Atmospheric Chemistry Experiment Research Articles

Aerosol extinction profiles at 525 nm and 1020 nm derived from ACE imager data: comparisons with GOMOS, SAGE II, SAGE III, POAM III, and OSIRIS

Abstract. The Canadian ACE (Atmospheric Chemistry Experiment) mission is dedicated to the retrieval of a large number of atmospheric trace gas species using the solar occultation technique in the infrared and UV/visible spectral domain. However, two additional solar disk imagers (at 525 nm and 1020 nm) were added for a number of reasons, including the retrieval of aerosol and cloud products. In this paper, we present first comparison results for these imager aerosol/cloud optical extinction coefficient profiles, with the ones derived from measurements performed by 3 solar occultation instruments (SAGE II, SAGE III, POAM III), one stellar occultation instrument (GOMOS) and one limb sounder (OSIRIS). The results indicate that the ACE imager profiles are of good quality in the upper troposphere/lower stratosphere, although the aerosol extinction for the visible channel at 525 nm contains a significant negative bias at higher altitudes, while the relative differences indicate that ACE profiles are almost always too high at 1020 nm. Both problems are probably related to ACE imager instrumental issues.

Intercomparison of UV-visible measurements of ozone and NO<sub>2</sub> during the Canadian Arctic ACE validation campaigns: 2004–2006

Abstract. The first three Canadian Arctic ACE validation campaigns were held during polar sunrise at Eureka, Nunavut, Canada (80° N, 86° W) from 2004 to 2006 in support of validation of the ACE (Atmospheric Chemistry Experiment) satellite mission. Three or four zenith-sky viewing UV-visible spectrometers have taken part in each of the three campaigns. The differential slant column densities and vertical column densities of ozone and NO2 from these instruments have been compared following the methods of the UV-visible Working Group of the NDACC (Network for Detection of Atmospheric Composition Change). The instruments are found to partially agree within the required accuracies for both species, although both the vertical and slant column densities are more scattered than required. This might be expected given the spatial and temporal variability of the Arctic stratosphere in spring. The vertical column densities are also compared to integrated total columns from ozonesondes and integrated partial columns from the ACE-FTS (ACE-Fourier Transform Spectrometer) and ACE-MAESTRO (ACE-Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) instruments on board ACE. For both species, the columns from the ground-based instruments and the ozonesondes are found to generally agree within their combined error bars. The ACE-FTS ozone partial columns and the ground-based total columns agree within 4.5%, averaged over the three campaigns. The ACE-MAESTRO ozone partial columns are generally smaller than those of the ground-based instruments, by an average of 9.9%, and are smaller than the ACE-FTS columns by an average of 14.4%. The ACE-FTS NO2 partial columns are an average of 13.4% smaller than the total columns from the ground-based instruments, as expected. The ACE-MAESTRO NO2 partial columns are larger than the total columns of the ground-based instruments by an average of 2.5% and are larger than the partial columns of the ACE-FTS by an average of 15.5%.

Validation of ACE-FTS satellite data in the upper troposphere/lower stratosphere (UTLS) using non-coincident measurements

Abstract. CO, O3, and H2O data in the upper troposphere/lower stratosphere (UTLS) measured by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) on Canada's SCISAT-1 satellite are validated using aircraft and ozonesonde measurements. In the UTLS, validation of chemical trace gas measurements is a challenging task due to small-scale variability in the tracer fields, strong gradients of the tracers across the tropopause, and scarcity of measurements suitable for validation purposes. Validation based on coincidences therefore suffers from geophysical noise. Two alternative methods for the validation of satellite data are introduced, which avoid the usual need for coincident measurements: tracer-tracer correlations, and vertical tracer profiles relative to tropopause height. Both are increasingly being used for model validation as they strongly suppress geophysical variability and thereby provide an "instantaneous climatology". This allows comparison of measurements between non-coincident data sets which yields information about the precision and a statistically meaningful error-assessment of the ACE-FTS satellite data in the UTLS. By defining a trade-off factor, we show that the measurement errors can be reduced by including more measurements obtained over a wider longitude range into the comparison, despite the increased geophysical variability. Applying the methods then yields the following upper bounds to the relative differences in the mean found between the ACE-FTS and SPURT aircraft measurements in the upper troposphere (UT) and lower stratosphere (LS), respectively: for CO ±9% and ±12%, for H2O ±30% and ±18%, and for O3 ±25% and ±19%. The relative differences for O3 can be narrowed down by using a larger dataset obtained from ozonesondes, yielding a high bias in the ACE-FTS measurements of 18% in the UT and relative differences of ±8% for measurements in the LS. When taking into account the smearing effect of the vertically limited spacing between measurements of the ACE-FTS instrument, the relative differences decrease by 5–15% around the tropopause, suggesting a vertical resolution of the ACE-FTS in the UTLS of around 1 km. The ACE-FTS hence offers unprecedented precision and vertical resolution for a satellite instrument, which will allow a new global perspective on UTLS tracer distributions.

Chemical isolation in the Asian monsoon anticyclone observed in Atmospheric Chemistry Experiment (ACE-FTS) data

Abstract. Evidence of chemical isolation in the Asian monsoon anticyclone is presented using chemical constituents obtained from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer instrument during summer (June–August) of 2004–2006. Carbon monoxide (CO) shows a broad maximum over the monsoon anticyclone region in the upper troposphere and lower stratosphere (UTLS); these enhanced CO values are associated with air pollution transported upward by convection, and confined by the strong anticyclonic circulation. Profiles inside the anticyclone show enhancement of tropospheric tracers CO, HCN, C2H6, and C2H2 between ~12 to 20 km, with maxima near 13–15 km. Strong correlations are observed among constituents, consistent with sources from near-surface pollution and biomass burning. Stratospheric tracers (O3, HNO3 and HCl) exhibit decreased values inside the anticyclone between ~12–20 km. These observations are further evidence of transport of lower tropospheric air into the UTLS region, and isolation of air within the anticyclone. The relative enhancements of tropospheric species inside the anticyclone are closely related to the photochemical lifetime of the species, with strongest enhancement for shorter lived species. Vertical profiles of the ratio of C2H2/CO (used to measure the relative age of air) suggest relatively rapid transport of fresh emissions up to the tropopause level inside the anticyclone.

The high Arctic in extreme winters: vortex, temperature, and MLS and ACE-FTS trace gas evolution

Abstract. The first three Arctic winters of the ACE mission represented two extremes of winter variability: Stratospheric sudden warmings (SSWs) in 2004 and 2006 were among the strongest, most prolonged on record; 2005 was a record cold winter. Canadian Arctic Atmospheric Chemistry Experiment (ACE) Validation Campaigns were conducted at Eureka (80° N, 86° W) during each of these winters. New satellite measurements from ACE-Fourier Transform Spectrometer (ACE-FTS), Sounding of the Atmosphere using Broadband Emission Radiometry (SABER), and Aura Microwave Limb Sounder (MLS), along with meteorological analyses and Eureka lidar temperatures, are used to detail the meteorology in these winters, to demonstrate its influence on transport, and to provide a context for interpretation of ACE-FTS and validation campaign observations. During the 2004 and 2006 SSWs, the vortex broke down throughout the stratosphere, reformed quickly in the upper stratosphere, and remained weak in the middle and lower stratosphere. The stratopause reformed at very high altitude, near 75 km. ACE measurements covered both vortex and extra-vortex conditions in each winter, except in late-February through mid-March 2004 and 2006, when the strong, pole-centered vortex that reformed after the SSWs resulted in ACE sampling only inside the vortex in the middle through upper stratosphere. The 2004 and 2006 Eureka campaigns were during the recovery from the SSWs, with the redeveloping vortex over Eureka. 2005 was the coldest winter on record in the lower stratosphere, but with an early final warming in mid-March. The vortex was over Eureka at the start of the 2005 campaign, but moved away as it broke up. Disparate temperature profile structure and vortex evolution resulted in much lower (higher) temperatures in the upper (lower) stratosphere in 2004 and 2006 than in 2005. Satellite temperatures agree well with lidar data up to 50–60 km, and ACE-FTS, MLS and SABER show good agreement in high-latitude temperatures throughout the winters. Consistent with a strong, cold upper stratospheric vortex and enhanced radiative cooling after the SSWs, MLS and ACE-FTS trace gas measurements show strongly enhanced descent in the upper stratospheric vortex in late January through March 2006 compared to that in 2005.

Validation of the Atmospheric Chemistry Experiment (ACE) version 2.2 temperature using ground-based and space-borne measurements

Abstract. An ensemble of space-borne and ground-based instruments has been used to evaluate the quality of the version 2.2 temperature retrievals from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS). The agreement of ACE-FTS temperatures with other sensors is typically better than 2 K in the stratosphere and upper troposphere and 5 K in the lower mesosphere. There is evidence of a systematic high bias (roughly 3–6 K) in the ACE-FTS temperatures in the mesosphere, and a possible systematic low bias (roughly 2 K) in ACE-FTS temperatures near 23 km. Some ACE-FTS temperature profiles exhibit unphysical oscillations, a problem fixed in preliminary comparisons with temperatures derived using the next version of the ACE-FTS retrieval software. Though these relatively large oscillations in temperature can be on the order of 10 K in the mesosphere, retrieved volume mixing ratio profiles typically vary by less than a percent or so. Statistical comparisons suggest these oscillations occur in about 10% of the retrieved profiles. Analysis from a set of coincident lidar measurements suggests that the random error in ACE-FTS version 2.2 temperatures has a lower limit of about ±2 K.

Tropospheric emission spectrometer (TES) and atmospheric chemistry experiment (ACE) measurements of tropospheric chemistry in tropical southeast Asia during a moderate El Niño in 2006

High spectral resolution Fourier transform spectrometer (FTS) measurements of tropospheric carbon monoxide (CO) distributions show mixing ratios over Indonesia during October 2006 of ∼200 ppbv (10 −9 per unit volume) in the middle troposphere. The elevated emissions were caused by intense and widespread Indonesian peat and forest fire emissions elevated compared to other years by the impact of a moderate El Niño/Soutern Oscillation (ENSO) event, which delayed that year's monsoon season and produced very dry conditions. Moderate resolution imaging spectrometer (MODIS) fire counts, atmospheric chemistry experiment (ACE) measurements of elevated mixing ratios of fire emission products and near infrared extinction, and back trajectory calculations for a sample measurement location near the time of maximum emissions provide additional evidence that the elevated 2006 emissions resulted primarily from the Indonesia fires. Lower CO mixing ratios measured by ACE and fewer MODIS fire counts in Indonesia during October 2005 indicate lower emissions than during 2006. Coincident profiles from the ACE agree within the uncertainties with those from the tropospheric emission spectrometer (TES) for pressure ranges and time periods with good TES sensitivity after accounting for its lower vertical sensitivity compared with the ACE FTS.

Submicrometer sulfur-rich particles in the middle troposphere: Aircraft observations from Australia to Japan

Individual aerosol particles were collected in the middle troposphere at 5–6 km altitude in the PACE-III (Pacific Atmospheric Chemistry Experiment) campaign, conducted between Melbourne in Australia (38°S) and Sendai in Japan (38°N) in July 1995. Particles collected on electron microscope grids were subsequently examined using a transmission electron microscope equipped with an energy-dispersive X-ray (EDX) analyzer. Based on the EDX analysis and morphological identification, particles were classified into seven categories, including sulfuric acid, sulfate, sea-salt and mineral particles. Within the radius range of 0.1–0.5 μm, S-rich particles (sulfuric acid and sulfate) were dominant (> 60%) in the observation regions. These particles are considered an important background aerosol component. The latitudinal distributions of S-rich particles containing potassium (K) and minerals were studied for all S-rich particles of 0.1–0.5 μm. The percentages of K-containing S-rich particles were > 20% north of 35°N and south of 15 S. S-rich particles with K were likely to have originated from biomass or biofuel burning on the continent and were transported through the middle troposphere. In addition, S-rich particles with minerals were often present in relatively high percentages (> 40%) in the northern mid-latitudes. The present study suggests that 30–70% of S-rich particles were influenced by material of surface origin north of approximately 30°N and south of 25°S, where westerly winds were dominant. The results obtained in this campaign were compared with those in the previous PACE-I campaign (January 1994). The comparison suggested that seasonal shifts of the locations of the ITCZ and wind belts play an important role in the formation of the seasonal difference in the spatial distributions of concentration and mixing properties of S-rich particles in the middle troposphere over the western Pacific.

ACE-FTS observation of a young biomass burning plume: first reported measurements of C<sub>2</sub>H<sub>4</sub>, C<sub>3</sub>H<sub>6</sub>O, H<sub>2</sub>CO and PAN by infrared occultation from space

Abstract. In the course of our study of the upper tropospheric composition with the infrared Atmospheric Chemistry Experiment – Fourier Transform Spectrometer (ACE–FTS), we found an occultation sequence that on 8 October 2005, sampled a remarkable plume near the east coast of Tanzania. Model simulations of the CO distribution in the Southern hemisphere are performed for this period and they suggest that the emissions for this event likely originated from a nearby forest fire, after which the plume was transported from the source region to the upper troposphere. Taking advantage of the very high signal-to-noise ratio of the ACE–FTS spectra over a wide wavenumber range (750–4400 cm−1), we present in-depth analyses of the chemical composition of this plume in the middle and upper troposphere, focusing on the measurements of weakly absorbing pollutants. For this specific biomass burning event, we report simultaneous observations of an unprecedented number of organic species. Measurements of C2H4 (ethene), C3H4 (propyne), H2CO (formaldehyde), C3H6O (acetone) and CH3COO2NO2 (peroxyacetylnitrate, abbreviated as PAN) are the first reported detections using infrared occultation spectroscopy from satellites. Based on the lifetime of the emitted species, we discuss the photochemical age of the plume and also report, whenever possible, the enhancement ratios relative to CO.

O3‐N2O correlations from the Atmospheric Chemistry Experiment: Revisiting a diagnostic of transport and chemistry in the stratosphere

Our knowledge of stratospheric O3‐N2O correlations is extended, and their potential for model‐measurement comparison assessed, using data from the Atmospheric Chemistry Experiment (ACE) satellite and the Canadian Middle Atmosphere Model (CMAM). ACE provides the first comprehensive data set for the investigation of interhemispheric, interseasonal, and height‐resolved differences of the O3‐N2O correlation structure. By subsampling the CMAM data, the representativeness of the ACE data is evaluated. In the middle stratosphere, where the correlations are not compact and therefore mainly reflect the data sampling, joint probability density functions provide a detailed picture of key aspects of transport and mixing, but also trace polar ozone loss. CMAM captures these important features, but exhibits a displacement of the tropical pipe into the Southern Hemisphere (SH). Below about 21 km, the ACE data generally confirm the compactness of the correlations, although chemical ozone loss tends to destroy the compactness during late winter/spring, especially in the SH. This allows a quantitative comparison of the correlation slopes in the lower and lowermost stratosphere (LMS), which exhibit distinct seasonal cycles that reveal the different balances between diabatic descent and horizontal mixing in these two regions in the Northern Hemisphere (NH), reconciling differences found in aircraft measurements, and the strong role of chemical ozone loss in the SH. The seasonal cycles are qualitatively well reproduced by CMAM, although their amplitude is too weak in the NH LMS. The correlation slopes allow a “chemical” definition of the LMS, which is found to vary substantially in vertical extent with season.

Global phosgene observations from the Atmospheric Chemistry Experiment (ACE) mission

The first study of the global distribution of atmospheric phosgene (COCl2) has been performed using solar occultation measurements from the Atmospheric Chemistry Experiment (ACE) satellite mission. A total of 5614 measured profiles spanning the period February 2004 through May 2006 were used in the study. The phosgene concentrations display a zonally symmetric pattern with the maximum concentration located approximately over the equator at about 25 km in altitude and the concentration decreases towards the poles. A layer of enhanced concentration of phosgene spans the lower stratosphere over all latitudes, with volume mixing ratios of 20–60 pptv. The ACE observations show lower phosgene concentrations in the stratosphere than were obtained from previous observations in the 1980s and 1990s. This has been attributed to a significant decrease in its source species, particularly two major sources CH3CCl3 and CCl4, since the introduction of restrictions required by the Montreal Protocol and its amendments.

Initial comparison of ozone and NO2 profiles from ACE‐MAESTRO with balloon and satellite data

Atmospheric retrievals of ozone and NO2 by the Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (MAESTRO) instrument which is part of the Atmospheric Chemistry Experiment (ACE) satellite aboard SCISAT are compared statistically with coincident measurements by ozonesondes, the Fourier Transform Spectrometer (ACE‐FTS) also aboard SCISAT, the SAGE III and the POAM III instruments. The ozone mixing ratio profiles from MAESTRO and ozonesondes agree within about 5–10% from 16–30 km in the northern middle and high latitudes. Further, ACE‐FTS and MAESTRO ozone profiles agree within ∼5–15% from 16–50 km. MAESTRO ozone profiles show a systematic bias which is opposite for sunrise (SR) and sunset (SS) events and was also seen in comparisons with SAGE III and POAM III ozone. MAESTRO SS ozone profiles mostly agree within 5–10% from 16–40 km with either SAGE III or POAM III SR or SS retrievals, but show a significant high bias from 40–55 km, reaching a maximum of ∼20–30%. MAESTRO SR ozone profiles show a low bias of ∼5–15% from 20–50 km, as compared to SAGE III and POAM III SR or SS measurements. The NO2 profiles agree within about 10–15% between ACE‐FTS and MAESTRO from 15–40 km for the SR and 22–35 km for the SS measurements. Further, MAESTRO NO2 profiles agree with SAGE III NO2 mostly within 10% from 25–40 km. MAESTRO NO2 profiles agree with POAM III SR profiles within 5–10% from 25–42 km. However, compared to POAM III SS profiles, MAESTRO NO2 profiles show a low bias between 20 and 25 km (∼30–50%), a high MAESTRO bias between 25 and 32 km (10–30%), and again a low bias above 33 km that increases with altitude to 50–60%.

Satellite boreal measurements over Alaska and Canada during June–July 2004: Simultaneous measurements of upper tropospheric CO, C2H6, HCN, CH3Cl, CH4, C2H2, CH3OH, HCOOH, OCS, and SF6 mixing ratios

Simultaneous ACE (Atmospheric Chemistry Experiment) upper tropospheric CO, C2H6, HCN, CH3Cl, CH4, C2H2, CH3OH, HCOOH, and OCS measurements show plumes up to 185 ppbv (10−9 per unit volume) for CO, 1.36 ppbv for C2H6, 755 pptv (10−12 per unit volume) for HCN, 1.12 ppbv for CH3Cl, 1.82 ppmv (10−6 per unit volume) for CH4, 0.178 ppbv for C2H2, 3.89 ppbv for CH3OH, 0.843 ppbv for HCOOH, and 0.48 ppbv for OCS in western Canada and Alaska at 50°N–68°N latitude between 29 June and 23 July 2004. Enhancement ratios and emission factors for HCOOH, CH3OH, HCN, C2H6, and OCS relative to CO at 250–350 hPa are inferred from measurements of young plumes compared with lower mixing ratios assumed to represent background conditions based on a CO emission factor derived from boreal measurements. Results are generally consistent with the limited data reported for various vegetative types and emission phases measured in extratropical forests including boreal forests. The low correlation between fire product emission mixing ratios and the SF6 mixing ratio is consistent with no significant SF6 emissions from the biomass fires.

The onboard imagers for the Canadian ACE SCISAT‐1 mission

The Atmospheric Chemistry Experiment (ACE) onboard the Canadian Space Agency’s SCISAT‐1 satellite has been in orbit since August of 2003. Its broad objective is to study the problem of stratospheric ozone depletion, particularly in the Arctic. The main instruments are two spectrometers, one an infrared Fourier Transform Spectrometer and the other a dual optical spectrophotometer sensitive in the UV and visible. Also included are two filtered imagers used to measure altitude profiles of atmospheric extinction and detect thin clouds. The nominal center wavelengths of the filters are 525 nm for the visible (VIS) imager and 1020 nm for the near‐infrared (NIR) imager. With the decommissioning of other satellite instruments used to monitor global aerosols [i.e., Stratospheric Aerosol and Gas Experiment II (SAGE II), SAGE III, Polar Ozone and Aerosol Measurement (POAM) III, Halogen Occultation Experiment (HALOE)], the imagers provide much needed continuity in this data record. The data product from the imagers is still, however, in a preliminary state. Funding restrictions in the prelaunch period were responsible for an incomplete characterization of the imagers’ optics and electronics and prevented corrections being made for the problems found during testing. Postlaunch data analysis to correct for image artifacts is ongoing. A comparison with coincidental measurements from SAGE II shows that systematic errors from the preliminary analysis are within 5 and 20% for the VIS and NIR imagers, respectively, for uninverted profiles of optical depth. Despite the preliminary nature of the imager results, a paper describing the imagers and the initial operational data processing code is timely because the data are already being used.

The ACE-MAESTRO instrument on SCISAT: description, performance, and preliminary results

The Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (MAESTRO) instrument on the SCISAT satellite is a simple, compact spectrophotometer for the measurement of atmospheric extinction, ozone, nitrogen dioxide, and other trace gases in the stratosphere and upper troposphere as part of the Atmospheric Chemistry Experiment (ACE) mission. We provide an overview of the instrument from requirements to realization, including optical design, prelaunch and on-orbit performance, and a preliminary examination of retrievals of ozone and NO(2).

Measurements of the [formula omitted][formula omitted]- and [formula omitted]-bands for determining temperature and pressure profiles from ACE–MAESTRO: Forward model and retrieval algorithm

The ACE-MAESTRO (Atmospheric Chemistry Experiment–Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) instrument on the SCISAT satellite is able to measure solar occultation absorption in the A - and B -bands of molecular oxygen with a spectral resolution of 2 nm. Profiles of total atmospheric density are derived by exploiting the constant and known mixing ratio of O 2 , and are used to determine profiles of pressure and temperature using hydrostatic balance and the ideal gas law. A highly accurate combined fast-line-by-line and extended correlated- k technique is implemented to fast forward model MAESTRO's O 2 absorption measurements, which ensures that errors in pressure and temperature resulting from the forward model approximation are essentially negligible. Estimated errors in pressure and temperature are determined for the A -, B -, and combined A – B -band retrievals for a typical retrieval, and demonstrate that pressure profiles should be derivable to within 1% and temperature to within 2 K over most altitudes using a combined A – B retrieval. The combined retrieval provides an improvement of up to 0.25% in pressure and 0.5 K in temperature over the A -band retrieval alone. The B -band could also be used alone below about 50 km, where its independent retrieval produces error estimates of 1–1.5% in pressure and 2–3 K in temperature.

N 2O and O 3 arctic column amounts from PARIS-IR observations: Retrievals, characterization and error analysis

Ground-based solar absorption infrared spectra were recorded in the Canadian Arctic during the early spring of 2004 using a moderate-resolution Fourier transform spectrometer, the Portable Atmospheric Research Interferometric Spectrometer for the Infrared (PARIS-IR). As part of the Canadian Arctic Atmospheric Chemistry Experiment (ACE) validation campaign, the PARIS-IR instrument recorded solar absorption spectra of the atmosphere from February to March 2004 as the Sun returned to the Arctic Stratospheric Ozone Observatory (AStrO) near Eureka, Nunavut, Canada (80.05°N, 86.42°W). In this paper, we briefly outline the PARIS-IR instrument configuration and data acquisition in the high Arctic. We discuss the retrieval methodology, characterization and error analysis associated with total and partial column retrievals. We compare the PARIS-IR measurements of N 2O and O 3 column amounts with those from the Fourier transform spectrometer (ACE-FTS) onboard the Canadian SCISAT-1 satellite and the ozonesonde data obtained at Eureka during the validation campaign.

Detection of elevated tropospheric hydrogen peroxide (H 2O 2) mixing ratios in atmospheric chemistry experiment (ACE) subtropical infrared solar occultation spectra

We report measurements of hydrogen peroxide (H 2O 2) profiles from infrared solar occultation spectra recorded at 0.02 cm −1 resolution by the atmospheric chemistry experiment (ACE) during 2004 and 2005. Mixing ratios as high as 1.7 ppbv (1 ppbv=1×10 −9 per unit volume) were measured in the subtropical troposphere. Back trajectories, fire count statistics, and simultaneous measurements of other species from the same occultation provide evidence that the elevated H 2O 2 mixing ratios originated from a young biomass-burning plume. The ACE time series show only a few cases with elevated H 2O 2 mixing ratios likely because of the short lifetime of H 2O 2 and the limited sampling during biomass-burning time periods.

Structure and conformational analysis of CFC-113 by density functional theory calculations and FTIR spectroscopy

Altitude-resolved volume mixing ratio profiles of CFC-113 have recently become available on a global scale with the Atmospheric Chemistry Experiment (ACE) satellite mission. However, the accuracy of the retrieval is currently limited by the uncertainties on the spectroscopic parameters of CFC-113. This paper reports on the geometrical structure, harmonic frequencies and intensities in the mid-infrared region of the two conformers of CFC-113 and the evaluation of whether theoretical calculations reproduce measurements. The calculations are performed using density functional theory at the B3LYP/6-311+G(3df) level. The molecular geometry parameters, the enthalpy difference and the potential barrier between conformers are calculated. The harmonic frequency of the normal modes of vibration are presented and accurately compared to experimental data. Overtones and combination bands are assigned in the 1200–2500 cm −1 region.

The NOAA Twin Otter and its role in BRACE: A comparison of aircraft and surface trace gas measurements

A DeHavilland DHC-6 Twin Otter, operated by the National Oceanic and Atmospheric Administration, was deployed in Tampa, FL to measure aerosols and primary and secondary trace gases in support of the Bay Regional Atmospheric Chemistry Experiment (BRACE). The Twin Otter repeatedly overflew the surface chemistry monitoring super site near Sydney, FL to assess the comparability of surface and airborne datasets and the spatial representativeness of the surface measurements. Prior to comparing the chemical datasets, we evaluated the comparability of the standards used to calibrate surface and airborne detectors, as well as the uniformity of wind fields aloft and at the surface. Under easterly flow, when the dearth of significant upwind emission sources promoted chemical homogeneity at Sydney, trace gas concentrations at the surface and aloft were generally well correlated; R 2 ranged from 0.4396 for H 2O 2 to 0.9738 for O 3, and was typically better than 0.70 for NO, NO 2, NO Y , HNO 3, HCHO, and SO 2. Mean ratios of aircraft-to-surface concentrations during 10 overflights of Sydney were as follows: 1.002±0.265 (NO), 0.948±0.183 (NO 2), 1.010±0.214 (NO Y ), 0.941±0.263 (HCHO), and 0.952±0.046 (O 3). Poorer agreement and larger variability in measured ratios were noted for SO 2 (1.764±0.559), HNO 3 (1.291±0.391), and H 2O 2 (1.200±0.657). Under easterly flow, surface measurements at Sydney were representative of conditions over horizontal scales as large as 50 km and agreed well with airborne values throughout the depth of the turbulently mixed boundary layer at mid-day. Westerly flow advected the Tampa urban plume over the site; under these conditions, as well as during transitional periods associated with the development of the land–sea breeze, surface conditions were representative of smaller spatial scales. Finally, we estimate possible errors in future measurement-model comparisons likely to arise from fine scale (or subgrid;<2 km) variability of trace gas concentrations. Large subgrid variations in concentration fields were observed downwind of large emission point sources, and persisted across multiple model grid cells (distances>4 km) in coherent plumes. Variability at the edges of the well-mixed urban plume, and at the interface of the land–sea breeze circulation, was significantly smaller. This suggests that even a failure of modeled wind fields to resolve the sea breeze return can induce moderate, but not overwhelming, errors in simulated concentration fields and dependent chemical processes.