018
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Improving air quality requires understanding of the atmospheric processes transforming nitrous oxides emitted by human activities into nitrates, an N form that may degrade natural ecosystems. Isotopes (∆17O, δ18O) are characterized in separate wet, particulate and gaseous nitrates for the first time. The gas ranges are distinct from those of the other nitrates, and the plume dynamics emerge as crucial in interpreting the results, which unravel key processes behind the distribution of nitrates.
Sergey Gromov, Carl A. M. Brenninkmeijer, and Patrick Jöckel
Atmos. Chem. Phys., 18, 9831–9843, https://doi.org/10.5194/acp-18-9831-2018, https://doi.org/10.5194/acp-18-9831-2018, 2018
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Using the observational data on 13C (CO) and 13C (CH4) from the extra-tropical Southern Hemisphere (ETSH) and EMAC model we (1) provide an independent, observation-based evaluation of Cl atom concentration variations in the ETSH throughout 1994–2000, (2) show that the role of tropospheric Cl as a sink of CH4 is seriously overestimated in the literature, (3) demonstrate that the 13C/12C ratio of CO is a sensitive indicator for the isotopic composition of reacted CH4 and therefore for its sources.
Richard P. Fiorella, Ryan Bares, John C. Lin, James R. Ehleringer, and Gabriel J. Bowen
Atmos. Chem. Phys., 18, 8529–8547, https://doi.org/10.5194/acp-18-8529-2018, https://doi.org/10.5194/acp-18-8529-2018, 2018
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Fossil fuel combustion produces water; where fossil fuel combustion is concentrated in urban areas, this humidity source may represent ~ 10 % of total humidity. In turn, this water vapor addition may alter urban meteorology, though the contribution of combustion vapor is difficult to measure. Using stable water isotopes, we estimate that up to 16 % of urban humidity may arise from combustion when the atmosphere is stable during winter, and develop recommendations for application in other cities.
Neda Amiri, Roya Ghahreman, Ofelia Rempillo, Travis W. Tokarek, Charles A. Odame-Ankrah, Hans D. Osthoff, and Ann-Lise Norman
Atmos. Chem. Phys., 18, 7757–7780, https://doi.org/10.5194/acp-18-7757-2018, https://doi.org/10.5194/acp-18-7757-2018, 2018
David M. Nelson, Urumu Tsunogai, Dong Ding, Takuya Ohyama, Daisuke D. Komatsu, Fumiko Nakagawa, Izumi Noguchi, and Takashi Yamaguchi
Atmos. Chem. Phys., 18, 6381–6392, https://doi.org/10.5194/acp-18-6381-2018, https://doi.org/10.5194/acp-18-6381-2018, 2018
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Atmospheric nitrate may be produced locally and/or come from upwind regions. To address this issue we measured oxygen and nitrogen isotopes of wet and dry nitrate deposition at nearby urban and rural sites. Our results suggest that, relative to nitrate in wet deposition in urban environments and wet and dry deposition in rural environments, nitrate in dry deposition in urban environments results from local NOx emissions more so than wet deposition, which is transported longer distances.
Pengzhen He, Becky Alexander, Lei Geng, Xiyuan Chi, Shidong Fan, Haicong Zhan, Hui Kang, Guangjie Zheng, Yafang Cheng, Hang Su, Cheng Liu, and Zhouqing Xie
Atmos. Chem. Phys., 18, 5515–5528, https://doi.org/10.5194/acp-18-5515-2018, https://doi.org/10.5194/acp-18-5515-2018, 2018
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We use observations of the oxygen isotopic composition of sulfate aerosol as a fingerprint to quantify various sulfate formation mechanisms during pollution events in Beijing, China. We found that heterogeneous reactions on aerosols dominated sulfate production in general; however, in-cloud reactions would dominate haze sulfate production when cloud liquid water content was high. The findings also suggest the heterogeneity of aerosol acidity should be parameterized in models.
Tesfaye A. Berhanu, Sönke Szidat, Dominik Brunner, Ece Satar, Rüdiger Schanda, Peter Nyfeler, Michael Battaglia, Martin Steinbacher, Samuel Hammer, and Markus Leuenberger
Atmos. Chem. Phys., 17, 10753–10766, https://doi.org/10.5194/acp-17-10753-2017, https://doi.org/10.5194/acp-17-10753-2017, 2017
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Fossil fuel CO2 is the major contributor of anthropogenic CO2 in the atmosphere, and accurate quantification is essential to better understand the carbon cycle. Such accurate quantification can be conducted based on radiocarbon measurements. In this study, we present radiocarbon measurements from a tall tower site in Switzerland. From these measurements, we have observed seasonally varying fossil fuel CO2 contributions and a biospheric CO2 component that varies diurnally and seasonally.
Markella Prokopiou, Patricia Martinerie, Célia J. Sapart, Emmanuel Witrant, Guillaume Monteil, Kentaro Ishijima, Sophie Bernard, Jan Kaiser, Ingeborg Levin, Thomas Blunier, David Etheridge, Ed Dlugokencky, Roderik S. W. van de Wal, and Thomas Röckmann
Atmos. Chem. Phys., 17, 4539–4564, https://doi.org/10.5194/acp-17-4539-2017, https://doi.org/10.5194/acp-17-4539-2017, 2017
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Nitrous oxide is the third most important anthropogenic greenhouse gas with an increasing mole fraction. To understand its natural and anthropogenic sources
we employ isotope measurements. Results show that while the N2O mole fraction increases, its heavy isotope content decreases. The isotopic changes observed underline the dominance of agricultural emissions especially at the early part of the record, whereas in the later decades the contribution from other anthropogenic sources increases.
Sakiko Ishino, Shohei Hattori, Joel Savarino, Bruno Jourdain, Susanne Preunkert, Michel Legrand, Nicolas Caillon, Albane Barbero, Kota Kuribayashi, and Naohiro Yoshida
Atmos. Chem. Phys., 17, 3713–3727, https://doi.org/10.5194/acp-17-3713-2017, https://doi.org/10.5194/acp-17-3713-2017, 2017
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We show the first simultaneous observations of triple oxygen isotopic compositions of atmospheric sulfate, nitrate, and ozone at Dumont d'Urville, coastal Antarctica. The contrasting seasonal trends between oxygen isotopes of ozone and those of sulfate and nitrate indicate that these signatures in sulfate and nitrate are mainly controlled by changes in oxidation chemistry. We also discuss the specific oxidation chemistry induced by the unique phenomena at the site.
Giulia Zazzeri, Dave Lowry, Rebecca E. Fisher, James L. France, Mathias Lanoisellé, Bryce F. J. Kelly, Jaroslaw M. Necki, Charlotte P. Iverach, Elisa Ginty, Miroslaw Zimnoch, Alina Jasek, and Euan G. Nisbet
Atmos. Chem. Phys., 16, 13669–13680, https://doi.org/10.5194/acp-16-13669-2016, https://doi.org/10.5194/acp-16-13669-2016, 2016
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Methane emissions estimates from the coal sector are highly uncertain. Precise δ13C isotopic signatures of methane sources can be used in atmospheric models for a methane budget assessment. Emissions from both underground and opencast coal mines in the UK, Australia and Poland were sampled and isotopically characterised using high-precision measurements of δ13C values. Representative isotopic signatures were provided, taking into account specific ranks of coal and mine type.
Qiang Huang, Jiubin Chen, Weilin Huang, Pingqing Fu, Benjamin Guinot, Xinbin Feng, Lihai Shang, Zhuhong Wang, Zhongwei Wang, Shengliu Yuan, Hongming Cai, Lianfang Wei, and Ben Yu
Atmos. Chem. Phys., 16, 11773–11786, https://doi.org/10.5194/acp-16-11773-2016, https://doi.org/10.5194/acp-16-11773-2016, 2016
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Atmospheric airborne mercury is of particular concern because, once inhaled, both Hg and its vectors might have adverse effects on human beings. In this study, we attempted to identify the sources of PM2.5-Hg in Beijing, China, using Hg isotopic composition. Large range and seasonal variations in both mass-dependent and mass-independent fractionations of Hg isotopes in haze particles demonstrate the usefulness of Hg isotopes for directly tracing the sources and its vectors in the atmosphere.
Qianjie Chen, Lei Geng, Johan A. Schmidt, Zhouqing Xie, Hui Kang, Jordi Dachs, Jihong Cole-Dai, Andrew J. Schauer, Madeline G. Camp, and Becky Alexander
Atmos. Chem. Phys., 16, 11433–11450, https://doi.org/10.5194/acp-16-11433-2016, https://doi.org/10.5194/acp-16-11433-2016, 2016
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The formation mechanisms of sulfate in the marine boundary layer are not well understood, which could result in large uncertainties in aerosol radiative forcing. We measure the oxygen isotopic composition (Δ17O) of sulfate collected in the MBL and analyze with a global transport model. Our results suggest that 33–50 % of MBL sulfate is formed via oxidation of S(IV) by hypohalous acids HOBr / HOCl in the aqueous phase, and the daily-mean HOBr/HOCl concentrations are on the order of 0.01–0.1 ppt.
Thomas Röckmann, Simon Eyer, Carina van der Veen, Maria E. Popa, Béla Tuzson, Guillaume Monteil, Sander Houweling, Eliza Harris, Dominik Brunner, Hubertus Fischer, Giulia Zazzeri, David Lowry, Euan G. Nisbet, Willi A. Brand, Jaroslav M. Necki, Lukas Emmenegger, and Joachim Mohn
Atmos. Chem. Phys., 16, 10469–10487, https://doi.org/10.5194/acp-16-10469-2016, https://doi.org/10.5194/acp-16-10469-2016, 2016
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A dual isotope ratio mass spectrometric system (IRMS) and a quantum cascade laser absorption spectroscopy (QCLAS)-based technique were deployed at the Cabauw experimental site for atmospheric research (CESAR) in the Netherlands and performed in situ, high-frequency (approx. hourly) measurements for a period of more than 5 months, yielding a combined dataset with more than 2500 measurements of both δ13C and δD.
Joël Savarino, William C. Vicars, Michel Legrand, Suzanne Preunkert, Bruno Jourdain, Markus M. Frey, Alexandre Kukui, Nicolas Caillon, and Jaime Gil Roca
Atmos. Chem. Phys., 16, 2659–2673, https://doi.org/10.5194/acp-16-2659-2016, https://doi.org/10.5194/acp-16-2659-2016, 2016
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Atmospheric nitrate is collected on the East Antarctic ice sheet. Nitrogen and oxygen stable isotopes and concentrations of nitrate are measured. Using a box model, we show that there is s systematic discrepancy between observations and model results. We suggest that this discrepancy probably results from unknown NOx chemistry above the Antarctic ice sheet. However, possible misconception in the stable isotope mass balance is not completely excluded.
T. A. Berhanu, J. Savarino, J. Erbland, W. C. Vicars, S. Preunkert, J. F. Martins, and M. S. Johnson
Atmos. Chem. Phys., 15, 11243–11256, https://doi.org/10.5194/acp-15-11243-2015, https://doi.org/10.5194/acp-15-11243-2015, 2015
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In this field study at Dome C, Antarctica, we investigated the effect of solar UV photolysis on the stable isotopes of nitrate in snow via comparison of two identical snow pits while exposing only one to solar UV. From the difference between the average isotopic fractionations calculated for each pit, we determined a purely photolytic nitrogen isotopic fractionation of -55.8‰, in good agreement with what has been recently determined in a laboratory study.
M. Saccon, A. Kornilova, L. Huang, S. Moukhtar, and J. Rudolph
Atmos. Chem. Phys., 15, 10825–10838, https://doi.org/10.5194/acp-15-10825-2015, https://doi.org/10.5194/acp-15-10825-2015, 2015
E. D. Sofen, B. Alexander, E. J. Steig, M. H. Thiemens, S. A. Kunasek, H. M. Amos, A. J. Schauer, M. G. Hastings, J. Bautista, T. L. Jackson, L. E. Vogel, J. R. McConnell, D. R. Pasteris, and E. S. Saltzman
Atmos. Chem. Phys., 14, 5749–5769, https://doi.org/10.5194/acp-14-5749-2014, https://doi.org/10.5194/acp-14-5749-2014, 2014
J. Wintel, E. Hösen, R. Koppmann, M. Krebsbach, A. Hofzumahaus, and F. Rohrer
Atmos. Chem. Phys., 13, 11059–11071, https://doi.org/10.5194/acp-13-11059-2013, https://doi.org/10.5194/acp-13-11059-2013, 2013
F. A. Haumann, A. M. Batenburg, G. Pieterse, C. Gerbig, M. C. Krol, and T. Röckmann
Atmos. Chem. Phys., 13, 9401–9413, https://doi.org/10.5194/acp-13-9401-2013, https://doi.org/10.5194/acp-13-9401-2013, 2013
C. J. Sapart, P. Martinerie, E. Witrant, J. Chappellaz, R. S. W. van de Wal, P. Sperlich, C. van der Veen, S. Bernard, W. T. Sturges, T. Blunier, J. Schwander, D. Etheridge, and T. Röckmann
Atmos. Chem. Phys., 13, 6993–7005, https://doi.org/10.5194/acp-13-6993-2013, https://doi.org/10.5194/acp-13-6993-2013, 2013
J. Erbland, W. C. Vicars, J. Savarino, S. Morin, M. M. Frey, D. Frosini, E. Vince, and J. M. F. Martins
Atmos. Chem. Phys., 13, 6403–6419, https://doi.org/10.5194/acp-13-6403-2013, https://doi.org/10.5194/acp-13-6403-2013, 2013
A. Guillon, K. Le Ménach, P.-M. Flaud, N. Marchand, H. Budzinski, and E. Villenave
Atmos. Chem. Phys., 13, 2703–2719, https://doi.org/10.5194/acp-13-2703-2013, https://doi.org/10.5194/acp-13-2703-2013, 2013
D. Ceburnis, A. Garbaras, S. Szidat, M. Rinaldi, S. Fahrni, N. Perron, L. Wacker, S. Leinert, V. Remeikis, M. C. Facchini, A. S. H. Prevot, S. G. Jennings, M. Ramonet, and C. D. O'Dowd
Atmos. Chem. Phys., 11, 8593–8606, https://doi.org/10.5194/acp-11-8593-2011, https://doi.org/10.5194/acp-11-8593-2011, 2011
A. M. Batenburg, S. Walter, G. Pieterse, I. Levin, M. Schmidt, A. Jordan, S. Hammer, C. Yver, and T. Röckmann
Atmos. Chem. Phys., 11, 6985–6999, https://doi.org/10.5194/acp-11-6985-2011, https://doi.org/10.5194/acp-11-6985-2011, 2011
B. Tuzson, S. Henne, D. Brunner, M. Steinbacher, J. Mohn, B. Buchmann, and L. Emmenegger
Atmos. Chem. Phys., 11, 1685–1696, https://doi.org/10.5194/acp-11-1685-2011, https://doi.org/10.5194/acp-11-1685-2011, 2011
Y. T. Fang, K. Koba, X. M. Wang, D. Z. Wen, J. Li, Y. Takebayashi, X. Y. Liu, and M. Yoh
Atmos. Chem. Phys., 11, 1313–1325, https://doi.org/10.5194/acp-11-1313-2011, https://doi.org/10.5194/acp-11-1313-2011, 2011
S. S. Assonov, C. A. M. Brenninkmeijer, T. J. Schuck, and P. Taylor
Atmos. Chem. Phys., 10, 8575–8599, https://doi.org/10.5194/acp-10-8575-2010, https://doi.org/10.5194/acp-10-8575-2010, 2010
U. Tsunogai, D. D. Komatsu, S. Daita, G. A. Kazemi, F. Nakagawa, I. Noguchi, and J. Zhang
Atmos. Chem. Phys., 10, 1809–1820, https://doi.org/10.5194/acp-10-1809-2010, https://doi.org/10.5194/acp-10-1809-2010, 2010
M. M. Frey, J. Savarino, S. Morin, J. Erbland, and J. M. F. Martins
Atmos. Chem. Phys., 9, 8681–8696, https://doi.org/10.5194/acp-9-8681-2009, https://doi.org/10.5194/acp-9-8681-2009, 2009
S. A. Vay, S. C. Tyler, Y. Choi, D. R. Blake, N. J. Blake, G. W. Sachse, G. S. Diskin, and H. B. Singh
Atmos. Chem. Phys., 9, 4973–4985, https://doi.org/10.5194/acp-9-4973-2009, https://doi.org/10.5194/acp-9-4973-2009, 2009
Cited articles
Albrecht, B. A.: Aerosols, cloud microphysics, and fractional cloudiness,
Science, 245, 1227–1230, 1989.
Andreae, M. O. and Crutzen, P. J.: Atmospheric Aerosols: Biogeochemical
Sources and Role in Atmospheric Chemistry, Science, 276, 1052–1058,
https://doi.org/10.1126/science.276.5315.1052, 1997.
Alexander, B., Park, R., Jacob, D., and Gong, S.: Transition metal-catalyzed
oxidation of atmospheric sulfur: Global implications for the sulfur budget,
J. Geophys. Res.-Atmos., 114, D02309, https://doi.org/10.1029/2008JD010486, 2009.
Alexander, B., Allman, D., Amos, H., Fairlie, T., Dachs, J., Hegg, D. A., and
Sletten, R. S.: Isotopic constraints on the formation pathways of sulfate
aerosol in the marine boundary layer of the subtropical northeast Atlantic
Ocean, J. Geophys. Res.-Atmos., 117, D06304, https://doi.org/10.1029/2011JD016773,
2012.
An, L., Che, H., Xue, M., Zhang, T., Wang, H., Wang, Y., Zhou, C., Zhao, H.,
Gui, K., and Zheng, Y.: Temporal and spatial variations in sand and dust
storm events in East Asia from 2007 to 2016: Relationships with surface
conditions and climate change, Sci. Total Environ., 633,
452–462, 2018.
Au Yang, D., Landais, G., Assayag, N., Widory, D., and Cartigny, P.: Improved
analysis of micro-and nanomole-scale sulfur multi-isotope compositions by gas
source isotope ratio mass spectrometry, Rapid Commun. Mass Sp., 30, 897–907, 2016.
Au Yang, D., Bardoux, G., Assayag, N., Laskar, C., Widory, D., and Cartigny,
P.: Atmospheric SO2 oxidation by NO2 plays no role in the mass independent
sulfur isotope fractionation of urban aerosols, Atmos. Environ., 193,
109–117, https://doi.org/10.1016/j.atmosenv.2018.09.007, 2018.
Bardouki, H., Liakakou, H., Economou, C., Sciare, J., Smolık, J., Ždìmal, V., Eleftheriadis, K., Lazaridis, M., Dye, C., and Mihalopoulos, N.:
Chemical composition of size-resolved atmospheric aerosols in the eastern
Mediterranean during summer and winter, Atmos. Environ., 37, 195–208,
2003.
Baroni, M., Thiemens, M. H., Delmas, R. J., and Savarino, J.:
Mass-independent sulfur isotopic compositions in stratospheric volcanic
eruptions, Science, 315, 84–87, 2007.
Baroni, M., Savarino, J., Cole-Dai, J., Rai, V. K., and Thiemens, M. H.:
Anomalous sulfur isotope compositions of volcanic sulfate over the last
millennium in Antarctic ice cores, J. Geophys. Res.-Atmos., 113, D20112,
https://doi.org/10.1029/2008JD010185, 2008.
Bauer, S. E. and Koch, D.: Impact of heterogeneous sulfate formation at
mineral dust surfaces on aerosol loads and radiative forcing in the Goddard
Institute for Space Studies general circulation model, J. Geophys.
Res.-Atmos., 110, D17202,
https://doi.org/10.1029/2005JD005870, 2005.
Becker, S. and Hirner, A.: Characterisation of Crude Oils by Carbon and
Sulphur Isotope Ratio Measurements as a Tool for Pollution Control, Isot. Environ. Healt. S, 34, 255–264, 1998.
Benson, D. R., Young, L.-H., Kameel, F. R., and Lee, S.-H.:
Laboratory-measured nucleation rates of sulfuric acid and water binary
homogeneous nucleation from the SO2+OH reaction, Geophys. Res.
Lett., 35, L11801, https://doi.org/10.1029/2008GL033387, 2008.
Berglen, T. F., Berntsen, T. K., Isaksen, I. S., and Sundet, J. K.: A global
model of the coupled sulfur/oxidant chemistry in the troposphere: The sulfur
cycle, J. Geophys. Res.-Atmos., 109, D19310, https://doi.org/10.1029/2003JD003948,
2004.
Bindeman, I., Eiler, J., Wing, B., and Farquhar, J.: Rare sulfur and triple
oxygen isotope geochemistry of volcanogenic sulfate aerosols, Geochim. Cosmochim. Ac., 71, 2326–2343, 2007.
Blackie, D., Blackwell-Whitehead, R., Stark, G., Pickering, J., Smith, P.,
Rufus, J., and Thorne, A.: High-resolution photoabsorption cross-section
measurements of SO2 at 198 K from 213 to 325 nm, J. Geophys.
Res.-Planet., 116, E03006, https://doi.org/10.1029/2010JE003707, 2011.
Boothe, A. C. and Homeyer, C. R.: Global large-scale
stratosphere–troposphere exchange in modern reanalyses, Atmos. Chem. Phys.,
17, 5537–5559, https://doi.org/10.5194/acp-17-5537-2017, 2017.
Boulet, D. and Melançon, S.: Bilan environnemental, Qualité de l'air
à Montréal, Rapport Annuel 2011, Ville de Montréal, Service des
infrastructures, du transport et de l'environnement, Direction de
l'environnement et du développement durable, Division de la planification
et du suivi environnemental, RSQA, 8, 2012.
Boulet, D. and Melançon, S.: Bilan environnemental, Qualité de l'air
à Montréal, Rapport Annuel 2013, Ville de Montréal, Service de
l'environnement Division de la planification et du suivi environnemental,
RSQA, 8, 2013.
Boy, M., Mogensen, D., Smolander, S., Zhou, L., Nieminen, T., Paasonen, P.,
Plass-Dülmer, C., Sipilä, M., Petäjä, T., Mauldin, L., Berresheim,
H., and Kulmala, M.: Oxidation of SO2 by stabilized Criegee
intermediate (sCI) radicals as a crucial source for atmospheric sulfuric acid
concentrations, Atmos. Chem. Phys., 13, 3865–3879,
https://doi.org/10.5194/acp-13-3865-2013, 2013.
Calhoun, J. A., Bates, T. S., and Charlson, R. J.: Sulfur isotope
measurements of submicrometer sulfate aerosol particles over the Pacific
Ocean, Geophys. Res. Lett., 18, 1877–1880, 1991.
Calvert, J. G., Su, F., Bottenheim, J. W., and Strausz, O. P.: Mechanism of
the homogeneous oxidation of sulfur dioxide in the troposphere, Atmos.
Environ., 12, 197–226, 1978.
Cao, C., Zheng, S., and Singh, R. P.: Characteristics of aerosol optical
properties and meteorological parameters during three major dust events
(2005–2010) over Beijing, China, Atmos. Res., 150, 129–142,
https://doi.org/10.1016/j.atmosres.2014.07.022, 2014.
Cheng, Y., Zheng, G., Wei, C., Mu, Q., Zheng, B., Wang, Z., Gao, M., Zhang,
Q., He, K., and Carmichael, G.: Reactive nitrogen chemistry in aerosol water
as a source of sulfate during haze events in China, Science Advances, 2,
e1601530, https://doi.org/10.1126/sciadv.1601530, 2016.
Chin, M., Diehl, T., Ginoux, P., and Malm, W.: Intercontinental transport of
pollution and dust aerosols: implications for regional air quality, Atmos.
Chem. Phys., 7, 5501–5517, https://doi.org/10.5194/acp-7-5501-2007, 2007.
Chkhetiani, O. G., Gledzer, E. B., Artamonova, M. S., and Iordanskii, M. A.:
Dust resuspension under weak wind conditions: direct observations and model,
Atmos. Chem. Phys., 12, 5147–5162, https://doi.org/10.5194/acp-12-5147-2012,
2012.
Clarisse, L., Fromm, M., Ngadi, Y., Emmons, L., Clerbaux, C., Hurtmans, D.,
and Coheur, P.-F.: Intercontinental transport of anthropogenic sulfur dioxide
and other pollutants: An infrared remote sensing case study, Geophys. Res.
Lett., 38, L19806, https://doi.org/10.1029/2011GL048976, 2011.
Coplen, T. B.: Guidelines and recommended terms for expression of
stable-isotope-ratio and gas-ratio measurement results, Rapid Commun. Mass Sp., 25, 2538–2560, 2011.
Cottle, P., Strawbridge, K., McKendry, I., O'Neill, N., and Saha, A.: A
pervasive and persistent Asian dust event over North America during spring
2010: lidar and sunphotometer observations, Atmos. Chem. Phys., 13,
4515–4527, https://doi.org/10.5194/acp-13-4515-2013, 2013.
Danielache, S. O., Hattori, S., Johnson, M. S., Ueno, Y., Nanbu, S., and
Yoshida, N.: Photoabsorption cross-section measurements of 32S,
33S, 34S, and 36S sulfur dioxide for the
B1B1-X1A1 absorption band, J. Geophys. Res.-Atmos., 117, D24301,
https://doi.org/10.1029/2012JD017464, 2012.
Dauphas, N. and Schauble, E. A.: Mass fractionation laws, mass-independent
effects, and isotopic anomalies, Annu. Rev. Earth Pl. Sc., 44, 709–783, 2016.
Defouilloy, C., Cartigny, P., Assayag, N., Moynier, F., and Barrat, J.-A.:
High-precision sulfur isotope composition of enstatite meteorites and
implications of the formation and evolution of their parent bodies,
Geochim. Cosmochim. Ac., 172, 393–409, 2016.
Diekrup, D., Hannington, M. D., Strauss, H., and Ginley, S. J.: Decoupling of
Neoarchean sulfur sources recorded in Algoma-type banded iron formation,
Earth Planet. Sc. Lett., 489, 1–7, 2018.
Ding, T., Valkiers, S., Kipphardt, H., De Bievre, P., Taylor, P.,
Gonfiantini, R., and Krouse, R.: Calibrated sulfur isotope abundance ratios
of three IAEA sulfur isotope reference materials and V-CDT with a
reassessment of the atomic weight of sulfur, Geochim. Cosmochim. Ac.,
65, 2433–2437, 2001.
Dupart, Y., King, S. M., Nekat, B., Nowak, A., Wiedensohler, A., Herrmann,
H., David, G., Thomas, B., Miffre, A., and Rairoux, P.: Mineral dust
photochemistry induces nucleation events in the presence of SO2,
P. Natl. Acad. Sci. USA, 109, 20842–20847, 2012.
Dupart, Y., Fine, L., D'Anna, B., and George, C.: Heterogeneous uptake of NO2
on Arizona Test Dust under UV-A irradiation: An aerosol flow tube study,
Aeolian Res., 15, 45–51, 2014.
Eldridge, D., Guo, W., and Farquhar, J.: Theoretical estimates of equilibrium
sulfur isotope effects in aqueous sulfur systems: Highlighting the role of
isomers in the sulfite and sulfoxylate systems, Geochim. Cosmochim. Ac., 195, 171–200, 2016.
Eltbaakh, Y. A., Ruslan, M. H., Alghoul, M., Othman, M. Y., Sopian, K., and
Fadhel, M.: Measurement of total and spectral solar irradiance: Overview of
existing research, Renew. Sust. Energ. Rev., 15, 1403–1426,
2011.
Environnement Canada: National Pollutant Release Inventory, available at:
http://donnees.ec.gc.ca/data/substances/plansreports/national-pollutant-release
(last access: 21 March 2019), 2013.
Fairlie, T. D., Jacob, D. J., Dibb, J. E., Alexander, B., Avery, M. A., van
Donkelaar, A., and Zhang, L.: Impact of mineral dust on nitrate, sulfate, and
ozone in transpacific Asian pollution plumes, Atmos. Chem. Phys., 10,
3999–4012, https://doi.org/10.5194/acp-10-3999-2010, 2010.
Farquhar, J., Bao, H., and Thiemens, M.: Atmospheric influence of Earth's
earliest sulfur cycle, Science, 289, 756–758, 2000.
Farquhar, J. and Wing, B. A.: Multiple sulfur isotopes and the evolution of
the atmosphere, Earth Planet. Sc. Lett., 213, 1–13, 2003.
Farquhar, J., Savarino, J., Airieau, S., and Thiemens, M. H.: Observation of
wavelength-sensitive mass-independent sulfur isotope effects during
SO2 photolysis: Implications for the early atmosphere, J. Geophys.
Res.-Planet., 106, 32829–32839, 2001.
Farquhar, J., Johnston, D. T., and Wing, B. A.: Implications of conservation
of mass effects on mass-dependent isotope fractionations: influence of
network structure on sulfur isotope phase space of dissimilatory sulfate
reduction, Geochim. Cosmochim. Ac., 71, 5862–5875, 2007.
Félix-Bermúdez, A., Delgadillo-Hinojosa, F., Huerta-Diaz, M.,
Camacho-Ibar, V., and Torres-Delgado, E.: Atmospheric Inputs of Iron and
Manganese to Coastal Waters of the Southern California Current System:
Seasonality, Santa Ana Winds, and Biogeochemical Implications, J. Geophys.
Res.-Oceans, 122, 9230–9254, https://doi.org/10.1002/2017JC013224, 2017.
Formenti, P., Schütz, L., Balkanski, Y., Desboeufs, K., Ebert, M., Kandler,
K., Petzold, A., Scheuvens, D., Weinbruch, S., and Zhang, D.: Recent progress
in understanding physical and chemical properties of African and Asian
mineral dust, Atmos. Chem. Phys., 11, 8231–8256,
https://doi.org/10.5194/acp-11-8231-2011, 2011.
Fu, X., Wang, S., Chang, X., Cai, S., Xing, J., and Hao, J.: Modeling
analysis of secondary inorganic aerosols over China: pollution
characteristics, and meteorological and dust impacts, Sci. Rep. UK, 6, 35992,
https://doi.org/10.1038/srep35992, 2016.
Gaffney, J., Premuzic, E., and Manowitz, B.: On the usefulness of sulfur
isotope ratios in crude oil correlations, Geochim. Cosmochim. Ac., 44,
135–139, 1980.
Gautier, E., Savarino, J., Erbland, J., and Farquhar, J.: SO2
oxidation kinetics leave a consistent isotopic imprint on volcanic ice core
sulfate, J. Geophys. Res.-Atmos., 123, https://doi.org/10.1029/2018JD028456, 2018.
George, C., Ammann, M., D'Anna, B., Donaldson, D., and Nizkorodov, S. A.:
Heterogeneous photochemistry in the atmosphere, Chem. Rev., 115, 4218–4258,
2015.
Gettelman, A., Hoor, P., Pan, L., Randel, W., Hegglin, M. I., and Birner, T.:
The extratropical upper troposphere and lower stratosphere, Rev. Geophys.,
49, RG3003, https://doi.org/10.1029/2011RG000355, 2011.
Golitsyn, G., Granberg, I., Aloyan, A., Andronova, A., Gorchakov, G.,
Ponomarev, V., and Shishkov, P.: Study of emissions and transport of dust
aerosol in Kalmykia Black Lands, J. Aerosol Sci., 1001, S725–S726,
1997.
Golitsyn, G., Granberg, I., Andronova, A., Ponomarev, V., Zilitinkevich, S.,
Smirnov, V., and Yablokov, M. Y.: Investigation of boundary layer fine
structure in arid regions: Injection of fine dust into the atmosphere, Water
Air Soil Poll., 3, 245–257, 2003.
Guieu, C., Loÿe-Pilot, M. D., Ridame, C., and Thomas, C.: Chemical
characterization of the Saharan dust end-member: Some biogeochemical
implications for the western Mediterranean Sea, J. Geophys. Res.-Atmos., 107,
https://doi.org/10.1029/2001JD000582, 2002.
Guo, Q., Zhu, G., Strauss, H., Peters, M., Chen, T., Yang, J., Wei, R., Tian,
L., and Han, X.: Tracing the sources of sulfur in Beijing soils with stable
sulfur isotopes, J. Geochem. Explor., 161, 112–118, 2016.
Guo, Z., Li, Z., Farquhar, J., Kaufman, A. J., Wu, N., Li, C., Dickerson, R.
R., and Wang, P.: Identification of sources and formation processes of
atmospheric sulfate by sulfur isotope and scanning electron microscope
measurements, J. Geophys. Res.-Atmos., 115, D00K07,
https://doi.org/10.1029/2009JD012893, 2010.
Han, L., Cheng, S., Zhuang, G., Ning, H., Wang, H., Wei, W., and Zhao, X.:
The changes and long-range transport of PM2.5 in Beijing in the past decade,
Atmos. Environ., 110, 186–195, 2015.
Han, X., Guo, Q., Liu, C., Fu, P., Strauss, H., Yang, J., Hu, J., Wei, L.,
Ren, H., and Peters, M.: Using stable isotopes to trace sources and formation
processes of sulfate aerosols from Beijing, China, Sci. Rep. UK, 6, 29958,
https://doi.org/10.1038/srep29958, 2016.
Han, X., Guo, Q., Strauss, H., Liu, C., Hu, J., Guo, Z., Wei, R., Peters,
M., Tian, L., and Kong, J.: Multiple sulfur isotope constraints on sources
and formation processes of sulfate in Beijing PM2.5 aerosol,
Environ. Sci. Technol., 51, 7794–7803, 2017.
Harris, E., Sinha, B., Foley, S., Crowley, J. N., Borrmann, S., and Hoppe,
P.: Sulfur isotope fractionation during heterogeneous oxidation of
SO2 on mineral dust, Atmos. Chem. Phys., 12, 4867–4884,
https://doi.org/10.5194/acp-12-4867-2012, 2012a.
Harris, E., Sinha, B., Hoppe, P., Crowley, J. N., Ono, S., and Foley, S.:
Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase
oxidation by OH radicals and aqueous oxidation by H2O2,
O3 and iron catalysis, Atmos. Chem. Phys., 12, 407–423,
https://doi.org/10.5194/acp-12-407-2012, 2012b.
Harris, E., Sinha, B., Hoppe, P., Foley, S., and Borrmann, S.: Fractionation
of sulfur isotopes during heterogeneous oxidation of SO2 on sea salt
aerosol: a new tool to investigate non-sea salt sulfate production in the
marine boundary layer, Atmos. Chem. Phys., 12, 4619–4631,
https://doi.org/10.5194/acp-12-4619-2012, 2012c.
Harris, E., Sinha, B., Hoppe, P., Foley, S., and Borrmann, S.: Fractionation
of sulfur isotopes during heterogeneous oxidation of SO2 on sea salt
aerosol: a new tool to investigate non-sea salt sulfate production in the
marine boundary layer, Atmos. Chem. Phys., 12, 4619–4631,
https://doi.org/10.5194/acp-12-4619-2012, 2012d.
Harris, E., Sinha, B., Hoppe, P., and Ono, S.: High-precision measurements of
33S and 34S fractionation during SO2 oxidation
reveal causes of seasonality in SO2 and sulfate isotopic
composition, Environ. Sci. Technol., 47, 12174–12183, 2013a.
Harris, E., Sinha, B., Van Pinxteren, D., Tilgner, A., Fomba, K. W.,
Schneider, J., Roth, A., Gnauk, T., Fahlbusch, B., and Mertes, S.: Enhanced
role of transition metal ion catalysis during in-cloud oxidation of
SO2, Science, 340, 727–730, 2013b.
Hattori, S., Schmidt, J. A., Johnson, M. S., Danielache, S. O., Yamada, A.,
Ueno, Y., and Yoshida, N.: SO2 photoexcitation mechanism links
mass-independent sulfur isotopic fractionation in cryospheric sulfate to
climate impacting volcanism, P. Natl. Acad. Sci. USA, 110, 17656–17661,
2013.
He, H., Wang, Y., Ma, Q., Ma, J., Chu, B., Ji, D., Tang, G., Liu, C., Zhang,
H., and Hao, J.: Mineral dust and NOx promote the conversion
of SO2 to sulfate in heavy pollution days, Sci. Rep. UK, 4, 4172,
https://doi.org/10.1038/srep04172, 2014.
Herrmann, H.: Kinetics of aqueous phase reactions relevant for atmospheric
chemistry, Chem. Rev., 103, 4691–4716, 2003.
Kok, J. F., Parteli, E. J., Michaels, T. I., and Karam, D. B.: The physics of
wind-blown sand and dust, Rep. Prog. Phys., 75, 106901, 2012.
Krouse, H. R. and Grinenko, V. A.: Stable isotopes: natural and anthropogenic
sulphur in the environment, published on behalf of the Scientifc Committee on
Problems of the Environment (SCOPE) of the International Council of
Scientific Unions (ICSU) in collaboration with the United Nations Environment
Programme by Wiley, Chichester, New York, 1991.
Kulmala, M., Vehkamäki, H., Petäjä, T., Dal Maso, M., Lauri, A.,
Kerminen, V.-M., Birmili, W., and McMurry, P. H.: Formation and growth rates
of ultrafine atmospheric particles: a review of observations, J. Aerosol
Sci., 35, 143–176, 2004.
Labidi, J., Cartigny, P., Birck, J., Assayag, N., and Bourrand, J.:
Determination of multiple sulfur isotopes in glasses: A reappraisal of the
MORB δ34S, Chem. Geol., 334, 189–198, 2012.
Lee, C. W., Savarino, J., Cachier, H., and Thiemens, M.: Sulfur
(32S, 33S, 34S, 36S) and oxygen
(16O, 17O, 18O) isotopic ratios of primary
sulfate produced from combustion processes, Tellus B, 54, 193–200, 2002.
Lee, Y. N. and Schwartz, S. E.: Kinetics of oxidation of aqueous sulfur (IV)
by nitrogen dioxide, Precipitation Scavenging, Dry Deposition, and
Resuspension, edited by: Pruppacher, H. R., Semonin, R. G., and Slinn, W. G.
N., Elsevier, New York, Vol. 1, 453–466, 1983.
Lelieveld, J., Evans, J., Fnais, M., Giannadaki, D., and Pozzer, A.: The
contribution of outdoor air pollution sources to premature mortality on a
global scale, Nature, 525, 367–371, 2015.
Levy, H., Horowitz, L. W., Schwarzkopf, M. D., Ming, Y., Golaz, J. C., Naik,
V., and Ramaswamy, V.: The roles of aerosol direct and indirect effects in
past and future climate change, J. Geophys. Res.-Atmos., 118, 4521–4532,
2013.
Lin, M., Zhang, Z., Su, L., Hill-Falkenthal, J., Priyadarshi, A., Zhang, Q.,
Zhang, G., Kang, S., Chan, C. Y., and Thiemens, M. H.: Resolving the impact
of stratosphere-to-troposphere transport on the sulfur cycle and surface
ozone over the Tibetan Plateau using a cosmogenic 35S tracer, J.
Geophys. Res.-Atmos., 121, 439–456, 2016.
Lin, M., Kang, S., Shaheen, R., Li, C., Hsu, S.-C., and Thiemens, M. H.:
Atmospheric sulfur isotopic anomalies recorded at Mt. Everest across the
Anthropocene, P. Natl. Acad. Sci. USA, 115, 6964–6969,
https://doi.org/10.1073/pnas.1801935115, 2018a.
Lin, M., Zhang, X., Li, M., Xu, Y., Zhang, Z., Tao, J., Su, B., Liu, L.,
Shen, Y., and Thiemens, M. H.: Five-S-isotope evidence of two distinct
mass-independent sulfur isotope effects and implications for the modern and
Archean atmospheres, P. Natl. Acad. Sci. USA, 115, 8541–8546, 2018b.
Longo, A. F., Vine, D. J., King, L. E., Oakes, M., Weber, R. J., Huey, L. G.,
Russell, A. G., and Ingall, E. D.: Composition and oxidation state of sulfur
in atmospheric particulate matter, Atmos. Chem. Phys., 16, 13389–13398,
https://doi.org/10.5194/acp-16-13389-2016, 2016.
Ma, J., Chu, B., Liu, J., Liu, Y., Zhang, H., and He, H.:
NOx promotion of SO2 conversion to sulfate: An
important mechanism for the occurrence of heavy haze during winter in
Beijing, Environ. Pollut., 233, 662–669, 2018.
Marticorena, B. and Bergametti, G.: Modeling the atmospheric dust cycle: 1.
Design of a soil-derived dust emission scheme, J. Geophys. Res.-Atmos., 100,
16415–16430, 1995.
Martin, E.: Volcanic Plume Impact on the Atmosphere and Climate: O-and
S-Isotope Insight into Sulfate Aerosol Formation, Geosciences, 8, 198,
https://doi.org/10.3390/geosciences8060198, 2018.
Mauldin III, R., Berndt, T., Sipilä, M., Paasonen, P., Petäjä,
T., Kim, S., Kurtén, T., Stratmann, F., Kerminen, V.-M., and Kulmala, M.:
A new atmospherically relevant oxidant of sulphur dioxide, Nature, 488,
193–196, 2012.
McKendry, I. G., Hacker, J. P., Stull, R., Sakiyama, S., Mignacca, D., and
Reid, K.: Long-range transport of Asian dust to the Lower Fraser Valley,
British Columbia, Canada, J. Geophys. Res.-Atmos., 106, 18361–18370,
https://doi.org/10.1029/2000JD900359, 2001.
Merikanto, J., Spracklen, D. V., Mann, G. W., Pickering, S. J., and Carslaw,
K. S.: Impact of nucleation on global CCN, Atmos. Chem. Phys., 9, 8601–8616,
https://doi.org/10.5194/acp-9-8601-2009, 2009.
Mertes, S., Galgon, D., Schwirn, K., Nowak, A., Lehmann, K., Massling, A.,
Wiedensohler, A., and Wieprecht, W.: Evolution of particle concentration and
size distribution observed upwind, inside and downwind hill cap clouds at
connected flow conditions during FEBUKO, Atmos. Environ., 39, 4233–4245,
2005a.
Mertes, S., Lehmann, K., Nowak, A., Massling, A., and Wiedensohler, A.: Link
between aerosol hygroscopic growth and droplet activation observed for
hill-capped clouds at connected flow conditions during FEBUKO, Atmos.
Environ., 39, 4247–4256, 2005b.
Molina, L. and Molina, M.: Absolute absorption cross sections of ozone in the
185-to 350-nm wavelength range, J. Geophys. Res.-Atmos., 91, 14501–14508,
1986.
Myhre, G., Shindell, D., Bréon, F.-M., Collins, W., Fuglestvedt, J.,
Huang, J., Koch, D., Lamarque, J.-F., Lee, D., Mendoza, B., Nakajima, T.,
Robock, A., Stephens, G., Takemura, T., and Zhang, H.: Anthropogenic and
Natural Radiative Forcing. In: Climate Change 2013: The Physical Science
Basis. Contribution of Working Group I to the Fifth Assessment Report of the
Intergovernmental Panel on Climate Change, edited by: Stocker, T. F., Qin, D.,
Plattner, G.-K., Tignor, M., Allen, S. K., Boschung, J., Nauels, A., Xia, Y., Bex, V., and
Midgley, P. M., Cambridge University Press, Cambridge, United Kingdom
and New York, NY, USA, 2013.
Newman, L. and Forrest, J.: Sulphur isotope measurements relevant to power
plant emissions in the northeastern United States, in: Stable isotopes:
Natural and Anthropogenic sulphur in the environment, edited by: Krouse, H. R. and Grinenko, V. A.,
John Wiley and Sons, 133–176, 1991.
Nielsen, H.: Isotopic composition of the major contributors to atmospheric
sulfur, Tellus, 26, 213–221, 1974.
Norman, A.-L., Anlauf, K., Hayden, K., Thompson, B., Brook, J. R., Li,
S.-M., and Bottenheim, J.: Aerosol sulphate and its oxidation on the Pacific
NW coast: S and O isotopes in PM2.5, Atmos. Environ., 40,
2676–2689, 2006.
Oduro, H., Van Alstyne, K. L., and Farquhar, J.: Sulfur isotope variability
of oceanic DMSP generation and its contributions to marine biogenic sulfur
emissions, P. Natl. Acad. Sci. USA, 109, 9012–9016,
2012.
Ono, S., Wing, B., Johnston, D., Farquhar, J., and Rumble, D.: Mass-dependent
fractionation of quadruple stable sulfur isotope system as a new tracer of
sulfur biogeochemical cycles, Geochim. Cosmochim. Ac., 70, 2238–2252,
2006a.
Ono, S., Wing, B., Rumble, D., and Farquhar, J.: High precision analysis of
all four stable isotopes of sulfur (32S, 33S,
34S and 36S) at nanomole levels using a laser
fluorination isotope-ratio-monitoring gas chromatography – mass spectrometry,
Chem. Geol., 225, 30–39, 2006b.
Ono, S., Whitehill, A., and Lyons, J.: Contribution of isotopologue
self-shielding to sulfur mass-independent fractionation during sulfur
dioxide photolysis, J. Geophys. Res.-Atmos., 118,
2444–2454, 2013.
Otake, T., Lasaga, A. C., and Ohmoto, H.: Ab initio calculations for
equilibrium fractionations in multiple sulfur isotope systems, Chem. Geol.,
249, 357–376, 2008.
Paris, R., Desboeufs, K. V., Formenti, P., Nava, S., and Chou, C.: Chemical
characterisation of iron in dust and biomass burning aerosols during
AMMA-SOP0/DABEX: implication for iron solubility, Atmos. Chem. Phys., 10,
4273–4282, https://doi.org/10.5194/acp-10-4273-2010, 2010.
Penner, J. E., Dickinson, R. E., and O'Neill, C. A.: Effects of aerosol from
biomass burning on the global radiation budget, Science, 256, 1432–1434,
1992.
Penner, J. E., Quaas, J., Storelvmo, T., Takemura, T., Boucher, O., Guo, H.,
Kirkevåg, A., Kristjánsson, J. E., and Seland, Ø.: Model
intercomparison of indirect aerosol effects, Atmos. Chem. Phys., 6,
3391–3405, https://doi.org/10.5194/acp-6-3391-2006, 2006.
Premuzic, E., Gaffney, J., and Manowitz, B.: The importance of sulfur isotope
ratios in the differentiation of Prudhoe Bay crude oils, J. Geochem. Explor.,
26, 151–159, 1986.
Prospero, J. M.: Saharan Dust Transport Over the North Atlantic Ocean and
Mediterranean: An Overview, in: The Impact of Desert Dust Across the
Mediterranean, edited by: Guerzoni, S. and Chester, R., Springer Netherlands,
Dordrecht, 133–151, 1996.
Ramanathan, V., Crutzen, P. J., Kiehl, T. J., and Rosenfeld, D.: Aerosols,
Climate, and the Hydrological Cycle, Science, 294, 2119–2124, 2001.
Ramanathan, V., Chung, C., Kim, D., Bettge, T., Buja, L., Kiehl, J.,
Washington, W., Fu, Q., Sikka, D., and Wild, M.: Atmospheric brown clouds:
Impacts on South Asian climate and hydrological cycle, P. Natl. Acad. Sci.
USA, 102, 5326–5333, 2005.
Rees, C., Jenkins, W., and Monster, J.: The sulphur isotopic composition of
ocean water sulphate, Geochim. Cosmochim. Ac., 42, 377–381, 1978.
Romero, A. B. and Thiemens, M. H.: Mass-independent sulfur isotopic
compositions in present-day sulfate aerosols, J. Geophys. Res.-Atmos.,
108, 4524, https://doi.org/10.1029/2003JD003660, 2003.
Sanusi, A. A., Norman, A.-L., Burridge, C., Wadleigh, M., and Tang, W.-W.:
Determination of the S isotope composition of methanesulfonic acid, Anal.
Chem., 78, 4964–4968, 2006.
Sarwar, G., Fahey, K., Kwok, R., Gilliam, R. C., Roselle, S. J., Mathur, R.,
Xue, J., Yu, J., and Carter, W. P.: Potential impacts of two SO2
oxidation pathways on regional sulfate concentrations: aqueous-phase
oxidation by NO2 and gas-phase oxidation by Stabilized Criegee
Intermediates, Atmos. Environ., 68, 186–197, 2013.
Sarwar, G., Simon, H., Fahey, K., Mathur, R., Goliff, W. S., and Stockwell,
W. R.: Impact of sulfur dioxide oxidation by Stabilized Criegee Intermediate
on sulfate, Atmos. Environ., 85, 204–214, 2014.
Savarino, J., Romero, A., Cole-Dai, J., Bekki, S., and Thiemens, M.: UV
induced mass-independent sulfur isotope fractionation in stratospheric
volcanic sulfate, Geophys. Res. Lett., 30, 2131, https://doi.org/10.1029/2003GL018134, 2003.
Seinfeld, J. H. and Pandis, S. N.: Atmospheric chemistry and physics: from
air pollution to climate change, 3. Edn, John Wiley & Sons, Inc., Hoboken, New Jersey,
2012.
Shaheen, R., Abaunza, M. M., Jackson, T. L., McCabe, J., Savarino, J., and
Thiemens, M. H.: Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol
and its implications for the Archean atmosphere, P. Natl. Acad. Sci. USA,
111, 11979–11983, 2014.
Sinha, B. W., Hoppe, P., Huth, J., Foley, S., and Andreae, M. O.: Sulfur
isotope analyses of individual aerosol particles in the urban aerosol at a
central European site (Mainz, Germany), Atmos. Chem. Phys., 8, 7217–7238,
https://doi.org/10.5194/acp-8-7217-2008, 2008.
Sipilä, M., Jokinen, T., Berndt, T., Richters, S., Makkonen, R., Donahue,
N. M., Mauldin III, R. L., Kurtén, T., Paasonen, P., Sarnela, N., Ehn, M.,
Junninen, H., Rissanen, M. P., Thornton, J., Stratmann, F., Herrmann, H.,
Worsnop, D. R., Kulmala, M., Kerminen, V.-M., and Petäjä, T.: Reactivity
of stabilized Criegee intermediates (sCIs) from isoprene and monoterpene
ozonolysis toward SO2 and organic acids, Atmos. Chem. Phys., 14,
12143–12153, https://doi.org/10.5194/acp-14-12143-2014, 2014.
Smith, J. and Batts, B.: The distribution and isotopic composition of sulfur
in coal, Geochim. Cosmochim. Ac., 38, 121–133, 1974.
Song, C. H. and Carmichael, G. R.: The aging process of naturally emitted
aerosol (sea-salt and mineral aerosol) during long range transport, Atmos.
Environ., 33, 2203–2218, 1999.
Sprenger, M. and Wernli, H.: A Northern Hemispheric climatology of
cross-tropopause exchange for the ERA15 time period (1979–1993), J. Geophys.
Res.-Atmos., 108, 8521, https://doi.org/10.1029/2002JD002636,
2003.
Tanaka, N., Rye, D. M., Xiao, Y., and Lasaga, A. C.: Use of stable sulfur
isotope systematics for evaluating oxidation reaction pathways and
in-cloud-scavenging of sulfur dioxide in the atmosphere, Geophys. Res. Lett.,
21, 1519–1522, 1994.
Thode, H., Monster, J., and Dunford, H.: Sulphur isotope geochemistry,
Geochim. Cosmochim. Ac., 25, 159–174, 1961.
Thomassot, E., O'Neil, J., Francis, D., Cartigny, P., and Wing, B. A.:
Atmospheric record in the Hadean Eon from multiple sulfur isotope
measurements in Nuvvuagittuq Greenstone Belt (Nunavik, Quebec), P. Natl.
Acad. Sci. USA, 112, 707–712, 2015.
Tomasi, C. and Lupi, A.: Primary and Secondary Sources of Atmospheric
Aerosol, Atmospheric Aerosols: Life Cycles and Effects on Air Quality and
Climate, Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany, 1–86, 2017.
Usher, C. R., Michel, A. E., and Grassian, V. H.: Reactions on mineral dust,
Chem. Rev., 103, 4883–4940, 2003.
Ville de Montréal: Reduced dependance on fossil fuels in Montréal, Ville de Montréal,
Reduced dependance on fossil fuels in Montréal, Office de consultation publique de Montréal,
32,
2015.
Wadleigh, M., Schwarcz, H., and Kramer, J.: Isotopic evidence for the origin
of sulphate in coastal rain, Tellus B, 48, 44–59, 1996.
Wagener, T., Guieu, C., Losno, R., Bonnet, S., and Mahowald, N.: Revisiting
atmospheric dust export to the Southern Hemisphere ocean: Biogeochemical
implications, Global Biogeochem. Cy., 22, GB2006, https://doi.org/10.1029/2007GB002984, 2008.
Wall, S. M., John, W., and Ondo, J. L.: Measurement of aerosol size
distributions for nitrate and major ionic species, Atmos. Environ., 22,
1649–1656, 1988.
Wasiuta, V., Lafrenière, M. J., Norman, A.-L., and Hastings, M. G.:
Summer deposition of sulfate and reactive nitrogen to two alpine valleys in
the Canadian Rocky Mountains, Atmos. Environ., 101, 270–285, 2015.
Watanabe, Y., Farquhar, J., and Ohmoto, H.: Anomalous fractionations of
sulfur isotopes during thermochemical sulfate reduction, Science, 324,
370–373, 2009.
Whitehill, A. R. and Ono, S.: Excitation band dependence of sulfur isotope
mass-independent fractionation during photochemistry of sulfur dioxide using
broadband light sources, Geochim. Cosmochim. Ac., 94, 238–253, 2012.
Whitehill, A. R., Xie, C., Hu, X., Xie, D., Guo, H., and Ono, S.: Vibronic
origin of sulfur mass-independent isotope effect in photoexcitation of
SO2 and the implications to the early earth's atmosphere, P. Natl.
Acad. Sci. USA, 110, 17697–17702, 2013.
Whitehill, A. R., Jiang, B., Guo, H., and Ono, S.: SO2 photolysis as
a source for sulfur mass-independent isotope signatures in stratospehric
aerosols, Atmos. Chem. Phys., 15, 1843–1864,
https://doi.org/10.5194/acp-15-1843-2015, 2015.
World Health Organization: Ambient (outdoor) air quality and health, 2016, available at:
http://www.who.int/mediacentre/factsheets/fs313/en/ (last access: 29
November 2017), 2016.
Yang, Y., Russell, L. M., Lou, S., Liao, H., Guo, J., Liu, Y., Singh, B., and
Ghan, S. J.: Dust-wind interactions can intensify aerosol pollution over
eastern China, Nat. Commun., 8, 15333, https://doi.org/10.1038/ncomms15333,
2017.
Yang, Y., Wang, H., Smith, S. J., Zhang, R., Lou, S., Qian, Y., Ma, P.-L.,
and Rasch, P. J.: Recent intensification of winter haze in China linked to
foreign emissions and meteorology, Sci. Rep. UK, 8, 2107, https://doi.org/10.1038/s41598-018-20437-7, 2018.
Ye, J., Abbatt, J. P. D., and Chan, A. W. H.: Novel pathway of SO2
oxidation in the atmosphere: reactions with monoterpene ozonolysis
intermediates and secondary organic aerosol, Atmos. Chem. Phys., 18,
5549–5565, https://doi.org/10.5194/acp-18-5549-2018, 2018.
Young, E. D., Galy, A., and Nagahara, H.: Kinetic and equilibrium
mass-dependent isotope fractionation laws in nature and their geochemical and
cosmochemical significance, Geochim. Cosmochim. Ac., 66, 1095–1104, 2002.
Yu, F. and Luo, G.: Simulation of particle size distribution with a global
aerosol model: contribution of nucleation to aerosol and CCN number
concentrations, Atmos. Chem. Phys., 9, 7691–7710,
https://doi.org/10.5194/acp-9-7691-2009, 2009.
Yu, Z., Jang, M., and Park, J.: Modeling atmospheric mineral aerosol
chemistry to predict heterogeneous photooxidation of SO2, Atmos.
Chem. Phys., 17, 10001–10017, https://doi.org/10.5194/acp-17-10001-2017,
2017.
Zhao, D., Song, X., Zhu, T., Zhang, Z., Liu, Y., and Shang, J.: Multiphase
oxidation of SO2 by NO2 on CaCO3 particles, Atmos.
Chem. Phys., 18, 2481–2493, https://doi.org/10.5194/acp-18-2481-2018, 2018.
Zhao, T., Gong, S., Zhang, X., Blanchet, J.-P., McKendry, I., and Zhou, Z.: A
simulated climatology of Asian dust aerosol and its trans-Pacific transport.
Part I: Mean climate and validation, J. Climate, 19, 88–103, 2006.
Zinger, I. and Delisle, C.: Quality of used-snow discharged in the
ST-Lawrence river, in the region of the Montreal Harbor, Water Air Soil
Poll., 39, 47–57, 1988.
Short summary
Sulfates present in urban aerosols collected worldwide usually exhibit 33S-anomalies whose origin remains unclear. Besides, the sulfate concentration is not very well modelled nowadays, which, coupled with the isotopic composition anomaly on the 33S, would highlight the presence of at least an additional oxidation pathway, different from O2+TMI, O3, OH, H2O2 and NO2. We suggest here the implication of two other possible oxidation pathways.
Sulfates present in urban aerosols collected worldwide usually exhibit 33S-anomalies whose...
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