Effect of sea-salt aerosol on tropospheric bromine chemistry

Abstract. Bromine radicals influence global tropospheric chemistry by depleting ozone and OH, and by oxidizing elemental mercury, sulfur species, and volatile organic compounds. Observations typically indicate a 50 % depletion of sea salt aerosol (SSA) bromide relative to seawater composition, implying that SSA debromination could be the dominant global source of tropospheric bromine. However, it has been difficult to reconcile this large source with the relatively low BrO concentrations observed in the marine boundary layer (MBL). Here we present a new mechanistic description of SSA debromination in the GEOS-Chem global atmospheric chemistry model with a detailed representation of halogen (Cl, Br, and I) chemistry. We show, for the first time, observed levels of SSA debromination can be reproduced in a manner consistent with observed BrO concentrations. Bromine radical sinks from the HOBr + S(IV) heterogeneous reactions and from ocean emission of acetaldehyde are found to be critical in moderating tropospheric BrO levels. The resulting HBr is rapidly taken up by SSA and also deposited. We find that the source of bromine radicals is mostly from SSA in the MBL, but from organobromines in the free troposphere. Simulated BrO in the MBL is generally much higher in winter than in summer due to a combination of greater SSA emission and weaker radiation. Outstanding issues are the model underestimate of free tropospheric BrO, driven by the HOBr + S(IV) reactions, and uncertainty regarding HBr uptake by SSA.

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Effect of sea salt aerosol on tropospheric bromine chemistry

Atmospheric Chemistry and Physics ◽

10.5194/acp-19-6497-2019 ◽

2019 ◽

Vol 19 (9) ◽

pp. 6497-6507 ◽

Cited By ~ 11

Author(s):

Lei Zhu ◽

Daniel J. Jacob ◽

Sebastian D. Eastham ◽

Melissa P. Sulprizio ◽

Xuan Wang ◽

...

Keyword(s):

Atmospheric Chemistry ◽

Marine Boundary Layer ◽

Elemental Mercury ◽

Sea Salt ◽

Heterogeneous Reactions ◽

Tropospheric Chemistry ◽

Mixing Ratios ◽

Sea Salt Aerosol ◽

The Tropics ◽

Outstanding Issue

Abstract. Bromine radicals influence global tropospheric chemistry by depleting ozone and by oxidizing elemental mercury and reduced sulfur species. Observations typically indicate a 50 % depletion of sea salt aerosol (SSA) bromide relative to seawater composition, implying that SSA debromination could be the dominant global source of tropospheric bromine. However, it has been difficult to reconcile this large source with the relatively low bromine monoxide (BrO) mixing ratios observed in the marine boundary layer (MBL). Here we present a new mechanistic description of SSA debromination in the GEOS-Chem global atmospheric chemistry model with a detailed representation of halogen (Cl, Br, and I) chemistry. We show that observed levels of SSA debromination can be reproduced in a manner consistent with observed BrO mixing ratios. Bromine radical sinks from the HOBr + S(IV) heterogeneous reactions and from ocean emission of acetaldehyde are critical in moderating tropospheric BrO levels. The resulting HBr is rapidly taken up by SSA and also deposited. Observations of SSA debromination at southern midlatitudes in summer suggest that model uptake of HBr by SSA may be too fast. The model provides a successful simulation of free-tropospheric BrO in the tropics and midlatitudes in summer, where the bromine radical sink from the HOBr + S(IV) reactions is compensated for by more efficient HOBr-driven recycling in clouds compared to previous GEOS-Chem versions. Simulated BrO in the MBL is generally much higher in winter than in summer due to a combination of greater SSA emission and slower conversion of bromine radicals to HBr. An outstanding issue in the model is the overestimate of free-tropospheric BrO in extratropical winter–spring, possibly reflecting an overestimate of the HOBr∕HBr ratio under these conditions where the dominant HOBr source is hydrolysis of BrNO3.

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Impact of reactive bromine chemistry in the troposphere

Atmospheric Chemistry and Physics ◽

10.5194/acp-4-2481-2004 ◽

2004 ◽

Vol 4 (11/12) ◽

pp. 2481-2497 ◽

Cited By ~ 191

Author(s):

R. von Glasow ◽

R. von Kuhlmann ◽

M. G. Lawrence ◽

U. Platt ◽

P. J. Crutzen

Keyword(s):

Atmospheric Chemistry ◽

Dimethyl Sulfide ◽

Marine Boundary Layer ◽

Transport Model ◽

Sea Salt ◽

Chemistry Transport Model ◽

Bromine Oxide ◽

Mixing Ratios ◽

Sea Salt Aerosol ◽

Field Campaigns

Abstract. Recently several field campaigns and satellite observations have found strong indications for the presence of bromine oxide (BrO) in the free troposphere. Using a global atmospheric chemistry transport model we show that BrO mixing ratios of a few tenths to 2 pmol mol-1 lead to a reduction in the zonal mean O3 mixing ratio of up to 18% in widespread areas and regionally up to 40% compared to a model run without bromine chemistry. A lower limit approach for the marine boundary layer, that does not explicitly include the release of halogens from sea salt aerosol, shows that for dimethyl sulfide (DMS) the effect is even larger, with up to 60% reduction of its tropospheric column. This is accompanied by dramatic changes in DMS oxidation pathways, reducing its cooling effect on climate. In addition there are changes in the HO2:OH ratio that also affect NOx and PAN. These results imply that potentially significant strong sinks for O3 and DMS have so far been ignored in many studies of the chemistry of the troposphere.

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Importance of reactive halogens in the tropical marine atmosphere: A regional modelling study using WRF-Chem

10.5194/acp-2017-903 ◽

2017 ◽

Cited By ~ 2

Author(s):

Alba Badia ◽

Claire E. Reeves ◽

Alex R. Baker ◽

Alfonso Saiz-Lopez ◽

Rainer Volkamer ◽

...

Keyword(s):

Atmospheric Chemistry ◽

Marine Boundary Layer ◽

Transport Model ◽

Model Performance ◽

Sea Salt ◽

Heterogeneous Reactions ◽

Regional Modelling ◽

Mixing Ratios ◽

Inorganic Iodine ◽

The Impact

Abstract. This study investigates the impact of halogens on atmospheric chemistry in the tropical troposphere and explores the sensitivity of this to uncertainties in the fluxes of halogens to the atmosphere and the chemical processing. To do this the regional chemistry transport model WRF-Chem has been extended, for the first time, to include halogen chemistry (bromine, chlorine and iodine chemistry), including heterogeneous recycling reactions involving sea-salt aerosol and other particles, reactions of Br with volatile organic compounds (VOCs), along with oceanic emissions of halocarbons, VOCs and inorganic iodine. The study focuses on the tropical East Pacific using field observations from the TORERO campaign (January–February 2012) to evaluate the model performance. Including all the new processes, the model does a reasonable job reproducing the observed mixing ratios of BrO and IO, albeit with some discrepancies, some of which can be attributed to difficulties in the model's ability to reproduce the observed halocarbons. This is somewhat expected given the large uncertainties in the air-sea fluxes of the halocarbons in a region where there are few observations of seawater concentrations. We see a considerable impact on the Bry partitioning when heterogeneous chemistry is included, with a greater proportion of the Bry in active forms such as BrO, HOBr and dihalogens. Including debromination of sea-salt increases BrO slightly throughout the free troposphere, but in the tropical marine boundary layer, where the sea-salt particles are plentiful and relatively acidic, debromination leads to overestimation of the observed BrO. However, it should be noted that the modelled BrO was extremely sensitive to the inclusion of reactions between Br and the VOCs, which convert Br to HBr, a far less reactive form of Bry. Excluding these reactions leads to modelled BrO mixing ratios greater than observed. The reactions between Br and aldehydes were found to be particularly important, despite the model underestimating the amount of aldehydes observed in the atmosphere. There are only small changes to Iy partitioning and IO when the heterogeneous reactions, primarly on sea-salt, are included. Our model results show that the tropospheric Ox loss due to halogens is 31 %. This loss is mostly due to I (16 %) and Br (14 %) and it is in good agreement with other estimates from state-of-the-art atmospheric chemistry models.

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The role of chlorine in global tropospheric chemistry

Atmospheric Chemistry and Physics ◽

10.5194/acp-19-3981-2019 ◽

2019 ◽

Vol 19 (6) ◽

pp. 3981-4003 ◽

Cited By ~ 47

Author(s):

Xuan Wang ◽

Daniel J. Jacob ◽

Sebastian D. Eastham ◽

Melissa P. Sulprizio ◽

Lei Zhu ◽

...

Keyword(s):

Boundary Layer ◽

Atmospheric Chemistry ◽

Sea Salt ◽

Tropospheric Chemistry ◽

Mixing Ratios ◽

Sea Salt Aerosol ◽

Oxidation Of Methane ◽

Heterogeneous Processes ◽

Marine Air ◽

Global Mean

Abstract. We present a comprehensive simulation of tropospheric chlorine within the GEOS-Chem global 3-D model of oxidant–aerosol–halogen atmospheric chemistry. The simulation includes explicit accounting of chloride mobilization from sea salt aerosol by acid displacement of HCl and by other heterogeneous processes. Additional small sources of tropospheric chlorine (combustion, organochlorines, transport from stratosphere) are also included. Reactive gas-phase chlorine Cl*, including Cl, ClO, Cl2, BrCl, ICl, HOCl, ClNO3, ClNO2, and minor species, is produced by the HCl+OH reaction and by heterogeneous conversion of sea salt aerosol chloride to BrCl, ClNO2, Cl2, and ICl. The model successfully simulates the observed mixing ratios of HCl in marine air (highest at northern midlatitudes) and the associated HNO3 decrease from acid displacement. It captures the high ClNO2 mixing ratios observed in continental surface air at night and attributes the chlorine to HCl volatilized from sea salt aerosol and transported inland following uptake by fine aerosol. The model successfully simulates the vertical profiles of HCl measured from aircraft, where enhancements in the continental boundary layer can again be largely explained by transport inland of the marine source. It does not reproduce the boundary layer Cl2 mixing ratios measured in the WINTER aircraft campaign (1–5 ppt in the daytime, low at night); the model is too high at night, which could be due to uncertainty in the rate of the ClNO2+Cl- reaction, but we have no explanation for the high observed Cl2 in daytime. The global mean tropospheric concentration of Cl atoms in the model is 620 cm−3 and contributes 1.0 % of the global oxidation of methane, 20 % of ethane, 14 % of propane, and 4 % of methanol. Chlorine chemistry increases global mean tropospheric BrO by 85 %, mainly through the HOBr+Cl- reaction, and decreases global burdens of tropospheric ozone by 7 % and OH by 3 % through the associated bromine radical chemistry. ClNO2 chemistry drives increases in ozone of up to 8 ppb over polluted continents in winter.

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The role of chlorine in tropospheric chemistry

10.5194/acp-2018-1088 ◽

2018 ◽

Cited By ~ 1

Author(s):

Xuan Wang ◽

Daniel J. Jacob ◽

Sebastian D. Eastham ◽

Melissa P. Sulprizio ◽

Lei Zhu ◽

...

Keyword(s):

Boundary Layer ◽

Atmospheric Chemistry ◽

Sea Salt ◽

Tropospheric Chemistry ◽

Mixing Ratios ◽

Sea Salt Aerosol ◽

Oxidation Of Methane ◽

Heterogeneous Processes ◽

Marine Air ◽

Global Mean

Abstract. We present a comprehensive simulation of tropospheric chlorine within the GEOS-Chem global 3-D model of oxidant-aerosol-halogen atmospheric chemistry. The simulation includes explicit accounting of chloride mobilization from sea-salt aerosol by acid displacement of HCl and by other heterogeneous processes. Additional sources of tropospheric chlorine (combustion, organochlorines, transport from stratosphere) are small in comparison. Reactive gas-phase chlorine Cl*, including Cl, ClO, Cl2, BrCl, ICl, HOCl, ClNO3, ClNO2, and minor species, is produced by the HCl + OH reaction and by heterogeneous conversion of sea-salt aerosol chloride to BrCl, ClNO2, Cl2, and ICl. The model simulates successfully the observed mixing ratios of HCl in marine air (highest at northern mid-latitudes) and the associated HNO3 decrease from acid displacement. It captures the high ClNO2 mixing ratios observed in continental surface air at night with chlorine of sea salt origin transported inland as HCl and fine aerosol. It simulates successfully the vertical profiles of HCl measured from aircraft, where enhancements in the continental boundary layer can again be explained by transport inland of the marine source. It does not reproduce the boundary layer Cl2 mixing ratios measured in the WINTER aircraft campaign (1–5 ppt in the daytime, low at night); the model is too high at night compared to WINTER observations, which could be due to uncertainty in the rate of the ClNO2 + Cl− reaction, but we have no explanation for the daytime observations. The global mean tropospheric concentration of Cl atoms in the model is 620 cm−3 and contributes 1.0 % of the global oxidation of methane, 20 % of ethane, 14 % of propane, and 4 % of methanol. Chlorine chemistry increases global mean tropospheric BrO by 85 %, mainly through the HOBr + Cl− reaction, and decreases global burdens of tropospheric ozone by 7 % and OH by 3 % through the associated bromine radical chemistry. ClNO2 chemistry drives increases in ozone of up to 8 ppb over polluted continents in winter.

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Inorganic bromine in the marine boundary layer: a critical review

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-3-2963-2003 ◽

2003 ◽

Vol 3 (3) ◽

pp. 2963-3050 ◽

Cited By ~ 6

Author(s):

R. Sander ◽

W. C. Keene ◽

A. A. P. Pszenny ◽

R. Arimoto ◽

G. P. Ayers ◽

...

Keyword(s):

Boundary Layer ◽

Gas Phase ◽

Marine Boundary Layer ◽

Sea Water ◽

Ocean Surface ◽

Sea Salt ◽

Future Research ◽

Laboratory Studies ◽

Model Calculations ◽

Sea Salt Aerosol

Abstract. The cycling of inorganic bromine in the marine boundary layer (mbl) has received increased attention in recent years. Bromide, a constituent of sea water, is injected into the atmosphere in association with sea-salt aerosol by breaking waves on the ocean surface. Measurements reveal that supermicrometer sea-salt aerosol is depleted in bromine by about 50% relative to conservative tracers, whereas marine submicrometer aerosol is often enriched in bromine. Model calculations, laboratory studies, and field observations strongly suggest that these depletions reflect the chemical transformation of particulate bromide to reactive inorganic gases that influence the processing of ozone and other important constituents of marine air. However, currently available techniques cannot reliably quantify many \\chem{Br}-containing compounds at ambient concentrations and, consequently, our understanding of inorganic Br cycling over the oceans and its global significance are uncertain. To provide a more coherent framework for future research, we have reviewed measurements in marine aerosol, the gas phase, and in rain. We also summarize sources and sinks, as well as model and laboratory studies of chemical transformations. The focus is on inorganic bromine over the open oceans, excluding the polar regions. The generation of sea-salt aerosol at the ocean surface is the major tropospheric source producing about 6.2 Tg/a of bromide. The transport of Br from continents (as mineral aerosol, and as products from biomass-burning and fossil-fuel combustion) can be of local importance. Transport of degradation products of long-lived Br-containing compounds from the stratosphere and other sources contribute lesser amounts. Available evidence suggests that, following aerosol acidification, sea-salt bromide reacts to form Br2 and BrCl that volatilize to the gas phase and photolyze in daylight to produce atomic Br and Cl. Subsequent transformations can destroy tropospheric ozone, oxidize dimethylsulfide (DMS) and hydrocarbons in the gas phase and S(IV) in aerosol solutions, and thereby potentially influence climate. The diurnal cycle of gas-phase \\Br and the corresponding particulate Br deficits are correlated. Higher values of Br in the gas phase during daytime are consistent with expectations based on photochemistry. Mechanisms that explain the widely reported accumulation of particulate Br in submicrometer aerosols are not yet understood. We expect that the importance of inorganic Br cycling will vary in the future as a function of both increasing acidification of the atmosphere (through anthropogenic emissions) and climate changes. The latter affects bromine cycling via meteorological factors including global wind fields (and the associated production of sea-salt aerosol), temperature, and relative humidity.

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Do organic surface films on sea salt aerosols influence atmospheric chemistry? – a model study

Atmospheric Chemistry and Physics ◽

10.5194/acp-7-5555-2007 ◽

2007 ◽

Vol 7 (21) ◽

pp. 5555-5567 ◽

Cited By ~ 27

Author(s):

L. Smoydzin ◽

R. von Glasow

Keyword(s):

Mass Transfer ◽

Liquid Phase ◽

Gas Phase ◽

Aqueous Phase ◽

Atmospheric Chemistry ◽

Organic Coating ◽

Sea Salt ◽

Tropospheric Chemistry ◽

Special Focus ◽

Sea Salt Aerosols

Abstract. Organic material from the ocean's surface can be incorporated into sea salt aerosol particles often producing a surface film on the aerosol. Such an organic coating can reduce the mass transfer between the gas phase and the aerosol phase influencing sea salt chemistry in the marine atmosphere. To investigate these effects and their importance for the marine boundary layer (MBL) we used the one-dimensional numerical model MISTRA. We considered the uncertainties regarding the magnitude of uptake reduction, the concentrations of organic compounds in sea salt aerosols and the oxidation rate of the organics to analyse the possible influence of organic surfactants on gas and liquid phase chemistry with a special focus on halogen chemistry. By assuming destruction rates for the organic coating based on laboratory measurements we get a rapid destruction of the organic monolayer within the first meters of the MBL. Larger organic initial concentrations lead to a longer lifetime of the coating but lead also to an unrealistically strong decrease of O3 concentrations as the organic film is destroyed by reaction with O3. The lifetime of the film is increased by assuming smaller reactive uptake coefficients for O3 or by assuming that a part of the organic surfactants react with OH. With regard to tropospheric chemistry we found that gas phase concentrations for chlorine and bromine species decreased due to the decreased mass transfer between gas phase and aerosol phase. Aqueous phase chlorine concentrations also decreased but aqueous phase bromine concentrations increased. Differences for gas phase concentrations are in general smaller than for liquid phase concentrations. The effect on gas phase NO2 or NO is very small (reduction less than 5%) whereas liquid phase NO2 concentrations increased in some cases by nearly 100%. We list suggestions for further laboratory studies which are needed for improved model studies.

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Variation of atmospheric volatile organic compounds over the Southern Indian Ocean (30 - 49°S)

Environmental Chemistry ◽

10.1071/en08072 ◽

2009 ◽

Vol 6 (1) ◽

pp. 70 ◽

Cited By ~ 29

Author(s):

Aurélie Colomb ◽

Valérie Gros ◽

Séverine Alvain ◽

Roland Sarda-Esteve ◽

Bernard Bonsang ◽

...

Keyword(s):

Volatile Organic Compounds ◽

Indian Ocean ◽

Organic Compounds ◽

Atmospheric Chemistry ◽

Marine Boundary Layer ◽

Global Scale ◽

Climate Impacts ◽

Southern Indian Ocean ◽

Oceanic Fronts ◽

Volatile Organic

Environmental context. Oceans represent 70% of the blue planet, and surprisingly, ocean emission in term of volatile organic compounds is poorly understood. The potential climate impacts on a global scale of various trace organic gases have been established, and the terrestrial inputs are well studied, but little is known about which of these can be emitted from oceanic sources. In the present study, atmospheric samples were taken over the Southern Indian Ocean, while crossing some oceanic fronts and different phytoplankton species. Such a study should aid in understanding oceanic emission, especially from phytoplankton, and will help modellers to determine concentrations of organic traces in the remote marine troposphere. Abstract. Considering its size and potential importance, the ocean is poorly characterised in terms of volatile organic compounds (VOC) that play important roles in global atmospheric chemistry. In order to better understand their potential sources and sinks over the Southern Indian Austral Ocean, shipborne measurements of selected species were made during the MANCHOT campaign during December 2004, on board the research vessel Marion Dufresne. Along the transect La Réunion to Kerguelen Island, air measurements of selected VOC (including dimethylsulfide (DMS) isoprene, carbonyls and organohalogens), carbon monoxide and ozone were performed, crossing subtropical, temperate and sub-Antarctic waters as well as pronounced subtropical and sub-Antarctic oceanic fronts. The remote marine boundary layer was characterised at latitudes 45–50°S. Oceanic fronts were associated with enhanced chlorophyll and biological activity in the seawater and elevated DMS and organohalogens in the atmosphere. These were compared with a satellite-derived phytoplankton distribution (PHYSAT). Diurnal variation for isoprene, terpenes, acetone and acetaldehyde was observed, analogously to recent results observed in mesocosm experiments.

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Observationally constrained analysis of sea salt aerosol in the marine atmosphere

10.5194/acp-2019-18 ◽

2019 ◽

Cited By ~ 1

Author(s):

Huisheng Bian ◽

Karl Froyd ◽

Daniel M. Murphy ◽

Jack Dibb ◽

Mian Chin ◽

...

Keyword(s):

Boundary Layer ◽

Atmospheric Chemistry ◽

Marine Boundary Layer ◽

Model Simulation ◽

In Situ Measurements ◽

Sea Salt ◽

Boreal Summer ◽

Integrated Analysis ◽

Marine Atmosphere

Abstract. Atmospheric sea salt plays important roles in marine cloud formation and atmospheric chemistry. We performed an integrated analysis of NASA GEOS model simulations run with the GOCART aerosol module, in situ measurements from the PALMS and SAGA instruments obtained during the NASA ATom campaign, and aerosol optical depth (AOD) measurements from AERONET Marine Aerosol Network (MAN) sun photometers and from MODIS satellite observations to better constrain sea salt in the marine atmosphere. ATom measurements and GEOS model simulation both show that sea salt concentrations over the Pacific and Atlantic oceans have a strong vertical gradient, varying up to four orders of magnitude from the marine boundary layer to free troposphere. The modeled residence times suggest that the lifetime of sea salt particles with dry diameter less than 3 μm is largely controlled by wet removal, followed next by turbulent process. During both boreal summer and winter, the GEOS simulated sea salt mass mixing ratios agree with SAGA measurements in the marine boundary layer (MBL) and with PALMS measurements above the MBL. However, comparison of AOD from GEOS with AERONET/MAN and MODIS aerosol retrievals indicated that the model underestimated AOD over the oceans where sea salt dominates. The apparent discrepancy of slightly overpredicted concentration and large underpredicted AOD could not be explained by biases in the model RH, which was found to be comparable to or larger than the in-situ measurements. This conundrum is at least partially explained by the sea salt size distribution; where the GEOS simulation has much less sea salt percentage-wise in the smaller particles than was observed by PALMS. Model sensitivity experiments indicated that the simulated sea salt is better correlated with measurements when the sea salt emission is calculated based on the friction velocity and with consideration of sea surface temperature dependence than that parameterized with the 10-m winds.

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Exploring ice core sea ice proxies through process-based modelling

10.5194/egusphere-egu2020-9013 ◽

2020 ◽

Author(s):

Rachael Rhodes ◽

Xin Yang ◽

Eric Wolff

Keyword(s):

Sea Ice ◽

Atmospheric Chemistry ◽

Ice Core ◽

Ice Cores ◽

Sea Salt ◽

Atmospheric Composition ◽

The Arctic ◽

Sea Salt Aerosol ◽

Aerosol Emission ◽

The Impact

It is important to understand the magnitude and rate of past sea ice changes, as well as their timing relative to abrupt shifts in other components of Earth&#8217;s climate system. Furthermore, records of past sea ice over the last few centuries are urgently needed to assess the scale of natural (internal) variability over decadal timescales. By continuously recording past atmospheric composition, polar ice cores have the potential to document changing sea ice conditions if atmospheric chemistry is altered. &#160;Sea salt aerosol, specifically sodium (Na), and bromine enrichment (Brenr, Br/Na enriched relative to seawater ratio) are two ice core sea ice proxies suggested following this premise.Here we aim to move beyond a conceptual understanding of the controls on Na and Brenr in ice cores by using process-based modelling to test hypotheses. We present results of experiments using a 3D global chemical transport model (p-TOMCAT) that represents marine aerosol emission, transport and deposition. Critically, the complex atmospheric chemistry of bromine is also included. Three fundamental issues will be examined: 1) the partitioning of Br between gas and aerosol phases, 2) sea salt aerosol production from first-year versus multi-year sea ice, and 3) the impact of increased acidity in the atmosphere due to human activity in the Arctic.

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