scholarly journals Production of HONO from heterogeneous uptake of NO<sub>2</sub> on illuminated TiO<sub>2</sub> aerosols measured by Photo-Fragmentation Laser Induced Fluorescence

2020 ◽  
Author(s):  
Joanna E. Dyson ◽  
Graham A. Boustead ◽  
Lauren T. Fleming ◽  
Mark Blitz ◽  
Daniel Stone ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Relative Humidity ◽  
Marine Boundary Layer ◽  
Laser Induced Fluorescence ◽  
Separate Experiment ◽  
Photon Flux ◽  
Uptake Coefficient ◽  
Mixing Ratios ◽  
Reactive Uptake Coefficient ◽  
Significant Production

Abstract. The rate of production of HONO from illuminated TiO2 aerosols in the presence of NO2 was measured using an aerosol flow tube coupled to a photo-fragmentation laser induced fluorescence detection apparatus. The reactive uptake coefficient of NO2 to form HONO, γNO2→HONO, was determined for NO2 mixing ratios in the range 34–400 ppb, with γNO2→HONO spanning the range (9.97 ± 3.52) × 10−6 to (1.26 ± 0.17) × 10−4 at a relative humidity of 15 ± 1 % and for a lamp photon flux of (1.63 ± 0.09) × 1016 photons cm−2 s −1 (integrated between 290 and 400 nm), which is similar to values of ambient actinic flux at midday. γNO2→HONO increased as a function of NO2 mixing ratio at low NO2 before peaking at (1.26 ± 0.17) × 10−4 at 51 ppb NO2 and then sharply decreasing at higher NO2 mixing ratios, rather than levelling off which would be indicative of surface saturation. The dependence of HONO production on relative humidity was also investigated, with a peak in production of HONO from TiO2 aerosol surfaces found at ~25 % RH. Possible mechanisms consistent with the observed trends in both the HONO production and reactive uptake coefficient were investigated using a zero-dimensional kinetic box model. The modelling studies supported a mechanism for HONO production on the aerosol surface involving two molecules of NO2, as well as a surface HONO loss mechanism which is dependent upon NO2. In a separate experiment, significant production of HONO was observed from illumination of mixed nitrate/TiO2 aerosols in the absence of NO2. However, no statistically significant production of HONO was seen from the illumination of pure nitrate aerosols. The rate of production of HONO observed from mixed nitrate/TiO2 aerosols was scaled to ambient conditions found at the Cape Verde Atmospheric Observatory (CVAO) in the remote tropical marine boundary layer. The rate of HONO production from aerosol particulate nitrate photolysis containing a photocatalyst was found to be similar to the missing HONO production rate necessary to reproduce observed concentrations of HONO at CVAO. These results provide evidence that particulate nitrate photolysis may have a significant impact on the production of HONO and hence NOx in the marine boundary layer where mixed aerosols containing nitrate and a photocatalytic species such as TiO2, as found in dust, are present.

scholarly journals Production of HONO from NO<sub>2</sub> uptake on illuminated TiO<sub>2</sub> aerosol particles and following the illumination of mixed TiO<sub>2</sub>∕ammonium nitrate particles

2021 ◽  
Vol 21 (7) ◽  
pp. 5755-5775
Author(s):  
Joanna E. Dyson ◽  
Graham A. Boustead ◽  
Lauren T. Fleming ◽  
Mark Blitz ◽  
Daniel Stone ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Relative Humidity ◽  
Marine Boundary Layer ◽  
Separate Experiment ◽  
Photon Flux ◽  
No Production ◽  
Uptake Coefficient ◽  
Ambient Conditions ◽  
Mixing Ratios ◽  
Reactive Uptake Coefficient

Abstract. The rate of production of HONO from illuminated TiO2 aerosols in the presence of NO2 was measured using an aerosol flow tube system coupled to a photo-fragmentation laser-induced fluorescence detection apparatus. The reactive uptake coefficient of NO2 to form HONO, γNO2→HONO, was determined for NO2 mixing ratios in the range 34–400 ppb, with γNO2→HONO spanning the range (9.97 ± 3.52) × 10−6 to (1.26 ± 0.17) × 10−4 at a relative humidity of 15 ± 1 % and for a lamp photon flux of (1.63 ± 0.09) ×1016 photons cm−2 s−1 (integrated between 290 and 400 nm), which is similar to midday ambient actinic flux values. γNO2→HONO increased as a function of NO2 mixing ratio at low NO2 before peaking at (1.26 ± 0.17) ×10-4 at ∼ 51 ppb NO2 and then sharply decreasing at higher NO2 mixing ratios rather than levelling off, which would be indicative of surface saturation. The dependence of HONO production on relative humidity was also investigated, with a peak in production of HONO from TiO2 aerosol surfaces found at ∼ 25 % RH. Possible mechanisms consistent with the observed trends in both the HONO production and reactive uptake coefficient were investigated using a zero-dimensional kinetic box model. The modelling studies supported a mechanism for HONO production on the aerosol surface involving two molecules of NO2, as well as a surface HONO loss mechanism which is dependent upon NO2. In a separate experiment, significant production of HONO was observed from illumination of mixed nitrate/TiO2 aerosols in the absence of NO2. However, no production of HONO was seen from the illumination of nitrate aerosols alone. The rate of production of HONO observed from mixed nitrate/TiO2 aerosols was scaled to ambient conditions found at the Cape Verde Atmospheric Observatory (CVAO) in the remote tropical marine boundary layer. The rate of HONO production from aerosol particulate nitrate photolysis containing a photocatalyst was found to be similar to the missing HONO production rate necessary to reproduce observed concentrations of HONO at CVAO. These results provide evidence that particulate nitrate photolysis may have a significant impact on the production of HONO and hence NOx in the marine boundary layer where mixed aerosols containing nitrate and a photocatalytic species such as TiO2, as found in dust, are present.

scholarly journals The influence of typhoons on atmospheric composition deduced from IAGOS measurements over Taipei

2020 ◽  
Vol 20 (6) ◽  
pp. 3945-3963
Author(s):  
Frank Roux ◽  
Hannah Clark ◽  
Kuo-Ying Wang ◽  
Susanne Rohs ◽  
Bastien Sauvage ◽  
...  
Keyword(s):  
Carbon Monoxide ◽  
Relative Humidity ◽  
Tropical Cyclones ◽  
Marine Boundary Layer ◽  
Chemical Species ◽  
Atmospheric Composition ◽  
Commercial Aircraft ◽  
Regular Feature ◽  
Mixing Ratios ◽  
The Vertical Distribution

Abstract. The research infrastructure IAGOS (In-Service Aircraft for a Global Observing System) equips commercial aircraft with instruments to monitor the composition of the atmosphere during flights around the world. In this article, we use data from two China Airlines aircraft based in Taipei (Taiwan) which provided daily measurements of ozone, carbon monoxide and water vapour throughout the summer of 2016. We present time series, from the surface to the upper troposphere, of ozone, carbon monoxide and relative humidity near Taipei, focusing on periods influenced by the passage of typhoons. We examine landing and take-off profiles in the vicinity of tropical cyclones using ERA-5 reanalyses to elucidate the origin of the anomalies in the vertical distribution of these chemical species. Results indicate a high ozone content in the upper- to middle-troposphere track of the storms. The high ozone mixing ratios are generally correlated with potential vorticity and anti-correlated with relative humidity, suggesting stratospheric origin. These results suggest that tropical cyclones participate in transporting air from the stratosphere to troposphere and that such transport could be a regular feature of typhoons. After the typhoons passed Taiwan, the tropospheric column was filled with substantially lower ozone mixing ratios due to the rapid uplift of marine boundary layer air. At the same time, the relative humidity increased, and carbon monoxide mixing ratios fell. Locally, therefore, the passage of typhoons has a positive effect on air quality at the surface, cleansing the atmosphere and reducing the mixing ratios of pollutants such as CO and O3.

scholarly journals Atmospheric bromoform at Mace Head, Ireland: seasonality and evidence for a peatland source

2005 ◽  
Vol 5 (11) ◽  
pp. 2927-2934 ◽  
Author(s):  
L. J. Carpenter ◽  
D. J. Wevill ◽  
S. O'Doherty ◽  
G. Spain ◽  
P. G. Simmonds
Keyword(s):  
Boundary Layer ◽  
Wind Direction ◽  
Marine Boundary Layer ◽  
Land Breeze ◽  
Peat Bogs ◽  
Mixing Ratios ◽  
The North ◽  
Prevailing Wind Direction ◽  
Atmospheric Observations ◽  
Summer Minimum

Abstract. In situ atmospheric observations of bromoform (CHBr3) made over a 2.5 year period at Mace Head, Ireland from May 2001- Dec 2003, including during the NAMBLEX (North Atlantic Marine Boundary Layer Experiment) campaign, show broad maxima from spring until autumn and winter minima, with mixing ratios of 5.3+1.0 pptv (mid March - mid October) and 1.8+0.8 pptv (December-February). This indicates that, unlike CHCl3, which has a summer minimum and winter maximum at Mace Head, local biological sources of CHBr3 have a greater influence on the atmospheric data than photochemical decay during long-range transport. The emission sources are predominantly macroalgal, but we find evidence for a small terrestrial flux from peatland ecosystems, which so far has not been accounted for in the CHBr3 budget. Sharp increases in CHCl3 and CHBr3 concentrations and decreases in O3 concentrations occurred at night when the wind direction switched from an ocean- to a land-based sector (land breeze) and the wind speed dropped to below 5 ms-1. These observations infer a shallow atmospheric boundary layer with increased O3 deposition and concentration of local emissions of both CHCl3 and CHBr3. The ratio of ΔCHCl3/ΔCHBr3 varied strongly according to the prevailing wind direction; from 0.60+0.15 in south-easterly (100-170° and northerly (340-20°) air to 2.5+0.4 in north-easterly (40-70°) air. Of these land-sectors, the south-easterly air masses are likely to be strongly influenced by macroalgal beds along the coast and the emission ratios probably reflect those from seaweeds in addition to land sources. The north-easterly airmasses however had an immediate fetch inland, which locally is comprised of coastal peatland ecosystems (peat bogs and coastal conifer plantations), previously identified as being strong sources of atmospheric CHCl3 under these conditions. Although we cannot entirely rule out other local land or coastal sources, our observations also suggest peatland ecosystem emissions of CHBr3. We use correlations between CHCl3 and CHBr3 during the north-easterly land breeze events in conjunction with previous estimates of local wetland CHCl3 release to tentatively deduce a global wetland CHBr3 source of 20.4(0.4-948) Gg yr-1, which is approximately 7% of the total global source.

scholarly journals Evidence for renoxification in the tropical marine boundary layer

2017 ◽  
Vol 17 (6) ◽  
pp. 4081-4092 ◽  
Author(s):  
Chris Reed ◽  
Mathew J. Evans ◽  
Leigh R. Crilley ◽  
William J. Bloss ◽  
Tomás Sherwen ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Organic Nitrogen ◽  
Marine Boundary Layer ◽  
Model Simulation ◽  
Cape Verde ◽  
Box Model ◽  
Nitrogen Species ◽  
Dominant Source ◽  
Mixing Ratios ◽  
Solar Noon

Abstract. We present 2 years of NOx observations from the Cape Verde Atmospheric Observatory located in the tropical Atlantic boundary layer. We find that NOx mixing ratios peak around solar noon (at 20–30 pptV depending on season), which is counter to box model simulations that show a midday minimum due to OH conversion of NO2 to HNO3. Production of NOx via decomposition of organic nitrogen species and the photolysis of HNO3 appear insufficient to provide the observed noontime maximum. A rapid photolysis of nitrate aerosol to produce HONO and NO2, however, is able to simulate the observed diurnal cycle. This would make it the dominant source of NOx at this remote marine boundary layer site, overturning the previous paradigm according to which the transport of organic nitrogen species, such as PAN, is the dominant source. We show that observed mixing ratios (November–December 2015) of HONO at Cape Verde (∼ 3.5 pptV peak at solar noon) are consistent with this route for NOx production. Reactions between the nitrate radical and halogen hydroxides which have been postulated in the literature appear to improve the box model simulation of NOx. This rapid conversion of aerosol phase nitrate to NOx changes our perspective of the NOx cycling chemistry in the tropical marine boundary layer, suggesting a more chemically complex environment than previously thought.

scholarly journals The effect of fatty acid surfactants on the uptake of nitric acid to deliquesced NaCl aerosol

2008 ◽  
Vol 8 (1) ◽  
pp. 687-725 ◽  
Author(s):  
K. Stemmler ◽  
A. Vlasenko ◽  
C. Guimbaud ◽  
M. Ammann
Keyword(s):  
Boundary Layer ◽  
Fatty Acids ◽  
Oleic Acid ◽  
Fatty Acid ◽  
Nitric Acid ◽  
Organic Compounds ◽  
Marine Boundary Layer ◽  
Water Soluble ◽  
Chemical Inhomogeneity ◽  
Uptake Coefficient

Abstract. Surface active organic compounds have been observed in marine boundary layer aerosol. Here, we investigate the effect such surfactants have on the uptake of nitric acid (HNO3), an important removal reaction of nitrogen oxides in the marine boundary layer. The uptake of gaseous HNO3 on deliquesced NaCl aerosol was measured in a flow reactor using HNO3 labelled with the short-lived radioactive isotope 13N. The uptake coefficient γ on pure deliquesced NaCl aerosol was γ=0.5±0.2 at 60% relative humidity and 30 ppb HNO3(g). The uptake coefficient was reduced by a factor of 5–50 when the aerosol was coated with saturated linear fatty acids with carbon chain lengths of 18 and 15 atoms in monolayer quantities. In contrast, neither shorter saturated linear fatty acids with 12 and 9 carbon atoms, nor coatings with the unsaturated oleic acid (C18, cis-double bond) had a detectable effect on the rate of HNO3 uptake. It is concluded that it is the structure of the monolayers formed, which determines their resistance towards HNO3 uptake. Fatty acids (C18 and C15), which form a highly ordered film in the so-called liquid condensed state, represent a significant barrier towards HNO3 uptake, while monolayers of shorter-chain fatty acids (C9, C12) and of the unsaturated oleic acid form a less ordered film in the liquid expanded state and do not hinder the uptake. Similarly, high contents of humic acids in the aerosol, a structurally inhomogeneous, quite water soluble mixture of oxidised high molecular weight organic compounds did not affect HNO3 uptake. As surfactant films on naturally occurring aerosol are expected to be less structured due to their chemical inhomogeneity, it is likely that their inhibitory effect on HNO3 uptake is smaller than that observed here for the C15 and C18 fatty acid monolayers.

scholarly journals Uptake of HO<sub>2</sub> radicals on Arizona test dust surface

2013 ◽  
Vol 13 (4) ◽  
pp. 8873-8900 ◽  
Author(s):  
Y. Bedjanian ◽  
M. N. Romanias ◽  
A. El Zein
Keyword(s):  
Relative Humidity ◽  
Flow Reactor ◽  
Uptake Coefficient ◽  
Gaseous Species ◽  
Local Conditions ◽  
Uv Irradiance ◽  
Reactive Uptake Coefficient ◽  
Kinetics Of ◽  
Geometric Surface ◽  
Dust Surface

Abstract. The interaction of HO2 radicals with solid films of Arizona Test Dust (ATD) was studied using a low pressure flow reactor (1–9 Torr) combined with a modulated molecular beam mass spectrometer for monitoring of the gaseous species involved. The reactive uptake coefficient of HO2 was measured from the kinetics of HO2 consumption on Pyrex rods coated with ATD as a function of HO2 concentration ((0.35–3.30) × 1012 molecule cm−3), relative humidity (RH = 0.02–94%), temperature (T = 275–320 K) and UV irradiance intensity (JNO2 = 0–0.012 s−1). The initial uptake coefficient was found to be independent of concentration of HO2, temperature and irradiation conditions, and to decrease with increasing relative humidity: γ0 = 1.2/(18.7 + RH1.1) (calculated using geometric surface area, with 30% estimated conservative uncertainty). An upper limit of 5% was found for the H2O2 forming pathway of the HO2 reaction with ATD surface. The results of the measurements indicate that HO2 loss on dust aerosol may be a non negligible sink for HOx species in the troposphere with the effect depending on specific local conditions.

scholarly journals Iodine oxide in the global marine boundary layer

2014 ◽  
Vol 14 (15) ◽  
pp. 22217-22243 ◽  
Author(s):  
C. Prados-Roman ◽  
C. A. Cuevas ◽  
T. Hay ◽  
R. P. Fernandez ◽  
A. S. Mahajan ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Atmospheric Chemistry ◽  
Ozone Depletion ◽  
Marine Boundary Layer ◽  
Geographical Pattern ◽  
Mixing Ratios ◽  
Field Campaigns ◽  
Ozone Depletion Potential ◽  
Ubiquitous Presence ◽  
Inorganic Precursors

Abstract. Emitted mainly by the oceans, iodine is a halogen compound important for atmospheric chemistry due to its high ozone depletion potential and effect on the oxidizing capacity of the atmosphere. Here we present a comprehensive dataset of iodine oxide (IO) measurements in the open marine boundary layer (MBL) made during the Malaspina 2010 circumnavigation. Results show IO mixing ratios ranging from 0.4 to 1 pmol mol−1 and, complemented with additional field campaigns, this dataset confirms through observations the ubiquitous presence of reactive iodine chemistry in the global marine environment. We use a global model with organic (CH3I, CH2ICl, CH2I2 and CH2IBr) and inorganic (HOI and I2) iodine ocean emissions to investigate the contribution of the different iodine source gases to the budget of IO in the global MBL. In agreement with previous estimates, our results indicate that, globally averaged, the abiotic precursors contribute about 75% to the iodine oxide budget. However, this work reveals a strong geographical pattern in the contribution of organic vs. inorganic precursors to reactive iodine in the global MBL.

scholarly journals In situ measurements of molecular iodine in the marine boundary layer: the link to macroalgae and the implications for O<sub>3</sub>, IO, OIO and NO<sub>x</sub>

2010 ◽  
Vol 10 (1) ◽  
pp. 361-390
Author(s):  
R.-J. Huang ◽  
K. Seitz ◽  
J. Buxmann ◽  
D. Poehler ◽  
K. E. Hornsby ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Marine Boundary Layer ◽  
Single Point ◽  
Molecular Iodine ◽  
In Situ Measurements ◽  
Gas Chromatography Mass Spectrometry ◽  
Optical Absorption Spectroscopy ◽  
Mixing Ratios ◽  
Concentration Levels

Abstract. "Single-point" in situ measurements of molecular iodine (I2) were carried out in the coastal marine boundary layer (MBL) using diffusion denuders in combination with a gas chromatography-mass spectrometry (GC-MS) method. Comparison measurements were taken at Mace Head and Mweenish Bay, on the West Coast of Ireland. The observed mixing ratios of I2 at Mweenish Bay are much higher than that at Mace Head, indicating the emissions of I2 are correlated with the local algal biomass density and algae species. The concentration levels of I2 were found to correlate inversely with tidal height and correlate positively with the concentration levels of O3 in the surrounding air. However, the released I2 can also lead to O3 destruction via the reaction of O3 with iodine atoms that are formed by the photolysis of I2 during the day and via the reaction of I2 with NOx at night. IO and OIO were measured by long-path differential optical absorption spectroscopy (LP-DOAS). The results show that the concentrations of both daytime and nighttime IO are correlated with the mixing ratios of I2. OIO was observed not only during the day but also, for the first time at both Mace Head and Mweenish Bay, at night. In addition, I2 was measured simultaneously by the LP-DOAS technique and compared with the "single-point" in situ measurement. The results suggest that the local algae sources dominate the inorganic iodine chemistry at Mace Head and Mweenish Bay.

scholarly journals NO<sub>3</sub> radical measurements in a polluted marine environment: links to ozone formation

2010 ◽  
Vol 10 (9) ◽  
pp. 4187-4206 ◽  
Author(s):  
R. McLaren ◽  
P. Wojtal ◽  
D. Majonis ◽  
J. McCourt ◽  
J. D. Halla ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Steady State ◽  
Marine Boundary Layer ◽  
Sea Breeze ◽  
Loss Coefficient ◽  
Heterogeneous Reactions ◽  
Rate Coefficients ◽  
Direct Reaction ◽  
First Order ◽  
Mixing Ratios

Abstract. Nighttime chemistry in polluted regions is dominated by the nitrate radical (NO3) including its direct reaction with natural and anthropogenic hydrocarbons, its reaction with NO2 to form N2O5, and subsequent reactions of N2O5 to form HNO3 and chlorine containing photolabile species. We report nighttime measurements of NO3, NO2, and O3, in the polluted marine boundary layer southwest of Vancouver, BC during a three week study in the summer of 2005. The concentration of N2O5 was calculated using the well known equilibrium, NO3+NO2↔N2O5. Median overnight mixing ratios of NO3, N2O5 and NO2 were 10.3 ppt, 122 ppt and 8.3 ppb with median N2O5/NO3 molar ratios of 13.1 and median nocturnal partitioning of 4.9%. Due to the high levels of NO2 that can inhibit approach to steady-state, we use a method for calculating NO3 lifetimes that does not assume the steady-state approximation. Median and average lifetimes of NO3 in the NO3-N2O5 nighttime reservoir were 1.1–2.3 min. We have determined nocturnal profiles of the pseudo first order loss coefficient of NO3 and the first order loss coefficients of N2O5 by regression of the NO3 inverse lifetimes with the [N2O5]/[NO3] ratio. Direct losses of NO3 are highest early in the night, tapering off as the night proceeds. The magnitude of the first order loss coefficient of N2O5 is consistent with, but not verification of, recommended homogeneous rate coefficients for reaction of N2O5 with water vapor early in the night, but increases significantly in the latter part of the night when relative humidity increases beyond 75%, consistent with heterogeneous reactions of N2O5 with aerosols with a rate constant khet=(1.2±0.4)×10−3 s−1−(1.6±0.4)×10−3 s−1. Analysis indicates that a correlation exists between overnight integrated N2O5 concentrations in the marine boundary layer, a surrogate for the accumulation of chlorine containing photolabile species, and maximum 1-h average O3 at stations in the Lower Fraser Valley the next day when there is clear evidence of a sea breeze transporting marine air into the valley. The range of maximum 1-h average O3 increase attributable to the correlation is ΔO3=+1.1 to +8.3 ppb throughout the study for the average of 20 stations, although higher increases are seen for stations far downwind of the coastal urban area. The correlation is still statistically significant on the second day after a nighttime accumulation, but with a different spatial pattern favouring increased O3 at the coastal urban stations, consistent with transport of polluted air back to the coast.

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