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At least 19 records

Spontaneous emission lifetimes in the ground electronic states of HD/+/ and H2/+/a

Because of their simplicity, H2(+) and its isotopic species are of particular interest to molecular theorists and experimentalists. If these ions are formed in excited vibrational states under conditions of highly improbable electron-ion recombination or other reactions, spontaneous emission will occur. The present note calculates the (vibrational quantum number, J prime = 0) state lifetimes under spontaneous emission for all 22 excited vibrations of HD(+) and all 19 excited vibrations of H2(+) in their ground electron states. The lifetimes presented in Tables I and III justify the assumption that spontaneous radiative processes are unimportant under certain realizable conditions. When spontaneous radiation plays a role, however, minimum lifetime at intermediate vibrational quantum number could lead to unusual vibrational distribution functions.

Peek, J. M.↗

On the effects of the ocean on atmospheric CFC-11 lifetimes and emissions

The ocean is a reservoir for CFC-11, a major ozone-depleting chemical. Anthropogenic production of CFC-11 dramatically decreased in the 1990s under the Montreal Protocol, which stipulated a global phase out of production by 2010. However, studies raise questions about current overall emission levels and indicate unexpected increases of CFC-11 emissions of about 10 Gg/yr after 2013 (based upon measured atmospheric concentrations and an assumed atmospheric lifetime). These findings heighten the need to understand processes that could affect the CFC-11 lifetime, including ocean fluxes. We evaluate how ocean uptake and release through 2300 affects CFC-11 lifetimes, emission estimates, and the long-term return of CFC-11 from the ocean reservoir. We show that ocean uptake yields a shorter total lifetime and larger inferred emission of atmospheric CFC-11 from 1930 to 2075 compared to estimates using only atmospheric processes. Ocean flux changes over time result in small but not completely negligible effects on the calculated unexpected emissions change (decreasing it by 0.4 ± 0.3 Gg/yr). Moreover, it is expected that the ocean will eventually become a source of CFC-11, increasing its total lifetime thereafter. Ocean outgassing should produce detectable increases in global atmospheric CFC-11 abundances by the mid-2100s, with emission of around 0.5 Gg/yr; this should not be confused with illicit production at that time. An illustrative model projection suggests that climate change is expected to make the ocean a weaker reservoir for CFC-11, advancing the detectable change in the global atmospheric mixing ratio by about 5 yr.

Anthropogenic production of CFC-11↗

Estimates of Power Plant NOx Emissions and Lifetimes from OMI NO2 Satellite Retrievals

Isolated power plants with well characterized emissions serve as an ideal test case of methods to estimate emissions using satellite data. In this study we evaluate the Exponentially-Modified Gaussian (EMG) method and the box model method based on mass balance for estimating known NOx emissions from satellite retrievals made by the Ozone Monitoring Instrument (OMI). We consider 29 power plants in the USA which have large NOx plumes that do not overlap with other sources and which have emissions data from the Continuous Emission Monitoring System (CEMS). This enables us to identify constraints required by the methods, such as which wind data to use and how to calculate background values. We found that the lifetimes estimated by the methods are too short to be representative of the chemical lifetime. Instead, we introduce a separate lifetime parameter to account for the discrepancy between estimates using real data and those that theory would predict. In terms of emissions, the EMG method required averages from multiple years to give accurate results, whereas the box model method gave accurate results for individual ozone seasons.

Emissions inventory↗

SO2 Emissions and Lifetimes: Estimates from Inverse Modeling Using In Situ and Global, Space-Based (SCIAMACHY and OMI) Observations

Top-down constraints on global sulfur dioxide (SO2) emissions are inferred through inverse modeling using SO2 column observations from two satellite instruments (SCIAMACHY and OMI). We first evaluated the S02 column observations with surface SO2 measurements by applying local scaling factors from a global chemical transport model (GEOS-Chem) to SO2 columns retrieved from the satellite instruments. The resulting annual mean surface SO2 mixing ratios for 2006 exhibit a significant spatial correlation (r=0.86, slope=0.91 for SCIAMACHY and r=0.80, slope = 0.79 for OMI) with coincident in situ measurements from monitoring networks throughout the United States and Canada. We evaluate the GEOS-Chem simulation of the SO2 lifetime with that inferred from in situ measurements to verity the applicability of GEOS-Chem for inversion of SO2 columns to emissions. The seasonal mean SO2 lifetime calculated with the GEOS-Chem model over the eastern United States is 13 h in summer and 48 h in winter, compared to lifetimes inferred from in situ measurements of 19 +/- 7 h in summer and 58 +/- 20 h in winter. We apply SO2 columns from SCIAMACHY and OMI to derive a top-down anthropogenic SO2 emission inventory over land by using the local GEOS-Chem relationship between SO2 columns and emissions. There is little seasonal variation in the top-down emissions (<15%) over most major industrial regions providing some confidence in the method. Our global estimate for annual land surface anthropogenic SO2 emissions (52.4 Tg S/yr from SCIAMACHY and 49.9 Tg S / yr from OMI) closely agrees with the bottom-up emissions (54.6 Tg S/yr) in the GEOS-Chem model and exhibits consistency in global distributions with the bottom-up emissions (r = 0.78 for SCIAMACHY, and r = 0.77 for OMI). However, there are significant regional differences.

Lee, Chulkyu↗

MODIS On-Orbit Thermal Emissive Bands Lifetime Performance

MODerate resolution Imaging Spectroradiometer (MODIS), a leading heritage sensor in the fleet of Earth Observing System for the National Aeronautics and Space Administration (NASA) is in space orbit on two spacecrafts. They are the Terra (T) and Aqua (A) platforms. Both instruments have successfully continued to operate beyond the 6 year design life time, with the T-MODIS currently functional beyond 15 years and the A-MODIS operating beyond 13 years respectively. The MODIS sensor characteristics include a spectral coverage from 0.41 micron 14.4 micron, of which wavelengths ranging from 3.7 micron 14. 4 micron cover the thermal infrared region also referred to as the Thermal Emissive Bands (TEBs). The TEBs is calibrated using a v-grooved BlackBody (BB) whose temperature measurements are traceable to the National Institute of Standards and Technology temperature scales. The TEBs calibration based on the onboard BB is extremely important for its high radiometric fidelity. In this paper, we provide a complete characterization of the lifetime instrument performance of both MODIS instruments in terms of the sensor gain, the Noise Equivalent difference Temperature, key instrument telemetry such as the BB lifetime trends, the instrument temperature trends, the Cold Focal Plane telemetry and finally, the total assessed calibration uncertainty of the TEBs.

Madhavan, Sriharsha↗

Model Evaluation of Methods for Estimating Surface Emissions and Chemical Lifetimes from Satellite Data

Column densities from satellite retrievals can provide valuable information for estimating emissions and chemical lifetimes objectively across the globe. To better understand the uncertainties associated with these estimates, we test four methods using simulated column densities from a point source: a box model approach, a 2D Gaussian fit, an Inverse Radius fit and an Exponentially-Modified Gaussian fit. The model results were simulated using the WRF and CAMx models for the year 2005, for a single point source outside Atlanta in Georgia, USA with specified emissions and three chemical scenarios: no chemical reactions, 12 h chemical lifetime and 1 h chemical lifetime. No other sources were included in the simulations. We find that the box model provides reliable estimates irrespective of plume speed and plume direction, if the plume speed and the chemical lifetime are known accurately. The 2D Gaussian fit was found to be sensitive to plume speed and direction, and requires omnidirectional dispersion in order to have a decent fit. However, the 2D Gaussian fit is only an approximate fit to the data, and the discrepancies mean that the results are dependent on the geographical domain used for the optimization. An Inverse Radius fit is introduced to correct this issue, which is found to provide improved emissions and lifetime estimates. The Exponentially-Modified Gaussian fit also gave improved estimates. It is however dependent on accurate plume rotation such that reported chemical lifetimes with this method could be significantly underestimated.

Emission inventory↗

Laser-induced fluorescence of phosphors for remote cryogenic thermometry

Remote cryogenic temperature measurements can be made by inducing fluorescence in phosphors with temperature-dependent emissions and measuring the emission lifetimes. The thermographic phosphor technique can be used for making precision, noncontact, cryogenic-temperature measurements in electrically hostile environments, such as high dc electric or magnetic fields. The National Aeronautics and Space Administration is interested in using these thermographic phosphors for mapping hot spots on cryogenic tank walls. Europium-doped lanthanum oxysulfide (La2O2S:Eu) and magnesium fluorogermanate doped with manganese (Mg4FGeO6:Mn) are suitable for low-temperature surface thermometry. Several emission lines, excited by a 337-nm ultraviolet laser, provide fluorescence lifetimes having logarithmic dependence with temperature from 4 to above 125 K. A calibration curve for both La2O2S:Eu and Mg4FGeO6:Mn is presented, as well as emission spectra taken at room temperature and 11 K.

Beshears, D. L.↗

Laser-induced fluorescence of phosphors for remote cryogenic thermometry

Remote cryogenic temperature measurements can be made by inducing fluorescence in phosphors with temperature-dependent emissions and measuring the emission lifetimes. The thermographic phosphor technique can be used for making precision, noncontact, cryogenic-temperature measurements in electrically hostile environments, such as high dc electric or magnetic fields. The National Aeronautics and Space Administration is interested in using these thermographic phosphors for mapping hot spots on cryogenic tank walls. Europium-doped lanthanum oxysulfide (La2O2S:Eu) and magnesium fluorogermanate doped with manganese (Mg4FGeO6:Mn) are suitable for low-temperature surface thermometry. Several emission lines, excited by a 337-nm ultraviolet laser, provide fluorescence lifetimes having logarithmic dependence with temperature from 4 to above 125 K. A calibration curve for both La2O2S:Eu and Mg4FGeO6:Mn is presented, as well as emission spectra taken at room temperature and 11 K.

Beshears, D. L.↗

On the uncertainty in single molecule fluorescent lifetime and energy emission measurements

Time-correlated single photon counting has recently been combined with mode-locked picosecond pulsed excitation to measure the fluorescent lifetimes and energy emissions of single molecules in a flow stream. Maximum likelihood (ML) and least square methods agree and are optimal when the number of detected photons is large however, in single molecule fluorescence experiments the number of detected photons can be less than 20, 67% of those can be noise and the detection time is restricted to 10 nanoseconds. Under the assumption that the photon signal and background noise are two independent inhomogeneous poisson processes, we derive the exact joint arrival time probably density of the photons collected in a single counting experiment performed in the presence of background noise. The model obviates the need to bin experimental data for analysis, and makes it possible to analyze formally the effect of background noise on the photon detection experiment using both ML or Bayesian methods. For both methods we derive the joint and marginal probability densities of the fluorescent lifetime and fluorescent emission. the ML and Bayesian methods are compared in an analysis of simulated single molecule fluorescence experiments of Rhodamine 110 using different combinations of expected background nose and expected fluorescence emission. While both the ML or Bayesian procedures perform well for analyzing fluorescence emissions, the Bayesian methods provide more realistic measures of uncertainty in the fluorescent lifetimes. The Bayesian methods would be especially useful for measuring uncertainty in fluorescent lifetime estimates in current single molecule flow stream experiments where the expected fluorescence emission is low. Both the ML and Bayesian algorithms can be automated for applications in molecular biology.

Brown, Emery N.↗

On the Uncertainty in Single Molecule Fluorescent Lifetime and Energy Emission Measurements

Time-correlated single photon counting has recently been combined with mode-locked picosecond pulsed excitation to measure the fluorescent lifetimes and energy emissions of single molecules in a flow stream. Maximum likelihood (ML) and least squares methods agree and are optimal when the number of detected photons is large, however, in single molecule fluorescence experiments the number of detected photons can be less than 20, 67 percent of those can be noise, and the detection time is restricted to 10 nanoseconds. Under the assumption that the photon signal and background noise are two independent inhomogeneous Poisson processes, we derive the exact joint arrival time probability density of the photons collected in a single counting experiment performed in the presence of background noise. The model obviates the need to bin experimental data for analysis, and makes it possible to analyze formally the effect of background noise on the photon detection experiment using both ML or Bayesian methods. For both methods we derive the joint and marginal probability densities of the fluorescent lifetime and fluorescent emission. The ML and Bayesian methods are compared in an analysis of simulated single molecule fluorescence experiments of Rhodamine 110 using different combinations of expected background noise and expected fluorescence emission. While both the ML or Bayesian procedures perform well for analyzing fluorescence emissions, the Bayesian methods provide more realistic measures of uncertainty in the fluorescent lifetimes. The Bayesian methods would be especially useful for measuring uncertainty in fluorescent lifetime estimates in current single molecule flow stream experiments where the expected fluorescence emission is low. Both the ML and Bayesian algorithms can be automated for applications in molecular biology.

Brown, Emery N.↗

Nebular Hydrogen Absorption in the Ejecta of Eta Carinae

Space Telescope Imaging Spectrograph (STIS) observations of Eta Carinae and immediate ejecta reveal narrow Balmer absorption lines in addition to the nebular-scattered broad P-Cygni absorptions. The narrow absorption correlates with apparent disk structure that separates the two Homunculus lobes. We trace these features about half way up the Northern lobe until the scattered stellar Balmer line doppler-shifts redward beyond the nebular absorption feature. Three-dimensional data cubes, made by mapping the Homunculus at Balmer alpha and Balmer beta with the 52 x 0.1 arcsecond aperture and about 5000 spectral resolving power, demonstrate that the absorption feature changes slowly in velocity with nebular position. We have monitored the stellar Balmer alpha line profile of the central source over the past four years. The equivalent width of the nebular absorption feature changes considerably between observations. The changes do not correlate with measured brightness of Eta Carinae. Likely clumps of neutral hydrogen with a scale size comparable to the stellar disk diameter are passing through the intervening light path on the timescales less than several months. The excitation mechanism involves Lyman alpha radiation (possibly the Lyman series plus Lyman continuum) and collisions leading to populating the 2S metastable state. Before the electron can jump to the ground state by two photon emission (lifetime about 1/8 second), a stellar Balmer photon is absorbed and the electron shifts to an NP level. We see the absorption feature in higher Balmer lines, and but not in Paschen lines. Indeed we see narrow nebular Paschen emission lines. At present, we do not completely understand the details of the absorption. Better understanding should lead to improved insight of the unique conditions around Eta Carinae that leads to these absorptions.

Gull, Theodore R.↗

Theoretical studies of Resonance Enhanced Stimulated Raman Scattering (RESRS) of frequency doubled Alexandrite laser wavelengths in cesium vapor

This work focused on understanding the effects of arbitrary transverse and longitudinal relaxation rates on the susceptibilities of coherently driven three-level systems. The approximation of a single relaxation rate often made in previous work is strongly invalidated by the variation in the spontaneous emission lifetime between various atomic level pairs in systems such as cesium. It is of great importance to the problem of nonlinear infrared generation to determine the dependence of both real and imaginary susceptibility on relaxation rates. The imaginary susceptibility on the pump transition determines the absorption of pump photons and the imaginary susceptibility on the laser transition determines the spectral dependence of the gain. This is of particular importance for pure Raman emission (i.e., absorption at linecenter of the gain transition) as it determines the tunability characteristics we are aiming to predict. The real susceptibility is important when cavities are used at the signal field as this will determine the loaded resonance of the Raman oscillator. Researchers show that in some cases which result from having different relaxation rates mode splitting may result, allowing more than one frequency to have the same Raman wavelength, possibly resulting in a temporal instability.

Lawandy, N. M.↗

Satellite-Based Evaluation of AeroCom Model Bias in Biomass Burning Regions

Global models are widely used to simulate biomass burning aerosol (BBA). Exhaustive evaluations on model representation of aerosol distributions and properties are fundamental to assess health and climate impacts of BBA. Here we conducted a comprehensive comparison of Aerosol Comparisons between Observations and Models (AeroCom) project model simulations with satellite observations. A total of 59 runs by 18 models from three AeroCom Phase-III experiments (i.e., biomass burning emissions, CTRL16, and CTRL19) and 14 satellite products of aerosols were used in the study. Aerosol optical depth (AOD) at 550 nm was investigated during the fire season over three key fire regions reflecting different fire dynamics (i.e., deforestation-dominated Amazon, Southern Hemisphere Africa where savannas are the key source of emissions, and boreal forest burning in boreal North America). The 14 satellite products were first evaluated against AErosol RObotic NETwork (AERONET) observations, with large uncertainties found. But these uncertainties had small impacts on the model evaluation that was dominated by modeling bias. Through a comparison with Polarization and Directionality of the Earth’s Reflectances measurements with the Generalized Retrieval of Aerosol and Surface Properties algorithm (POLDER-GRASP), we found that the modeled AOD values were biased by −93 % to 152 %, with most models showing significant underestimations even for the state-of-the-art aerosol modeling techniques (i.e., CTRL19). By scaling up BBA emissions, the negative biases in modeled AOD were significantly mitigated, although it yielded only negligible improvements in the correlation between models and observations, and the spatial and temporal variations in AOD biases did not change much. For models in CTRL16 and CTRL19, the large diversity in modeled AOD was in almost equal measures caused by diversity in emissions, lifetime, and the mass extinction coefficient (MEC). We found that in the AeroCom ensemble, BBA lifetime correlated significantly with particle deposition (as expected) and in turn correlated strongly with precipitation. Additional analysis based on Cloud-Aerosol LIdar with Orthogonal Polarization (CALIOP) aerosol profiles suggested that the altitude of the aerosol layer in the current models was generally too low, which also contributed to the bias in modeled lifetime. Modeled MECs exhibited significant correlations with the Ångström exponent (AE, an indicator of particle size). Comparisons with the POLDER-GRASP-observed AE suggested that the models tended to overestimate the AE (underestimated particle size), indicating a possible underestimation of MECs in models. The hygroscopic growth in most models generally agreed with observations and might not explain the overall underestimation of modeled AOD. Our results imply that current global models contain biases in important aerosol processes for BBA (e.g., emissions, removal, and optical properties) that remain to be addressed in future research.

biomass burning aerosols↗

Polar Coronal Hole Ephemeral Regions, the Fast Solar Wind and the Global Magnetic Dynamo

The X-Ray Telescope aboard Hinode has been regularly observing both the north and south solar polar coronal holes from November 2006 through March 2009. We use the observations of emerged flux regions within the coronal hole as evidenced by small x-ray bright points to study the physical properties of these regions. The width of the emerged flux region loop footpoints, the duration of the x-ray emission lifetime for the emerged flux region, the latitude of formation and whether an x-ray or EUV jet was observed were all recorded. In the present work we detail these observations and show a dependence on the width of the emerged flux region (bright point) to the number of x-ray jets observed. The distribution of base width is then related to a power law for number of emerged flux regions as a function of base width.

Cirtain, Jonathan W.↗

Miniature Sensor Probe for O2, CO2, and H2O Monitoring in Portable Life Support Systems

A miniature sensor probe, composed of four sensors which monitor the partial pressure of O2, CO2, H2O, and temperature, designed to operate in the portable life support system (PLSS), has been demonstrated. The probe provides an important advantage over existing technology in that it is able to operate reliably while wet. These luminescence-based fiber optic sensors consist of an indicator chemistry immobilized in a polymeric film, whose emission lifetime undergoes a strong change upon a reversible interaction with the target gas. Each sensor includes chemistry specifically sensitive to one target parameter. All four sensors are based on indicator chemistries that include luminescent dyes from the same chemical family, and therefore exhibit similar photochemical properties, which allow performing measurements of all the sensors by a single, compact, low-power optoelectronic unit remotely connected to the sensors by an electromagnetic interference-proof optical fiber cable. For space systems, using these miniature sensor elements with remote optoelectronics provides unmatched design flexibility for measurements in highly constrained volume systems such as the PLSS. A 10 mm diameter and 15 mm length prototype multiparameter probe was designed, fabricated, tested, and demonstrated over a wide operational range of gas concentration, humidity, and temperature relevant to operation in the PLSS. The sensors were evaluated for measurement range, precision, accuracy, and response time in temperatures ranging from 50 aF-150 aF and relative humidity from dry to 100% RH. Operation of the sensors in water condensation conditions was demonstrated wherein the sensors not only tolerated liquid water but actually operated while wet.

Delgado, Jesus↗

AeroCom Phase III Multi-Model Evaluation of the Aerosol Life Cycle and Optical Properties Using Ground and Space-Based Remote Sensing as Well as Surface In Situ Observations

Within the framework of the AeroCom (Aerosol Comparisons between Observations and Models) initiative, the state-of-the-art modelling of aerosol optical properties is assessed from 14 global models participating in the phase III control experiment (AP3). The models are similar to CMIP6/AerChemMIP Earth System Models (ESMs) and provide a robust multi-model ensemble. Inter-model spread of aerosol species lifetimes and emissions appears to be similar to that of mass extinction coefficients (MECs), suggesting that aerosol optical depth (AOD) uncertainties are associated with a broad spectrum of parameterised aerosol processes. Total AOD is approximately the same as in AeroCom phase I (AP1) simulations. However, we find a 50 % decrease in the optical depth (OD) of black carbon (BC), attributable to a combination of decreased emissions and lifetimes. Relative contributions from sea salt (SS) and dust (DU) have shifted from being approximately equal in AP1 to SS contributing about 2∕3 of the natural AOD in AP3. This shift is linked with a decrease in DU mass burden, a lower DU MEC, and a slight decrease in DU lifetime, suggesting coarser DU particle sizes in AP3 compared to AP1. Relative to observations, the AP3 ensemble median and most of the participating models underestimate all aerosol optical properties investigated, that is, total AOD as well as fine and coarse AOD (AODf, AODc), Ångström exponent (AE), dry surface scattering (SCdry), and absorption (ACdry) coefficients. Compared to AERONET, the models underestimate total AOD by ca. 21 % ± 20 % (as inferred from the ensemble median and interquartile range). Against satellite data, the ensemble AOD biases range from −37 % (MODIS-Terra) to −16 % (MERGED-FMI, a multi-satellite AOD product), which we explain by differences between individual satellites and AERONET measurements themselves. Correlation coefficients (R) between model and observation AOD records are generally high (R>0.75), suggesting that the models are capable of capturing spatio-temporal variations in AOD. We find a much larger underestimate in coarse AODc (∼ −45 % ± 25 %) than in fine AODf (∼ −15 % ± 25 %) with slightly increased inter-model spread compared to total AOD. These results indicate problems in the modelling of DU and SS. The AODc bias is likely due to missing DU over continental land masses (particularly over the United States, SE Asia, and S. America), while marine AERONET sites and the AATSR SU satellite data suggest more moderate oceanic biases in AODc. Column AEs are underestimated by about 10 % ± 16 %. For situations in which measurements show AE > 2, models underestimate AERONET AE by ca. 35 %. In contrast, all models (but one) exhibit large overestimates in AE when coarse aerosol dominates (bias ca. +140 % if observed AE < 0.5). Simulated AE does not span the observed AE variability. These results indicate that models overestimate particle size (or underestimate the fine-mode fraction) for fine-dominated aerosol and underestimate size (or overestimate the fine-mode fraction) for coarse-dominated aerosol. This must have implications for lifetime, water uptake, scattering enhancement, and the aerosol radiative effect, which we can not quantify at this moment. Comparison against Global Atmosphere Watch (GAW) in situ data results in mean bias and inter-model variations of −35 % ± 25 % and −20 % ± 18 % for SCdry and ACdry, respectively. The larger underestimate of SCdry than ACdry suggests the models will simulate an aerosol single scattering albedo that is too low. The larger underestimate of SCdry than ambient air AOD is consistent with recent findings that models overestimate scattering enhancement due to hygroscopic growth. The broadly consistent negative bias in AOD and surface scattering suggests an underestimate of aerosol radiative effects in current global aerosol models. Considerable inter-model diversity in the simulated optical properties is often found in regions that are, unfortunately, not or only sparsely covered by ground-based observations. This includes, for instance, the Sahara, Amazonia, central Australia, and the South Pacific. This highlights the need for a better site coverage in the observations, which would enable us to better assess the models, but also the performance of satellite products in these regions. Using fine-mode AOD as a proxy for present-day aerosol forcing estimates, our results suggest that models underestimate aerosol forcing by ca. −15 %, however, with a considerably large interquartile range, suggesting a spread between −35 % and +10 %.

space-based remote sensing↗