scholarly journals Intercomparison of two Comparative Reactivity Method instruments in the Mediterranean basin during summer 2013

2015 ◽  
Vol 8 (5) ◽  
pp. 5065-5104 ◽  
Author(s):  
N. Zannoni ◽  
S. Dusanter ◽  
V. Gros ◽  
R. Sarda Esteve ◽  
V. Michoud ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Loss Rate ◽  
Chemical Species ◽  
Ambient Air ◽  
Data Sets ◽  
Least Squares Fit ◽  
The Mediterranean ◽  
Differential Corrections ◽  
Well Correlation ◽  
Comparative Reactivity

Abstract. The hydroxyl radical (OH) plays a key role in the atmosphere, as it initiates most of the oxidation processes of Volatile Organic Compounds (VOCs), and can ultimately lead to the formation of ozone and Secondary Organic Aerosols (SOA). There are still uncertainties associated with the OH budget assessed using current models of atmospheric chemistry and direct measurements of OH sources and sinks have proved to be valuable tools to improve our understanding of the OH chemistry. The total first order loss rate of OH, or total OH reactivity, can be directly measured using three different methods, such as: total OH Loss rate Measurement, Laser Induced Pump and Probe Technique and Comparative Reactivity Method. Observations of total OH reactivity are usually coupled to individual measurements of reactive compounds in the gas phase, which are used to calculate the OH reactivity. Studies using the three methods have highlighted that a significant fraction of OH reactivity is often not explained by individually measured reactive compounds and could be associated to unmeasured or unknown chemical species. Therefore accurate and reproducible measurements of OH reactivity are required. The Comparative Reactivity Method (CRM) has demonstrated to be an advantageous technique with an extensive range of applications, and for this reason it has been adopted by several research groups since its development. However, this method also requires careful corrections to derive ambient OH reactivity. Herein we present an intercomparison exercise of two CRM instruments (CRM-LSCE and CRM-MD), conducted during July 2013 at the Mediterranean site of Ersa, Cape Corsica, France. We discuss in detail the experimental approach adopted and how the data sets were processed for both instruments. Corrections required for the two instruments lead to higher values of reactivity in ambient air; overall 20% increase for CRM-MD and 49% for CRM-LSCE compared to the raw data. We show that ambient OH reactivity measured by the two instruments agrees very well (correlation described by a linear least squares fit with a slope of 1 and R2 of 0.75). This study highlights that ambient measurements of OH reactivity with differently configured CRM instruments yield consistent results in a low NOx, terpene rich environment, despite differential corrections relevant to each instrument. Conducting more intercomparison exercises, involving more CRM instruments operated under different ambient and instrumental settings will help in assessing the variability induced due to instrument specific corrections further.

scholarly journals Intercomparison of two comparative reactivity method instruments inf the Mediterranean basin during summer 2013

2015 ◽  
Vol 8 (9) ◽  
pp. 3851-3865 ◽  
Author(s):  
N. Zannoni ◽  
S. Dusanter ◽  
V. Gros ◽  
R. Sarda Esteve ◽  
V. Michoud ◽  
...  
Keyword(s):  
Loss Rate ◽  
Ambient Air ◽  
Data Sets ◽  
Raw Data ◽  
Intercomparison Exercise ◽  
Least Squares Fit ◽  
The Mediterranean ◽  
Plant Emissions ◽  
Ambient Measurements ◽  
Comparative Reactivity

Abstract. The hydroxyl radical (OH) plays a key role in the atmosphere, as it initiates most of the oxidation processes of volatile organic compounds (VOCs), and can ultimately lead to the formation of ozone and secondary organic aerosols (SOAs). There are still uncertainties associated with the OH budget assessed using current models of atmospheric chemistry and direct measurements of OH sources and sinks have proved to be valuable tools to improve our understanding of the OH chemistry. The total first order loss rate of OH, or total OH reactivity, can be directly measured using three different methods, such as the following: total OH loss rate measurement, laser-induced pump and probe technique and comparative reactivity method. Observations of total OH reactivity are usually coupled to individual measurements of reactive compounds in the gas phase, which are used to calculate the OH reactivity. Studies using the three methods have highlighted that a significant fraction of OH reactivity is often not explained by individually measured reactive compounds and could be associated to unmeasured or unknown chemical species. Therefore accurate and reproducible measurements of OH reactivity are required. The comparative reactivity method (CRM) has demonstrated to be an advantageous technique with an extensive range of applications, and for this reason it has been adopted by several research groups since its development. However, this method also requires careful corrections to derive ambient OH reactivity. Herein we present an intercomparison exercise of two CRM instruments, CRM-LSCE (Laboratoire des Sciences du Climat et de l'Environnement) and CRM-MD (Mines Douai), conducted during July 2013 at the Mediterranean site of Ersa, Cape Corsica, France. The intercomparison exercise included tests to assess the corrections needed by the two instruments to process the raw data sets as well as OH reactivity observations. The observation was divided in three parts: 2 days of plant emissions (8–9 July), 2 days of ambient measurements (10–11 July) and 2 days (12–13 July) of plant emissions. We discuss in detail the experimental approach adopted and how the data sets were processed for both instruments. Corrections required for the two instruments lead to higher values of reactivity in ambient air; overall 20 % increase for CRM-MD and 49 % for CRM-LSCE compared to the raw data. We show that ambient OH reactivity measured by the two instruments agrees very well (correlation described by a linear least squares fit with a slope of 1 and R2 of 0.75). This study highlights that ambient measurements of OH reactivity with differently configured CRM instruments yield consistent results in a low NOx (NO + NO2), terpene rich environment, despite differential corrections relevant to each instrument. Conducting more intercomparison exercises, involving more CRM instruments operated under different ambient and instrumental settings will help in assessing the variability induced due to instrument-specific corrections further.

scholarly journals Characterization of Total OH Reactivity in a Rapeseed Field: Results from the COV3ER Experiment in April 2017

Atmosphere ◽  
2020 ◽  
Vol 11 (3) ◽  
pp. 261
Author(s):  
Sandy Bsaibes ◽  
Valérie Gros ◽  
François Truong ◽  
Christophe Boissard ◽  
Dominique Baisnée ◽  
...  
Keyword(s):  
Loss Rate ◽  
Transfer Reaction ◽  
Inorganic Compounds ◽  
Ambient Air ◽  
Proton Transfer Reaction ◽  
Temperature Dependent ◽  
Flight Mass Spectrometry ◽  
Dynamic Chamber ◽  
Comparative Reactivity

Croplands remain poorly studied ecosystems in terms of total hydroxyl radical (OH) reactivity, especially when compared to forests. As part of the COV3ER project, total OH reactivity (ROH), defined as the total loss rate of OH due to its reaction with reactive species in the atmosphere, was characterized in a rapeseed field (Grignon, France) during the blooming season in April 2017. Measurements were performed in a dynamic chamber as well as in ambient air using the Comparative Reactivity Method (CRM). Complementary measurements of organic (including a proton transfer reaction quadrupole ion–time of flight mass spectrometry, PTRQi-ToFMS) and inorganic compounds were also performed in order to calculate the expected OH reactivity and evaluate the missing fraction. Measured ROH varied diurnally in the dynamic chamber (mROHchamber) with maxima around 20 to 30 s−1 at midday and minima during dark hours, following the variability of the enclosed branch VOCsrapeseed, which is light- and temperature-dependent. Oxygenated VOCs were the major compounds emitted by the rapeseed crop. However, in terms of contribution to OH reactivity, isoprene accounted for 40% during the daytime, followed by acetaldehyde (21%) and monoterpenes (18%). The comparison between mROHchamber and calculated ROH (cROHchamber) exhibited little or no difference during dark hours, whereas a maximum difference appeared around midday, highlighting a significant missing fraction (46% on average during daytime) mainly related to biogenic temperature- and/or light-dependent emissions.

scholarly journals Interpretation of the Chemical and Physical Time-Series Retrieved from Sentik Glacier, Ladakh Himalaya, India

1984 ◽  
Vol 30 (104) ◽  
pp. 66-76 ◽  
Author(s):  
Paul A. Mayewski ◽  
W. Berry Lyons ◽  
N. Ahmad ◽  
Gordon Smith ◽  
M. Pourchet
Keyword(s):  
Time Series ◽  
Chemical Species ◽  
Data Sets ◽  
Reactive Iron ◽  
Physical Time ◽  
Ladakh Himalaya ◽  
Data Density ◽  
Mass Circulation ◽  
The Himalaya ◽  
Analysis Of Time Series

AbstractSpectral analysis of time series of a c. 17 ± 0.3 year core, calibrated for total ß activity recovered from Sentik Glacier (4908m) Ladakh, Himalaya, yields several recognizable periodicities including subannual, annual, and multi-annual. The time-series, include both chemical data (chloride, sodium, reactive iron, reactive silicate, reactive phosphate, ammonium, δD, δ(18O) and pH) and physical data (density, debris and ice-band locations, and microparticles in size grades 0.50 to 12.70 μm). Source areas for chemical species investigated and general air-mass circulation defined from chemical and physical time-series are discussed to demonstrate the potential of such studies in the development of paleometeorological data sets from remote high-alpine glacierized sites such as the Himalaya.

scholarly journals Sunset–sunrise difference in solar occultation ozone measurements (SAGE II, HALOE, and ACE–FTS) and its relationship to tidal vertical winds

2015 ◽  
Vol 15 (2) ◽  
pp. 829-843 ◽  
Author(s):  
T. Sakazaki ◽  
M. Shiotani ◽  
M. Suzuki ◽  
D. Kinnison ◽  
J. M. Zawodny ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Seasonal Variations ◽  
Climate Model ◽  
Transport Model ◽  
Stratospheric Aerosol ◽  
Data Sets ◽  
Chemical Transport Model ◽  
Latitude Range ◽  
Solar Occultation ◽  
Vertical Winds

Abstract. This paper contains a comprehensive investigation of the sunset–sunrise difference (SSD, i.e., the sunset-minus-sunrise value) of the ozone mixing ratio in the latitude range of 10° S–10° N. SSD values were determined from solar occultation measurements based on data obtained from the Stratospheric Aerosol and Gas Experiment (SAGE) II, the Halogen Occultation Experiment (HALOE), and the Atmospheric Chemistry Experiment–Fourier transform spectrometer (ACE–FTS). The SSD was negative at altitudes of 20–30 km (−0.1 ppmv at 25 km) and positive at 30–50 km (+0.2 ppmv at 40–45 km) for HALOE and ACE–FTS data. SAGE II data also showed a qualitatively similar result, although the SSD in the upper stratosphere was 2 times larger than those derived from the other data sets. On the basis of an analysis of data from the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) and a nudged chemical transport model (the specified dynamics version of the Whole Atmosphere Community Climate Model: SD–WACCM), we conclude that the SSD can be explained by diurnal variations in the ozone concentration, particularly those caused by vertical transport by the atmospheric tidal winds. All data sets showed significant seasonal variations in the SSD; the SSD in the upper stratosphere is greatest from December through February, while that in the lower stratosphere reaches a maximum twice: during the periods March–April and September–October. Based on an analysis of SD–WACCM results, we found that these seasonal variations follow those associated with the tidal vertical winds.

Effect of Water Vapor and SOx in Air on the Cathodes of Solid Oxide Fuel Cells

2007 ◽  
Vol 1041 ◽  
Author(s):  
Seon Hye Kim ◽  
Toshihiro Ohshima ◽  
Yusuke Shiratori ◽  
Kohei Itoh ◽  
Kazunari Sasaki
Keyword(s):  
Water Vapor ◽  
Solid Oxide Fuel Cells ◽  
Degradation Mechanism ◽  
Chemical Species ◽  
Cell Voltage ◽  
Ambient Air ◽  
Open Circuit ◽  
Constant Current ◽  
Constant Current Density

AbstractAmbient air is used as an oxygen source in SOFCs to be commercialized. Various chemical species which can lead to poisoning of SOFC cathodes are included as minor constitutions in air, such as water vapor, SOx, NOx and NaCl etc. However, their effects on the cathode performance have not yet well known, even though they are expected to cause a degradation of the electrode performance and to reduce the long-term durability of SOFCs. Therefore, in this study, we focused on the poisoning caused by water vapor and SOx in the oxygen source to clarify their effects on SOFCs performances and to reveal the degradation mechanism of cathodes. SOFCs with typical electrolyte-supported structure were used in this work, which were composed with ScSZ (10 mol% Sc2O3, 1mol% CeO2, 89 mol% ZrO2) plate with the thickness of 200 µm as electrolyte, NiO-ScSZ (mixture of 56 wt% NiO and 44 wt% ScSZ) porous layer as anode, and two cathode layers of LSM ((La0.8Sr0.2)0.98MnO3) and LSM-ScSZ (mixture of 50 wt% LSM and 50 wt% ScSZ). Power generation characteristics of the cells had been analyzed by measuring cell voltage at a constant current density (200 mA/cm2) and by comparing changes in cell impedance, upon supplying the artificially-contaminated air with water vapor or SOx, to the SOFC cathodes at various operational temperatures. High-resolution FESEM (S-5200, Hitachi) was used to analyze microstructural changes caused by the impurities. Mg Kα radiation from a monochromatized X-ray source was used for XPS measurements (ESCA-3400, KRATOS). AC impedance was measured at various temperatures under the open circuit voltage condition by an impedance analyzer (Solatron 1255B/SI 1287, Solatron), in a frequency range from 0.1 to 105 Hz with an amplitude of 10 mV.

scholarly journals The Detailed Emissions Scaling, Isolation, and Diagnostic (DESID) module in the Community Multiscale Air Quality (CMAQ) Modeling System version 5.3

2020 ◽  
Author(s):  
Benjamin N. Murphy ◽  
Christopher G. Nolte ◽  
Fahim Sidi ◽  
Jesse O. Bash ◽  
K. Wyat Appel ◽  
...  
Keyword(s):  
Air Quality ◽  
Atmospheric Chemistry ◽  
Chemical Species ◽  
Energy System ◽  
Reduced Form ◽  
Chemistry Research ◽  
Control Interface ◽  
Source Contributions ◽  
Areas Of Interest ◽  
Multiple Chemical

Abstract. Air quality modeling for research and regulatory applications often involves executing many emissions sensitivity cases to quantify impacts of hypothetical scenarios, estimate source contributions or quantify uncertainties. Despite the prevalence of this task, conventional approaches for perturbing emissions in chemical transport models like the Community Multiscale Air Quality (CMAQ) model require extensive offline creation and finalization of alternative emissions input files. This workflow tends to be time-consuming, error-prone, inconsistent among model users and difficult to document while consuming increased computer storage space. The Detailed Emissions Scaling, Isolation, and Diagnostic (DESID) module, a component of CMAQv5.3 and beyond, addresses these limitations by performing these modifications online during the air quality simulation. Further, the model contains an Emission Control Interface which allows users to prescribe both simple and highly complex emissions scaling operations with control over individual or multiple chemical species, emissions sources, and spatial areas of interest. DESID further enhances the transparency of its operations with extensive error-checking and optional gridded output of processed emission fields. These new features are of high value to many air quality applications including routine perturbation studies, atmospheric chemistry research, and coupling with external models (e.g. energy system models, reduced-form models).

scholarly journals A review of approaches to estimate wildfire plume injection height within large scale atmospheric chemical transport models – Part 1

2015 ◽  
Vol 15 (6) ◽  
pp. 9767-9813 ◽  
Author(s):  
R. Paugam ◽  
M. Wooster ◽  
S. R. Freitas ◽  
M. Val Martin
Keyword(s):  
Large Scale ◽  
Atmospheric Transport ◽  
Source Region ◽  
Chemical Species ◽  
Chemical Conversion ◽  
Ambient Air ◽  
Transport Models ◽  
Fire Emissions ◽  
Fire Smoke ◽  
In Fire

Abstract. Landscape fires produce smoke containing a very wide variety of chemical species, both gases and aerosols. For larger, more intense fires that produce the greatest amounts of emissions per unit time, the smoke tends initially to be transported vertically or semi-vertically close by the source region, driven by the intense heat and convective energy released by the burning vegetation. The column of hot smoke rapidly entrains cooler ambient air, forming a rising plume within which the fire emissions are transported. This characteristics of this plume, and in particular the height to which it rises before releasing the majority of the smoke burden into the wider atmosphere, are important in terms of how the fire emissions are ultimately transported, since for example winds at different altitudes maybe quite different. This difference in atmospheric transport then may also affect the longevity, chemical conversion and fate of the plumes chemical consituents, with for example very high plume injection heights being associated with extreme long-range atmospheric transport. Here we review how such landscape-scale fire smoke plume injection heights are represented in larger scale atmospheric transport models aiming to represent the impacts of wildfire emissions on component of the Earth system. The use of satellite Earth observation (EO) data is commonly used for this, and detail the EO datasets capable of being used to remotely assess wildfire plume height distributions and the driving characteristics of the causal fires. We also discus both the physical mechanisms and dynamics taking place in fire plumes, and investigate the efficiency and limitations of currently available injection height parameterizations. Finally, we conclude by suggestion some future parameterization developments and ideas on EO data selection that maybe relevant to the instigation of enhanced methodologies aimed at injection height representation.

scholarly journals The Improved Comparative Reactivity Method (ICRM): measurements of OH reactivity at high-NO<sub>X</sub> conditions in ambient air

2020 ◽  
Author(s):  
Wenjie Wang ◽  
Jipeng Qi ◽  
Jun Zhou ◽  
Bin Yuan ◽  
Yuwen Peng ◽  
...  
Keyword(s):  
Operation Mode ◽  
Original System ◽  
Ambient Air ◽  
Field Studies ◽  
Oh Radicals ◽  
Crm System ◽  
Maximum Decrease ◽  
Order Of Magnitude ◽  
Technological Improvements ◽  
Comparative Reactivity

Abstract. The comparative reactivity method (CRM) has been developed more than a decade to measure OH reactivity (i.e. OH loss frequency) in both laboratory and field studies. However, accurate OH reactivity quantification remains challenging under real ambient condition, especially for OH reactivity measurements in high-NOX (e.g. > 10 ppbv) environments, as ambient NO enhance regeneration of OH radicals in the CRM reactor. To resolve this problem, we design a new improved CRM reactor (ICRM) and add NO into the system continuously, so that the HO2 radical concentration is suppressed. We confirmed the appropriate level of NO by determining the maximum decrease in the pyrrole level caused by regenerated OH radicals from NO + HO2. VOC-induced RO2 radicals in the ICRM reactor were also found to react with NO, which lead to the re-generation of OH radicals thus the underestimation of OH reactivity. This effect was quantified by the calibration of representative VOC species at different NO levels, and the correction coefficients obtained were used to correct the measured OH reactivity. All these efforts resulted in reducing the uncertainty of the NO-artifact correction by at least an order of magnitude compared to the original CRM system. Additionally, these technological improvements also considerably reduced the systematic errors from pyrrole photolysis that exists in the original system. A new operation mode was proposed for ICRM, which is able to avoid the interference resulting from OH radicals produced by photolysis of residual humidity and save time for ambient measurement. The ICRM system was employed in a field campaign to measure OH reactivity and performed well with ambient NO levels ranged from 0 to 50 ppbv, which were typically observed in urban and suburban atmosphere.

scholarly journals Model – TCCON comparisons of column-averaged methane with a focus on the stratosphere

2016 ◽  
Author(s):  
Andreas Ostler ◽  
Ralf Sussmann ◽  
Prabir K. Patra ◽  
Sander Houweling ◽  
Marko De Bruine ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Transport Model ◽  
Meteorological Data ◽  
Michelson Interferometer ◽  
Total Carbon ◽  
Data Sets ◽  
Transport Models ◽  
Improved Model ◽  
The Impact ◽  
Chemistry Experiment

Abstract. The distribution of methane (CH4) in the stratosphere can be a major driver of spatial variability in the dry-air column-averaged CH4 mixing ratio (XCH4), which is being measured increasingly for the assessment of CH4 surface emissions. Chemistry-transport models (CTMs) therefore need to simulate the tropospheric and stratospheric fractional columns of XCH4 accurately for estimating surface emissions from XCH4. Simulations from three CTMs are tested against XCH4 observations from the Total Carbon Column Network (TCCON). We analyze how the model-TCCON agreement in XCH4 depends on the model representation of stratospheric CH4 distributions. Model equivalents of TCCON XCH4 are computed with stratospheric CH4 fields from both the model simulations and from satellite-based CH4 distributions from MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) and MIPAS CH4 fields adjusted to ACE-FTS (Atmospheric Chemistry Experiment Fourier Transform Spectrometer) observations. In comparison to simulated model fields we find an improved model-TCCON XCH4 agreement for all models with MIPAS-based stratospheric CH4 fields. For the Atmospheric Chemistry Transport Model (ACTM) the average XCH4 bias is significantly reduced from 38.1 ppb to 13.7 ppb, whereas small improvements are found for the models TM5 (Transport Model, version 5; from 8.7 ppb to 4.3 ppb), and LMDz (Laboratoire de Météorologie Dynamique model with Zooming capability; from 6.8 ppb to 4.3 ppb), respectively. MIPAS stratospheric CH4 fields adjusted to ACE-FTS reduce the average XCH4 bias for ACTM (3.3 ppb), but increase the average XCH4 bias for TM5 (10.8 ppb) and LMDz (20.0 ppb). These findings imply that the range of satellite-based stratospheric CH4 is insufficient to resolve a possible stratospheric contribution to differences in total column CH4 between TCCON and TM5 or LMDz. Applying transport diagnostics to the models indicates that model-to-model differences in the simulation of stratospheric transport, notably the age of stratospheric air, can largely explain the inter-model spread in stratospheric CH4 and, hence, its contribution to XCH4. This implies that there is a need to better understand the impact of individual model transport components (e.g., physical parameterization, meteorological data sets, model horizontal/vertical resolution) on modeled stratospheric CH4.

Sign in / Sign up

Export Citation Format

Share Document