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Sen, B.

Publications and source records attributed to Sen, B..

At least 19 records

Observed and Modeled HOCl Profiles in the Midlatitude Stratosphere: Implication for Ozone Loss

Vertical profiles of stratospheric HOCl calculated with a diurnal steady-state photochemical model that uses currently recommended reaction rates and photolysis cross sections underestimate observed profiles of HOCl obtained by two balloon-borne instruments, FIRS-2 (a far-infrared emission spectrometer) and MkIV (a mid-infrared, solar absorption spectrometer). Considerable uncertainty (a factor of two) persists in laboratory measurements of the rate constant (k(sub 1)) for the reaction ClO + HO2 yields HOCl + O2. Agreement between modeled and measured HOCl can be attained using a value of k(sub 1) from Stimpfle et al. (1979) that is about a factor-of-two faster than the currently recommended rate constant. Comparison of modeled and measured HOCl suggests that models using the currently recommended value for k(sub 1) may underestimate the role of the HOCl catalytic cycle for ozone depletion, important in the midlatitude lower stratosphere.

temperature dependence↗

Space-Based Near-Infrared CO2 Measurements: Testing the Orbiting Carbon Observatory Retrieval Algorithm and Validation Concept Using SCIAMACHY Observations over Park Falls, Wisconsin

Space-based measurements of reflected sunlight in the near-infrared (NIR) region promise to yield accurate and precise observations of the global distribution of atmospheric CO2. The Orbiting Carbon Observatory (OCO) is a future NASA mission, which will use this technique to measure the column-averaged dry air mole fraction of CO2 (XCO2) with the precision and accuracy needed to quantify CO2 sources and sinks on regional scales (approx.1000 x 1000 sq km and to characterize their variability on seasonal timescales. Here, we have used the OCO retrieval algorithm to retrieve XCO2 and surface pressure from space-based Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) measurements and from coincident ground-based Fourier transform spectrometer (FTS) measurements of the O2 A band at 0.76 mm and the 1.58 mm CO2 band for Park Falls,Wisconsin. Even after accounting for a systematic error in our representation of the O2 absorption cross sections, we still obtained a positive bias between SCIAMACHY and FTS XCO2 retrievals of approx.3.5%. Additionally, the retrieved surface pressures from SCIAMACHY systematically underestimate measurements of a calibrated pressure sensor at the FTS site. These findings lead us to speculate about inadequacies in the forward model of our retrieval algorithm. By assuming a 1% intensity offset in the O2 A band region for the SCIAMACHY XCO2 retrieval, we significantly improved the spectral fit and achieved better consistency between SCIAMACHY and FTS XCO2 retrievals. We compared the seasonal cycle of XCO2 at Park Falls from SCIAMACHY and FTS retrievals with calculations of the Model of Atmospheric Transport and Chemistry/Carnegie-Ames-Stanford Approach (MATCH/CASA) and found a good qualitative agreement but with MATCH/CASA underestimating the measured seasonal amplitude. Furthermore, since SCIAMACHY observations are similar in viewing geometry and spectral range to those of OCO, this study represents an important test of the OCO retrieval algorithm and validation concept using NIR spectra measured from space. Finally, we argue that significant improvements in precision and accuracy could be obtained from a dedicated CO2 instrument such as OCO, which has much higher spectral and spatial resolutions than SCIAMACHY. These measurements would then provide critical data for improving our understanding of the carbon cycle and carbon sources and sinks.

carbon dioxide↗

Measured and modeled HOCl profiles in the mid-latitude stratosphere : implication for ozone loss

The HOCl catalytic cycle is an efficient ozone loss mechanism in the lower mid-latitude stratosphere. We use a diurnal steady-state photochemical model to calculate profiles of HOCl for conditions encountered by a number of high-altitude balloon flights. To assess how well this model represents ozone loss by the HOCl cycle, we compare our calculations of HOCl and its precursors Cl0 and HO2 with measurements obtained by an FTIR solar absorption spectrometer (MkIV), a far-infrared emission spectrometer (FIRS-2), and a submillimetenvave limb sounder (SLS). We then evaluate these comparisons in light of a number of recent laboratory studies of the main formation mechanism of HOCl, the reaction of Cl0 + HO2. Those studies measured both the reaction rate constant and the quantum yield for a second product pathway, formation of HCl.

stratosphere↗

The Interaction Between Dynamics and Chemistry of Ozone in the Set-up Phase of the Northern Hemisphere Polar Vortex

The morphology and evolution of the stratospheric ozone (O3) distribution at high latitudes in the Northern Hemisphere (NH) are examined for the late summer and fall seasons of 1999. This time period sets the O3 initial condition for the SOLVE/THESEO field mission performed during winter 1999-2000. In situ and satellite data are used along with a three-dimensional model of chemistry and transport (CTM) to determine the key processes that control the distribution of O3 in the lower-to-middle stratosphere. O3 in the vortex at the beginning of the winter season is found to be nearly constant from 500 to above 800 K with a value at 3 ppmv +/- approx. 10%. Values outside the vortex are up to a factor of 2 higher and increase significantly with potential temperature. The seasonal time series of data from POAM shows that relatively low O3 mixing ratios, which characterize the vortex in late fall, are already present at high latitudes at the end of summer before the vortex circulation sets up. Analysis of the CTM output shows that the minimum O3 and increase in variance in late summer are the result of: 1) stirring of polar concentric O3 gradients by nascent wave-driven transport, and 2) an acceleration of net photochemical loss with decreasing solar illumination. The segregation of low O3 mixing ratios into the vortex as the circulation strengthens through the fall suggests a possible feedback role between O3 chemistry and the vortex formation dynamics. Trajectory calculations from O3 sample points early in the fall, however, show only a weak correlation between initial O3 mixing ratio and potential vorticity later in the season consistent with order-of-magnitude calculations for the relative importance of O3 in the fall radiative balance at high latitudes. The possible connection between O3 chemistry and the dynamics of vortex formation does suggest that these feedbacks and sensitivities need to be better understood in order to make confident predictions of the recovery of NH O3.

Kawa, S. R.↗

Remotely Operating a Fourier Transform Spectrometer for Atmospheric Remote Sensing

This paper describes how the MkIV instrument was adapted for remote operation from the Barcroft site, where the harsh winter conditions make access difficult. Some of the main technical challenges will be discussed including, (i) operation from solar panels and batteries, (ii) cooling the detectors with LN2, (iii) instrument control and monitoring over a cellular phone, and (iv) data storage, processing and analysis. Finally, MkIV spectra measured from Barcroft and compared with those measured from JPL to highlight the advantages of the higher altitude site.

Blavier, J.-F.↗

Ground-Based Measurements of Stratospheric Composition from Mt. Barcroft, California

The MkIV is an FTIR spectrometer designed and built at JPL in the 1980's for remote sensing the composition of the Earth's atmosphere by solar absorption spectrometry. Optically, MkIV is very similar to the JPL ATMOS instrument, which flew three times on the Space Shuttle. Both use double-passed configurations with a KBr beamsplitter and compensator, in order to cover the mid-infrared. The main advantage of the MkIV is that it uses two detectors in parallel, a HgCdTe photoconductor for the long wavelengths and an InSb photodiode for the short wavelengths, allowing the entire 650 to 5650/cm region to be measured simultaneously. At a 10 kHz sampling rate, each 130 cm OPD interferogram takes 3 minutes to acquire. This paper describes how the MkIV instrument was adapted for remote operation from the Barcroft site, where the harsh winter conditions make access difficult. Some of the main technical challenges will be discussed including, (i) operation from solar panels and batteries, (ii) cooling the detectors with LN2, (iii) instrument control and monitoring over a cellular phone, and (iv) data storage, processing and analysis. Finally, MkIV spectra measured from Barcroft are compared with those measured from JPL to highlight the advantages of the higher altitude site.

Toon, G. C.↗

The Interaction Between Dynamics and Chemistry of Ozone in the Set-Up Phase of the Northern Hemisphere Polar Vortex

Understanding stratospheric ozone loss to the point of accurately predicting ozone in the future requires correctly distinguishing chemical from transport-induced changes in ozone. For example, evaluating the impact of chlorine reduction in controlling stratospheric ozone loss requires estimating the amount of ozone lost in chemical reactions in the polar winter and spring. The Northern Hemisphere winter polar region is a particularly crucial and interesting area because it appears that the Northern vortex may currently be poised near the threshold of extreme ozone destruction such as that which now occurs annually in the Antarctic ozone "hole." In this presentation we explore the interaction of ozone transport and chemistry through the Northern late summer and fall seasons as the vortex circulation becomes established. This phase of the seasonal cycle determines the starting point for heterogeneous processes and chlorine-driven loss that take control in the winter vortex. Using a combination of profile data from POAM, HALOE, and in situ measurements, we show that relatively low ozone at high latitudes in the middle stratosphere is associated with vortex airmasses and that these ozone abundances evolve photochemically from characteristically higher values at the end of the summer. The zonal variance of ozone mixing ratio also increases greatly at this time consistent with increasing wave-driven transport. Comparison with a three-dimensional chemistry-transport model is used to generalize the findings from the limited set of observations and quantify the relative roles of transport and chemistry in determining the ozone mixing ratio distributions.

Kawa, S.R.↗

The Budget and Partitioning of Stratospheric Chlorine During the 1997 Arctic Summer

Volume mixing ratio profiles of HCl, HOCl, ClNO3, CH3Cl, CFC-12, and CFC-11, CCl4, HCFC-22, and CFC-113 were measured simultaneously from 9 to 38 km by the Jet Propulsion Laboratory MkIV Fourier Transform Infrared solar absorption spectrometer during two balloon flights from Fairbanks, Alaska (64.8 N), on May 8 and July 8, 1997. The altitude variation of total organic chlorine (CCl(sub y)), total inorganic chlorine (Cl(sub y)), and the nearly constant value (3.7 +/- 0.2 ppbv) of their sum (Cl(sub TOT)) demonstrates that the stratospheric chlorine species available to react with O3 are supplied by the decomposition of organic chlorinated compounds whose abundances are well quantified. Measured profiles of HCl and ClNO3 agree well with profiles found by photochemical model (differences < 10% for altitudes below 35 km) constrained by various other constituents measured by MkIV. The production of HCl by ClO + OH plays a relatively small role in the partitioning of HCl and ClNO3 for the sampled air masses. However, better agreement with the measured profiles of HCl and ClNO3 is obtained when this source of HCl is included in the model. Both the measured and calculated [ClNO3]/[HCl] ratios exhibit the expected near linear variation with [O3](sup 2)/[CH4] over a broad range of altitudes. MkIV measurements of HCl, ClNO3, and CCl(sub y) agree well with ER-2 in situ observations of these quantities for directly comparable air masses. These results demonstrate good understanding of the budget of stratospheric chlorine and that the partitioning of inorganic chlorine is accurately described by photochemical models that employ JPL97 reaction rates and production of HCl from ClO + OH for the environmental conditions encountered: relatively warm temperatures, long periods of solar illumination, and relatively low aerosol surface areas.

Sen, B.↗

The Budget and Partitioning of Stratospheric Chlorine During the 1997 Arctic Summer

Volume mixing ratio profiles of HCl, HOCl, ClNO3, CH3Cl, CFC-12, CFC-11, CCl4, HCFC-22, and CFC-113 were measured simultaneously from 9 to 38 km by the Jet Propulsion Laboratory MkIV Fourier Transform Infrared solar absorption spectrometer during two balloon flights from Fairbanks, Alaska (64.8 N), on May 8 and July 8, 1997. The altitude variation of total organic chlorine (CCly) total inorganic chlorine (Cly), and the nearly constant value (3.7 +/- 0.2 ppbv) of their sum (Cl(sub TOT)) demonstrates that the stratospheric chlorine species available to react with O3 are supplied by the decomposition of organic chlorinated compounds whose abundances are well quantified. Measured profiles of HCl and ClNO3 agree well with profiles found by photochemical model (differences < 10% for altitudes below 35 km) constrained by various other constituents measured by MkIV. The production of HCl by ClO + OH plays a relatively small role in the partitioning of HCl and ClNO3 for the sampled air masses. However, better agreement with the measured profiles of HCl and ClNO3 is obtained when this source of HCl is included in the model. Both the measured and calculated [ClNO3]/[HCl] ratios exhibit the expected near linear variation with [O3]2/[CH4] over a broad range of altitudes. MkIV measurements of HCl, ClNO3, and CC1y agree well with ER-2 in situ observations of these quantities for directly comparable air masses. These results demonstrate good understanding of the budget of stratospheric chlorine and that the partitioning of inorganic chlorine is accurately described by photochemical models that employ JPL97 reaction rates and production of HCl from ClO + OH for the environmental conditions encountered: relatively warm temperatures, long periods of solar illumination, and relatively low aerosol surface areas.

Sen, B.↗