scholarly journals Characterization of soluble bromide measurements and a case study of BrO observations during ARCTAS

2011 ◽  
Vol 11 (9) ◽  
pp. 26999-27030 ◽  
Author(s):  
J. Liao ◽  
L. G. Huey ◽  
E. Scheuer ◽  
J. E. Dibb ◽  
R. E. Stickel ◽  
...  
Keyword(s):  
Detection Efficiency ◽  
Hydrogen Bromide ◽  
The Arctic ◽  
Ionization Mass ◽  
Atmospheric Conditions ◽  
Vertical Column ◽  
Bromine Oxide ◽  
Mist Chamber

Abstract. A focus of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was examination of bromine photochemistry in the spring time, high latitude troposphere based on aircraft and satellite measurements of BrO and related species. The NASA DC-8 aircraft utilized a chemical ionization mass spectrometry (CIMS) instrument to measure BrO and a mist chamber (MC) to measure soluble bromide. We have determined that the MC detection efficiency to molecular bromine (Br2), hypobromous acid (HOBr), bromine oxide (BrO), and hydrogen bromide (HBr) as soluble bromide (Br−) was 0.9±0.1, 1.06±0.30, 0.4±0.1, and 0.95±0.1, respectively. These efficiency factors were used to estimate soluble bromide levels along the DC-8 flight track of 17 April 2008 from photochemical calculations constrained to in situ BrO measured by CIMS. During this flight, the highest levels of soluble bromide and BrO were observed and atmospheric conditions were ideal for the space-borne observation of BrO. The good agreement (R2 = 0.76; slope = 0.98; intercept = −3.5 pptv) between modeled and observed soluble bromide, when BrO was above detection limit (>2 pptv) under unpolluted conditions (NO < 100 pptv), indicates that the CIMS BrO measurements were consistent with the MC soluble bromide. Tropospheric BrO vertical column densities (BROTROPVCD) derived from CIMS BrO observations compare well with BROTROPVCD from OMI on 17 April 2008.

scholarly journals Characterization of soluble bromide measurements and a case study of BrO observations during ARCTAS

2012 ◽  
Vol 12 (3) ◽  
pp. 1327-1338 ◽  
Author(s):  
J. Liao ◽  
L. G. Huey ◽  
E. Scheuer ◽  
J. E. Dibb ◽  
R. E. Stickel ◽  
...  
Keyword(s):  
Detection Efficiency ◽  
Hydrogen Bromide ◽  
The Arctic ◽  
Ionization Mass ◽  
Atmospheric Conditions ◽  
Vertical Column ◽  
Bromine Oxide ◽  
Mixing Ratios ◽  
Mist Chamber

Abstract. A focus of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was examination of bromine photochemistry in the spring time high latitude troposphere based on aircraft and satellite measurements of bromine oxide (BrO) and related species. The NASA DC-8 aircraft utilized a chemical ionization mass spectrometer (CIMS) to measure BrO and a mist chamber (MC) to measure soluble bromide. We have determined that the MC detection efficiency to molecular bromine (Br2), hypobromous acid (HOBr), bromine oxide (BrO), and hydrogen bromide (HBr) as soluble bromide (Br−) was 0.9±0.1, 1.06+0.30/−0.35, 0.4±0.1, and 0.95±0.1, respectively. These efficiency factors were used to estimate soluble bromide levels along the DC-8 flight track of 17 April 2008 from photochemical calculations constrained to in situ BrO measured by CIMS. During this flight, the highest levels of soluble bromide and BrO were observed and atmospheric conditions were ideal for the space-borne observation of BrO. The good agreement (R2 = 0.76; slope = 0.95; intercept = −3.4 pmol mol−1) between modeled and observed soluble bromide, when BrO was above detection limit (>2 pmol mol−1) under unpolluted conditions (NO<10 pmol mol−1), indicates that the CIMS BrO measurements were consistent with the MC soluble bromide and that a well characterized MC can be used to derive mixing ratios of some reactive bromine compounds. Tropospheric BrO vertical column densities (BrOVCD) derived from CIMS BrO observations compare well with BrOTROPVCD from OMI on 17 April 2008.

scholarly journals Bromine measurements in ozone depleted air over the Arctic Ocean

2010 ◽  
Vol 10 (2) ◽  
pp. 3827-3860 ◽  
Author(s):  
J. A. Neuman ◽  
J. B. Nowak ◽  
L. G. Huey ◽  
J. B. Burkholder ◽  
J. E. Dibb ◽  
...  
Keyword(s):  
Arctic Ocean ◽  
Ozone Depletion ◽  
Marine Boundary Layer ◽  
Temperature Inversion ◽  
The Arctic ◽  
Ionization Mass ◽  
The Arctic Ocean ◽  
Mist Chamber ◽  
Active Bromine

Abstract. In situ measurements of ozone, photochemically active bromine compounds, and other trace gases over the Arctic Ocean in April 2008 are used to examine the chemistry and geographical extent of ozone depletion in the arctic marine boundary layer (MBL). Data were obtained from the NOAA WP-3D aircraft during the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC) study and the NASA DC-8 aircraft during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) study. Fast (1 s) and sensitive (detection limits at the low pptv level) measurements of BrCl and BrO were obtained from three different chemical ionization mass spectrometer (CIMS) instruments, and soluble bromide was measured with a mist chamber. The CIMS instruments also detected Br2. Subsequent laboratory studies showed that HOBr rapidly converts to Br2 on the Teflon instrument inlets. This detected Br2 is identified as active bromine and represents a lower limit of the sum HOBr+Br2. The measured active bromine is shown to likely be HOBr during daytime flights in the arctic. In the MBL over the Arctic Ocean, soluble bromide and active bromine were consistently elevated and ozone was depleted. Ozone depletion and active bromine enhancement were confined to the MBL that was capped by a temperature inversion at 200–500 m altitude. In ozone-depleted air, BrO rarely exceeded 10 pptv and was always substantially lower than soluble bromide that was as high as 40 pptv. BrCl was rarely enhanced above the 2-pptv detection limit, either in the MBL, over Alaska, or in the arctic free troposphere.

scholarly journals Bromine measurements in ozone depleted air over the Arctic Ocean

2010 ◽  
Vol 10 (14) ◽  
pp. 6503-6514 ◽  
Author(s):  
J. A. Neuman ◽  
J. B. Nowak ◽  
L. G. Huey ◽  
J. B. Burkholder ◽  
J. E. Dibb ◽  
...  
Keyword(s):  
Arctic Ocean ◽  
Ozone Depletion ◽  
Marine Boundary Layer ◽  
Temperature Inversion ◽  
The Arctic ◽  
Ionization Mass ◽  
The Arctic Ocean ◽  
Mist Chamber ◽  
Active Bromine

Abstract. In situ measurements of ozone, photochemically active bromine compounds, and other trace gases over the Arctic Ocean in April 2008 are used to examine the chemistry and geographical extent of ozone depletion in the arctic marine boundary layer (MBL). Data were obtained from the NOAA WP-3D aircraft during the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC) study and the NASA DC-8 aircraft during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) study. Fast (1 s) and sensitive (detection limits at the low pptv level) measurements of BrCl and BrO were obtained from three different chemical ionization mass spectrometer (CIMS) instruments, and soluble bromide was measured with a mist chamber. The CIMS instruments also detected Br2. Subsequent laboratory studies showed that HOBr rapidly converts to Br2 on the Teflon instrument inlets. This detected Br2 is identified as active bromine and represents a lower limit of the sum HOBr + Br2. The measured active bromine is shown to likely be HOBr during daytime flights in the arctic. In the MBL over the Arctic Ocean, soluble bromide and active bromine were consistently elevated and ozone was depleted. Ozone depletion and active bromine enhancement were confined to the MBL that was capped by a temperature inversion at 200–500 m altitude. In ozone-depleted air, BrO rarely exceeded 10 pptv and was always substantially lower than soluble bromide that was as high as 40 pptv. BrCl was rarely enhanced above the 2 pptv detection limit, either in the MBL, over Alaska, or in the arctic free troposphere.

scholarly journals ASDToolkit: A Novel MATLAB Processing Toolbox for ASD Field Spectroscopy Data

2020 ◽  
Author(s):  
Kathryn Elmer ◽  
Raymond Soffer ◽  
J. Pablo Arroyo-Mora ◽  
Margaret Kalacska
Keyword(s):  
Individual Characteristics ◽  
Atmospheric Conditions ◽  
Current Effort ◽  
Data Product ◽  
Field Spectroscopy ◽  
The Individual ◽  
Solar Position ◽  
Derived Data

Over the past 30 years, the use of field spectroscopy has risen in importance in remote sensing studies for the characterization of the surface reflectance of materials in situ within a broad range of applications. Potential uses range from measurements of individual targets of interest (e.g. vegetation, soils, validation targets etc.), to characterizing the contributions of different materials within larger spatially-mixed areas as would be representative of the spatial resolution captured by a sensor pixel (UAV to satellite scale). As such, it is essential that a complete and rigorous assessment of both the data-acquisition procedures, and the suitability of the derived data product be carried out. The measured energy from solar-reflected range spectroradiometers is influenced by the viewing and illumination geometries and the illumination conditions which vary due to changes in solar position and atmospheric conditions. By applying corrections, the estimated absolute reflectance (Rabs) of targets can be calculated. This property is independent of illumination intensity or conditions and is the metric commonly suggested to be used to compare spectra even when data are collected by different sensors or acquired under different conditions. By standardizing the process of estimated Rabs, as is provided in the described toolkit, consistency and repeatability in processing are ensured and the otherwise labor intensive and error-prone processing steps are streamlined. The resultant end data product (Rabs) represents our best current effort to generate consistent and comparable ground spectra which have been corrected for viewing and illumination geometries as well as other factors such as the individual characteristics of the reference panel used during acquisition.

scholarly journals Characterization of the cloud microphysical and optical properties and aerosol-cloud interaction in the Arctic from in situ ground-based measurements during the CLIMSLIP-NyA campaign, Svalbard

2017 ◽  
Author(s):  
Gwennolé Guyot ◽  
Frans Olofson ◽  
Peter Tunved ◽  
Christophe Gourbeyre ◽  
Guy Fevbre ◽  
...  
Keyword(s):  
Indirect Effect ◽  
Climate Models ◽  
Droplet Diameter ◽  
Arctic Region ◽  
The Arctic ◽  
Blowing Snow ◽  
Aerosol Cloud ◽  
Arctic Aerosol

Abstract. This study will focus on cloud microphysical and optical characterization of three different types of episodes encountered during the ground based CLIMSLIP-NyA campaign performed in Ny-Alesund, Svalbard: the Mixed Phase Cloud (MPC), snow precipitation and Blowing Snow (BS) events. These in situ cloud measurements will be combined with aerosol measurements and air mass backtrajectory simulations to qualify and parameterize the arctic aerosol cloud interaction and to assess the influence of anthropogenic pollution transported into the Arctic. The results show a cloud bimodal distribution with the droplet mode at 10 µm and the crystal mode centered at 250 µm, for the MPC cases. The precipitation cases presents a crystal distribution centered around 350 µm with mostly of dendritic shape. The BS cases show a higher concentration but smaller crystals, centered between 150 and 200 µm, with mainly irregular crystals. A polluted case, where aerosol properties are influenced by anthropogenic emission from Europe and East Asia, was compared to a clean case with local aerosol sources. These anthropogenic emissions seem to cause higher Black Carbon, aerosol and droplet concentrations, a more pronounced accumulation mode, smaller droplet sizes and a higher activation fraction Fa. Moreover, the activation diameter decreases as the droplet diameter increases and Fa increases showing that smaller particles are activated and droplets grow when the aerosol number decreases. This is in agreement with the first (Twomey) and second (Albrecht) aerosol indirect effect. The quantification of the variations of droplet concentration and size leads to IE (Indirect Effect) and NE (Nucleation Efficiency) coefficients values around 0.2 and 0.43, respectively. These values are close to those found by other studies in the arctic region which confirms these parameterizations of arctic aerosol-cloud interaction in climate models.

scholarly journals Bromine Speciation in Volcanic Plumes: New in-situ Derivatization LC-MS Method for the Determination of Gaseous Hydrogen Bromide by Gas Diffusion Denuder Sampling

2020 ◽  
Author(s):  
Alexandra Gutmann ◽  
Nicole Bobrowski ◽  
Marcello Liotta ◽  
Thorsten Hoffmann
Keyword(s):  
Matrix Effects ◽  
Hydrogen Bromide ◽  
Gas Diffusion ◽  
Gaseous Hydrogen ◽  
Ionization Mass ◽  
Volcanic Plumes ◽  
Analytical Approaches ◽  
In Situ Derivatization

Abstract. The chemical characterization of volcanic gas emissions gives insights into the interior of volcanoes. Monitoring of BrO/SO2-ratios has recently been correlated with changes in the activity of a volcano. BrO and SO2 can both be measured autonomously and simultaneously with the same instruments from a safe distance, making their ratio potentially a strong monitoring tool. However, BrO is not a primary emitted volcanic volatile and there exist still uncertainties about the formation of BrO in volcanic plumes, mostly due to the lack of analytical approaches for the accurate speciation of certain key compounds. This study describes a new method for the determination of the BrO precursor, the gaseous hydrogen bromide (HBr), by quantitative collection in denuder samplers. Gas diffusion denuders use the difference in diffusion coefficients to separate gaseous from particle-phase compounds. Gaseous HBr molecules are immobilized with an organic coating at the inner walls of the denuder tubes when pumped through the denuders. Five different coatings using 1,2-epoxycyclooctane, trans-oxirane-2,3-dicarboxylic acid, 2,3-epoxy-3-phenylpropanoic acid, 9,10-epoxystearic acid, 5,6-epoxy-5,6-dihydro-[1,10]-phenanthroline (EP) were tested as denuder coatings. EP proved to be a suitable coating reagent, which at the same time, transfers the analyte into an appropriate derivate to be analyzed by high-performance liquid chromatography coupled to electrospray ionization mass spectrometry (in situ derivatization). Coating amount, breakthrough, matrix effects and the storage behavior have been characterized. No considerable cross-sensitivity with hydrogen chloride or other bromine species such as molecular bromine was observed. The comparison of HBr determination using EP-coated denuders and Raschig Tubes as alkaline traps in the laboratory showed a deviation of 2 ± 11 % for gaseous HBr between the two methods. This allows considering HBr determined by denuders as a fraction of total bromine determined by Raschig Tubes. Since other bromine species (e.g. elemental bromine, bromine oxides) are also collected and determined as bromide by Raschig Tubes, but exclusively HBr in EP-coated denuders, the method presented here allows more accurate speciation of gaseous bromine compounds and their application in volcanic plumes. The denuder sampling setup was applied with complementary denuder systems and alkaline traps in the plume of Masaya (Nicaragua) in 2016. HBr concentrations in the range between 0.44 and 2.27 ppb were measured with limits of detection and quantification below 0.1 and 0.3 ppb respectively at typical ground-based sampling conditions. The relative contribution of HBr as a fraction of total bromine decreased from 75 ± 11 % at Santiago rim (214 m distance to the volcanic emission source) to 36 ± 8 % on Nindiri rim (740 m distance). Our findings are in good agreement with previous estimations of the HBr conversion from the chemistry box model (CAABA/MECCA).

scholarly journals Bromine speciation in volcanic plumes: new in situ derivatization LC-MS method for the determination of gaseous hydrogen bromide by gas diffusion denuder sampling

2021 ◽  
Vol 14 (10) ◽  
pp. 6395-6406
Author(s):  
Alexandra Gutmann ◽  
Nicole Bobrowski ◽  
Marcello Liotta ◽  
Thorsten Hoffmann
Keyword(s):  
Collection Efficiency ◽  
Hydrogen Bromide ◽  
Chemical Characterization ◽  
Gas Diffusion ◽  
Gaseous Hydrogen ◽  
Ionization Mass ◽  
Volcanic Gas ◽  
Relative Standard ◽  
In Situ Derivatization

Abstract. The chemical characterization of volcanic gas emissions gives insights into the interior of volcanoes. Bromine species have been correlated with changes in the activity of a volcano. In order to exploit the volcanic bromine gases, we need to understand what happens to them after they are outgassed into the atmosphere. This study aims to shed light on the conversion of bromospecies after degassing. The method presented here allows for the specific analysis of gaseous hydrogen bromide (HBr) in volcanic environments. HBr is immobilized by reaction with 5,6-epoxy-5,6-dihydro-[1,10]-phenanthroline (EP), which acts as an inner coating inside of diffusion denuder tubes (in situ derivatization). The derivative is analyzed by high-performance liquid chromatography coupled to electrospray ionization mass spectrometry (HPLC-ESI-MS). The collection efficiency for HBr (99.5 %), the collection efficiency for HBr alongside HCl (98.1 %), and the relative standard deviation of comparable samples (8 %) have been investigated. The comparison of the new denuder-based method and Raschig tubes as alkaline traps resulted on average in a relative bias between both methods of 10 ± 6 %. The denuder sampling setup was applied in the plume of Masaya (Nicaragua) in 2016. HBr concentrations in the range between 0.44 and 1.97 ppb were measured with limits of detection and quantification below 0.1 and 0.3 ppb respectively. The relative contribution of HBr as a fraction of total bromine decreased from 75 ± 11 % at the Santiago crater (214 m distance to the volcanic emission source) to 36 ± 8 % on the Nindiri rim (740 m distance). A comparison between our data and the previously calculated HBr, based on the CAABA/MECCA box model, showed a slightly higher trend for the HBr fraction on average than expected from the model. Data gained from this new method can further refine model runs in the future.

scholarly journals Synthesis and Characterization of 12CaO·7Al2O3 Slags: The Effects of Impurities and Atmospheres on the Phase Relations

2020 ◽  
Vol 51 (6) ◽  
pp. 2689-2710
Author(s):  
Fabian Imanasa Azof ◽  
Kai Tang ◽  
Jinglin You ◽  
Jafar Safarian
Keyword(s):  
Room Temperature ◽  
Intermediate Phase ◽  
Atmospheric Conditions ◽  
X Ray Diffraction ◽  
Alumina Crucible ◽  
Electron Probe Micro Analyzer ◽  
Low Concentrations ◽  
A Minor

AbstractSynthesis of crystalline slags of 12CaO·7Al2O3 phase from the corresponding melt compositions in different atmospheric conditions and different purities is investigated. Observations using a thermogravimetry coupled with differential thermal analysis showed that the dehydration of a zeolitic 12CaO·7Al2O3 phase occur at 770 °C to 1390 °C before it congruently melts at 1450 °C. The X-ray diffraction pattern of the slag showed that a single 12CaO·7Al2O3 phase is produced from a mixture, which has small SiO2 impurity with a 49:51 mass ratio of CaO to Al2O3. A scanning electron microscope and electron probe micro-analyzer showed that a minor Ca-Al-Si-O-containing phase is in equilibrium with a grain-less 12CaO·7Al2O3 phase. Moreover, 12CaO·7Al2O3 is unstable at room temperature when the high-purity molten slag is solidified under oxidizing conditions contained in an alumina crucible. On the other hand, a high-temperature in-situ Raman spectroscopy of a slag that was made of a higher purity CaO-Al2O3 mixture showed that 5CaO·3Al2O3 phase is an unstable/intermediate phase in the the CaO-Al2O3 system, which is decomposed to 12CaO·7Al2O3 above 1100 °C upon heating in oxidizing conditions. It was found that 5CaO·3Al2O3 is present at room temperature when the 12CaO·7Al2O3 dissociates to a mixture of 5CaO·3Al2O3, 3CaO·Al2O3, and CaO·Al2O3 phases during the cooling of the slag at 1180 °C ± 20 °C in reducing atmosphere. It is proposed that low concentrations of Si stabilize 12CaO·7Al2O3 (mayenite), in which Si is a solid solution in its lattice, which is named Si-mayenite. Regarding the calculated CaO-Al2O3-SiO2 diagram in this study, this phase may contain a maximum of 4.7 wt pct SiO2, which depends on the total SiO2 in the system and the Ca/Al ratio.

scholarly journals ASDToolkit: A Novel MATLAB Processing Toolbox for ASD Field Spectroscopy Data

Data ◽  
2020 ◽  
Vol 5 (4) ◽  
pp. 96
Author(s):  
Kathryn Elmer ◽  
Raymond J. Soffer ◽  
J. Pablo Arroyo-Mora ◽  
Margaret Kalacska
Keyword(s):  
Individual Characteristics ◽  
Atmospheric Conditions ◽  
Data Product ◽  
Field Spectroscopy ◽  
The Individual ◽  
Solar Position ◽  
Derived Data ◽  
Processing Steps

Over the past 30 years, the use of field spectroscopy has risen in importance in remote sensing studies for the characterization of the surface reflectance of materials in situ within a broad range of applications. Potential uses range from measurements of individual targets of interest (e.g., vegetation, soils, validation targets) to characterizing the contributions of different materials within larger spatially mixed areas as would be representative of the spatial resolution captured by a sensor pixel (UAV to satellite scale). As such, it is essential that a complete and rigorous assessment of both the data acquisition procedures and the suitability of the derived data product be carried out. The measured energy from solar-reflective range spectroradiometers is influenced by the viewing and illumination geometries and the illumination conditions, which vary due to changes in solar position and atmospheric conditions. By applying corrections, the estimated absolute reflectance (Rabs) of targets can be calculated. This property is independent of illumination intensity or conditions, and is the metric commonly suggested to be used to compare spectra even when data are collected by different sensors or acquired under different conditions. By standardizing the process of estimated Rabs, as is provided in the described toolkit, consistency and repeatability in processing are ensured and the otherwise labor-intensive and error-prone processing steps are streamlined. The resultant end data product (Rabs) represents our current best effort to generate consistent and comparable ground spectra that have been corrected for viewing and illumination geometries as well as other factors such as the individual characteristics of the reference panel used during acquisition.

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