Intercomparison of MAX-DOAS vertical profile retrieval algorithms: studies on field data from the CINDI-2 campaign

Abstract. The second Cabauw Intercomparison of Nitrogen Dioxide measuring Instruments (CINDI-2) took place in Cabauw (the Netherlands) in September 2016 with the aim of assessing the consistency of multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of tropospheric species (NO2, HCHO, O3, HONO, CHOCHO and O4). This was achieved through the coordinated operation of 36 spectrometers operated by 24 groups from all over the world, together with a wide range of supporting reference observations (in situ analysers, balloon sondes, lidars, long-path DOAS, direct-sun DOAS, Sun photometer and meteorological instruments). In the presented study, the retrieved CINDI-2 MAX-DOAS trace gas (NO2, HCHO) and aerosol vertical profiles of 15 participating groups using different inversion algorithms are compared and validated against the colocated supporting observations, with the focus on aerosol optical thicknesses (AOTs), trace gas vertical column densities (VCDs) and trace gas surface concentrations. The algorithms are based on three different techniques: six use the optimal estimation method, two use a parameterized approach and one algorithm relies on simplified radiative transport assumptions and analytical calculations. To assess the agreement among the inversion algorithms independent of inconsistencies in the trace gas slant column density acquisition, participants applied their inversion to a common set of slant columns. Further, important settings like the retrieval grid, profiles of O3, temperature and pressure as well as aerosol optical properties and a priori assumptions (for optimal estimation algorithms) have been prescribed to reduce possible sources of discrepancies. The profiling results were found to be in good qualitative agreement: most participants obtained the same features in the retrieved vertical trace gas and aerosol distributions; however, these are sometimes at different altitudes and of different magnitudes. Under clear-sky conditions, the root-mean-square differences (RMSDs) among the results of individual participants are in the range of 0.01–0.1 for AOTs, (1.5–15) ×1014molec.cm-2 for trace gas (NO2, HCHO) VCDs and (0.3–8)×1010molec.cm-3 for trace gas surface concentrations. These values compare to approximate average optical thicknesses of 0.3, trace gas vertical columns of 90×1014molec.cm-2 and trace gas surface concentrations of 11×1010molec.cm-3 observed over the campaign period. The discrepancies originate from differences in the applied techniques, the exact implementation of the algorithms and the user-defined settings that were not prescribed. For the comparison against supporting observations, the RMSDs increase to a range of 0.02–0.2 against AOTs from the Sun photometer, (11–55)×1014molec.cm-2 against trace gas VCDs from direct-sun DOAS observations and (0.8–9)×1010molec.cm-3 against surface concentrations from the long-path DOAS instrument. This increase in RMSDs is most likely caused by uncertainties in the supporting data, spatiotemporal mismatch among the observations and simplified assumptions particularly on aerosol optical properties made for the MAX-DOAS retrieval. As a side investigation, the comparison was repeated with the participants retrieving profiles from their own differential slant column densities (dSCDs) acquired during the campaign. In this case, the consistency among the participants degrades by about 30 % for AOTs, by 180 % (40 %) for HCHO (NO2) VCDs and by 90 % (20 %) for HCHO (NO2) surface concentrations. In former publications and also during this comparison study, it was found that MAX-DOAS vertically integrated aerosol extinction coefficient profiles systematically underestimate the AOT observed by the Sun photometer. For the first time, it is quantitatively shown that for optimal estimation algorithms this can be largely explained and compensated by considering biases arising from the reduced sensitivity of MAX-DOAS observations to higher altitudes and associated a priori assumptions.

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Intercomparison of MAX-DOAS vertical profile retrieval algorithms: studies on field data from the CINDI-2 campaign

10.5194/amt-2019-456 ◽

2020 ◽

Cited By ~ 8

Author(s):

Jan-Lukas Tirpitz ◽

Udo Frieß ◽

François Hendrick ◽

Carlos Alberti ◽

Marc Allaart ◽

...

Keyword(s):

Lower Troposphere ◽

Trace Gas ◽

Optical Absorption Spectroscopy ◽

Measuring Instruments ◽

Visible Radiation ◽

Radiation Spectra ◽

Tropospheric Aerosol ◽

Wide Range ◽

Sun Photometer ◽

Low Sensitivity

Abstract. Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) is a well-established ground-based measurement technique for the detection of aerosols and trace gases particularly in the boundary layer and the lower troposphere: ultraviolet- and visible radiation spectra of skylight are analysed to obtain information on different atmospheric parameters, integrated over the light path from space to the instrument. An appropriate set of spectra recorded under different viewing geometries ("Multi-Axis") allows retrieval of tropospheric aerosol and trace gas vertical distributions by applying numerical inversion methods. The second Cabauw Intercomparison of Nitrogen Dioxide measuring Instruments (CINDI-2) took place in Cabauw (The Netherlands) in September 2016 with the aim of assessing the consistency of MAX-DOAS measurements of tropospheric species (NO2, HCHO, O3, HONO, CHOCHO and O4). This was achieved through the coordinated operation of 36 spectrometers operated by 24 groups from all over the world, together with a wide range of supporting reference observations (in situ analysers, balloon sondes, lidars, Long-Path DOAS, sun photometer and others). In the presented study, the retrieved CINDI-2 MAX-DOAS trace gas (NO2, HCHO) and aerosol vertical profiles of 15 participating groups using different inversion algorithms are compared and validated against the colocated supporting observations. The profiles were found to be in good qualitative agreement: most participants obtained the same features in the retrieved vertical trace gas and aerosol distributions, however sometimes at different altitudes and of different intensity. Under clear sky conditions, the root-mean-square differences of aerosol optical thicknesses, trace gas (NO2, HCHO) vertical columns and surface concentrations among the results of individual participants vary between 0.01–0.1, (1.5–15) x 1014 molec cm-2 and (0.3–8) x 1010 molec cm-3, respectively. For the comparison against supporting observations, these values increase to 0.02–0.2, (11–55) x 1014 molec cm-2 and (0.8–9) x 1010 molec cm-3. It is likely that a large part of this increase is caused by imperfect spatio-temporal overlap of the different observations. In contrast to what is often assumed, the MAX-DOAS vertically integrated extinction profiles and the sun photometer total aerosol optical thickness were found to not necessarily being comparable quantities, unless information on the real aerosol vertical distribution is available to account for the low sensitivity of MAX-DOAS observations at higher altitudes.

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Field measurements of trace gases and aerosols emitted by peat fires in Central Kalimantan, Indonesia, during the 2015 El Niño

Atmospheric Chemistry and Physics ◽

10.5194/acp-16-11711-2016 ◽

2016 ◽

Vol 16 (18) ◽

pp. 11711-11732 ◽

Cited By ~ 83

Author(s):

Chelsea E. Stockwell ◽

Thilina Jayarathne ◽

Mark A. Cochrane ◽

Kevin C. Ryan ◽

Erianto I. Putra ◽

...

Keyword(s):

Optical Properties ◽

El Niño ◽

El Nino ◽

Trace Gases ◽

Field Measurements ◽

Optical Data ◽

Trace Gas ◽

Aerosol Optical Properties ◽

Central Kalimantan ◽

Peat Fires

Abstract. Peat fires in Southeast Asia have become a major annual source of trace gases and particles to the regional–global atmosphere. The assessment of their influence on atmospheric chemistry, climate, air quality, and health has been uncertain partly due to a lack of field measurements of the smoke characteristics. During the strong 2015 El Niño event we deployed a mobile smoke sampling team in the Indonesian province of Central Kalimantan on the island of Borneo and made the first, or rare, field measurements of trace gases, aerosol optical properties, and aerosol mass emissions for authentic peat fires burning at various depths in different peat types. This paper reports the trace gas and aerosol measurements obtained by Fourier transform infrared spectroscopy, whole air sampling, photoacoustic extinctiometers (405 and 870 nm), and a small subset of the data from analyses of particulate filters. The trace gas measurements provide emission factors (EFs; grams of a compound per kilogram biomass burned) for up to ∼  90 gases, including CO2, CO, CH4, non-methane hydrocarbons up to C10, 15 oxygenated organic compounds, NH3, HCN, NOx, OCS, HCl, etc. The modified combustion efficiency (MCE) of the smoke sources ranged from 0.693 to 0.835 with an average of 0.772 ± 0.053 (n  =  35), indicating essentially pure smoldering combustion, and the emissions were not initially strongly lofted. The major trace gas emissions by mass (EF as g kg−1) were carbon dioxide (1564 ± 77), carbon monoxide (291 ± 49), methane (9.51 ± 4.74), hydrogen cyanide (5.75 ± 1.60), acetic acid (3.89 ± 1.65), ammonia (2.86 ± 1.00), methanol (2.14 ± 1.22), ethane (1.52 ± 0.66), dihydrogen (1.22 ± 1.01), propylene (1.07 ± 0.53), propane (0.989 ± 0.644), ethylene (0.961 ± 0.528), benzene (0.954 ± 0.394), formaldehyde (0.867 ± 0.479), hydroxyacetone (0.860 ± 0.433), furan (0.772 ± 0.035), acetaldehyde (0.697 ± 0.460), and acetone (0.691 ± 0.356). These field data support significant revision of the EFs for CO2 (−8 %), CH4 (−55 %), NH3 (−86 %), CO (+39 %), and other gases compared with widely used recommendations for tropical peat fires based on a lab study of a single sample published in 2003. BTEX compounds (benzene, toluene, ethylbenzene, xylenes) are important air toxics and aerosol precursors and were emitted in total at 1.5 ± 0.6 g kg−1. Formaldehyde is probably the air toxic gas most likely to cause local exposures that exceed recommended levels. The field results from Kalimantan were in reasonable agreement with recent lab measurements of smoldering Kalimantan peat for “overlap species,” lending importance to the lab finding that burning peat produces large emissions of acetamide, acrolein, methylglyoxal, etc., which were not measurable in the field with the deployed equipment and implying value in continued similar efforts. The aerosol optical data measured include EFs for the scattering and absorption coefficients (EF Bscat and EF Babs, m2 kg−1 fuel burned) and the single scattering albedo (SSA) at 870 and 405 nm, as well as the absorption Ångström exponents (AAE). By coupling the absorption and co-located trace gas and filter data we estimated black carbon (BC) EFs (g kg−1) and the mass absorption coefficient (MAC, m2 g−1) for the bulk organic carbon (OC) due to brown carbon (BrC). Consistent with the minimal flaming, the emissions of BC were negligible (0.0055 ± 0.0016 g kg−1). Aerosol absorption at 405 nm was ∼  52 times larger than at 870 nm and BrC contributed ∼  96 % of the absorption at 405 nm. Average AAE was 4.97 ± 0.65 (range, 4.29–6.23). The average SSA at 405 nm (0.974 ± 0.016) was marginally lower than the average SSA at 870 nm (0.998 ± 0.001). These data facilitate modeling climate-relevant aerosol optical properties across much of the UV/visible spectrum and the high AAE and lower SSA at 405 nm demonstrate the dominance of absorption by the organic aerosol. Comparing the Babs at 405 nm to the simultaneously measured OC mass on filters suggests a low MAC ( ∼  0.1) for the bulk OC, as expected for the low BC/OC ratio in the aerosol. The importance of pyrolysis (at lower MCE), as opposed to glowing (at higher MCE), in producing BrC is seen in the increase of AAE with lower MCE (r2 =  0.65).

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Field measurements of trace gases and aerosols emitted by peat fires in Central Kalimantan, Indonesia during the 2015 El Niño

10.5194/acp-2016-411 ◽

2016 ◽

Cited By ~ 4

Author(s):

Chelsea E. Stockwell ◽

Thilina Jayarathne ◽

Mark A. Cochrane ◽

Kevin C. Ryan ◽

Erianto I. Putra ◽

...

Keyword(s):

Optical Properties ◽

El Niño ◽

El Nino ◽

Trace Gases ◽

Field Measurements ◽

Optical Data ◽

Trace Gas ◽

Aerosol Optical Properties ◽

Central Kalimantan ◽

Peat Fires

Abstract. Peat fires in Southeast Asia have become a major annual source of trace gases and particles to the regional-global atmosphere. The assessment of their influence on atmospheric chemistry, climate, air quality, and health has been uncertain partly due to a lack of field measurements of the smoke characteristics. During the strong 2015 El Niño event we deployed a mobile smoke sampling team in the Indonesian province of Central Kalimantan on the island of Borneo and made the first, or rare, field measurements of trace gases, aerosol optical properties, and aerosol mass emissions for authentic peat fires burning at various depths in different peat types. This paper reports the trace gas and aerosol measurements obtained by Fourier transform infrared spectroscopy, whole air sampling, photoacoustic extinctiometers (405 and 870 nm), and a small subset of the data from analyses of particulate filters. The trace gas measurements provide emission factors (EFs, g compound per kg biomass burned) for CO2, CO, CH4, non-methane hydrocarbons up to C10, 15 oxygenated organic compounds, NH3, HCN, NOx, OCS, HCl, etc.; up to ~90 gases in all. The modified combustion efficiency (MCE) of the smoke sources ranged from 0.693 to 0.835 with an average of 0.772 ± 0.053 (n = 35) indicating essentially pure smoldering combustion and the emissions were not initially strongly lofted. The major trace gas emissions by mass (EF as g/kg) were: carbon dioxide (1564 ± 77), carbon monoxide (291 ± 49), methane (9.51 ± 4.74), hydrogen cyanide (5.75 ± 1.60), acetic acid (3.89 ± 1.65), ammonia (2.86 ± 1.00), methanol (2.14 ± 1.22), ethane (1.52 ± 0.66), dihydrogen (1.22 ± 1.01), propylene (1.07 ± 0.53), propane (0.989 ± 0.644), ethylene (0.961 ± 0.528), benzene (0.954 ± 0.394), formaldehyde (0.867 ± 0.479), hydroxyacetone (0.860 ± 0.433), furan (0.772 ± 0.035), acetaldehyde (0.697 ± 0.460), and acetone (0.691 ± 0.356). These field data support significant revision of the EFs for CO2 (−8 %), CH4 (−55 %), NH3 (−86 %), CO (+39 %) and other gases compared with widely-used recommendations for tropical peat fires based on a lab study of a single sample published in 2003. BTEX compounds (benzene, toluene, ethylbenzene, xylenes) are important air toxics and aerosol precursors and were emitted in total at 1.5 ± 0.6 g/kg. Formaldehyde is probably the air toxic gas most likely to cause local exposures that exceed recommended levels. The field results from Kalimantan were in reasonable agreement with recent (2012) lab measurements of smoldering Kalimantan peat for “overlap species,” lending importance to the lab finding that burning peat produces large emissions of acetamide, acrolein, methylglyoxal, etc., which were not measureable in the field with the deployed equipment and implying value in continued similar efforts. The aerosol optical data measured include EFs for the scattering and absorption coefficients (EF Bscat and EF Babs, m2/kg fuel burned) and the single scattering albedo (SSA) at 870 and 405 nm, as well as the absorption Ångstrӧm exponents (AAE). By coupling the absorption and co-located trace gas and filter data we estimated black carbon (BC) EFs (g/kg) and the mass absorption coefficient (MAC, m2/g) for the bulk organic carbon (OC) due to brown carbon (BrC). Consistent with the minimal flaming, the emissions of BC were negligible (0.0055 ± 0.0016 g/kg). Aerosol absorption at 405 nm was ~52 times larger than at 870 nm and BrC contributed ~96 % of the absorption at 405 nm. Average AAE was 4.97 ± 0.65 (range, 4.29–6.23). The average SSA at 405 nm (0.974 ± 0.016) was marginally lower than the average SSA at 870 nm (0.998 ± 0.001). These data facilitate modeling climate-relevant aerosol optical properties across much of the UV/visible spectrum and the high AAE and lower SSA at 405 nm demonstrate the dominance of absorption by the organic aerosol. Comparing the Babs at 405 nm to the simultaneously measured OC mass on filters suggests a low MAC (~0.1) for the bulk OC, as expected for the low BC / OC ratio in the aerosol. The importance of pyrolysis (at lower MCE), as opposed to glowing (at higher MCE), in producing BrC is seen in the increase of AAE with lower MCE (r2 = 0.65).

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Assessment of column aerosol optical properties using ground-based sun-photometer at urban Harbin, Northeast China

Journal of Environmental Sciences ◽

10.1016/j.jes.2018.02.003 ◽

2018 ◽

Vol 74 ◽

pp. 50-57 ◽

Cited By ~ 14

Author(s):

Qixiang Chen ◽

Yuan Yuan ◽

Xing Huang ◽

Zhihong He ◽

Heping Tan

Keyword(s):

Optical Properties ◽

Northeast China ◽

Aerosol Optical Properties ◽

Sun Photometer

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Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE): emissions of trace gases and light-absorbing carbon from wood and dung cooking fires, garbage and crop residue burning, brick kilns, and other sources

Atmospheric Chemistry and Physics ◽

10.5194/acp-16-11043-2016 ◽

2016 ◽

Vol 16 (17) ◽

pp. 11043-11081 ◽

Cited By ~ 55

Author(s):

Chelsea E. Stockwell ◽

Ted J. Christian ◽

J. Douglas Goetz ◽

Thilina Jayarathne ◽

Prakash V. Bhave ◽

...

Keyword(s):

Optical Properties ◽

Organic Compounds ◽

Crop Residue ◽

Emission Factors ◽

Trace Gas ◽

Aerosol Optical Properties ◽

Wood Fuel ◽

Brick Kilns ◽

Crop Residue Burning ◽

Testing Experiment

Abstract. The Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) campaign took place in and around the Kathmandu Valley and in the Indo-Gangetic Plain (IGP) of southern Nepal during April 2015. The source characterization phase targeted numerous important but undersampled (and often inefficient) combustion sources that are widespread in the developing world such as cooking with a variety of stoves and solid fuels, brick kilns, open burning of municipal solid waste (a.k.a. trash or garbage burning), crop residue burning, generators, irrigation pumps, and motorcycles. NAMaSTE produced the first, or rare, measurements of aerosol optical properties, aerosol mass, and detailed trace gas chemistry for the emissions from many of the sources. This paper reports the trace gas and aerosol measurements obtained by Fourier transform infrared (FTIR) spectroscopy, whole-air sampling (WAS), and photoacoustic extinctiometers (PAX; 405 and 870 nm) based on field work with a moveable lab sampling authentic sources. The primary aerosol optical properties reported include emission factors (EFs) for scattering and absorption coefficients (EF Bscat, EF Babs, in m2 kg−1 fuel burned), single scattering albedos (SSAs), and absorption Ångström exponents (AAEs). From these data we estimate black and brown carbon (BC, BrC) emission factors (g kg−1 fuel burned). The trace gas measurements provide EFs (g kg−1) for CO2, CO, CH4, selected non-methane hydrocarbons up to C10, a large suite of oxygenated organic compounds, NH3, HCN, NOx, SO2, HCl, HF, etc. (up to ∼ 80 gases in all). The emissions varied significantly by source, and light absorption by both BrC and BC was important for many sources. The AAE for dung-fuel cooking fires (4.63 ± 0.68) was significantly higher than for wood-fuel cooking fires (3.01 ± 0.10). Dung-fuel cooking fires also emitted high levels of NH3 (3.00 ± 1.33 g kg−1), organic acids (7.66 ± 6.90 g kg−1), and HCN (2.01 ± 1.25 g kg−1), where the latter could contribute to satellite observations of high levels of HCN in the lower stratosphere above the Asian monsoon. HCN was also emitted in significant quantities by several non-biomass burning sources. BTEX compounds (benzene, toluene, ethylbenzene, xylenes) were major emissions from both dung- (∼ 4.5 g kg−1) and wood-fuel (∼ 1.5 g kg−1) cooking fires, and a simple method to estimate indoor exposure to the many measured important air toxics is described. Biogas emerged as the cleanest cooking technology of approximately a dozen stove–fuel combinations measured. Crop residue burning produced relatively high emissions of oxygenated organic compounds (∼ 12 g kg−1) and SO2 (2.54 ± 1.09 g kg−1). Two brick kilns co-firing different amounts of biomass with coal as the primary fuel produced contrasting results. A zigzag kiln burning mostly coal at high efficiency produced larger amounts of BC, HF, HCl, and NOx, with the halogenated emissions likely coming from the clay. The clamp kiln (with relatively more biomass fuel) produced much greater quantities of most individual organic gases, about twice as much BrC, and significantly more known and likely organic aerosol precursors. Both kilns were significant SO2 sources with their emission factors averaging 12.8 ± 0.2 g kg−1. Mixed-garbage burning produced significantly more BC (3.3 ± 3.88 g kg−1) and BTEX (∼ 4.5 g kg−1) emissions than in previous measurements. For all fossil fuel sources, diesel burned more efficiently than gasoline but produced larger NOx and aerosol emission factors. Among the least efficient sources sampled were gasoline-fueled motorcycles during start-up and idling for which the CO EF was on the order of ∼ 700 g kg−1 – or about 10 times that of a typical biomass fire. Minor motorcycle servicing led to minimal if any reduction in gaseous pollutants but reduced particulate emissions, as detailed in a companion paper (Jayarathne et al., 2016). A small gasoline-powered generator and an “insect repellent fire” were also among the sources with the highest emission factors for pollutants. These measurements begin to address the critical data gap for these important, undersampled sources, but due to their diversity and abundance, more work is needed.

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Aerosol Optical Properties of Pacaya Volcano Plume Measured with a Portable Sun-Photometer

Geosciences ◽

10.3390/geosciences8020036 ◽

2018 ◽

Vol 8 (2) ◽

pp. 36 ◽

Cited By ~ 2

Author(s):

Pasquale Sellitto ◽

Letizia Spampinato ◽

Giuseppe Salerno ◽

Alessandro La Spina

Keyword(s):

Optical Properties ◽

Aerosol Optical Properties ◽

Sun Photometer ◽

Pacaya Volcano

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Use of a Maximum Entropy Method as a Regularization Technique during the Retrieval of Trace Gas Profiles from Limb Sounding Measurements

Journal of Atmospheric and Oceanic Technology ◽

10.1175/jtech1951.1 ◽

2006 ◽

Vol 23 (12) ◽

pp. 1657-1667 ◽

Cited By ~ 3

Author(s):

J. Steinwagner ◽

G. Schwarz ◽

S. Hilgers

Keyword(s):

Maximum Entropy ◽

Random Noise ◽

A Priori ◽

Michelson Interferometer ◽

Simulated Data ◽

Optimal Estimation ◽

Initial Guess ◽

Entropy Method ◽

Trace Gas ◽

Regularization Techniques

Abstract The retrieval of trace gas profiles from radiance measurements of limb sounding instruments represents an inverse problem: vertical profiles of mixing ratios have to be extracted from sequences of horizontally measured radiances recorded by a spectrometer. Typically, these retrievals are plagued by random noise and systematic errors, necessitating the use of regularization techniques during inversion calculations. In the following, the use of selected maximum entropy operators as a regularization tool is discussed and their performance with conventional optimal estimation and Tikhonov-type regularization techniques is compared. The main gain with the proposed maximum entropy operators is that no a priori knowledge is needed; a reasonable initial guess profile is fully sufficient. The approach is verified by using simulated data of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument, an infrared Fourier transform spectrometer flown on the European Envisat mission.

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