Estimating European volatile organic compound emissions using satellite observations of formaldehyde from the Ozone Monitoring Instrument

Emission of non-methane Volatile Organic Compounds (VOCs) to the atmosphere stems from biogenic and human activities, and their estimation is difficult because of the many and not fully understood processes involved. In order to narrow down the uncertainty related to VOC emissions, which negatively reflects on our ability to simulate the atmospheric composition, we exploit satellite observations of formaldehyde (HCHO), an ubiquitous oxidation product of most VOCs, focusing on Europe. HCHO column observations from the Ozone Monitoring Instrument (OMI) reveal a marked seasonal cycle with a summer maximum and winter minimum. In summer, the oxidation of methane and other long-lived VOCs supply a slowly varying background HCHO column, while HCHO variability is dominated by most reactive VOC, primarily biogenic isoprene followed in importance by biogenic terpenes and anthropogenic VOCs. The chemistry-transport model CHIMERE qualitatively reproduces the temporal and spatial features of the observed HCHO column, but display regional biases which are attributed mainly to incorrect biogenic VOC emissions, calculated with the Model of Emissions of Gases and Aerosol from Nature (MEGAN) algorithm. These "bottom-up" or a-priori emissions are corrected through a Bayesian inversion of the OMI HCHO observations. Resulting "top-down" or a-posteriori isoprene emissions are lower than "bottom-up" by 40% over the Balkans and by 20% over Southern Germany, and higher by 20% over Iberian Peninsula, Greece and Italy. We conclude that OMI satellite observations of HCHO can provide a quantitative "top-down" constraint on the European "bottom-up" VOC inventories

Improved ozone profile retrievals from GOME data with degradation correction in reflectance

We present a simple method to perform degradation correction to Global Ozone Monitoring Experiment (GOME) reflectance spectra by comparing the average reflectance for 60° N–60° S with that at the beginning of GOME observations (July–December 1995) after removing the dependences on solar zenith angle and seasonal variation. The results indicate positive biases of up to ~15–25% in the wavelength range 289–370 nm during 2000–2002; the degradation also exhibits significant dependence on wavelength and viewing zenith angle. These results are consistent with previous studies using radiative transfer models and ozone observations. The degradation causes retrieval biases of up to ~3% (10 DU, 1 DU=2.69×10¹⁶ molecules cm^−2), 30% (10 DU), 10%, and 40% in total column ozone, tropospheric column ozone, stratospheric ozone and tropospheric ozone, respectively, from our GOME ozone profile retrieval algorithm. In addition, retrieval biases due to degradation vary significantly with latitude. The application of this degradation correction improves the retrievals relative to Dobson and ozonesonde measurements at Hohenpeißenberg station during 2000–2003 and improves the spatiotemporal consistency of retrieval quality during 1996–2003. However, because this method assumes that the deseasonalized globally-averaged reflectance does not change much with time, retrievals with this correction may be inadequate for trend analysis. In addition, it does not correct for instrument biases that have occurred since launch

Mapping isoprene emissions over North America using formaldehyde column observations from space

We present a methodology for deriving emissions of volatile organic compounds (VOC) using space-based column observations of formaldehyde (HCHO) and apply it to data from the Global Ozone Monitoring Experiment (GOME) satellite instrument over North America during July 1996. The HCHO column is related to local VOC emissions, with a spatial smearing that increases with the VOC lifetime. Isoprene is the dominant HCHO precursor over North America in summer, and its lifetime (≃1 hour) is sufficiently short that the smearing can be neglected. We use the Goddard Earth Observing System global 3-D model of tropospheric chemistry (GEOS-CHEM) to derive the relationship between isoprene emissions and HCHO columns over North America and use these relationships to convert the GOME HCHO columns to isoprene emissions. We also use the GEOS-CHEM model as an intermediary to validate the GOME HCHO column measurements by comparison with in situ observations. The GEOS-CHEM model including the Global Emissions Inventory Activity (GEIA) isoprene emission inventory provides a good simulation of both the GOME data (r2 = 0.69, n = 756, bias = +11%) and the in situ summertime HCHO measurements over North America (r2 = 0.47, n = 10, bias = −3%). The GOME observations show high values over regions of known high isoprene emissions and a day-to-day variability that is consistent with the temperature dependence of isoprene emission. Isoprene emissions inferred from the GOME data are 20% less than GEIA on average over North America and twice those from the U.S. EPA Biogenic Emissions Inventory System (BEIS2) inventory. The GOME isoprene inventory when implemented in the GEOS-CHEM model provides a better simulation of the HCHO in situ measurements than either GEIA or BEIS2 (r2 = 0.71, n = 10, bias = −10%)

Impact of using different ozone cross sections on ozone profile retrievals from Global Ozone Monitoring Experiment (GOME) ultraviolet measurements

We investigate the effect of using three different cross section data sets on ozone profile retrievals from Global Ozone Monitoring Experiment (GOME) ultraviolet measurements (289–307 nm, 326–337 nm). These include Bass-Paur, Brion, and GOME flight model cross sections (references below). Using different cross sections can significantly affect the retrievals, by up to 12 Dobson Units (DU, 1 DU=2.69×10<sup>16</sup> molecules cm<sup>−2</sup>) in total column ozone, up to 10 DU in tropospheric column ozone, and up to 100% in retrieved ozone values for individual atmospheric layers. Compared to using the Bass-Paur and GOME flight model cross sections, using the Brion cross sections not only reduces fitting residuals by 15–60% in the Huggins bands, but also improves retrievals, especially in the troposphere, as seen from validation against ozonesonde measurements. Therefore, we recommend using the Brion cross section for ozone profile retrievals from ultraviolet measurements. The total column ozone retrieved using the GOME flight model cross sections is systematically lower, by 7–10 DU, than that retrieved using the Brion and Bass-Paur cross sections and is also systematically lower than Total Ozone Mapping Spectrometer (TOMS) observations. This study demonstrates the need for improved ozone cross section measurements in the ultraviolet to improve profile retrievals of this key atmospheric constituent

Characteristics of tropospheric ozone depletion events in the Arctic spring: analysis of the ARCTAS, ARCPAC, and ARCIONS measurements and satellite BrO observations

Arctic ozone depletion events (ODEs) are caused by halogen catalyzed ozone loss. In situ chemistry, advection of ozone-poor air mass, and vertical mixing in the lower troposphere are important factors affecting ODEs. To better characterize the ODEs, we analyze the combined set of surface, ozonesonde, and aircraft in situ measurements of ozone and bromine compounds during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS), the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC), and the Arctic Intensive Ozonesonde Network Study (ARCIONS) experiments (April 2008). Tropospheric BrO columns retrieved from satellite measurements and back trajectory calculations are also used to investigate the characteristics of observed ODEs. In situ observations from these field experiments are inadequate to validate tropospheric BrO columns derived from satellite measurements. In view of this difficulty, we construct an ensemble of tropospheric column BrO estimates from two satellite (OMI and GOME-2) measurements and with three independent methods of calculating stratospheric BrO columns. Furthermore, we select analysis methods that do not depend on the absolute magnitude of column BrO, such as time-lagged correlation analysis of ozone and tropospheric column BrO, to understand characteristics of ODEs. Time-lagged correlation analysis between in situ (surface and ozonesonde) measurements of ozone and satellite derived tropospheric BrO columns indicates that the ODEs are due to either local halogen-driven ozone loss or short-range (∼1 day) transport from nearby regions with ozone depletion. The effect of in situ ozone loss is also evident in the diurnal variation difference between low (10th and 25th percentiles) and higher percentiles of surface ozone concentrations at Alert, Canada. Aircraft observations indicate low-ozone air mass transported from adjacent high-BrO regions. Correlation analyses of ozone with potential temperature and time-lagged tropospheric BrO column show that the vertical extent of local ozone loss is surprisingly deep (1–2 km) at Resolute and Churchill, Canada. The unstable boundary layer during ODEs at Churchill could potentially provide a source of free-tropospheric BrO through convective transport and explain the significant negative correlation between free-tropospheric ozone and tropospheric BrO column at this site

Quenched Narrow-Line Laser Cooling of 40Ca to Near the Photon Recoil Limit

We present a cooling method that should be generally applicable to atoms with narrow optical transitions. This technique uses velocity-selective pulses to drive atoms towards a zero-velocity dark state and then quenches the excited state to increase the cooling rate. We demonstrate this technique of quenched narrow-line cooling by reducing the 1-D temperature of a sample of neutral 40Ca atoms. We velocity select and cool with the 1S0(4s2) to 3P1(4s4p) 657 nm intercombination line and quench with the 3P1(4s4p) to 1S0(4s5s) intercombination line at 553 nm, which increases the cooling rate eight-fold. Limited only by available quenching laser power, we have transferred 18 % of the atoms from our initial 2 mK velocity distribution and achieved temperatures as low as 4 microK, corresponding to a vrms of 2.8 cm/s or 2 recoils at 657 nm. This cooling technique, which is closely related to Raman cooling, can be extended to three dimensions.Comment: 5 pages, 4 figures; Submitted to PRA Rapid Communication

Global satellite analysis of the relation between aerosols and short-lived trace gases

The spatial and temporal correlations between concurrent satellite observations of aerosol optical thickness (AOT) from the Moderate Resolution Imaging Spectroradiometer (MODIS) and tropospheric columns of nitrogen dioxide (NO<sub>2</sub>), sulfur dioxide (SO<sub>2</sub>), and formaldehyde (HCHO) from the Ozone Monitoring Instrument (OMI) are used to infer information on the global composition of aerosol particles. When averaging the satellite data over large regions and longer time periods, we find significant correlation between MODIS AOT and OMI trace gas columns for various regions in the world. This shows that these enhanced aerosol and trace gas concentrations originate from common sources, such as fossil fuel combustion, biomass burning, and organic compounds released from the biosphere. This leads us to propose that satellite-inferred AOT to NO<sub>2</sub> ratios for regions with comparable photochemical regimes can be used as indicators for the relative regional pollution control of combustion processes. Indeed, satellites observe low AOT to NO<sub>2</sub> ratios over the eastern United States and western Europe, and high AOT to NO<sub>2</sub> ratios over comparably industrialized regions in eastern Europe and China. Emission databases and OMI SO<sub>2</sub> observations over these regions suggest a much stronger sulfur contribution to aerosol formation than over the well-regulated areas of the eastern United States and western Europe. Furthermore, satellite observations show AOT to NO<sub>2</sub> ratios are a factor 100 higher over biomass burning regions than over industrialized areas, reflecting the unregulated burning practices with strong primary particle emissions in the tropics compared to the heavily controlled combustion processes in the industrialized Northern Hemisphere. Simulations with a global chemistry transport model (GEOS-Chem) capture most of these variations, although on regional scales significant differences are found. Wintertime aerosol concentrations show strongest correlations with NO<sub>2</sub> throughout most of the Northern Hemisphere. During summertime, AOT is often (also) correlated with enhanced HCHO concentrations, reflecting the importance of secondary organic aerosol formation in that season. We also find significant correlations between AOT and HCHO over biomass burning regions, the tropics in general, and over industrialized regions in southeastern Asia. The distinct summertime maximum in AOT (0.4 at 550 nm) and HCHO over the southeastern United States strengthens existing hypotheses that local emissions of volatile organic compounds lead to the formation of secondary organic aerosols there. GEOS-Chem underestimates the AOT over the southeastern United States by a factor of 2, most likely due to too strong precipitation and too low SOA yield in the model

Analysis of satellite-derived Arctic tropospheric BrO columns in conjunction with aircraft measurements during ARCTAS and ARCPAC

We derive tropospheric column BrO during the ARCTAS and ARCPAC field campaigns in spring 2008 using retrievals of total column BrO from the satellite UV nadir sensors OMI and GOME-2 using a radiative transfer model and stratospheric column BrO from a photochemical simulation. We conduct a comprehensive comparison of satellite-derived tropospheric BrO column to aircraft in-situ observations of BrO and related species. The aircraft profiles reveal that tropospheric BrO, when present during April 2008, was distributed over a broad range of altitudes rather than being confined to the planetary boundary layer (PBL). Perturbations to the total column resulting from tropospheric BrO are the same magnitude as perturbations due to longitudinal variations in the stratospheric component, so proper accounting of the stratospheric signal is essential for accurate determination of satellite-derived tropospheric BrO. We find reasonably good agreement between satellite-derived tropospheric BrO and columns found using aircraft in-situ BrO profiles, particularly when satellite radiances were obtained over bright surfaces (albedo \u3e0.7), for solar zenith angl

The Unique OMI HCHO/NO2 Feature During the 2008 Beijing Summer Olympics: Implications for Ozone Production Sensitivity

In preparation of the Beijing Summer Olympic and Paralympics Games, strict controls were imposed between July and September 2008 on motor vehicle traffic and industrial emissions to improve air quality for the competitors. We assessed chemical sensitivity of ozone production to these controls using Ozone Monitoring Instrument (OMI) column measurements of formaldehyde (HCHO) and nitrogen dioxide (NO2), where their ratio serves as a proxy for the sensitivity. During the emission controls, HCHO/NO2 increased and indicated a NOx-limited regime, in contrast to the same period in the preceding three years when the ratio indicates volatile organic carbon (VOC)-limited and mixed NOx-VOC-limited regimes. After the emission controls were lifted, observed NO2 and HCHO/NO2 returned to their previous values. The 2005-2008 OMI record shows that this transition in regimes was unique as ozone production in Beijing was rarely NOx-limited. OMI measured summertime increases in HCHO of around 13% in 2008 compared to prior years, the same time period during which MODIS vegetation indices increased. The OMI HCHO increase may be due to higher biogenic emissions of HCHO precursors, associated with Beijing's greening initiative for the Olympics. However, NO2 and HCHO were also found to be well-correlated during the summer months. This indicates an anthropogenic VOC contribution from vehicle emissions to OMI HCHO and is a plausible explanation for the relative HCHO minimum observed in August 2008, concurrent with a minimum in traffic emissions. We calculated positive trends in 2005-2008 OMI HCHO and NO2 of about +1 x 10(exp 14) Molec/ square M-2 and +3 x 10(exp 13) molec CM-2 per month, respectively. The positive trend in NO2 may be an indicator of increasing vehicular traffic since 2005, while the positive trend in HCHO may be due to a combined increase in anthropogenic and biogenic emissions since 2005

Collisions of cold magnesium atoms in a weak laser field

We use quantum scattering methods to calculate the light-induced collisional loss of laser-cooled and trapped magnesium atoms for detunings up to 30 atomic linewidths to the red of the 1S_0-1P_1 cooling transition. Magnesium has no hyperfine structure to complicate the theoretical studies. We evaluate both the radiative and nonradiative mechanisms of trap loss. The radiative escape mechanism via allowed 1Sigma_u excitation is dominant for more than about one atomic linewidth detuning. Molecular vibrational structure due to photoassociative transitions to bound states begins to appear beyond about ten linewidths detuning.Comment: 4 pages with 3 embedded figure