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At least 19 records

Spectrophotometry of comets at optical wavelengths

Techniques for spectrophotometry of comets are discussed, and results are reviewed for line and continuum spectrophotometry of comets at optical wavelengths. The techniques considered include photographic spectroscopy and spectrophotometry, photoelectric spectrophotometry, and methods based on the use of image dissector scanners, Fourier-transform instruments, and Fabry-Perot spectrometers. Results are summarized for the study of cometary emission features due to C2, CN, CH, OH, NH, C3, NH2, O, H, CO(plus), and H2O(plus). Relative abundances of various species in comets are examined, along with continuum spectrophotometry of the nuclei, comas, and tails of comets.

Ahearn, M. F.↗

Neptunium redox speciation and determination of its total concentration in dissolved fuel simulant solutions by spectrophotometry

Here, two new approaches to measure Np concentration in dissolved used nuclear fuel simulant (aqueous feed for PUREX process) by spectrophotometry are developed. The first approach is based on chemical reduction of Np in the feed to its tetravalent state using ascorbic acid with simultaneous conversion of Pu(IV) to Pu(III). Interfering effects from light absorbing fission and corrosion products are accounted for by measuring optical absorbance spectrum of aqueous raffinate after extraction of U, Np, and Pu by tributyl phosphate in dodecane. The second approach uses no chemical treatment at all and relies on spontaneous valency adjustment of Np to Np(V) by dilution of the feed with water to reduce its acidity to low decimolar range of nitric acid concentration. Results of Np determination in the feed by spectrophotometry are in good agreement with its concentration measured by ICP-MS.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Slitless spectrophotometry with forward modelling: Principles and application to measuring atmospheric transmission

Context.In the next decade, many optical surveys will aim to answer the question of the nature of dark energy by measuring its equation-of-state parameter at the per mill level. This requires trusting the photometric calibration of the survey with a precision never reached so far on many sources of systematic uncertainties. The measurement of the on-site atmospheric transmission for each exposure, or for each season or for the full survey on average, can help reach the per mill precision for the magnitudes. Aims.This work aims at proving the ability to use slitless spectroscopy for standard-star spectrophotometry and its use to monitor on-site atmospheric transmission as needed, for example, by theVera C. RubinObservatory Legacy Survey of Space and Time supernova cosmology program. We fully deal with the case of a disperser in the filter wheel, which is the configuration chosen in theRubinAuxiliary Telescope. Methods.The theoretical basis of slitless spectrophotometry is at the heart of our forward-model approach to extract spectroscopic information from slitless data. We developed a publicly available software calledSpectractor, which implements each ingredient of the model and finally performs a fit of a spectrogram model directly on image data to obtain the spectrum. Results.We show through simulations that our model allows us to understand the structure of spectrophotometric exposures. We also demonstrate its use on real data by solving specific issues and illustrating that our procedure allows the improvement of the model describing the data. Finally, we discuss how this approach can be used to directly extract atmospheric transmission parameters from the data and thus provide the base for on-site atmosphere monitoring. We show the efficiency of the procedure in simulations and test it on the limited available data set.

Astronomy & Astrophysics↗

Feasibility Study of Spectrophotometry to Support a Promethium Production Program at ORNL

Optical spectroscopy can be used to optimize analytical measurements for lanthanide elements and provide real-time feedback to help guide production operations. This study evaluates spectrophotometry for the determination of samarium (Sm 3+ ) and neodymium (Nd 3+ ) in aqueous and organic solutions at concentrations relevant to a promethium (Pm) program separation scheme. Detection limits approached 0.5 mM for Nd 3+ and 2 mM for Sm 3+ using Ocean Insight spectrophotometers. Additionally, Sm 3+ detection limits using laser fluorescence spectra for Sm 3+ approached single ppm (mg∙L -1 ) levels. An absorption spectrum containing Nd and Pm is also reported and discussed. This work demonstrates proofof-principle concepts for applying spectrophotometry to online monitoring applications in support of a future Pm production program.

47 OTHER INSTRUMENTATION↗

Optical spectrophotometry of comet Tempel 2 far from the sun

With the advent of mission planning for spacecraft encounters with comets in the 1980s, the lack of basic data on cometary nuclei has become quite apparent and a real problem. More effort is needed on all comets, with special attention given to probable space flight targets such as Tempel 2. The paper presents medium-spectral-resolution spectrophotometry of P/Tempel 2, made at heliocentric distances of 2.66 and 3.02 AU on two dates in 1978. It is shown that optical spectrophotometry of comet Tempel 2 near 3 AU heliocentric distance places strict limits on its activity, the modeled CN production rate having an upper limit of 6 times 10 to the 21st molecules per sec. The observations of P/Tempel 2 are compatible with a bare nucleus of 1.6 km radius (geometric albedo = 0.15) and somewhat redder than the sun.

Spinrad, H.↗

Airborne stellar spectrophotometry from 1.2 to 5.5 microns - Absolute calibration and spectra of stars earlier than M3

Airborne infrared spectrophotometry (1.2-5.5 microns, 1.5% resolution) is presented for 13 stars which have been extensively used as infrared calibration objects: alpha Lyr, alpha CMA, alpha UMi, beta Dra, and mu Her; the K giants beta Gem, alpha UMa, alpha Boo, gamma-1 And, and alpha Tau; and the M giants beta And, beta Peg, and alpha Cet. These spectra, obtained using NASA's Kuiper Airborne Observatory and Lear Jet Observatory, are virtually free of the interfering effects of terrestrial absorptions. Absolute calibration of the spectrophotometry was based on the theoretical model of alpha Lyr by Schild, Peterson, and Oke (1971), which fits photometric measurements at shorter wavelengths. The resulting flux densities are compared with previous ground-based photometry.

Strecker, D. W.↗

Preparation of Ion Exchange Films for Solid-Phase Spectrophotometry and Solid-Phase Fluorometry

Atomic spectroscopy has dominated the field of trace inorganic analysis because of its high sensitivity and selectivity. The advantages gained by the atomic spectroscopies come with the disadvantage of expensive and often complicated instrumentation. Solid-phase spectroscopy, in which the analyte is preconcentrated on a solid medium followed by conventional spectrophotometry or fluorometry, requires less expensive instrumentation and has considerable sensitivity and selectivity. The sensitivity gains come from preconcentration and the use of chromophore (or fluorophore) developers and the selectivity is achieved by use of ion exchange conditions that favor the analyte in combination with speciative chromophores. Little work has been done to optimize the ion exchange medium (IEM) associated with these techniques. In this report we present a method for making ion exchange polymer films, which considerably simplify the solid-phase spectroscopic techniques. The polymer consists of formaldehyde-crosslinked polyvinyl alcohol with polyacrylic acid entrapped therein. The films are a carboxylate weak cation exchanger in the calcium form. They are mechanically sturdy and optically transparent in the ultraviolet and visible portion of the spectrum, which makes them suitable for spectrophotometry and fluorometry.

Hill, Carol M.↗

Comparing Designed Training Sets to Optimize Multivariate Regression Models for Pr, Nd, and Nitric Acid Using Spectrophotometry

Chemometric regression models were developed for the quantification of praseodymium (Pr, 0–1000 µg/mL), neodymium (Nd, 0–1000 µg/mL), and nitric acid (HNO 3 , 0.1–5 M) using spectrophotometry. Designed calibration sets were composed of 20 samples each: 10 model points and 10 lack-of-fit (LOF) points. The D-optimal designs effectively minimized the number of samples required to build models, and each design resulted in similar prediction performance, suggesting that statistical design of experiments can provide a reliable framework for selecting training set samples in three-variable systems. Partial least squares regression (PLSR) models were validated against a one-factor-at-a-time validation set composed of 125 samples (three variables, five levels). The top PLS-1 models resulted in average percent root mean square error of prediction error values of 3.5%, 1.7%, and 1.2% for Pr(III), Nd(III), and HNO 3 , respectively. Power set augmentations of the model and LOF samples were investigated to optimize the number of training set samples. PLSR models built using just required model points (10) had similar predictive capabilities as models including the LOF points (20) but with fewer samples. The number of validation samples was also varied systematically to learn how many samples are needed to validate regression models. This work addresses long-standing questions in the field of chemometrics to help make this approach amenable to the near-real-time quantification of hazardous species in remote settings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Partial Least Squares, Experimental Design, and Near-Infrared Spectrophotometry for the Remote Quantification of Nitric Acid Concentration and Temperature

Near-infrared spectrophotometry and partial least squares regression (PLSR) were evaluated to create a pleasantly simple yet effective approach for measuring HNO3 concentration with varying temperature levels. A training set, which covered HNO3 concentrations (0.1–8 M) and temperature (10–40 °C), was selected using a D-optimal design to minimize the number of samples required in the calibration set for PLSR analysis. The top D-optimal-selected PLSR models had root mean squared error of prediction values of 1.4% for HNO 3 and 4.0% for temperature. The PLSR models built from spectra collected on static samples were validated against flow tests including HNO 3 concentration and temperature gradients to test abnormal conditions (e.g., bubbles) and the model performance between sample points in the factor space. Based on cross-validation and prediction modeling statistics, the designed near-infrared absorption approach can provide remote, quantitative analysis of HNO 3 concentration and temperature for production-oriented applications in facilities where laser safety challenges would inhibit the implementation of other optical techniques (e.g., Raman spectroscopy) and in which space, time, and/or resources are constrained. The experimental design approach effectively minimized the number of samples in the training set and maintained or improved PLSR model performance, which makes the described chemometric approach more amenable to nuclear field applications.

07 ISOTOPE AND RADIATION SOURCES↗