Sensitivity of sulphur dioxide oxidation in sea salt to nitric acid and ammonia gas phase concentrations

1997 ◽  
Vol 102 (D19) ◽  
pp. 23241-23249 ◽  
Author(s):  
Nicola A. Clegg ◽  
Ralf Toumi
Keyword(s):  
Nitric Acid ◽  
Gas Phase ◽  
Sulphur Dioxide ◽  
Sea Salt ◽  
Ammonia Gas

scholarly journals The composition and variability of atmospheric aerosol over Southeast Asia during 2008

2012 ◽  
Vol 12 (2) ◽  
pp. 1083-1100 ◽  
Author(s):  
W. Trivitayanurak ◽  
P. I. Palmer ◽  
M. P. Barkley ◽  
N. H. Robinson ◽  
H. Coe ◽  
...  
Keyword(s):  
Southeast Asia ◽  
Gas Phase ◽  
Biomass Burning ◽  
Organic Aerosol ◽  
Sea Salt ◽  
Dust Aerosol ◽  
Small Scale ◽  
Formation Mechanisms ◽  
Sulphate Aerosol ◽  
Phase Oxidation

Abstract. We use a nested version of the GEOS-Chem global 3-D chemistry transport model to better understand the composition and variation of aerosol over Borneo and the broader Southeast Asian region in conjunction with aircraft and satellite observations. Our focus on Southeast Asia reflects the importance of this region as a source of reactive organic gases and aerosols from natural forests, biomass burning, and food and fuel crops. We particularly focus on July 2008 when the UK BAe-146 research aircraft was deployed over northern Malaysian Borneo as part of the ACES/OP3 measurement campaign. During July 2008 we find using the model that Borneo (defined as Borneo Island and the surrounding Indonesian islands) was a net exporter of primary organic aerosol (42 kT) and black carbon aerosol (11 kT). We find only 13% of volatile organic compound oxidation products partition to secondary organic aerosol (SOA), with Borneo being a net exporter of SOA (15 kT). SOA represents approximately 19% of the total organic aerosol over the region. Sulphate is mainly from aqueous-phase oxidation (68%), with smaller contributions from gas-phase oxidation (15%) and advection into the regions (14%). We find that there is a large source of sea salt, as expected, but this largely deposits within the region; we find that dust aerosol plays only a relatively small role in the aerosol burden. In contrast to coincident surface measurements over Northern Borneo that find a pristine environment with evidence for substantial biogenic SOA formation we find that the free troposphere is influenced by biomass burning aerosol transported from the northwest of the Island and further afield. We find several transport events during July 2008 over Borneo associated with elevated aerosol concentrations, none of which coincide with the aircraft flights. We use MODIS aerosol optical depths (AOD) data and the model to put the July campaign into a longer temporal perspective. We find that Borneo is where the model has the least skill at reproducing the data, where the model has a negative bias of 76% and only captures 14% of the observed variability. This model performance reflects the small-scale island-marine environment and the mix of aerosol species, with the model showing more skill at reproducing observed AOD over larger continental regions such as China where AOD is dominated by one aerosol type. The model shows that AOD over Borneo is approximately evenly split between organic and sulphate aerosol with sea salt representing 10–20% during May–September; we find a similar breakdown over continental Southeast Asia but with less sea salt aerosol and more dust aerosol. In contrast, East China AOD is determined mainly by sulphate aerosol and a seasonal source of dust aerosol, as expected. Realistic sensitivity runs, designed to test our underlying assumptions about emissions and chemistry over Borneo, show that model AOD is most sensitive to isoprene emissions and organic gas-phase partitioning but all fail to improve significantly upon the control model calculation. This emphasises the multi-faceted dimension of the problem and the need for concurrent and coordinated development of BVOC emissions, and BVOC chemistry and organic aerosol formation mechanisms.

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.

Protonated nitric acid. Structure and relative stability of isomeric H2NO3+ ions in the gas phase

1990 ◽  
Vol 112 (3) ◽  
pp. 1014-1018 ◽  
Author(s):  
Fulvio Cacace ◽  
Marina Attina ◽  
Giulia De Petris ◽  
Maurizio Speranza
Keyword(s):  
Nitric Acid ◽  
Gas Phase ◽  
Relative Stability ◽  
Acid Structure

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

2007 ◽  
Vol 7 (21) ◽  
pp. 5555-5567 ◽  
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.

The reaction of chlorine atoms, Cl(3 2pJ), with nitric acid in the gas phase

1982 ◽  
Vol 18 (1) ◽  
pp. 39-46 ◽  
Author(s):  
R.H. Clark ◽  
D. Husain ◽  
J.Y. Jezequel
Keyword(s):  
Nitric Acid ◽  
Gas Phase ◽  
Chlorine Atoms

Modeling the Effect of Chlorine Emissions on Ozone Levels over the Eastern United States

2007 ◽  
Vol 46 (7) ◽  
pp. 1009-1019 ◽  
Author(s):  
Golam Sarwar ◽  
Prakash V. Bhave
Keyword(s):  
New York ◽  
New Jersey ◽  
Gas Phase ◽  
Sea Salt ◽  
Daily Maximum ◽  
Eastern United States ◽  
Sea Salt Aerosols ◽  
Ozone Concentrations ◽  
Houston Area ◽  
Effect Of Chlorine

Abstract This paper presents model estimates of the effect of chlorine emissions on atmospheric ozone concentrations in the eastern United States. The model included anthropogenic molecular chlorine emissions, anthropogenic hypochlorous acid emissions from cooling towers and swimming pools, and chlorine released from sea-salt aerosols. The release of chlorine emissions from sea-salt aerosols was modeled using heterogeneous reactions involving chloride ions in aerosols and three gas-phase species. The gas-phase chlorine chemistry was combined with the Carbon Bond Mechanism and incorporated into the Community Multiscale Air Quality modeling system. Air quality model simulations were performed for July 2001 and the results obtained with and without chlorine emissions were analyzed. When chlorine emissions were included in the model, ozone concentrations increased in the Houston, Texas, and New York–New Jersey areas. The daily maximum 1-h ozone concentrations increased by up to 12 parts per billion by volume (ppbv) in the Houston area and 6 ppbv in the New York–New Jersey area. The daily maximum 8-h ozone concentrations increased by up to 8 ppbv in the Houston area and 4 ppbv in the New York–New Jersey area. The monthly average daily maximum 1-h ozone concentration increased by up to 3 ppbv in the Houston area, but the increases in the monthly average daily maximum 1-h ozone concentration in the New York–New Jersey area were small. Chlorine emissions and chemistry enhanced the volatile organic compound oxidation rates and, thereby, increased the ozone production rate.

scholarly journals Nitric Acid–Sea Salt Reactions: Implications for Nitrogen Deposition to Water Surfaces

2000 ◽  
Vol 39 (5) ◽  
pp. 725-731 ◽  
Author(s):  
S. C. Pryor ◽  
L. L. Sørensen
Keyword(s):  
Nitric Acid ◽  
Dry Deposition ◽  
Deposition Velocity ◽  
Sea Salt ◽  
Neutral Stability ◽  
Particle Phase ◽  
Spatial And Temporal Patterns ◽  
Wind Speeds ◽  
Horizontal Transport ◽  
Marine Surface Layer

Abstract Many previous studies have indicated the importance of nitric acid (HNO3) reactions on sea salt particles for flux divergence of HNO3 in the marine surface layer. The potential importance of this reaction in determining the spatial and temporal patterns of nitrogen dry deposition to marine ecosystems is investigated using models of sea spray generation and particle- and gas-phase dry deposition. Under horizontally homogeneous conditions with near-neutral stability and for wind speeds between 3.5 and 10 m s−1, transfer of HNO3 to the particle phase to form sodium nitrate may decrease the deposition velocity of nitrogen by over 50%, leading to greater horizontal transport prior to deposition to the sea surface. Conversely, for wind speeds above 10 m s−1, transfer of nitrogen to the particle phase would increase the deposition rate and hence decrease horizontal transport prior to surface removal.

Unexpected Reactivity of Amidogen Radical in the Gas Phase Degradation of Nitric Acid

2014 ◽  
Vol 136 (19) ◽  
pp. 6834-6837 ◽  
Author(s):  
Josep M. Anglada ◽  
Santiago Olivella ◽  
Albert Solé
Keyword(s):  
Nitric Acid ◽  
Gas Phase
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