Kinetics and mechanism of the heterogeneous reaction of N2O5 with mineral dust particles

2012 ◽  
Vol 14 (24) ◽  
pp. 8551 ◽  
Author(s):  
M. J. Tang ◽  
J. Thieser ◽  
G. Schuster ◽  
J. N. Crowley
Keyword(s):  
Mineral Dust ◽  
Heterogeneous Reaction ◽  
Kinetics And Mechanism ◽  
Dust Particles

Kinetics of the heterogeneous reaction of nitric acid with mineral dust particles: an aerosol flowtube study

2009 ◽  
Vol 11 (36) ◽  
pp. 7921 ◽  
Author(s):  
A. Vlasenko ◽  
T. Huthwelker ◽  
H. W. Gäggeler ◽  
M. Ammann
Keyword(s):  
Nitric Acid ◽  
Mineral Dust ◽  
Heterogeneous Reaction ◽  
Dust Particles ◽  
Kinetics Of

scholarly journals Direct observations of the atmospheric processing of Asian mineral dust

2007 ◽  
Vol 7 (5) ◽  
pp. 1213-1236 ◽  
Author(s):  
R. C. Sullivan ◽  
S. A. Guazzotti ◽  
D. A. Sodeman ◽  
K. A. Prather
Keyword(s):  
Mineral Dust ◽  
Heterogeneous Reaction ◽  
Field Studies ◽  
Dust Particles ◽  
Reaction Products ◽  
Transport Pathway ◽  
Air Masses ◽  
Atmospheric Processing ◽  
Acid Reaction ◽  
The Individual

Abstract. The accumulation of secondary acids and ammonium on individual mineral dust particles during ACE-Asia has been measured with an online single-particle mass spectrometer, the ATOFMS. Changes in the amounts of sulphate, nitrate, and chloride mixed with dust particles correlate with air masses from different source regions. The uptake of secondary acids depended on the individual dust particle mineralogy; high amounts of nitrate accumulated on calcium-rich dust while high amounts of sulphate accumulated on aluminosilicate-rich dust. Oxidation of S(IV) to S(VI) by iron in the aluminosilicate dust is a possible explanation for this enrichment of sulphate, which has important consequences for the fertilization of remote oceans by soluble iron. This study shows the segregation of sulphate from nitrate and chloride in individual aged dust particles for the first time. A transport and aging timeline provides an explanation for the observed segregation. Our data suggests that sulphate became mixed with the dust first. This implies that the transport pathway is more important than the reaction kinetics in determining which species accumulate on mineral dust. Early in the study, dust particles in volcanically influenced air masses were mixed predominately with sulphate. Dust mixed with chloride then dominated over sulphate and nitrate when a major dust front reached the R. V. Ronald Brown. We hypothesize that the rapid increase in chloride on dust was due to mixing with HCl(g) released from acidified sea salt particles induced by heterogeneous reaction with volcanic SO2(g), prior to the arrival of the dust front. The amount of ammonium mixed with dust correlated strongly with the total amount of secondary acid reaction products in the dust. Submicron dust and ammonium sulphate were internally mixed, contrary to frequent reports that they exist as external mixtures. The size distribution of the mixing state of dust with these secondary species validates previous mechanisms of the atmospheric processing of dust and generally agrees with simulated aerosol chemistry from the STEM-2K3 model. This series of novel results has important implications for improving the treatment of dust in global chemistry models and highlights a number of key processes that merit further investigation through laboratory and field studies.

scholarly journals Kinetics and mechanism of the uptake of N<sub>2</sub>O<sub>5</sub> on mineral dust at 298 K

2005 ◽  
Vol 5 (4) ◽  
pp. 5645-5667
Author(s):  
S. Seisel ◽  
C. Börensen ◽  
R. Vogt ◽  
R. Zellner
Keyword(s):  
Steady State ◽  
Mineral Dust ◽  
Heterogeneous Reaction ◽  
Kinetics And Mechanism ◽  
Saharan Dust ◽  
Uptake Coefficient ◽  
Uptake Rates ◽  
Hydrolysis Of ◽  
Dust Surface ◽  
Initial Uptake

Abstract. The heterogeneous reaction of N2O5 with mineral (Saharan) dust has been studied at T=298 K using a combination of Knudsen and DRIFTS cell for kinetic and product investigations, respectively. The initial uptake coefficient has been determined to be γ=(8.0±0.3)·10−2. This uptake slowly saturates into a steady state uptake of γ=(1.3±0.3)10−2 suggesting that reaction of N2O5 with the mineral dust surface and hydrolysis of N2O5 on the surface take place simultaneously. Moreover, the product investigations suggest that N2O5 is irreversibly taken up forming nitrate on the surface. The uptake rates of N2O5 on Saharan dust are large enough to influence the photo-oxidant budget of the atmosphere.

scholarly journals Aerosol optical depth retrievals at the Izaña Atmospheric Observatory from 1941 to 2013 by using artificial neural networks

2016 ◽  
Vol 9 (1) ◽  
pp. 53-62 ◽  
Author(s):  
R. D. García ◽  
O. E. García ◽  
E. Cuevas ◽  
V. E. Cachorro ◽  
A. Barreto ◽  
...  
Keyword(s):  
Neural Networks ◽  
Time Series ◽  
Artificial Neural Networks ◽  
Aerosol Optical Depth ◽  
Optical Depth ◽  
Mineral Dust ◽  
Dust Particles ◽  
Filter Radiometer ◽  
Artificial Neural

Abstract. This paper presents the reconstruction of a 73-year time series of the aerosol optical depth (AOD) at 500 nm at the subtropical high-mountain Izaña Atmospheric Observatory (IZO) located in Tenerife (Canary Islands, Spain). For this purpose, we have combined AOD estimates from artificial neural networks (ANNs) from 1941 to 2001 and AOD measurements directly obtained with a Precision Filter Radiometer (PFR) between 2003 and 2013. The analysis is limited to summer months (July–August–September), when the largest aerosol load is observed at IZO (Saharan mineral dust particles). The ANN AOD time series has been comprehensively validated against coincident AOD measurements performed with a solar spectrometer Mark-I (1984–2009) and AERONET (AErosol RObotic NETwork) CIMEL photometers (2004–2009) at IZO, obtaining a rather good agreement on a daily basis: Pearson coefficient, R, of 0.97 between AERONET and ANN AOD, and 0.93 between Mark-I and ANN AOD estimates. In addition, we have analysed the long-term consistency between ANN AOD time series and long-term meteorological records identifying Saharan mineral dust events at IZO (synoptical observations and local wind records). Both analyses provide consistent results, with correlations  >  85 %. Therefore, we can conclude that the reconstructed AOD time series captures well the AOD variations and dust-laden Saharan air mass outbreaks on short-term and long-term timescales and, thus, it is suitable to be used in climate analysis.

scholarly journals The Impact of Ambient Atmospheric Mineral-Dust Particles on the Calcification of Lungs

Minerals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 125
Author(s):  
Mariola Jabłońska ◽  
Janusz Janeczek ◽  
Beata Smieja-Król
Keyword(s):  
Mineral Dust ◽  
Smoking Habit ◽  
Lower Lobe ◽  
Ambient Air ◽  
Dust Particles ◽  
Masking Effect ◽  
Amorphous Calcium Carbonate ◽  
Calcium Salts ◽  
The Impact ◽  
First Time

For the first time, it is shown that inhaled ambient air-dust particles settled in the human lower respiratory tract induce lung calcification. Chemical and mineral compositions of pulmonary calcium precipitates in the lung right lower-lobe (RLL) tissues of 12 individuals who lived in the Upper Silesia conurbation in Poland and who had died from causes not related to a lung disorder were determined by transmission and scanning electron microscopy. Whereas calcium salts in lungs are usually reported as phosphates, calcium salts precipitated in the studied RLL tissue were almost exclusively carbonates, specifically Mg-calcite and calcite. These constituted 37% of the 1652 mineral particles examined. Mg-calcite predominated in the submicrometer size range, with a MgCO3 content up to 50 mol %. Magnesium plays a significant role in lung mineralization, a fact so far overlooked. The calcium phosphate (hydroxyapatite) content in the studied RLL tissue was negligible. The predominance of carbonates is explained by the increased CO2 fugacity in the RLL. Carbonates enveloped inhaled mineral-dust particles, including uranium-bearing oxides, quartz, aluminosilicates, and metal sulfides. Three possible pathways for the carbonates precipitation on the dust particles are postulated: (1) precipitation of amorphous calcium carbonate (ACC), followed by its transformation to calcite; (2) precipitation of Mg-ACC, followed by its transformation to Mg-calcite; (3) precipitation of Mg-free ACC, causing a localized relative enrichment in Mg ions and subsequent heterogeneous nucleation and crystal growth of Mg-calcite. The actual number of inhaled dust particles may be significantly greater than was observed because of the masking effect of the carbonate coatings. There is no simple correlation between smoking habit and lung calcification.

scholarly journals On realistic size equivalence and shape of spheroidal Saharan mineral dust particles applied in solar and thermal radiative transfer calculations

2011 ◽  
Vol 11 (9) ◽  
pp. 4469-4490 ◽  
Author(s):  
S. Otto ◽  
T. Trautmann ◽  
M. Wendisch
Keyword(s):  
Land Surface ◽  
Mineral Dust ◽  
Single Scattering ◽  
Radiative Heating ◽  
Dust Particles ◽  
Axis Ratio ◽  
Solar Cooling ◽  
Prolate Shape ◽  
Spheroidal Model

Abstract. Realistic size equivalence and shape of Saharan mineral dust particles are derived from in-situ particle, lidar and sun photometer measurements during SAMUM-1 in Morocco (19 May 2006), dealing with measured size- and altitude-resolved axis ratio distributions of assumed spheroidal model particles. The data were applied in optical property, radiative effect, forcing and heating effect simulations to quantify the realistic impact of particle non-sphericity. It turned out that volume-to-surface equivalent spheroids with prolate shape are most realistic: particle non-sphericity only slightly affects single scattering albedo and asymmetry parameter but may enhance extinction coefficient by up to 10 %. At the bottom of the atmosphere (BOA) the Saharan mineral dust always leads to a loss of solar radiation, while the sign of the forcing at the top of the atmosphere (TOA) depends on surface albedo: solar cooling/warming over a mean ocean/land surface. In the thermal spectral range the dust inhibits the emission of radiation to space and warms the BOA. The most realistic case of particle non-sphericity causes changes of total (solar plus thermal) forcing by 55/5 % at the TOA over ocean/land and 15 % at the BOA over both land and ocean and enhances total radiative heating within the dust plume by up to 20 %. Large dust particles significantly contribute to all the radiative effects reported. They strongly enhance the absorbing properties and forward scattering in the solar and increase predominantly, e.g., the total TOA forcing of the dust over land.

scholarly journals Modelling Atmospheric Mineral Aerosol Chemistry to Predict Heterogeneous Photooxidation of SO<sub>2</sub>

2017 ◽  
Author(s):  
Zechen Yu ◽  
Myoseon Jang ◽  
Jiyeon Park
Keyword(s):  
Mineral Dust ◽  
Uv Light ◽  
Full Range ◽  
Saharan Dust ◽  
Dust Particles ◽  
Oh Radicals ◽  
Desorption Kinetics ◽  
So2 Oxidation ◽  
Photocatalytic Ability ◽  
Sulfate Formation

Abstract. The photocatalytic ability of airborne mineral dust particles is known to heterogeneously promote SO2 oxidation, but prediction of this phenomenon is not fully taken into account by current models. In this study, the Atmospheric Mineral Aerosol Reaction (AMAR) model was developed to capture the influence of air-suspended mineral dust particles on sulfate formation in various environments. In the model, SO2 oxidation proceeds in three phases including the gas phase, the inorganic-salted aqueous phase (non-dust phase), and the dust phase. Dust chemistry is described as the adsorption-desorption kinetics (gas-particle partitioning) of SO2 and NOx. The reaction of adsorbed SO2 on dust particles occurs via two major paths: autoxidation of SO2 in open air and photocatalytic mechanisms under UV light. The kinetic mechanism of autoxidation was first leveraged using controlled indoor chamber data in the presence of Arizona Test Dust (ATD) particles without UV light, and then extended to photochemistry. With UV light, SO2 photooxidation was promoted by surface oxidants (OH radicals) that are generated via the photocatalysis of semiconducting metal oxides (electron–hole theory) of ATD particles. This photocatalytic rate constant was derived from the integration of the combinational product of the dust absorbance spectrum and wave-dependent actinic flux for the full range of wavelengths of the light source. The predicted concentrations of sulfate and nitrate using the AMAR model agreed well with outdoor chamber data that were produced under natural sunlight. For seven consecutive hours of photooxidation of SO2 in an outdoor chamber, dust chemistry at the low NOx level was attributed to 70 % of total sulfate (60 ppb SO2, 290 μg m−3 ATD, and NOx less than 5 ppb). At high NOx (> 50 ppb of NOx with low hydrocarbons), sulfate formation was also greatly promoted by dust chemistry, but it was significantly suppressed by the competition between NO2 and SO2 that both consume the dust-surface oxidants (OH radicals or ozone). The AMAR model, derived in this study with ATD particles, will provide a platform for predicting sulfate formation in the presence of authentic dust particles (e.g. Gobi and Saharan dust).

scholarly journals Simulation of heterogeneous photooxidation of SO<sub>2</sub> and NO<sub><i>x</i></sub> in the presence of Gobi Desert dust particles under ambient sunlight

2018 ◽  
Vol 18 (19) ◽  
pp. 14609-14622 ◽  
Author(s):  
Zechen Yu ◽  
Myoseon Jang
Keyword(s):  
Urban Areas ◽  
Mineral Dust ◽  
Buffering Capacity ◽  
Dust Particles ◽  
Gobi Desert ◽  
Heterogeneous Chemistry ◽  
Desert Dust ◽  
Malachite Green Dye ◽  
Photodegradation Rate ◽  
Nitrate Salts

Abstract. To improve the simulation of the heterogeneous oxidation of SO2 and NOx in the presence of authentic mineral dust particles under ambient environmental conditions, the explicit kinetic mechanisms were constructed in the Atmospheric Mineral Aerosol Reaction (AMAR) model. The formation of sulfate and nitrate was divided into three phases: the gas phase, the non-dust aqueous phase, and the dust phase. In particular, AMAR established the mechanistic role of dust chemical characteristics (e.g., photoactivation, hygroscopicity, and buffering capacity) in heterogeneous chemistry. The photoactivation kinetic process of different dust particles was built into the model by measuring the photodegradation rate constant of an impregnated surrogate (malachite green dye) on a dust filter sample (e.g., Arizona test dust – ATD – and Gobi Desert dust – GDD) using an online reflective UV–visible spectrometer. The photoactivation parameters were integrated with the heterogeneous chemistry to predict the formation of reactive oxygen species on dust surfaces. A mathematical equation for the hygroscopicity of dust particles was also included in the AMAR model to process the multiphase partitioning of trace gases and in-particle chemistry. The buffering capacity of dust, which is related to the neutralization of dust alkaline carbonates with inorganic acids, was included in the model to dynamically predict the hygroscopicity of aged dust. The AMAR model simulated the formation of sulfate and nitrate using experimental data obtained in the presence of authentic mineral dust under ambient sunlight using a large outdoor smog chamber (University of Florida Atmospheric Photochemical Outdoor Reactor, UF-APHOR). Overall, the influence of GDD on the heterogeneous chemistry was much greater than that of ATD. Based on the model analysis, GDD enhanced the sulfate formation mainly via its high photoactivation capability. In the case of NO2 oxidation, dust-phase nitrate formation is mainly regulated by the buffering capacity of dust. The measured buffering capacity of GDD was 2 times greater than that of ATD, and consequently, the maximum nitrate concentration with GDD was nearly 2 times higher than that with ATD. The model also highlights that in urban areas with high NOx concentrations, hygroscopic nitrate salts quickly form via titration of the carbonates in the dust particles, but in the presence of SO2, the nitrate salts are gradually depleted by the formation of sulfate.

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