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At least 55 records · Page 3

Differential Radiometers Using Fabry-Perot Interferometric Technique for Remote Sensing Determination of Various Atmospheric Trace Gases

New type of remote sensing instrument based upon the Fabry-Perot inte rferometric technique has been developed at NASA's Goddard Space Flight Center. Fabry-Perot interferometry (FPI) is a well known, powerful spectroscopic technique and one of its many applications is to be use d to measure greenhouse gases and also some harmful species in the at mosphere. With this technique, absorption of particular species is me asured and related to its concentration. A solid Fabry-Perot etalon is used as a frequency filter to restrict the measurement to particular absorption bands of the gas of interest. With adjusting the thicknes s of the etalon that separation (in frequency) of the transmitted fri nges can be made equal to the almost constant separation of the gas a bsorption lines. By adjusting the temperature of the etalon, which changes the index of refi-action of its material, the transmission fring es can be brought into nearly exact correspondence with absorption li nes of the particular species. With this alignment between absorption lines and fringes, changes in the amount of a species in the atmosph ere strongly affect the amount of light transmitted by the etalon and can be related to gas concentration. The instrument that we have dev eloped detects the absorption of various atmospheric trace gases in d irect or reflected sunlight. Our instrument employing Fabry-Perot interferometer makes use of two features to achieve high sensitivity. The first is high spectral resolution enabling one to match the width of an atmospheric absorption feature by the instrumental band pass. The second is high optical throughput enabled by using multiple spectral lines simultaneously. For any species that one wishes to measure, thi s first feature is available while the use of multiple spectral features can be employed only for species with suitable spectra and freedom from interfering species in the same wavelength region. We have deve loped an instrument for use as ground based, airborne and satellite s ensor for gases such as carbon dioxide (1570 nm), oxygen (762 nm and 768 nm lines sensitive to changes in oxygen pressure and oxygen temper ature) and water vapor (940 nm). Our current goal is to develop an ul tra precise, inexpensive, ground based device suitable for wide deplo yment as a validation instrument for the Orbiting Carbon Observatory (OCO) satellite. We show sensitivity measurements for CO2, 02, and H2 O, compare our measurements to those obtained using other types of sensors and discuss some of the peculiarities that must be addressed in order to provide the very high quality column detection required for solving problems about global distribution of greenhouse gases and cl imatological models. In another area of research we are interested in developing a small-size channel for CO2 capable of doing simultaneous measurements with the AERONET (Aerosol Robotic Network) at NASA, God dard to study the hypothesis that atmospheric aerosols affect the reg ional terrestrial carbon cycle. We present recent data from our groun d based measurements of O2, CO2, H2O and (13)CO2 and discuss extensio n of the technique to new species and applications.

Georgieva, E. M.↗

Materials surface contamination analysis

The original research objective was to demonstrate the ability of optical fiber spectrometry to determine contamination levels on solid rocket motor cases in order to identify surface conditions which may result in poor bonds during production. The capability of using the spectral features to identify contaminants with other sensors which might only indicate a potential contamination level provides a real enhancement to current inspection systems such as Optical Stimulated Electron Emission (OSEE). The optical fiber probe can easily fit into the same scanning fixtures as the OSEE. The initial data obtained using the Guided Wave Model 260 spectrophotometer was primarily focused on determining spectra of potential contaminants such as HD2 grease, silicones, etc. However, once we began taking data and applying multivariate analysis techniques, using a program that can handle very large data sets, i.e., Unscrambler 2, it became apparent that the techniques also might provide a nice scientific tool for determining oxidation and chemisorption rates under controlled conditions. As the ultimate power of the technique became recognized, considering that the chemical system which was most frequently studied in this work is water + D6AC steel, we became very interested in trying the spectroscopic techniques to solve a broad range of problems. The complexity of the observed spectra for the D6AC + water system is due to overlaps between the water peaks, the resulting chemisorbed species, and products of reaction which also contain OH stretching bands. Unscrambling these spectral features, without knowledge of the specific species involved, has proven to be a formidable task.

Workman, Gary L.↗

Alkali Cation Inhibition of Imidazolium-Mediated Electrochemical CO 2 Reduction on Silver

Imidazolium-based ionic liquids have led to enhanced CO 2 electroreduction activity due to cation effects at the cathode surface, stabilizing the reaction intermediates and decreasing the activation energy. In aqueous media, alkali cations are also known to improve CO 2 reduction activity on metals such as Ag, with the enhancement attributed to electrical double layer effects and trending with the size of the alkali cation. However, the effect of a mixed catholyte solution of alkali cations in the presence of an imidazolium-based ionic liquid has not been well-explored. Herein, 1-ethyl-3-methylimidazolium tetrafluoroborate, [EMIM][BF 4 ], in water was investigated with alkali salts to unravel the interaction effects for CO 2 electroreduction on Ag. Although both [EMIM] + and alkali cations have individually improved CO 2 to CO conversion on Ag in water, electrochemical results showed that alkali cations hindered imidazolium-mediated CO 2 electroreduction in most conditions. Li + , in particular, was sharply inhibitory compared to other alkali cations and strongly redirected the selectivity to hydrogen evolution. The nature of the alkali cation inhibition was investigated with spectroscopic techniques, including in situ surface-enhanced Raman spectroscopy (SERS) and dynamic electrochemical impedance spectroscopy (DEIS). Along with computational insights from density functional theory (DFT), the electrochemical and spectroscopic data suggest that alkali cations inhibit [EMIM]-mediated CO 2 reduction by competing for surface adsorption sites, preventing the potential-dependent structural reorientation of imidazolium, and promoting hydrogen evolution by bringing solvated water to the cathode surface.

cations↗

Witnessing Entanglement and Quantum Correlations in Condensed Matter: A Review

The detection and certification of entanglement and quantum correlations in materials is of fundamental and far-reaching importance, and has seen significant recent progress. It impacts both the understanding of the basic science of quantum many-body phenomena as well as the identification of systems suitable for novel technologies. Frameworks suitable to condensed matter that connect measurements to entanglement and coherence have been developed in the context of quantum information theory. These take the form of entanglement witnesses and quantum correlation measures. Here, the underlying theory of these quantities, their relation to condensed matter experimental techniques, and their application to real materials are comprehensively reviewed. In addition, their usage in, e.g., protocols, the relative advantages and disadvantages of witnesses and measures, and future prospects in, e.g., correlated electrons, entanglement dynamics, and entangled spectroscopic probes, are presented. Consideration is given to the interdisciplinary nature of this emerging research and substantial ongoing progress by providing an accessible and practical treatment from fundamentals to application. Particular emphasis is placed on quantities accessible to collective measurements, including by susceptibility and spectroscopic techniques. This includes the magnetic susceptibility witness, one-tangle, concurrence and two-tangle, two-site quantum discord, and quantum coherence measures such as the quantum Fisher information.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Remote determination of exposure degree and iron concentration of lunar soils using VIS-NIR spectroscopic methods

On the Moon, space weathering processes such as micrometeorite bombardment alter the optical properties of lunar soils. As a consequence, lunar soil optical properties are a function not only of composition, but of degree of exposure on the lunar surface as well. In order to accurately assess the compositional properties of the lunar surface using remotely acquired visible and near-infrared spectroscopic data, it is thus necessary either (1) to compare optical properties only of soils characterized by similar degrees of exposure or (2) to otherwise normalize or remove the optical effects due to exposure. Laboratory spectroscopic data for lunar soils are used to develop and test remote spectrocopic methods for determining degree of exposure and for distinguishing between the optical effects due to exposure and those due to composition. A method employing a ratio between reflectances within and outside of the 1 micrometer Fe(2+) crystal field absorption band was developed for remotely identifying highland soils that have reached a steady-state maturity. The relative optical properties of these soils are a function solely of composition and as such can be directly compared. Spectroscopic techniques for accurate quantitative determination of iron content for lunar highland soils are investigated as well. It is shown that approximations of the 1 micrometer Fe(2+) absorption band depth using few to several channel multispectral data or spectroscopic data of inadequate spectral range cannot be used with confidence for compositional analysis. However, band depth measurements derived from continuum-removed high spectral resolution data can be used to calculate the weight percent FeO and relative proportion of iron-bearing silicates in mature lunar highland and mare/highland mixture soils. A preliminary effort to calibrate telescopic band depth to laboratory soil measurements is described.

Fischer, Erich M.↗

Diode laser absorption sensors for gas-dynamic and combustion flows

Recent advances in room-temperature, near-IR and visible diode laser sources for tele-communication, high-speed computer networks, and optical data storage applications are enabling a new generation of gas-dynamic and combustion-flow sensors based on laser absorption spectroscopy. In addition to conventional species concentration and density measurements, spectroscopic techniques for temperature, velocity, pressure and mass flux have been demonstrated in laboratory, industrial and technical flows. Combined with fibreoptic distribution networks and ultrasensitive detection strategies, compact and portable sensors are now appearing for a variety of applications. In many cases, the superior spectroscopic quality of the new laser sources compared with earlier cryogenic, mid-IR devices is allowing increased sensitivity of trace species measurements, high-precision spectroscopy of major gas constituents, and stable, autonomous measurement systems. The purpose of this article is to review recent progress in this field and suggest likely directions for future research and development. The various laser-source technologies are briefly reviewed as they relate to sensor applications. Basic theory for laser absorption measurements of gas-dynamic properties is reviewed and special detection strategies for the weak near-IR and visible absorption spectra are described. Typical sensor configurations are described and compared for various application scenarios, ranging from laboratory research to automated field and airborne packages. Recent applications of gas-dynamic sensors for air flows and fluxes of trace atmospheric species are presented. Applications of gas-dynamic and combustion sensors to research and development of high-speed flows aeropropulsion engines, and combustion emissions monitoring are presented in detail, along with emerging flow control systems based on these new sensors. Finally, technology in nonlinear frequency conversion, UV laser materials, room-temperature mid-IR materials and broadly tunable multisection devices is reviewed to suggest new sensor possibilities.

Non-NASA Center↗

Disentangling interlayer confinement and pore surface adsorption in functionalized smectites for tunable ethylene gas capture

Smectite-based adsorbents are increasingly being studied as sustainable packaging materials for scavenging ethylene, a plant hormone that accelerates fruit ripening. However, the mechanisms governing their uptake and retention remain poorly understood. Here, to tackle this question we systematically investigate ethylene gas-solid interactions in pristine, acid-activated, and choline-functionalized montmorillonites using a complementary combination of structural, gravimetric, and spectroscopic techniques, including inelastic neutron scattering. We experimentally distinguish ethylene populations associated with interlayer confinement, mesopore, and external surface adsorption. We show that chemical functionalization distinctly controls adsorption pathways: acid activation enhances total uptake by generating mesoporous adsorption sites and promoting partial interlayer intercalation, yielding capacities comparable to those of leading smectite-based adsorbents, while choline functionalization promotes preferential confinement and stabilization of guest molecules within the interlayer galleries. Advanced spectroscopic analysis provides molecular-level insight into confinement environments and interaction strengths. We also establish clear structure-property relationships by correlating uptake values derived from independent techniques, linking chemical modification, accessible adsorption domains, and retention behavior. These findings provide general design principles for tuning gas-solid interactions in functionalized layered silicates and highlight their potential as adaptable platforms for sustainable ethylene gas capture and selective adsorption technologies.

Ethylene adsorption mechanism↗

Measurement of the fundamental vibration-rotation spectrum of ClO

The ClO fundamental absorption band near 850/cm is observed, with a tunable PbSnTe diode laser used as a source of monochromatic radiation. The chlorine monoxide concentration in the absorption tube was measured indirectly via a UV transmission technique. Frequencies and assignments for the ClO lines, and band centers and rotational constants for the ClO fundamental vibration, are tabulated. Diatomic vibration-rotation transitions within and between electronic substates are discussed. The tunable diode laser is valuable for studying the hyperfine structure. The IR spectroscopic technique is developed in order to monitor chlorine monoxide concentration in the stratosphere, since the short-lived ClO is a crucial intermediate participant in reactions involving destruction of stratospheric ozone.

Menzies, R. T.↗

Spectrophotometry of Dust in Comet Hale-Bopp

Comets, such as Hale-Bopp (C/1995 O1), are frozen reservoirs of primitive solar nebula dust grains and ices. Analysis of the composition of cometary dust grains from infrared spectroscopic techniques permits an estimation of the types of organic and inorganic materials that constituted the early primitive solar nebula. In addition, the cometary bombardment of the Earth (approximately 3.5 Gy ago) supplied the water for the oceans and brought organic materials to Earth which may have been biogenic. Spectroscopic observations of comet Hale-Bopp suggest the possible presence of organic hydrocarbon species, silicate and olivine dust grains, and water ice. Spectroscopy near 3 microns obtained in Nov 1996 r=2.393 AU, delta=3.034 AU) shows a feature which we attribute to PAH emission. The spatial morphology of the 3.28 microns PAH feature is also presented. Optical and infrared spectrophotometric observations of comets convey valuable information about the spatial distribution and properties of dust and gas within the inner coma. In the optical and NIR shortward of 2 microns, the observed light is primarily scattered sunlight from the dust grains. At longer wavelengths, particularly in the 10 gm window, thermal emission from these grains dominates the radiation allowing an accurate estimate of grain sizes and chemical composition. Here we present an initial analysis of spectra taken with the NASA HIFOGS at 7-14 microns as part of a multiwavelength temporal study of the "comet of the century".

Witteborn, Fred C.↗

Carbon-13 and proton nuclear magnetic resonance analysis of shale-derived refinery products and jet fuels and of experimental referee broadened-specification jet fuels

A proton and carbon-13 nuclear magnetic resonance (NMR) study was conducted of Ashland shale oil refinery products, experimental referee broadened-specification jet fuels, and of related isoprenoid model compounds. Supercritical fluid chromatography techniques using carbon dioxide were developed on a preparative scale, so that samples could be quantitatively separated into saturates and aromatic fractions for study by NMR. An optimized average parameter treatment was developed, and the NMR results were analyzed in terms of the resulting average parameters; formulation of model mixtures was demonstrated. Application of novel spectroscopic techniques to fuel samples was investigated.

Dalling, D. K.↗

[Methods Used for Monitoring Cure Reactions in Real-time in an Autoclave]

The goal of the research was to investigate methods for monitoring cure reactions in real-time in an autoclave. This is of particular importance to NASA Langley Research Center because polyimides were proposed for use in the High Speed Civil Transport (HSCT) program. Understanding the cure chemistry behind the polyimides would allow for intelligent processing of the composites made from their use. This work has led to two publications in peer-reviewed journals and a patent. The journal articles are listed as Appendix A which is on the instrument design of the research and Appendix B which is on the cure chemistry. Also, a patent has been awarded for the instrumental design developed under this grant which is given as Appendix C. There has been a significant amount of research directed at developing methods for monitoring cure reactions in real-time within the autoclave. The various research efforts can be categorized as methods providing either direct chemical bonding information or methods that provide indirect chemical bonding information. Methods falling into the latter category are fluorescence, dielectric loss, ultrasonic and similar type methods. Correlation of such measurements with the underlying chemistry is often quite difficult since these techniques do not allow monitoring of the curing chemistry which is ultimately responsible for material properties. Direct methods such as vibrational spectroscopy, however, can often be easily correlated with the underlying chemistry of a reaction. Such methods include Raman spectroscopy, mid-IR absorbance, and near-IR absorbance. With the recent advances in fiber-optics, these spectroscopic techniques can be applied to remote on-line monitoring.

Cooper, John B.↗

Microsampling techniques for infrared spectroscopic analysis of lunar and terrestrial minerals

Microsampling techniques have been developed for infrared analysis of single mineral grains from lunar rocks and dusts, allowing a detailed molecular structure characterization of these complex fine-grained samples. The methods include special devices for isolating single grains, preparing micropellets from the grains, and obtaining in situ microspecular reflectance spectra from grains in polished rock samples. Although specifically developed for the work on lunar samples, the special techniques for single grain infrared analysis were found to be equally useful in studies of complex terrestrial mineral samples. For example, infrared microanalysis has contributed substantially in solving problems concerned with our natural resources, such as the structural characterization of minerals from commercial iron ores, marine deposits, coal, and fly ash derived from coal.

Estep, P. A.↗

The Origin, Composition and History of Comets from Spectroscopic Studies

A wealth of information essential to understanding the composition and physical structure of cometary ice and hence gain deep insight into the comet's origin and history, can be gleaned by carrying out a full range of spectroscopic studies on the returned sample. These studies ought to be among the first performed as they are generally non-destructive and will provide a broad data bank which will be crucial in planning subsequent analysis. Examples of the spectroscopic techniques along with relative sensitivities and transitions probed, are discussed. Different kind of "spectroscopy" is summarized, with emphasis placed on the kind of information each provides. Infrared spectroscopy should be the premier method of analysis as the mid-IR absorption spectrum of a substance contains more global information about the identity and structure of that material than any other property. In fact, the greatest strides in our understanding of the composition of interstellar ices (thought by many to be the primordial material from which comets have formed) have been taken during the past ten years or so because this was when high quality infrared spectra of the interstellar medium (ISM) first became available. The interpretation of the infrared spectra of mixtures, such as expected in comets, is often (not always) ambiguous. Consequently, a full range of other non-destructive, complementary spectroscopic measurements are required to fully characterize the material, to probe for substances for which the IR is not well suited and to lay the groundwork for future analysis. Given the likelihood that the icy component (including some of the organic and mineral phases) of the returned sample will be exceedingly complex, these techniques must be intensely developed over the next decade and then made ready to apply flawlessly to what will certainly be one of the most precious, and most challenging, samples ever analyzed.

Allamandola, L. J.↗

Icy Satellites of the Planets, and the Work of V.I. Moroz

The satellites of the giant planets are highly varied in size and density, indicating a wide range of compositions. The principal components of these satellites are ices of many different compositions (with H2O the most abundant) and varying amounts of silicate rocky material. Many different ices have been found by spectroscopic techniques both from Earth-based observatories and from planetary spacecraft. Three of the Galilean satellites of Jupiter exhibit H2O ice on their surfaces, while small amounts of CO2 are present on Ganymede and Callisto. The volcanic satellite Io has abundant SO2 ice and frost deposits. Saturn s satellites have surfaces dominated by H2O ice, but CO2 is also present on most of them, and in the cases of the low-albedo satellites Iapetus and Phoebe, there is evidence of complex hydrocarbons mixed with the surface materials. The large Uranian satellites also have H2O-dominated surfaces, but CO2 has also been discovered on two of them. Neptune s largest satellite, Triton, show spectroscopic evidence for six different ices, including N2, CH4, CO, CO2, H2O, and C2H6. The latter ice is a photochemical product from the action of sunlight on Triton's atmosphere. Pluto is similar to Triton, although CO2 has not been found. Pluto s large satellite, Charon, shows evidence for an ammonia hydrate on part of its surface. V. I. Moroz was a pioneer in the application of near-infrared detectors to astronomical sources. Using a prism spectrometer he measured the spectra of the Galilean satellites of Jupiter, and in 1966 he published the first near-infrared spectra, noting the appearance of H2O ice as a major component of Europa and Ganymede. This discovery, and the techniques of Moroz measurements help set the stage for the broad extension of the study of planetary, satellite, and asteroid surfaces through reflectance spectroscopy in the near-infrared.

Cruikshank, Dale P.↗

The Electron Spectro-Microscopy (ESM) Beamline at NSLS-II

Photoelectron spectroscopy is a primary tool for the study of the electronic structure of materials and the chemical composition of surfaces. High-resolution angle-resolved photoemission spectroscopy (ARPES) has the unique ability to map the energy bands in momentum space. Furthermore, going beyond the single particle picture, the self-energy corrections caused by correlations in solids can be extracted from the analysis of the emission line shape. The current level of refinement, in terms of energy and angular resolution (ΔE < 1 meV, Δθ < 0.1°), makes the technique sensitive to the lowest energy excitations and the dynamics of electrons, which in turn virtually determine all the macroscopic properties of any system and govern the chemical, electrical, magnetic, and physical processes. Similarly important, X-ray photoelectron microscopy (XPEEM), combined with the low-energy electron microscopy (LEEM), is indispensable in probing the complexity of chemical, structural, electronic and magnetic properties of surfaces and shallow interfaces, with the spatial resolution of few tens of nanometer (nm). The Electron-Spectro-Microscopy beamline (ESM) has been recently commissioned at NSLS-II and is now in operation. The primary spectroscopic technique is photoemission, performed over a wide energy range with control of light polarization and in a variety of flux/resolution conditions. The beamline has two experimental end stations that allow to perform ARPES and XPEEM/LEEM, separately. The ARPES end station focuses on high energy-resolution work, with spot-size of a few microns. The XPEEM/LEEM end station is a full-field microscope (XPEEM) operating either with the synchrotron generated X-rays (XPEEM), or with an internal electron gun (LEEM). Spatial resolution is crucial in studies of newly synthesized complex materials since they are often initially available only as small specimens (typically micron size). Furthermore, chemical inhomogeneities on surfaces are often an integral part of surface chemical processes. Finally, the ESM beamline with X-ray spots of few microns is optimized to study the electronic structure of novel materials with microscopy capabilities.

47 OTHER INSTRUMENTATION↗

Feasibility Investigation for Performing Fireball Temperature Tests

NASA Johnson Space Center White Sands Test Facility (WSTF) was requested by the Launch Abort Subpanel and the Power Systems Subpanel of the Interagency Nuclear Safety Review Panel to investigate the feasibility of using spectroscopic techniques to measure propellant fireball gas temperatures. This report outlines the modeling and experimental approaches and results of this investigation. Descriptions of the theoretical particle temperature and mass effusion models are presented along with the results of the survivability of small plutonium dioxide (less than or equal to 1000 microns diameter) particles entrained in various propellant fireball scenarios. The experimental test systems used to measure the hydroxide radical, water, and particle graybody spectral emissions and absorptions are discussed. Spectral results along with temperatures extracted by analyzing the spectral features are presented for the flames investigated in the laboratory environment. Methods of implementing spectroscopic measurements for future testing using the WSTF Large-scale Hydrogen/Oxygen Explosion Facility are discussed, and the accuracy expected for these measurements is estimated from laboratory measurements.

Tapphorn, Ralph M.↗

Submillimeter Laboratory Investigations: Spectroscopy and Collisions

Currently, millimeter-wave and submillimeter-wave spectroscopy is conducted in our laboratory on several different types of spectrometers. Our standard spectrometer utilizes the output of a phase-locked klystron operating in the 40-60 GHz region, which is sent into a crossed-waveguide harmonic generator, or "multiplier". The high frequency millimeter-and submillimeter-wave radiation is transmitted via quasi-optical techniques through an absorption cell and then onto a detector, which is either an InSb hot electron bolometer cooled to 1.4 K or a Si bolometer cooled to 0.3 K. The detector response is sent to a computer for measurement and analysis. The frequency range produced and detected in this manner goes from 80 GHz to upwards of 1 THz. Spectra are normally taken with source modulation, with line frequencies typically measured to an accuracy of 50-100 kHz. Higher accuracy is available when needed. Recently, we developed a new, broad-band spectrometer in our laboratory based on a free-running backward wave oscillator (BWO) of Russian manufacture as the primary source of radiation. The so-called FASSST (fast-scan submillimeter spectroscopic technique) system uses fast-scan and optical calibration methods rather than the traditional locking techniques. The output power from the BWO is split such that 90% goes into the absorption cell while 10% is coupled to a 40-meter Fabry-Perot cavity, which yields fringe? for frequency measurement. Results from this spectrometer on the spectrum of nitric acid (HNO3) show that 100 GHz of spectral data can be obtained in 5 seconds with a measurement accuracy of 50 kHz. Currently, the frequency range of the FASSST system in our laboratory is roughly 100-700 GHz.

Herbst, Eric↗

Quantitative Studies of the Optical and UV Spectra of Galactic Early B Supergiants

We undertake an optical and ultraviolet spectroscopic analysis of a sample of 20 Galactic B0-B5 supergiants of luminosity classes Ia, Ib, Iab, and II. Fundamental stellar parameters are obtained from optical diagnostics and a critical comparison of the model predictions to observed UV spectral features is made. Methods. Fundamental parameters (e.g., T(sub eff), log L(sub *), mass-loss rates and CNO abundances) are derived for individual stars using CMFGEN, a nLTE, line-blanketed model atmosphere code. The impact of these newly derived parameters on the Galactic B supergiant Ten scale, mass discrepancy, and wind-momentum luminosity relation is examined. Results. The B supergiant temperature scale derived here shows a reduction of about 1000-3000 K compared to previous results using unblanketed codes. Mass-loss rate estimates are in good agreement with predicted theoretical values, and all of the 20 BO-B5 supergiants analysed show evidence of CNO processing. A mass discrepancy still exists between spectroscopic and evolutionary masses, with the largest discrepancy occuring at log (L/(solar)L approx. 5.4. The observed WLR values calculated for B0-B0.7 supergiants are higher than predicted values, whereas the reverse is true for B1-B5 supergiants. This means that the discrepancy between observed and theoretical values cannot be resolved by adopting clumped (i.e., lower) mass-loss rates as for O stars. The most surprising result is that, although CMFGEN succeeds in reproducing the optical stellar spectrum accurately, it fails to precisely reproduce key UV diagnostics, such as the N v and C IV P Cygni profiles. This problem arises because the models are not ionised enough and fail to reproduce the full extent of the observed absorption trough of the P Cygni profiles. Conclusions. Newly-derived fundamental parameters for early B supergiants are in good agreement with similar work in the field. The most significant discovery, however, is the failure of CMFGEN to predict the correct ionisation fraction for some ions. Such findings add further support to revising the current standard model of massive star winds, as our understanding of these winds is incomplete without a precise knowledge of the ionisation structure and distribution of clumping in the wind. Key words. techniques: spectroscopic - stars: mass-loss - stars: supergiants - stars: abundances - stars: atmospheres - stars: fundamental parameters

Searle, S. C.↗