The photodynamics of bacteriorhodopsin were studied by transient absorption and gain measurements after excitation with femtosecond pulses at 620 nm. With probing pulses at longer wavelengths (A> 770 nm) the previously reported formation of the J intermediate (with a time constant of 500f 100 fs) was confirmed. With probing pulses around 700 nm, a faster process with a relaxation time of 200 rt 70 fs was observed. The data analysis strongly suggests that this kinetic constant describes the reactive motion of the polyatomic molecule on its excited-state potential energy surface, i.e. one observes directly the incipient isomerization of the retinal molecule. The minimum of the S, potential energy surface reached in 200 fs lies approximately 13300 cm-' above the ground state of bacteriorhodopsin and from this minimum the intermediate J is formed with a time constant of 500 fs.

The 2007 National Research Council (NRC) Decadal Survey on Earth Science and Applications from Space recommended Active Sensing of CO(2) Emissions over Nights, Days, and Seasons (ASCENDS) as a midterm, Tier II, NASA space mission. ITT Exelis, formerly ITT Corp., and NASA Langley Research Center have been working together since 2004 to develop and demonstrate a prototype laser absorption spectrometer for making high-precision, column CO(2) mixing ratio measurements needed for the ASCENDS mission. This instrument, called the multifunctional fiber laser lidar (MFLL), operates in an intensity-modulated, continuous wave mode in the 1.57 μm CO(2) absorption band. Flight experiments have been conducted with the MFLL on a Lear-25, UC-12, and DC-8 aircraft over a variety of different surfaces and under a wide range of atmospheric conditions. Very high-precision CO(2) column measurements resulting from high signal-to-noise ratio (>1300) column optical depth (OD) measurements for a 10 s (~1 km) averaging interval have been achieved. In situ measurements of atmospheric CO(2) profiles were used to derive the expected CO(2) column values, and when compared to the MFLL measurements over desert and vegetated surfaces, the MFLL measurements were found to agree with the in situ-derived CO(2) columns to within an average of 0.17% or ~0.65 ppmv with a standard deviation of 0.44% or ~1.7 ppmv. Initial results demonstrating ranging capability using a swept modulation technique are also presented.

With nearly 1 million observations of column-mean carbon dioxide concentration (X CO 2 ) per day, the Orbiting Carbon Observatory 2 (OCO-2) presents exciting possibilities for monitoring the global carbon cycle, including the detection of subcontinental column CO 2 variations. While the OCO-2 data set has been shown to achieve target precision and accuracy on a single-sounding level, the validation of X CO 2 spatial gradients on subcontinental scales remains challenging. In this work, we investigate the use of an integrated path differential absorption (IPDA) lidar for evaluation of OCO-2 observations via NASA's Atmospheric Carbon and Transport (ACT)-America project. The project has completed eight clear-sky underflights of OCO-2 with the Multifunctional Fiber Laser Lidar (MFLL)-along with a suite of in situ instruments-giving a precisely colocated, high-resolution validation data set spanning nearly 3,800 km across four seasons. We explore the challenges and opportunities involved in comparing the MFLL and OCO-2 X CO 2 data sets and evaluate their agreement on synoptic and local scales. We find that OCO-2 synoptic-scale gradients generally agree with those derived from the lidar, typically to ±0.1 ppm per degree latitude for gradients ranging in strength from 0 to 1 ppm per degree latitude. CO 2 reanalysis products also typically agree to ±0.25 ppm per degree when compared with an in situ-informed CO 2 "curtain." Real X CO 2 features at local scales, however, remain challenging to observe and validate from space, with correlation coefficients typically below 0.35 between OCO-2 and the MFLL. Even so, ACT-America data have helped investigate interesting local X CO 2 patterns and identify systematic spurious cloud-related features in the OCO-2 data set.

The Atmospheric Carbon and Transport (ACT) – America NASA Earth Venture Suborbital Mission set out to improve regional atmospheric greenhouse gas (GHG) inversions by exploring the intersection of the strong GHG fluxes and vigorous atmospheric transport that occurs within the midlatitudes. Two research aircraft instrumented with remote and in situ sensors to measure GHG mole fractions, associated trace gases, and atmospheric state variables collected 1140.7 flight hours of research data, distributed across 305 individual aircraft sorties, coordinated within 121 research flight days, and spanning five, six-week seasonal flight campaigns in the central and eastern United States. Flights sampled 31 synoptic sequences, including fair weather and frontal conditions, at altitudes ranging from the atmospheric boundary layer to the upper free troposphere. The observations were complemented with global and regional GHG flux and transport model ensembles. We found that midlatitude weather systems contain large spatial gradients in GHG mole fractions, in patterns that were consistent as a function of season and altitude. We attribute these patterns to a combination of regional terrestrial fluxes and inflow from the continental boundaries. These observations, when segregated according to altitude and air mass, provide a variety of quantitative insights into the realism of regional CO2 and CH4 fluxes and atmospheric GHG transport realizations. The ACT-America data set and ensemble modeling methods provide benchmarks for the development of atmospheric inversion systems. As global and regional atmospheric inversions incorporate ACT-America’s findings and methods, we anticipate these systems will produce increasingly accurate and precise sub-continental GHG flux estimates.

We present an evaluation of airborne Intensity-Modulated Continuous-Wave (IM-CW) lidar measurements of atmospheric column CO2 mole fractions during the ACT-America project. This lidar system transmits online and offline wavelengths simultaneously on the 1.57111-µm CO2 absorption line, with each modulated wavelength using orthogonal swept frequency waveforms. After the spectral characteristics of this system were calibrated through short-path measurements, we used the HITRAN spectroscopic database to calculate the average-column CO2 mole fraction (XCO2) from the lidar measured optical depths. Using in situ measurements of meteorological parameters and CO2 concentrations for calibration data, we demonstrate that our lidar CO2 measurements were consistent from season to season and had an absolute calibration error (standard deviation) of 0.80 ppm when compared to XCO2 values calculated from in situ measurements. By using a 10-second or longer moving average, a precision of 1 ppm or better was obtained. The estimated CO2 measurement precision for 0.1-s, 1-s, 10-s, and 60-s averages were determined to be 3.4 ppm 1.2 ppm, 0.43 ppm, and 0.26 ppm, respectively. These correspond to measurement signal-to-noise ratios of 120, 330, 950, and 1600, respectively. The drift in XCO2 over one-hour of flight time was found to be below 0.1 ppm. These analyses demonstrate that the measurement stability, precision and accuracy are all well below the thresholds needed to study synoptic-scale variations in atmospheric XCO2. This article has been accepted for publication and undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process which may lead to differences between this version and the Version of Record. Please cite this article as