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Satellite observations of formaldehyde (HCHO) columns provide top-down information on emissions of highly reactive volatile organic compounds (VOCs). We examine the long-term trends in HCHO columns observed by the Ozone Monitoring Instrument (OMI) from 2005 to 2014 across North America. Biogenic isoprene is the dominant source of HCHO and its emission has a large temperature dependence. After correcting for this dependence, we find a general pattern of increases in much of North America but decreases in the southeastern US. Over the Houston-Galveston-Brazoria industrial area, HCHO columns decreased by 2.2% a-1 from 2005 to 2014, consistent with trends in emissions of anthropogenic VOCs. Over the Cold Lake Oil Sands in the southern Alberta in Canada, HCHO columns increased by 3.8% a-1, consistent with the increase in crude oil production there. HCHO variability in the northwestern US and Midwest could be related to afforestation and corn silage production. Although NOx levels can affect the HCHO yield from isoprene oxidation, we find that decreases in anthropogenic NOx emissions made only a small contribution to the observed HCHO trends.

Balloon-borne observations of concentrations of OH, HO2, H2O, and O3 in the middle and upper stratosphere are used to test our understanding of HOx photochemistry. Assuming our photochemical model is complete, the measured [OH] and [HO2] above 38 km (where HOx partitioning is no longer dependent on [NO]) are modeled best by calculations that use a 25% reduction in the ratio of the reaction rate constants for O+HO2 and O+OH as well as either a 25% reduction of the rate constant of OH+HO2 (the primary HOx sink) or a 25% increase in HOx production. All of these changes are consistent with the uncertainties in the recommended rate constants. The kinetic parameters required to explain our observations of [OH] and [HO2] do not lead to a resolution of the long-standing “ozone deficit problem” above 45 km.

The Global Ozone Monitoring Experiment (GOME), launched on the ESA ERS-2 satellite in April 1995, measures solar back scatter spectra from which atmospheric BrO columns may be derived globally with high precision (slant column uncertainties of ±3×1013 cm−2 or less). Obtaining such precision requires additional characterization of GOME spectra, reference spectra that are well calibrated in wavelength, and a fitting method capable of reproducing measurements to several parts in 104. This paper describes these elements of the data processing and gives examples of BrO distributions in the stratosphere and enhanced tropospheric BrO in the polar springtime.

We show that atmospheric UV/visible backscatter spectra obtained by the Global Ozone Monitoring Experiment (GOME) spectrometer on board the ESA ERS-2 satellite may be used to retrieve column amounts of key trace species associated with smoke cloud combustion from biomass burning events. This paper focuses on the recent rain forest burning in SE Asia (August–October 1997). For ground scenes with low cloudiness, differential absorption fitting applied to backscatter spectra yields column distributions of NO2 and H2CO in and around smoke-polluted regions. A two-fold increase in the vertical NO2 content is apparent over large parts of the smoke cloud; this clearly indicates the ability of GOME to measure tropospheric NO2 content. H2CO is detected only in areas closest to combustion sources. Slant column amounts in the range 2.5 - 4 × 1016 mol cm−2 have been determined; these correspond with previous estimations of vertical columns of H2CO for biomass Savannah burning.

We present laboratory measurements of the absorption cross sections of the ν5 band (540–580 cm−1) of chlorine nitrate made under stratospheric conditions of temperature and pressure. We use the measured cross sections and observed mid-infrared stratospheric emission spectra to retrieve mid-latitude vertical mixing ratio profiles for both day and night in the altitude range 20–34 km, and compare the results with a sunset profile obtained simultaneously from solar absorption measurements of the ν4 Q branch at 780 cm−1. The profiles obtained using these two methods are shown to be in excellent agreement, validating retrievals using the ν4 band. We also find good agreement in this altitude range between the observed day/night ratio and the results of a 1-D photochemical model

We measured column abundances of HF, HCl, O3, HNO3, and H2O on the NASA DC-8 during the AASE II campaign, using thermal emission spectroscopy. We made multiple traversals of the Arctic vortex and surroundings. Using HF as a tracer, we remove the effects of subsidence from the measured column abundances; perturbations in the resulting column abundances are attributed to chemical processing. We find that by January 1992 the stratospheric column in the vortex had been chemically depleted by about (55+/-10)% in HCl and (35+/-10)% in O3, and enhanced by about (15+/-10)% in HNO3 and (0+/-10)% in H2O.

[1] Anthropogenic emissions of nitrogen oxides (NOx) can change rapidly due to economic growth or control measures. Bottom-up emissions estimated using source-specific emission factors and activity statistics require years to compile and can become quickly outdated. We present a method to use satellite observations of tropospheric NO2 columns to estimate changes in NOx emissions. We use tropospheric NO2 columns retrieved from the SCIAMACHY satellite instrument for 2003–2009, the response of tropospheric NO2 columns to changes in NOx emissions determined from a global chemical transport model (GEOS-Chem), and the bottom-up anthropogenic NOx emissions for 2006 to hindcast and forecast the inventories. We evaluate our approach by comparing bottom-up and hindcast emissions for 2003. The two inventories agree within 6.0% globally and within 8.9% at the regional scale with consistent trends in western Europe, North America, and East Asia. We go on to forecast emissions for 2009. During 2006–2009, anthropogenic NOx emissions over land increase by 9.2% globally and by 18.8% from East Asia. North American emissions decrease by 5.7%.

[1] Emission of bromine from sea-salt aerosol, frost flowers, ice leads, and snow results in the nearly complete removal of surface ozone during Arctic spring. Regions of enhanced total column BrO observed by satellites have traditionally been associated with these emissions. However, airborne measurements of BrO and O3 within the convective boundary layer (CBL) during the ARCTAS and ARCPAC field campaigns at times bear little relation to enhanced column BrO. We show that the locations of numerous satellite BrO “hotspots” during Arctic spring are consistent with observations of total column ozone and tropopause height, suggesting a stratospheric origin to these regions of elevated BrO. Tropospheric enhancements of BrO large enough to affect the column abundance are also observed, with important contributions originating from above the CBL. Closure of the budget for total column BrO, albeit with significant uncertainty, is achieved by summing observed tropospheric partial columns with calculated stratospheric partial columns provided that natural, short-lived biogenic bromocarbons supply between 5 and 10 ppt of bromine to the Arctic lowermost stratosphere. Proper understanding of bromine and its effects on atmospheric composition requires accurate treatment of geographic variations in column BrO originating from both the stratosphere and troposphere.

An upper limit is measured for stratospheric HBr from three balloon flights. The observations were made with the FIRS-2 far-infrared Fourier transform spectrometer. The 1sigma upper limits from the 1988, 1989, and 1990 balloon flights are 13 pptv at 35 km, 7 pptv at 32 km, and 3 pptv at 31 km, respectively. Combining all 3 flights, the weighted average 1sigma upper limit for HBr is 4 pptv at 32 km. This value is significantly smaller than the only other previously published spectroscopic value of 20 +/- 7 pptv (2sigma), but is consistent with a theoretical estimate which predicts roughly 0.4 pptv at this altitude.

[1] Global Ozone Monitoring Experiment (GOME) observations from 1997-2000 have revealed the Tibetan Middle Tropospheric Ozone Minimum (TMTOM), a low-ozone layer that occurs in the middle troposphere over the Tibetan Plateau (TP) in June. Ozone profiles were derived from GOME observations and validated by ozonesonde measurements at two stations (Lhasa and Xining) over the TP. The mean bias is 5-10% within the troposphere. The ozone profiles reveal the TMTOM phenomenon occurs in the middle troposphere (8-13 km) over the middle and eastern TP in June. Dynamical field analyses showed that the TMTOM accompanies the onset of the Asian summer monsoon. The low-ozone air from the Bay of Bengal is transported into the middle troposphere over the TP by southwest currents while the lower troposphere over the TP is still occupied by ozone-rich air blocked by the transport barrier of the Himalayas. The TMTOM was most prominent in June 1998 likely linked to the occurrence of the intense El Nino of 1997-1998 because the Tibetan anticyclone is of large area and has strong intensity during El Nino years. The occurrence of the TMTOM can serve as an indicator of the phase of evolution of the Asian summer monsoon.

The first unequivocal measurement of hydrogen peroxide in the stratosphere have been made, a concentration profile obtained from a balloon platform using Fourier transform thermal emission spectroscopy in the far infrared. Measurements were made using the 112/cm R-Q5 branch of the rotational-torsional spectrum, with some confirmation from the 94/cm R-Q4 branch. The volume mixing ratio of H2O2 is 1.6 x 10 to the -10th at 38.4 km, decreasing to 0.6 x 10 to the -10th at 23.8 km, with uncertainties of about 16 percent. These measurements are compared to a recent stratospheric model calculation.

We present retrievals of IO total columns from the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) satellite instrument. We analyze data for October 2005 in the polar regions to demonstrate for the first time the capability to measure IO column abundances from space. During the period of analysis (i.e. Southern Hemisphere springtime), enhanced IO vertical columns over 3 x 10(exp 13) molecules cm(exp -2) are observed around coastal Antarctica; by contrast during that time in the Arctic region IO is consistently below the calculated instrumental detection limit for individual radiance spectra (2-4 x 10(exp 12) molecules cm(exp -2) for slant columns). The levels reported here are in reasonably good agreement with previous ground-based measurements at coastal Antarctica. These results also demonstrate that IO is widespread over sea-ice covered areas in the Southern Ocean. The occurrence of elevated IO and its hitherto unrecognized spatial distribution suggest an efficient iodine activation mechanism at a synoptic scale over coastal Antarctica.

[1] We perform a study for characterizing the vertical resolution of tropospheric ozone profile retrievals from the combination of simulated ultraviolet (UV) and thermal infrared (TIR) observations that are representative of the EOS Aura Ozone Monitoring Instrument (OMI) and the Tropospheric Emission Spectrometer (TES). Under the low thermal contrast conditions used for this simulation, we find that estimating ozone profiles by combining UV and TIR radiances results in a factor of two or more improvement in the ability to resolve boundary layer ozone, as compared with either instrument alone. In addition, there is a substantial improvement in the vertical resolution of ozone in the free troposphere (between 20% and 60%) as compared to the TES vertical resolution. This study points towards the importance of combining multiple spectral regions for dramatically improving the sounding of tropospheric trace gases.

Measurements of BrO suggest that inorganic bromine (Br_y) at and above the tropopause is 4 to 8 ppt greater than assumed in models used in past ozone trend assessment studies. This additional bromine is likely carried to the stratosphere by short-lived biogenic compounds and their decomposition products, including tropospheric BrO. Including this additional bromine in an ozone trend simulation increases the computed ozone depletion over the past ∼25 years, leading to better agreement between measured and modeled ozone trends. This additional Br_y (assumed constant over time) causes more ozone depletion because associated BrO provides a reaction partner for ClO, which increases due to anthropogenic sources. Enhanced Br_y causes photochemical loss of ozone below ∼14 km to change from being controlled by HO_x catalytic cycles (primarily HO_2+O_3) to a situation where loss by the BrO+HO_2 cycle is also important.

Column observations of NO2 by GOME and CO by MOPITT over North America and surrounding oceans for April 2000 are analyzed using a regional chemical transport model. Transient enhancements in these measurements due to lightning NOx production or convective transport are examined. Evidence is found for lightning enhancements of NO2 over the continent and western North Atlantic and for convective transport enhancements of CO over the ocean. The two independent satellite measurements show consistent enhancements related to convective events. Model results suggest that the enhancements are particularly large in the lower troposphere due to convective downdrafts of lightning NOx and shallow convection of CO, implying that low-altitude aircraft in situ observations are potentially critical for evaluating the model simulations and validating satellite observations of these transient features.

Using a simple photochemical model we derive the mixing ratio profile of ClO in the altitude range 20–38 km from simultaneous measurements of HO2, OH, HOCl, temperature, pressure, and ozone. The measurements were made with the FIRS-2 far-infrared spectrometer during a balloon flight on September 29, 1992. We compare the derived ClO with the ClO profile obtained by the SLS instrument while flying on the same gondola. The good agreement between the two profiles validates our simple model and confirms the relevant rate constants and photolysis cross sections.

[1] Springtime near-surface ozone depletion has been observed at northern high latitudes. Due to limited observations, the spatial and temporal extent of low O3 concentrations near the surface is still unknown. A regional 3-D chemistry and transport model is applied to simulate surface O3 depletion catalyzed by bromine radicals at northern high latitudes in March and April 2000. Satellite observations of BrO column by the ESA Global Ozone Monitoring Experiment (GOME) were processed to specify the BrO concentrations in the lower troposphere. In view of the GOME measurement and model uncertainties, the model results show an adequate agreement with the O3 depletion events observed at two surface sites, Alert, Canada (82.5°N, 62.3°W) and Barrow, Alaska (71.3°N, 156.6°W), and by airborne in situ and DIAL instrument during the TOPSE experiments at northern high latitudes. Low O3 events at Alert appear to be mostly driven by transport of O3-poor air from high BrO regions. Model results indicate that low O3 concentrations (

[1] Formaldehyde (HCHO) columns measured from space by solar UV backscatter allow mapping of reactive hydrocarbon emissions. The principal contributor to these emissions during the growing season is the biogenic hydrocarbon isoprene, which is of great importance for driving regional and global tropospheric chemistry. We present seven years (1995–2001) of HCHO column data for North America from the Global Ozone Monitoring Experiment (GOME), and show that the general seasonal and interannual variability of these data is consistent with knowledge of isoprene emission. There are some significant regional discrepancies with the seasonal patterns predicted from current isoprene emission models, and we suggest that these may reflect flaws in the models. The interannual variability of HCHO columns observed by GOME appears to follow the interannual variability of surface temperature, as expected from current isoprene emission models.

Using an NBS laser-based tunable far-infrared spectrometer, the air- and oxygen-broadening coefficients were measured for the J = 10 - 10, N = 11 - 9 O2 rotational transition at 60.46/cm (1.812 THz). The air-broadening coefficient is 5.04 + or - 0.38 x 10 to the -7th/cm/Pa (0.0511 + or - 0.0039/cm/atm) (HWHM) at 245 + or - 6 K; the oxygen-broadening coefficient is 4.92 + or - 0.47 x 10 to the -7th/cm/Pa (0.0499 + or - 0.0048/cm/atm) (HWHM) at 259 + or -2 K. These direct experimental measurements of the air-broadening coefficient should improve the accuracy of retrieval calculations for far-infrared stratospheric balloon experiments which use O2 rotational lines to calibrate the viewing geometry.

Thermal emission from three rotational lines of H(Cl-35) and H(Cl-37) was observed with a Fourier transform spectrometer from a balloon platform at 28.9 km. The measured HCl line-of-sight density at 1.9 deg elevation above 28.9 km is 4.7 + or - 1.3 x 10 to the 15th/sq cm, implying an average volume mixing ratio of 0.8 + or - 0.2 x 10 to the -9th at the mean sampling altitude of 32.5 km. For a uniform mixing ratio model, this corresponds to a vertical column density of 2.4 + or - 0.6 x 10 to the 14th/sq cm. This result is in reasonable agreement with near infrared spectroscopic determinations and an abundance from a chemical sampling technique of HCl at this altitude; a pressure modulator radiometer measurement yields a significantly higher amount of HCl.