Glyoxal vertical columns from GOME-2 backscattered light measurements and comparisons with a global model
TL;DR: In this article, a two-step DOAS approach was used to calculate glyoxal vertical column densities from nadir backscattered radiances measured from 2007 to 2009 by the spaceborne GOME-2/METOP-A sensor.
Abstract: . Glyoxal vertical column densities have been retrieved from nadir backscattered radiances measured from 2007 to 2009 by the spaceborne GOME-2/METOP-A sensor. The retrieval algorithm is based on the DOAS technique and optimized settings have been used to determine glyoxal slant columns. The liquid water absorption is accounted for using a two-step DOAS approach, leading to a drastic improvement of the fit quality over remote clear water oceans. Air mass factors are calculated by means of look-up tables of weighting functions pre-calculated with the LIDORT v3.3 radiative transfer model and using a priori glyoxal vertical distributions provided by the IMAGESv2 chemical transport model. The total error estimate comprises random and systematic errors associated to the DOAS fit, the air mass factor calculation and the cloud correction. The highest glyoxal vertical column densities are mainly observed in continental tropical regions, while the mid-latitude columns strongly depend on the season with maximum values during warm months. An anthropogenic signature is also observed in highly populated regions of Asia. Comparisons with glyoxal columns simulated with IMAGESv2 in different regions of the world generally point to a missing glyoxal source, most probably of biogenic origin.
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TL;DR: In this article, the authors present the new version (v14) of the BIRA-IASB algorithm for the retrieval of formaldehyde (H2CO) columns from spaceborne UV-visible sensors.
Abstract: . We present the new version (v14) of the BIRA-IASB algorithm for the retrieval of formaldehyde (H2CO) columns from spaceborne UV–visible sensors. Applied to OMI measurements from Aura and to GOME-2 measurements from MetOp-A and MetOp-B, this algorithm is used to produce global distributions of H2CO representative of mid-morning and early afternoon conditions. Its main features include (1) a new iterative DOAS scheme involving three fitting intervals to better account for the O2–O2 absorption, (2) the use of earthshine radiances averaged in the equatorial Pacific as reference spectra, and (3) a destriping correction and background normalisation resolved in the across-swath position. For the air mass factor calculation, a priori vertical profiles calculated by the IMAGES chemistry transport model at 09:30 and 13:30 LT are used. Although the resulting GOME-2 and OMI H2CO vertical columns are found to be highly correlated, some systematic differences are observed. Afternoon columns are generally larger than morning ones, especially in mid-latitude regions. In contrast, over tropical rainforests, morning H2CO columns significantly exceed those observed in the afternoon. These differences are discussed in terms of the H2CO column variation between mid-morning and early afternoon, using ground-based MAX-DOAS measurements available from seven stations in Europe, China and Africa. Validation results confirm the capacity of the combined satellite measurements to resolve diurnal variations in H2CO columns. Furthermore, vertical profiles derived from MAX-DOAS measurements in the Beijing area and in Bujumbura are used for a more detailed validation exercise. In both regions, we find an agreement better than 15 % when MAX-DOAS profiles are used as a priori for the satellite retrievals. Finally, regional trends in H2CO columns are estimated for the 2004–2014 period using SCIAMACHY and GOME-2 data for morning conditions, and OMI for early afternoon conditions. Consistent features are observed, such as an increase of the columns in India and central–eastern China, and a decrease in the eastern US and Europe. We find that the higher horizontal resolution of OMI combined with a better sampling and a more favourable illumination at midday allow for more significant trend estimates, especially over Europe and North America. Importantly, in some parts of the Amazonian forest, we observe with both time series a significant downward trend in H2CO columns, spatially correlated with areas affected by deforestation.
161 citations
TL;DR: In this paper, an improved GOME-2 NO2 retrieval is described which reduces the scatter of the individual NO2 columns globally but in particular in the region of the Southern Atlantic Anomaly.
Abstract: . Satellite observations of nitrogen dioxide (NO2) provide valuable information on both stratospheric and tropospheric composition. Nadir measurements from GOME, SCIAMACHY, OMI, and GOME-2 have been used in many studies on tropospheric NO2 burdens, the importance of different NOx emissions sources and their change over time. The observations made by the three GOME-2 instruments will extend the existing data set by more than a decade, and a high quality of the data as well as their good consistency with existing time series is of particular importance. In this paper, an improved GOME-2 NO2 retrieval is described which reduces the scatter of the individual NO2 columns globally but in particular in the region of the Southern Atlantic Anomaly. This is achieved by using a larger fitting window including more spectral points, and by applying a two step spike removal algorithm in the fit. The new GOME-2 data set is shown to have good consistency with SCIAMACHY NO2 columns. Remaining small differences are shown to be linked to changes in the daily solar irradiance measurements used in both GOME-2 and SCIAMACHY retrievals. In the large retrieval window, a not previously identified spectral signature was found which is linked to deserts and other regions with bare soil. Inclusion of this empirically derived pseudo cross-section significantly improves the retrievals and potentially provides information on surface properties and desert aerosols. Using the new GOME-2 NO2 data set, a long-term average of tropospheric columns was computed and high-pass filtered. The resulting map shows evidence for pollution from several additional shipping lanes, not previously identified in satellite observations. This illustrates the excellent signal to noise ratio achievable with the improved GOME-2 retrievals.
131 citations
TL;DR: The first detection of glyoxal (CHOCHO) over the tropical Pacific Ocean in the Marine Boundary Layer (MBL) was made by means of the University of Colorado Ship Multi-Axis Differential Optical Absorption Spectroscopy (CU SMAX-DOAS) instrument aboard the research vessel Ronald H. Brown as mentioned in this paper.
Abstract: . We present the first detection of glyoxal (CHOCHO) over the remote tropical Pacific Ocean in the Marine Boundary Layer (MBL). The measurements were conducted by means of the University of Colorado Ship Multi-Axis Differential Optical Absorption Spectroscopy (CU SMAX-DOAS) instrument aboard the research vessel Ronald H. Brown. The research vessel was on a cruise in the framework of the VAMOS Ocean-Cloud-Atmosphere-Land Study – Regional Experiment (VOCALS-REx) and the Tropical Atmosphere Ocean (TAO) projects lasting from October 2008 through January 2009 (74 days at sea). The CU SMAX-DOAS instrument features a motion compensation system to characterize the pitch and roll of the ship and to compensate for ship movements in real time. We found elevated mixing ratios of up to 140 ppt CHOCHO located inside the MBL up to 3000 km from the continental coast over biologically active upwelling regions of the tropical Eastern Pacific Ocean. This is surprising since CHOCHO is very short lived (atmospheric life time ~2 h) and highly water soluble (Henry's Law constant H = 4.2 × 105 M/atm). This CHOCHO cannot be explained by transport of it or its precursors from continental sources. Rather, the open ocean must be a source for CHOCHO to the atmosphere. Dissolved Organic Matter (DOM) photochemistry in surface waters is a source for Volatile Organic Compounds (VOCs) to the atmosphere, e.g. acetaldehyde. The extension of this mechanism to very soluble gases, like CHOCHO, is not straightforward since the air-sea flux is directed from the atmosphere into the ocean. For CHOCHO, the dissolved concentrations would need to be extremely high in order to explain our gas-phase observations by this mechanism (40–70 μM CHOCHO, compared to ~0.01 μM acetaldehyde and 60–70 μM DOM). Further, while there is as yet no direct measurement of VOCs in our study area, measurements of the CHOCHO precursors isoprene, and/or acetylene over phytoplankton bloom areas in other parts of the oceans are too low (by a factor of 10–100) to explain the observed CHOCHO amounts. We conclude that our CHOCHO data cannot be explained by currently understood processes. Yet, it supports first global source estimates of 20 Tg/year CHOCHO from the oceans, which likely is a significant source of secondary organic aerosol (SOA). This chemistry is currently not considered by atmospheric models.
121 citations
TL;DR: In this article, the authors presented a new dataset of formaldehyde vertical columns retrieved from observations of GOME-2 on board the EUMETSAT MetOp-A platform between 2007 and 2011.
Abstract: . We present a new dataset of formaldehyde vertical columns retrieved from observations of GOME-2 on board the EUMETSAT MetOp-A platform between 2007 and 2011. The new retrieval scheme, which has been optimised for GOME-2, includes a two-step fitting procedure that strongly reduces the impact of spectral interferences between H2CO and BrO, and a modified DOAS approach that better handles ozone absorption effects at moderately low sun elevations. Owing to these new features, the noise in the H2CO slant columns is reduced by up to 40% in comparison to baseline retrieval settings used operationally. Also, the previously reported underestimation of the H2CO columns in tropical and mid-latitude regions has been largely eliminated, improving the agreement with coincident SCIAMACHY observations. To compensate for the drift of the GOME-2 slit function and to mitigate the instrumental degradation effects on H2CO retrievals, an asymmetric Gaussian line-shape is fitted during the irradiance calibration. Additionally, external parameters used in the tropospheric air mass factor computation (surface reflectances, cloud parameters and a priori profile shapes of H2CO) have been updated using most recent databases. Similar updates were also applied to the historical datasets of GOME and SCIAMACHY, leading to the generation of a consistent multi-mission H2CO data record covering the time period from 1997 until 2011. Comparing the resulting time series of monthly averaged H2CO vertical columns in 12 large regions worldwide, the correlation coefficient between SCIAMACHY and GOME-2 columns is generally higher than 0.8 in the overlap period, and linear regression slopes differ by less than 10% from unity in most of the regions. In comparison to SCIAMACHY, the largely improved spatial sampling of GOME-2 allows for a better characterisation of formaldehyde distribution at the regional scale and/or at shorter timescales, leading to a better identification of the emission sources of non-methane volatile organic compounds.
119 citations
Cooperative Institute for Research in Environmental Sciences1, University of Colorado Boulder2, National Center for Atmospheric Research3, Princeton University4, Langley Research Center5, University of Wisconsin-Madison6, National Oceanic and Atmospheric Administration7, Hong Kong University of Science and Technology8
TL;DR: In this paper, the results of two research flights (RF12, RF17) over the tropical Eastern Pacific Ocean (tEPO) as part of the "Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated hydrocarbons" (TORERO) project are presented.
Abstract: . Tropospheric chemistry of halogens and organic carbon over tropical oceans modifies ozone and atmospheric aerosols, yet atmospheric models remain largely untested for lack of vertically resolved measurements of bromine monoxide (BrO), iodine monoxide (IO) and small oxygenated hydrocarbons like glyoxal (CHOCHO) in the tropical troposphere. BrO, IO, glyoxal, nitrogen dioxide (NO2), water vapor (H2O) and O2–O2 collision complexes (O4) were measured by the University of Colorado Airborne Multi-AXis Differential Optical Absorption Spectroscopy (CU AMAX-DOAS) instrument, aerosol extinction by high spectral resolution lidar (HSRL), in situ aerosol size distributions by an ultra high sensitivity aerosol spectrometer (UHSAS) and in situ H2O by vertical-cavity surface-emitting laser (VCSEL) hygrometer. Data are presented from two research flights (RF12, RF17) aboard the National Science Foundation/National Center for Atmospheric Research Gulfstream V aircraft over the tropical Eastern Pacific Ocean (tEPO) as part of the "Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated hydrocarbons" (TORERO) project (January/February 2012). We assess the accuracy of O4 slant column density (SCD) measurements in the presence and absence of aerosols. Our O4-inferred aerosol extinction profiles at 477 nm agree within 6% with HSRL in the boundary layer and closely resemble the renormalized profile shape of Mie calculations constrained by UHSAS at low (sub-Rayleigh) aerosol extinction in the free troposphere. CU AMAX-DOAS provides a flexible choice of geometry, which we exploit to minimize the SCD in the reference spectrum (SCDREF, maximize signal-to-noise ratio) and to test the robustness of BrO, IO and glyoxal differential SCDs. The RF12 case study was conducted in pristine marine and free tropospheric air. The RF17 case study was conducted above the NOAA RV Ka'imimoana (TORERO cruise, KA-12-01) and provides independent validation data from ship-based in situ cavity-enhanced DOAS and MAX-DOAS. Inside the marine boundary layer (MBL) no BrO was detected (smaller than 0.5 pptv), and 0.2–0.55 pptv IO and 32–36 pptv glyoxal were observed. The near-surface concentrations agree within 30% (IO) and 10% (glyoxal) between ship and aircraft. The BrO concentration strongly increased with altitude to 3.0 pptv at 14.5 km (RF12, 9.1 to 8.6° N; 101.2 to 97.4° W). At 14.5 km, 5–10 pptv NO2 agree with model predictions and demonstrate good control over separating tropospheric from stratospheric absorbers (NO2 and BrO). Our profile retrievals have 12–20 degrees of freedom (DoF) and up to 500 m vertical resolution. The tropospheric BrO vertical column density (VCD) was 1.5 × 1013 molec cm−2 (RF12) and at least 0.5 × 1013 molec cm−2 (RF17, 0–10 km, lower limit). Tropospheric IO VCDs correspond to 2.1 × 1012 molec cm−2 (RF12) and 2.5 × 1012 molec cm−2 (RF17) and glyoxal VCDs of 2.6 × 1014 molec cm−2 (RF12) and 2.7 × 1014 molec cm−2 (RF17). Surprisingly, essentially all BrO as well as the dominant IO and glyoxal VCD fraction was located above 2 km (IO: 58 ± 5%, 0.1–0.2 pptv; glyoxal: 52 ± 5%, 3–20 pptv). To our knowledge there are no previous vertically resolved measurements of BrO and glyoxal from aircraft in the tropical free troposphere. The atmospheric implications are briefly discussed. Future studies are necessary to better understand the sources and impacts of free tropospheric halogens and oxygenated hydrocarbons on tropospheric ozone, aerosols, mercury oxidation and the oxidation capacity of the atmosphere.
91 citations
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TL;DR: In this article, the authors developed a new emission inventory for Asia (Regional Emission inventory in ASia (REAS) Version 1.1) for the period 1980-2020.
Abstract: . We developed a new emission inventory for Asia (Regional Emission inventory in ASia (REAS) Version 1.1) for the period 1980–2020. REAS is the first inventory to integrate historical, present, and future emissions in Asia on the basis of a consistent methodology. We present here emissions in 2000, historical emissions for 1980–2003, and projected emissions for 2010 and 2020 of SO2, NOx, CO, NMVOC, black carbon (BC), and organic carbon (OC) from fuel combustion and industrial sources. Total energy consumption in Asia more than doubled between 1980 and 2003, causing a rapid growth in Asian emissions, by 28% for BC, 30% for OC, 64% for CO, 108% for NMVOC, 119% for SO2, and 176% for NOx. In particular, Chinese NOx emissions showed a marked increase of 280% over 1980 levels, and growth in emissions since 2000 has been extremely high. These increases in China were mainly caused by increases in coal combustion in the power plants and industrial sectors. NMVOC emissions also rapidly increased because of growth in the use of automobiles, solvents, and paints. By contrast, BC, OC, and CO emissions in China showed decreasing trends from 1996 to 2000 because of a reduction in the use of biofuels and coal in the domestic and industry sectors. However, since 2000, Chinese emissions of these species have begun to increase. Thus, the emissions of air pollutants in Asian countries (especially China) showed large temporal variations from 1980–2003. Future emissions in 2010 and 2020 in Asian countries were projected by emission scenarios and from emissions in 2000. For China, we developed three emission scenarios: PSC (policy success case), REF (reference case), and PFC (policy failure case). In the 2020 REF scenario, Asian total emissions of SO2, NOx, and NMVOC were projected to increase substantially by 22%, 44%, and 99%, respectively, over 2000 levels. The 2020 REF scenario showed a modest increase in CO (12%), a lesser increase in BC (1%), and a slight decrease in OC (−5%) compared with 2000 levels. However, it should be noted that Asian total emissions are strongly influenced by the emission scenarios for China.
1,388 citations
"Glyoxal vertical columns from GOME-..." refers methods in this paper
...In particular, the annual anthropogenic NMVOC emissions are obtained from the RETRO database for 2000 (available at: retro.enes.org/dataemissions.shtml), except over Asia, where we use the REAS inventory for anthropogenic CO, NOx and NMVOC emissions (Ohara et al., 2007)....
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TL;DR: In this paper, an update to the previous protocol is presented, which has been used to define degradation schemes for 107 non-aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3).
Abstract: . Kinetic and mechanistic data relevant to the tropospheric degradation of volatile organic compounds (VOC), and the production of secondary pollutants, have previously been used to define a protocol which underpinned the construction of a near-explicit Master Chemical Mechanism. In this paper, an update to the previous protocol is presented, which has been used to define degradation schemes for 107 non-aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3). The treatment of 18 aromatic VOC is described in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the reactions of the radical intermediates and the further degradation of first and subsequent generation products. Emphasis is placed on updating the previous information, and outlining the methodology which is specifically applicable to VOC not considered previously (e.g. a - and b -pinene). The present protocol aims to take into consideration work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Application of MCM v3 in appropriate box models indicates that the representation of isoprene degradation provides a good description of the speciated distribution of oxygenated organic products observed in reported field studies where isoprene was the dominant emitted hydrocarbon, and that the a -pinene degradation chemistry provides a good description of the time dependence of key gas phase species in a -pinene/NOX photo-oxidation experiments carried out in the European Photoreactor (EUPHORE). Photochemical Ozone Creation Potentials (POCP) have been calculated for the 106 non-aromatic non-methane VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. Where applicable, the values are compared with those calculated with previous versions of the MCM.
1,274 citations
"Glyoxal vertical columns from GOME-..." refers methods in this paper
...…et al., 2008; Butler et al., 2008) is used, whereas for the other species the oxidation scheme is designed so as to reproduce the glyoxal yields derived from box model simulations using the quasiexplicit Master Chemical Mechanism (http://mcm.leeds.ac. uk/MCM/home.htt, Saunders et al., 2003)....
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...All reference cross-section data sets, listed in Table 1, have been degraded at the GOME2 resolution using the slit function data measured by Siddans et al.(2006). The Ring effect is treated as a pseudo-absorber for which a reference spectrum, calculated as in Chance and Spurr(1997), is also included in the fit....
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TL;DR: It is proposed that natural VOC oxidation, notably of isoprene, recycles OH efficiently in low-NOx air through reactions of organic peroxy radicals, which demonstrates that the biosphere maintains a remarkable balance with the atmospheric environment.
Abstract: Terrestrial vegetation, especially tropical rain forest, releases vast quantities of volatile organic compounds (VOCs) to the atmosphere, which are removed by oxidation reactions and deposition of reaction products. The oxidation is mainly initiated by hydroxyl radicals (OH), primarily formed through the photodissociation of ozone. Previously it was thought that, in unpolluted air, biogenic VOCs deplete OH and reduce the atmospheric oxidation capacity. Conversely, in polluted air VOC oxidation leads to noxious oxidant build-up by the catalytic action of nitrogen oxides (NO(x) = NO + NO2). Here we report aircraft measurements of atmospheric trace gases performed over the pristine Amazon forest. Our data reveal unexpectedly high OH concentrations. We propose that natural VOC oxidation, notably of isoprene, recycles OH efficiently in low-NO(x) air through reactions of organic peroxy radicals. Computations with an atmospheric chemistry model and the results of laboratory experiments suggest that an OH recycling efficiency of 40-80 per cent in isoprene oxidation may be able to explain the high OH levels we observed in the field. Although further laboratory studies are necessary to explore the chemical mechanism responsible for OH recycling in more detail, our results demonstrate that the biosphere maintains a remarkable balance with the atmospheric environment.
767 citations
"Glyoxal vertical columns from GOME-..." refers methods in this paper
...For isoprene, the MIM2+ chemical mechanism (Lelieveld et al., 2008; Butler et al., 2008) is used, whereas for the other species the oxidation scheme is designed so as to reproduce the glyoxal yields derived from box model simulations using the quasiexplicit Master Chemical Mechanism…...
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01 Jan 2008
686 citations
"Glyoxal vertical columns from GOME-..." refers methods in this paper
...Glyoxal is characterized by absorption bands in the visible region (400–460 nm), making its detection possible using the Differential Optical Absorption Spectroscopy (DOAS) technique (Platt and Stutz, 2008), as primarily demonstrated by Volkamer et al.(2005b)....
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...Glyoxal is characterized by absorption bands in the visible region (400–460 nm), making its detection possible using the Differential Optical Absorption Spectroscopy (DOAS) technique (Platt and Stutz , 2008), as primarily demonstrated by Volkamer et al.(2005b). However, such measurements remain challenging, especially from spaceborne instruments, due to the overall faintness of the CHOCHO signal....
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...The glyoxal vertical column retrievals from the GOME-2 spectra are based on the DOAS technique (Platt and Stutz, 2008), which implies a two step procedure....
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TL;DR: In this article, the authors measured the NO2 absorption cross-section from 42 000 to 10 000 cm−1 (238-1000 nm) with a Fourier transform spectrometer (at the resolution of 2 cm− 1, 0.01 nm at 240 nm to 0.2 nm at 1000 nm).
Abstract: The NO2 absorption cross-section has been measured from 42 000 to 10 000 cm−1 (238–1000 nm) with a Fourier transform spectrometer (at the resolution of 2 cm−1, 0.01 nm at 240 nm to 0.2 nm at 1000 nm) and a 5 m temperature controlled multiple reflection cell. The uncertainty on the cross-section is estimated to be less than 3% below 40 000 cm−1 (λ > 250 nm) at 294 K, 3% below 30 000 cm−1 (λ > 333 nm) at 220 K, but reaches 10% for higher wavenumbers. Temperature and pressure effects have been observed. Comparison with data from the literature generally shows a good agreement for wavenumbers between 37 500 and 20 000 cm−1 (267–500 nm). Outside these limits, the difference can reach several percent.
684 citations