scholarly journals Uptake of HNO<sub>3</sub> to deliquescent sea-salt particles: a study using the short-lived radioactive isotope tracer <sup>13</sup>N

2002 ◽  
Vol 2 (4) ◽  
pp. 249-257 ◽  
Author(s):  
C. Guimbaud ◽  
F. Arens ◽  
L. Gutzwiller ◽  
H. W. Gäggeler ◽  
M. Ammann
Keyword(s):  
Gas Phase ◽  
Data Interpretation ◽  
Accommodation Coefficient ◽  
Sea Salt ◽  
Uptake Coefficient ◽  
Concentration Data ◽  
Isotope Tracer ◽  
Sea Salt Aerosol ◽  
The North ◽  
Mass Accommodation Coefficient

Abstract. The uptake of HNO3 to deliquescent airborne sea-salt particles (RH = 55%, P = 760 torr, T = 300 K) at concentrations from 2 to 575 ppbv is measured in an aerosol flow tube using 13N as a tracer. Small particles (<approx> 70 nm diameter) are used in order to minimize the effect of diffusion in the gas phase on the mass transfer. Below 100 ppbv, an uptake coefficient (gupt) of 0.50 ± 0.20 is derived. At higher concentrations, the uptake coefficient decreases along with the consumption of aerosol chloride. Data interpretation is further supported by using the North American Aerosol Inorganics Model (AIM), which predicts the aqueous phase activities of ions and the gas-phase partial pressures of H2O, HNO3, and HCl at equilibrium for the NaCl/HNO3/H2O system. These simulations show that the low concentration data are obtained far from equilibrium, which implies that the uptake coefficient derived is equal to the mass accommodation coefficient under these conditions. The observed uptake coefficient can serve as input to modeling studies of atmospheric sea-salt aerosol chemistry. The main sea-salt aerosol burden in the marine atmosphere is represented by coarse mode particles (> 1 µm diameter). This implies that diffusion in the gas-phase is the limiting step to HNO3 uptake until the sea-salt has been completely processed.

scholarly journals Uptake of HNO<sub>3</sub> to deliquescent sea-salt particles

2002 ◽  
Vol 2 (3) ◽  
pp. 739-763 ◽  
Author(s):  
C. Guimbaud ◽  
F. Arens ◽  
L. Gutzwiller ◽  
H. W. Gäggeler ◽  
M. Ammann
Keyword(s):  
Gas Phase ◽  
Data Interpretation ◽  
Accommodation Coefficient ◽  
Sea Salt ◽  
Uptake Coefficient ◽  
Concentration Data ◽  
Sea Salt Aerosol ◽  
The North ◽  
Partial Pressures ◽  
Mass Accommodation Coefficient

Abstract. The uptake of HNO3 to deliquescent airborne sea-salt particles (RH = 55%, P = 760 torr, T = 300 K) at concentrations from 2 to 575 ppbv is measured in an aerosol flow tube using 13N as a tracer. Small particles (~ 70 nm diameter) are used in order to minimize the effect of diffusion in the gas phase on the mass transfer. Below 100 ppbv, an uptake coefficient (gupt) of 0.50 ± 0.20 is derived. At higher concentrations, the uptake coefficient decreases along with the consumption of aerosol chloride. Data interpretation is further supported by using the North American Aerosol Inorganics Model (AIM), which predicts the aqueous phase activities of ions and the gas-phase partial pressures of H2O, HNO3, and HCl at equilibrium for the NaCl/HNO3/H2O system. These simulations show that the low concentration data are obtained far from equilibrium, which implies that the uptake coefficient derived is equal to the mass accommodation coefficient under these conditions. The observed uptake coefficient can serve as input to modeling studies of atmospheric sea-salt aerosol chemistry. The main sea-salt aerosol burden in the marine atmosphere is represented by coarse mode particles (> 1 mm diameter). This implies that diffusion in the gas-phase is the limiting step to HNO3 uptake until the sea-salt has been completely processed.

scholarly journals Accommodation coefficient of HOBr on deliquescent sodium bromide aerosol particles

2002 ◽  
Vol 2 (1) ◽  
pp. 1-28 ◽  
Author(s):  
M. Wachsmuth ◽  
H. W. Gäggeler ◽  
R. von Glasow ◽  
M. Ammann
Keyword(s):  
Ozone Depletion ◽  
Aerosol Particles ◽  
Accommodation Coefficient ◽  
Sea Salt ◽  
Sodium Bromide ◽  
Radioactive Isotopes ◽  
The Arctic ◽  
Sea Salt Aerosol ◽  
Mass Accommodation Coefficient ◽  
Salt Brine

Abstract. Uptake of HOBr on sea salt aerosol, sea salt brine or ice is believed to be a key process providing a source of photolabile bromine (Br2) and sustaining ozone depletion cycles in the arctic troposphere. In the present study, uptake of HOBr on sodium bromide (NaBr) aerosol particles was investigated at an extremely low HOBr concentration of 300 cm-3 using the short-lived radioactive isotopes 83-86Br. Under these conditions, at maximum one HOBr molecule was taken up per particle. The rate of uptake was clearly limited by the mass accommodation coefficient, which was calculated to be 0.6±0.2. This value is a factor of 10 larger than estimates used in earlier models. The atmospheric implications are discussed using the box model "MOCCA'', showing that the increase of the accommodation coefficient of HOBr by a factor of 10 only slightly affects net ozone loss, but significantly increases chlorine release.

scholarly journals Accommodation coefficient of HOBr on deliquescent sodium bromide aerosol particles

2002 ◽  
Vol 2 (2) ◽  
pp. 121-131 ◽  
Author(s):  
M. Wachsmuth ◽  
H. W. Gäggeler ◽  
R. von Glasow ◽  
M. Ammann
Keyword(s):  
Ozone Depletion ◽  
Aerosol Particles ◽  
Accommodation Coefficient ◽  
Sea Salt ◽  
Sodium Bromide ◽  
Radioactive Isotopes ◽  
The Arctic ◽  
Sea Salt Aerosol ◽  
Mass Accommodation Coefficient ◽  
Salt Brine

Abstract. Uptake of HOBr on sea salt aerosol, sea salt brine or ice is believed to be a key process providing a source of photolabile bromine (Br2) and sustaining ozone depletion cycles in the Arctic troposphere. In the present study, uptake of HOBr on sodium bromide (NaBr) aerosol particles was investigated at an extremely low HOBr concentration of 300 cm-3 using the short-lived radioactive isotopes 83-86Br. Under these conditions, at maximum one HOBr molecule was taken up per particle. The rate of uptake was clearly limited by the mass accommodation coefficient, which was calculated to be 0.6 ± 0.2. This value is a factor of 10 larger than estimates used in earlier models. The atmospheric implications are discussed using the box model "MOCCA'', showing that the increase of the accommodation coefficient of HOBr by a factor of 10 only slightly affects net ozone loss, but significantly increases chlorine release.

scholarly journals Inorganic bromine in the marine boundary layer: a critical review

2003 ◽  
Vol 3 (3) ◽  
pp. 2963-3050 ◽  
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.

scholarly journals Constraining nucleation, condensation, and chemistry in oxidation flow reactors using size-distribution measurements and aerosol microphysical modelling

2018 ◽  
Author(s):  
Anna L. Hodshire ◽  
Brett B. Palm ◽  
M. Lizabeth Alexander ◽  
Qijing Bian ◽  
Pedro Campuzano-Jost ◽  
...  
Keyword(s):  
Size Distribution ◽  
Gas Phase ◽  
Organic Compounds ◽  
Rate Constants ◽  
Accommodation Coefficient ◽  
Uptake Coefficient ◽  
Flow Reactors ◽  
Reactive Uptake Coefficient ◽  
Fragmentation Reactions ◽  
Gas Phase Fragmentation

Abstract. Oxidation flow reactors (OFRs) allow the concentration of a given atmospheric oxidant to be increased beyond ambient levels in order to study secondary organic aerosol (SOA) formation and aging over varying periods of equivalent aging by that oxidant. Previous studies have used these reactors to determine the bulk OA mass and chemical evolution. To our knowledge, no OFR study has focused on the interpretation of the evolving aerosol size distributions. In this study, we use size distribution measurements of the OFR and an aerosol microphysics model to learn about size-dependent processes in the OFR. Specifically, we use OFR exposures between 0.09–0.9 equivalent days of OH aging from the 2011 BEACHON-RoMBAS and the GoAmazon2014/5 field campaigns. We use simulations in the TOMAS (TwO-Moment Aerosol Sectional) microphysics box model to constrain the following parameters in the OFR: (1) the rate constant of gas-phase functionalization reactions of organic compounds with OH, (2) the rate constant of gas-phase fragmentation reactions of organic compounds with OH, (3) the reactive uptake coefficient for heterogeneous fragmentation reactions with OH, (4) the nucleation rate constants for three different nucleation schemes, and (5) an effective accommodation coefficient that accounts for possible particle diffusion limitations of particles larger than 60 nm in diameter. We find the best model-to-measurement agreement when the accommodation coefficient of the larger particles (Dp > 60 nm) was 0.1 or lower (with an accommodation coefficient of 1 for smaller particles), which suggests a diffusion limitation in the larger particles. When using these low accommodation-coefficient values, the model agrees with measurements when using a published H2SO4-organics nucleation mechanism and previously published values of rate constants for gas-phase oxidation reactions. Further, gas-phase fragmentation was found to have a significant impact upon the size distribution, and including fragmentation was necessary for accurately simulating the distributions in the OFR. The model was insensitive to the value of the reactive uptake coefficient on these aging timescales. Monoterpenes and isoprene could explain 24–95 % of the observed change in total volume of aerosol in the OFR, with ambient semivolatile and intermediate-volatility organic compounds (S/IVOCs) appearing to explain the remainder of the change in total volume. These results provide support to the mass-based findings of previous OFR studies, give insight to important size-distribution dynamics in the OFR, and enable the design of future OFR studies focused on new particle formation and/or microphysical processes.

scholarly journals Importance of the surface reaction OH+Cl<sup>-</sup> on sea salt aerosol for the chemistry of the marine boundary layer – a model study

2006 ◽  
Vol 6 (3) ◽  
pp. 3657-3685 ◽  
Author(s):  
R. von Glasow
Keyword(s):  
Boundary Layer ◽  
Gas Phase ◽  
Marine Boundary Layer ◽  
Sulfur Cycle ◽  
Sea Salt ◽  
Sea Salt Aerosol ◽  
Sulfate Production ◽  
Model Study ◽  
Additional Production ◽  
A Minor

Abstract. The reaction of the hydroxyl radical with chloride on the surface of sea salt aerosol producing gas phase Cl2 and particulate OH- and its implications for the chemistry of the marine boundary layer under coastal, remote, and very remote conditions have been investigated with a numerical model. This reaction had been suggested by Laskin et al. (2003) to play a major role in the sulfur cycle in the marine boundary layer by increasing the sulfate production in sea salt by O3 oxidation due to the additional production of alkalinity in the particle. Based on literature data a new &amp;quotbest estimate'' for the rate coefficient of the reaction was deduced and applied, showing that the additional initial sulfate production by this reaction is less than 1%, therefore having only a minor impact on sulfate production. Even though the gas phase concentration of Cl2 increased strongly in the model the concentration of Cl radicals increased by less than 5% for the &amp;quotbest guess'' case. Additional feedbacks between the cycles of chlorine and sulfur in the marine boundary layer are discussed as well as a two-stage acidification of large fresh sea salt aerosol.

scholarly journals Constraining nucleation, condensation, and chemistry in oxidation flow reactors using size-distribution measurements and aerosol microphysical modeling

2018 ◽  
Vol 18 (16) ◽  
pp. 12433-12460 ◽  
Author(s):  
Anna L. Hodshire ◽  
Brett B. Palm ◽  
M. Lizabeth Alexander ◽  
Qijing Bian ◽  
Pedro Campuzano-Jost ◽  
...  
Keyword(s):  
Size Distribution ◽  
Gas Phase ◽  
Organic Compounds ◽  
Rate Constants ◽  
Accommodation Coefficient ◽  
Uptake Coefficient ◽  
Flow Reactors ◽  
Reactive Uptake Coefficient ◽  
Fragmentation Reactions ◽  
Gas Phase Fragmentation

Abstract. Oxidation flow reactors (OFRs) allow the concentration of a given atmospheric oxidant to be increased beyond ambient levels in order to study secondary organic aerosol (SOA) formation and aging over varying periods of equivalent aging by that oxidant. Previous studies have used these reactors to determine the bulk OA mass and chemical evolution. To our knowledge, no OFR study has focused on the interpretation of the evolving aerosol size distributions. In this study, we use size-distribution measurements of the OFR and an aerosol microphysics model to learn about size-dependent processes in the OFR. Specifically, we use OFR exposures between 0.09 and 0.9 equivalent days of OH aging from the 2011 BEACHON-RoMBAS and GoAmazon2014/5 field campaigns. We use simulations in the TOMAS (TwO-Moment Aerosol Sectional) microphysics box model to constrain the following parameters in the OFR: (1) the rate constant of gas-phase functionalization reactions of organic compounds with OH, (2) the rate constant of gas-phase fragmentation reactions of organic compounds with OH, (3) the reactive uptake coefficient for heterogeneous fragmentation reactions with OH, (4) the nucleation rate constants for three different nucleation schemes, and (5) an effective accommodation coefficient that accounts for possible particle diffusion limitations of particles larger than 60 nm in diameter. We find the best model-to-measurement agreement when the accommodation coefficient of the larger particles (Dp > 60 nm) was 0.1 or lower (with an accommodation coefficient of 1 for smaller particles), which suggests a diffusion limitation in the larger particles. When using these low accommodation-coefficient values, the model agrees with measurements when using a published H2SO4-organics nucleation mechanism and previously published values of rate constants for gas-phase oxidation reactions. Further, gas-phase fragmentation was found to have a significant impact upon the size distribution, and including fragmentation was necessary for accurately simulating the distributions in the OFR. The model was insensitive to the value of the reactive uptake coefficient on these aging timescales. Monoterpenes and isoprene could explain 24 %–95 % of the observed change in total volume of aerosol in the OFR, with ambient semivolatile and intermediate-volatility organic compounds (S/IVOCs) appearing to explain the remainder of the change in total volume. These results provide support to the mass-based findings of previous OFR studies, give insight to important size-distribution dynamics in the OFR, and enable the design of future OFR studies focused on new particle formation and/or microphysical processes.

scholarly journals Iron(III)-induced activation of chloride from artificial sea-salt aerosol

2015 ◽  
Vol 12 (4) ◽  
pp. 461 ◽  
Author(s):  
Julian Wittmer ◽  
Sergej Bleicher ◽  
Johannes Ofner ◽  
Cornelius Zetzsch
Keyword(s):  
Gas Phase ◽  
Particle Diameter ◽  
Steel Production ◽  
Oxidative Capacity ◽  
Sea Salt ◽  
Initial Surface ◽  
Sea Salt Aerosol ◽  
Glacial Flour ◽  
Natural Aerosols ◽  
Simulation Chamber

Environmental context Inorganic, natural aerosols (sea-salt, mineral dust, glacial flour) and contributions of anthropogenic components (fly ash, dust from steel production and processing, etc.) contain iron that can be dissolved as FeIII in saline media. This study investigates photochemical processes in clouds and aerosols producing gas-phase Cl as a function of salt- and gas-phase composition employing a simulation chamber. Atomic Cl may contribute to the oxidative capacity of the troposphere, and our findings imply local sources. Abstract Artificial sea-salt aerosol, containing FeIII at various compositions, was investigated in a simulation chamber (made of Teflon) for the influence of pH and of the tropospheric trace gases NO2, O3 and SO2 on the photochemical activation of chloride. Atomic chlorine (Cl) was detected in the gas phase and quantified by the radical clock technique. Dilute brines with known FeIII content were nebulised until the relative humidity reached 70–90%. The resulting droplets (most abundant particle diameter: 0.35–0.46µm, initial surface area: up to 3×10–2cm2cm–3) were irradiated with simulated sunlight, and the consumption of a test mixture of hydrocarbons was evaluated for Cl, Br and OH. The initial rate of atomic Cl production per aerosol surface increased with FeIII and was ~1.9×1018 atoms cm–2s–1atCl–/FeIII=13. The presence of NO2 (~20 ppb) increased it to ~7×1018 atoms cm–2s–1, the presence of O3 (630 ppb) to ~9×1018 atoms cm–2s–1 and the presence of SO2 at 20 and 200 ppb inhibited the release slightly to ~1.7 and ~1.1×1018 atoms cm–2s–1. The observed production of atomic Cl is discussed with respect to pH and speciation of the photolabile aqueous FeIII complexes.

scholarly journals Atmospheric salt deposition in a tropical mountain rainforest at the eastern Andean slopes of south Ecuador – Pacific or Atlantic origin?

2016 ◽  
Vol 16 (15) ◽  
pp. 10241-10261 ◽  
Author(s):  
Sandro Makowski Giannoni ◽  
Katja Trachte ◽  
Ruetger Rollenbeck ◽  
Lukas Lehnert ◽  
Julia Fuchs ◽  
...  
Keyword(s):  
Sea Salt ◽  
Equatorial Atlantic ◽  
Concentration Data ◽  
Air Masses ◽  
Salt Deposition ◽  
The North ◽  
The Andes ◽  
Tropical Mountain ◽  
Southern Ecuador ◽  
Sea Salt Deposition

Abstract. Sea salt (NaCl) has recently been proven to be of the utmost importance for ecosystem functioning in Amazon lowland forests because of its impact on herbivory, litter decomposition and, thus, carbon cycling. Sea salt deposition should generally decline as distance from its marine source increases. For the Amazon, a negative east–west gradient of sea salt availability is assumed as a consequence of the barrier effect of the Andes Mountains for Pacific air masses. However, this generalized pattern may not hold for the tropical mountain rainforest in the Andes of southern Ecuador. To analyse sea salt availability, we investigated the deposition of sodium (Na+) and chloride (Cl−), which are good proxies of sea spray aerosol. Because of the complexity of the terrain and related cloud and rain formation processes, sea salt deposition was analysed from both, rain and occult precipitation (OP) along an altitudinal gradient over a period between 2004 and 2009. To assess the influence of easterly and westerly air masses on the deposition of sodium and chloride over southern Ecuador, sea salt aerosol concentration data from the Monitoring Atmospheric Composition and Climate (MACC) reanalysis data set and back-trajectory statistical methods were combined. Our results, based on deposition time series, show a clear difference in the temporal variation of sodium and chloride concentration and Na+ ∕ Cl− ratio in relation to height and exposure to winds. At higher elevations, sodium and chloride present a higher seasonality and the Na+ ∕ Cl− ratio is closer to that of sea salt. Medium- to long-range sea salt transport exhibited a similar seasonality, which shows the link between our measurements at high elevations and the sea salt synoptic transport. Although the influence of the easterlies was predominant regarding the atmospheric circulation, the statistical analysis of trajectories and hybrid receptor models revealed a stronger impact of the north equatorial Atlantic, Caribbean, and Pacific sea salt sources on the atmospheric sea salt concentration in southern Ecuador. The highest concentration in rain and cloud water was found between September and February when air masses originated from the north equatorial Atlantic, the Caribbean Sea and the equatorial Pacific. Together, these sources accounted for around 82.4 % of the sea salt budget over southern Ecuador.

scholarly journals Estimation of Secondary Organic Aerosol Viscosity from Explicit Modeling of Gas-Phase Oxidation of Isoprene and α-pinene

2021 ◽  
Author(s):  
Tommaso Galeazzo ◽  
Richard Valorso ◽  
Ying Li ◽  
Marie Camredon ◽  
Bernard Aumont ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Relative Humidity ◽  
Gas Phase ◽  
Fine Particulate Matter ◽  
Bulk Diffusion ◽  
Accommodation Coefficient ◽  
Gas Phase Reactions ◽  
High Molar Mass ◽  
Chemical Mechanisms ◽  
Mass Accommodation Coefficient

Abstract. Secondary organic aerosols (SOA) are major components of atmospheric fine particulate matter, affecting climate and air quality. Mounting evidence exists that SOA can adopt glassy and viscous semisolid states, impacting formation and partitioning of SOA. In this study, we conduct explicit modeling of isoprene photooxidation and α-pinene ozonolysis and subsequent SOA formation using the GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) model. Our recently-developed parameterizations to predict glass transition temperature of organic compounds are implemented into a box model with explicit gas-phase chemical mechanisms to simulate viscosity of SOA. The effects of chemical composition, relative humidity, mass loadings and mass accommodation on particle viscosity are investigated in comparison with measurements of SOA viscosity. The simulated viscosity of isoprene SOA agrees well with viscosity measurements as a function of relative humidity, while the model underestimates viscosity of α-pinene SOA by a few orders of magnitude. This difference may be due to missing processes in the model including gas-phase dimerization and particle-phase reactions leading to the formation of high molar mass compounds that would increase particle viscosity. Additional simulations imply that kinetic limitations of bulk diffusion and reduction in mass accommodation coefficient may also play a role in enhancing particle viscosity by suppressing condensation of semi-volatile compounds. The developed model is a useful tool for analysis and investigation of the interplay among gas-phase reactions, particle chemical composition and SOA phase state.

Sign in / Sign up

Export Citation Format

Share Document