Multi-Year Elevation Changes Near the West Margin of the Greenland Ice Sheet from Satellite Radar Altimetry

Mean changes in the surface elevation near the west margin of the Greenland ice sheet are measured using Seasat altimetry and altimetry from the Geosat Exact Repeat Mission (ERM). The Seasat data extend from early July through early October 1978. The ERM data extend from winter 1986-87 through fall 1988. Both seasonal and multi-year changes are measured using altimetry referenced to GEM T2 orbits. The possible effects of orbit error are minimized by adjusting the orbits into a common ocean surface. Seasonal mean changes in the surface height are recognizable during the Geosat ERM. The multi-year measurements indicate the surface was lower by 0.4 +/- 0.4 m on average in late summer 1987 than in late summer 1978. The surface was lower by 0.2 +/- 0.5 m on average in late summer 1988 than in late summer 1978. As a control case, the computations art also carried out using altimetry referenced to orbits not adjusted into a common ocean surface

Comparison of Surface Elevation Changes of the Greenland and Antarctic Ice Sheets from Radar and Laser Altimetry

A primary purpose of satellite altimeter measurements is determination of the mass balances of the Greenland and Antarctic ice sheets and changes with time by measurement of changes in the surface elevations. Since the early 1990's, important measurements for this purpose have been made by radar altimeters on ERS-l and 2, Envisat, and CryoSat and a laser altimeter on ICESat. One principal factor limiting direct comparisons between radar and laser measurements is the variable penetration depth of the radar signal and the corresponding location of the effective depth of the radar-measured elevation beneath the surface, in contrast to the laser-measured surface elevation. Although the radar penetration depth varies significantly both spatially and temporally, empirical corrections have been developed to account for this effect. Another limiting factor in direct comparisons is caused by differences in the size of the laser and radar footprints and their respective horizontal locations on the surface. Nevertheless, derived changes in elevation, dHldt, and time-series of elevation, H(t), have been shown to be comparable. For comparisons at different times, corrections for elevation changes caused by variations in the rate offrrn compaction have also been developed. Comparisons between the H(t) and the average dH/dt at some specific locations, such as the Vostok region of East Antarctic, show good agreement among results from ERS-l and 2, Envisat, and ICESat. However, Greenland maps of dHidt from Envisat and ICESat for the same time periods (2003-2008) show some areas of significant differences as well as areas of good agreement. Possible causes of residual differences are investigated and described

ICESat GLAS Altimetry Measurements: Received Signal Dynamic Range and Saturation Correction

NASAs Ice, Cloud, and land Elevation Satellite (ICESat), which operated between 2003 and 2009, made the first satellite-based global lidar measurement of Earths ice sheet elevations, sea-ice thickness and vegetation canopy structure. The primary instrument on ICESat was the Geoscience Laser Altimeter System (GLAS), which measured the distance from the spacecraft to Earths surface via the roundtrip travel time of individual laser pulses. GLAS utilized pulsed lasers and a direct detection receiver consisting of a silicon avalanche photodiode (SiAPD) and a waveform digitizer. Early in the mission, the peak power of the received signal from snow and ice surfaces was found to span a wider dynamic range than planned, often exceeding the linear dynamic range of the GLAS 1064-nm detector assembly. The resulting saturation of the receiver distorted the recorded signal and resulted in range biases as large as 50 cm for ice and snow-covered surfaces. We developed a correction for this saturation range bias based on laboratory tests using a spare flight detector, and refined the correction by comparing GLAS elevation estimates to those derived from Global Positioning System (GPS) surveys over the calibration site at the salar de Uyuni, Bolivia. Applying the saturation correction largely eliminated the range bias due to receiver saturation for affected ICESat measurements over Uyuni and significantly reduced the discrepancies at orbit crossovers located on flat regions of the Antarctic ice sheet

Syntheses, Characterization, Density Functional Theory Calculations, and Activity of Tridentate SNS Zinc Pincer Complexes Based on Bis-Imidazole or Bis-Triazole Precursors

A series of tridentate pincer ligands, each possessing two sulfur- and one nitrogen-donor functionalities (SNS), based on bis-imidazole or bis-triazole salts were metallated with ZnCl2 to give new tridentate SNS pincer zinc(II) complexes [(SNS)ZnCl]+. The zinc complexes serve as models for the zinc active site in liver alcohol dehydrogenase (LADH) and were characterized with single crystal X-ray diffraction, 1H, 13C, and HSQC NMR spectroscopies, electrospray mass spectrometry, and elemental analysis. The zinc complexes feature SNS donor atoms and pseudotetrahedral geometry about the zinc center, as is seen for liver alcohol dehydrogenase. The bond lengths and bond angles of the zinc complexes correlate well to those in horse LADH. The SNS ligand precursors were characterized with 1H, 13C, and HSQC NMR spectroscopies, elemental analysis, and cyclic voltammetry, and were found to be redox active. Gaussian calculations were performed and agree with the experimentally observed oxidation potentials for the pincer ligand precursors. The zinc complexes were screened for the reduction of electron-poor aldehydes in the presence of a hydrogen donor, 1-benzyl-1,4-dihydronicotinamide (BNAH), and it was determined that they enhance the reduction of electron-poor aldehydes. The SNS zinc pincer complexes with bis-triazole ligand precursors exhibit higher activity for the reduction of 4-nitrobenzaldehyde than do SNS zinc pincer complexes with bis-imidazole ligand precursors. Quantitative stoichiometric conversion was seen for the reduction of pyridine-2-carboxaldehyde via SNS zinc pincer complexes with either bis-imidazole or bis-triazole ligand precursors

Syntheses, characterization, density functional theory calculations, and activity of tridentate SNS zinc pincer complexes

A series of tridentate SNS ligand precursors were metallated with ZnCl2 to give new tridentate SNS pincer zinc complexes. The zinc complexes serve as models for the zinc active site in liver alcohol dehydrogenase (LADH) and were characterized with single crystal X-ray diffraction, 1H, 13C, and HSQC NMR spectroscopies and electrospray mass spectrometry. The bond lengths and bond angles of the zinc complexes correlate well to those in horse LADH. The zinc complexes feature SNS donor atoms and pseudotetrahedral geometry about the zinc center, as is seen for liver alcohol dehydrogenase. The SNS ligand precursors were characterized with 1H, 13C, and HSQC NMR spectroscopies and cyclic voltammetry, and were found to be redox active. Gaussian calculations were performed and agree quite well with the experimentally observed oxidation potential for the pincer ligand. The zinc complexes were screened for the reduction of electron poor aldehydes in the presence of a hydrogen donor, 1-benzyl-1,4-dihydronicotinamide (BNAH). The zinc complexes enhance the reduction of electron poor aldehydes. Density functional theory calculations were performed to better understand why the geometry about the zinc center is pseudo-tetrahedral rather than pseudo-square planar, which is seen for most pincer complexes. For the SNS tridentate pincer complexes, the data indicate that the pseudo-tetrahedral geometry was 43.8 kcal/mol more stable than the pseudo-square planar geometry. Density functional theory calculations were also performed on zinc complexes with monodentate ligands and the data indicate that the pseudo-tetrahedral geometry was 30.6 kcal/mol more stable than pseudo-square planar geometry. Overall, the relative stabilities of the pseudo-tetrahedral and pseudo-square planar systems are the same for this coordination environment whether the ligand set is a single tridentate SNS system or is broken into three separate units. The preference of a d10 Zn center to attain a tetrahedral local environment trumps any stabilization gained by removal of constraints within the ligand set

ICESat/GLAS Altimetry Measurements: Received Signal Dynamic Range and Saturation Correction.

NASA's Ice, Cloud, and land Elevation Satellite (ICESat), which operated between 2003 and 2009, made the first satellite-based global lidar measurement of Earth's ice sheet elevations, sea-ice thickness and vegetation canopy structure. The primary instrument on ICESat was the Geoscience Laser Altimeter System (GLAS), which measured the distance from the spacecraft to Earth's surface via the roundtrip travel time of individual laser pulses. GLAS utilized pulsed lasers and a direct detection receiver consisting of a silicon avalanche photodiode (Si APD) and a waveform digitizer. Early in the mission, the peak power of the received signal from snow and ice surfaces was found to span a wider dynamic range than planned, often exceeding the linear dynamic range of the GLAS 1064-nm detector assembly. The resulting saturation of the receiver distorted the recorded signal and resulted in range biases as large as ~50 cm for ice and snow-covered surfaces. We developed a correction for this "saturation range bias" based on laboratory tests using a spare flight detector, and refined the correction by comparing GLAS elevation estimates to those derived from Global Positioning System (GPS) surveys over the calibration site at the salar de Uyuni, Bolivia. Applying the saturation correction largely eliminated the range bias due to receiver saturation for affected ICESat measurements over Uyuni and significantly reduced the discrepancies at orbit crossovers located on flat regions of the Antarctic ice sheet