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At least 379 records · Page 21

Transformative Impacts of Laser-Induced Breakdown Spectroscopy on Environmental and Biological Research at Oak Ridge National Laboratory

This manuscript will present an advancement of transformative research that has been conducted at Oak Ridge National Laboratory (ORNL) over a 25-year period (2000–2025) on a variety of environmental and biological matrices. These investigations derived a fundamental understanding of how elemental detection and analysis of these matrices led to the knowledge and discovery of natural processes in plants and the environment. Each project led to the initiation of a new research area which unearthed awesome and novel breakthroughs. Highlights are listed below: 1. The preliminary research at ORNL centered on the detection of aerosols utilizing Laser-induced Breakdown Spectroscopy (LIBS) technology. The Clean Air Act Amendment (CAAA) of 1990 highlighted the importance of identifying hazardous air pollutants (HAPs) due to their impact on environmental and human health, thereby underscoring the need to detect various toxic elements. Research in aerosol chemistry aimed to identify these harmful elements released by factories during periods of increased emissions in their manufacturing processes. LIBS emerged as the most effective method for real-time, in situ measurements of metal species in both gaseous and aerosol phases. 2. An understanding of the presence of total carbon in soils gives perspective on how to develop carbon sequestration strategies. The recognition that carbon sinks can evolve back to carbon sources to emit back to the atmosphere was an important consideration. Also, the concentration of carbon in soil indicates the health of land areas for growing crops successfully. 3. The direct detection of most of the elements in a wood sample in a single emission spectrum, without sample preparation, encouraged the research to use the LIBS technique for preservative treated wood coupled with use of multivariate statistical methodology. Additionally, it encouraged the researchers to try to differentiate natural woods from different parts of the country, and it was successfully demonstrated that LIBS coupled with MVA analysis could differentiate wood of different species from each other and of similar species grown in different environments based on their elemental spectra. This was a breakthrough since it revealed a systematic approach to connect elemental scarcity and abundance to either drought or typical rainfall conditions for the hardwood trees grown in specific areas. 4. Furthermore, the research progressed to reveal physiological and developmental processes contributing to biomass production such that the variation in leaf elemental composition increases our understanding of terrestrial nutrient cycles, as well as tracking the transfer of toxic elements from soils to living organisms. 5. Recently another breakthrough viz., ionomics initiated the correlation of elements to specific genes, uncovering the function that the element performed in the plant. More recently, this has been extended from plants to fungi as well as fungi growing in symbiotic relations with plants.

09 BIOMASS FUELS↗

Approach to using 3D laser-induced breakdown spectroscopy (LIBS) data to explore the interaction of FLiNaK and FLiBe molten salts with nuclear-grade graphite

Nuclear graphite has historically been a key component of many nuclear reactor designs and has emerged as key to numerous advanced nuclear reactor design concepts. Molten salt reactors (MSRs) are one broad group of advanced reactor designs currently being pursued by industry for commercialization. Several MSR designs under consideration use graphitic materials that directly interface with a molten salt, whether it is a fuel salt, coolant salt, or both. Therefore, the interaction of graphite materials with molten salts must be understood. To gain this required understanding, a range of data is needed including porosity, strength, and composition as a function of different salt exposure parameters. In this study, a laser-induced breakdown spectroscopy (LIBS) measurement and data analysis methodology was developed to obtain spatially resolved elemental composition information for graphite samples exposed to a molten fluoride salt. Traditional univariate emission line analysis of atomic, ionic, and molecular optical emission signals was coupled via correlation analysis with spectral decomposition of the data using principal component analysis. Elemental depth profiling and elemental mapping were also performed to visualize salt–graphite interactions. LIBS was demonstrated to be useful for measuring key analytes such as fluorine and hydrogen, which are troublesome for other analysis techniques. Evidence for complex behavior was found, thereby demonstrating the usefulness of the developed approach for future systematic studies.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Laser-induced fluorescence spectroscopy for combustion diagnostics

The types of spectroscopic and collisional measurements that are needed to develop laser-induced fluorescence as a diagnostic technique are discussed, with emphasis placed on combustion measurements. The spectroscopic measurements under collision-free conditions include production of radicals, excitation scan studies, lifetime measurements, and fluorescence scans. The collisional studies discussed here are quenching, energy transfer, and polarization phenomena. The results of recent laboratory experiments are presented.

Crosley, D. R.↗

High-resolution laser-induced fluorescence spectroscopy of 28 Si 16 O + and 29 Si 16 O + in a cryogenic buffer-gas cell

Here, the electronic, laser-induced fluorescence spectrum of the B 2 Σ + ← X 2 Σ + transition in 28 Si 16 O + and 29 Si 16 O + has been recorded in a cryogenic buffer gas cell at K. Molecular constants are extracted for both 28 Si 16 O + and 29 Si 16 O + , including the Fermi contact hyperfine constant for both the B and X states of 29 Si 16 O + , and used in a discussion of the suitability of SiO in future quantum information experiments.

47 OTHER INSTRUMENTATION↗

Diagnostics of Carbon Nanotube Formation in a Laser Produced Plume: An Investigation of the Metal Catalyst by Laser Ablation Atomic Fluorescence Spectroscopy

Carbon nanotubes, elongated molecular tubes with diameters of nanometers and lengths in microns, hold great promise for material science. Hopes for super strong light-weight material to be used in spacecraft design is the driving force behind nanotube work at JSC. The molecular nature of these materials requires the appropriate tools for investigation of their structure, properties, and formation. The mechanism of nanotube formation is of particular interest because it may hold keys to controlling the formation of different types of nanotubes and allow them to be produced in much greater quantities at less cost than is currently available. This summer's work involved the interpretation of data taken last summer and analyzed over the academic year. The work involved diagnostic studies of carbon nanotube formation processes occurring in a laser-produced plume. Laser ablation of metal doped graphite to produce a plasma plume in which carbon nanotubes self assemble is one method of making carbon nanotube. The laser ablation method is amenable to applying the techniques of laser spectroscopy, a powerful tool for probing the energies and dynamics of atomic and molecular species. The experimental work performed last summer involved probing one of the metal catalysts, nickel, by laser induced fluorescence. The nickel atom was studied as a function of oven temperature, probe laser wavelength, time after ablation, and position in the laser produced plume. This data along with previously obtained data on carbon was analyzed over the academic year. Interpretations of the data were developed this summer along with discussions of future work. The temperature of the oven in which the target is ablated greatly influences the amount of material ablated and the propagation of the plume. The ablation conditions and the time scale of atomic and molecular lifetimes suggest that initial ablation of the metal doped carbon target results in atomic and small molecular species. The metal atoms survive for several milliseconds while the gaseous carbon atoms and small molecules nucleate more rapidly. Additional experiments and the development of in situ methods for carbon nanotube detection would allow these results to be interpreted from the perspective of carbon nanotube formation.

deBoer, Gary↗

Tunable diode laser Stark modulation spectroscopy for rotational assignment of the HNO3 7.5-micron band

The technique of Stark modulation spectroscopy for unraveling and assigning rotationally resolved dense molecular spectra has been employed using a tunable diode laser (TDL) source. Doppler-limited absorption and Stark modulation spectra of the HNO3 7.5-micron band near the 1326/cm band origin are presented with preliminary values of the excited-state rovibrational constants derived from both TDL and Bomem Fourier transform IR spectra.

Webster, C. R.↗

Effective utilization of quantum-cascade distributed-feedback lasers in absorption spectroscopy

A variable duty cycle quasi-cw frequency scanning technique was applied to reduce thermal effects resulting from the high heat dissipation of type I quantum-cascade lasers. This technique was combined with a 100-m path-length multipass cell and a zero-air background-subtraction technique to enhance detection sensitivity to a parts-in-10(9) (ppb) concentration level for spectroscopic trace-gas detection of CH4, N2O, H2O, and C2H5OH in ambient air at 7.9 micrometers. A new technique for analysis of dense high resolution absorption spectra was applied to detection of ethanol in ambient air, yielding a 125-ppb detection limit.

NASA Discipline Environmental Health↗

Analysis of liquid petroleum using a laser-induced breakdown spectroscopy instrument

Here, a prototype analyzer for the direct LIBS analysis of nebulized liquid samples was developed and tested, particularly for the analysis of petroleum, organic solvents and aqueous solutions. The LIBS analyzer requires about 750 µl of liquid sample, 1 liter of N 2 gas, and 10 s of the analysis time to record 100 spectra. The limits of detection in oil and solvent are as low as 0.01–0.04 ppm for Li, Mg, and Cu. They increase for the difficult elements, such as Pb and Hg (7-10 ppm), Cl (250 ppm), and S (~0.7%). The relative standard deviation of measuring 100 ppm vanadium in oil and solvent was 1.5%. The LIBS detection limits and repeatability are better than required by the standard method ASTM D5185 for the analysis of lubricating oils in ICP-OES. Several petroleum samples were analyzed by LIBS and the quantitative results for V, Ni, and Fe compared to the ICP-OES data. Light crude oils can be nebulized and analyzed directly. Medium crude oils require minimal dilution at least 1:1, otherwise errors of determination become large. Presumably, utilization of the internal standard and chemometrics can be useful to correct for the matrix effects. In addition to the trace element analysis, the LIBS prototype demonstrated ability to measure the hydrogen-to-carbon ratio in organic liquid samples. Several unidentified features were observed in the carbon spectrum. Their possible origin is discussed.

02 PETROLEUM↗

Infrared and far-infrared laser magnetic resonance spectroscopy of the GeH radical - Determination of ground state parameters

The GeH radical has been detected in its ground 2 Pi state in the gas phase reaction of fluorine atoms with GeH4 by laser magnetic resonance techniques. Rotational transitions within both 2 Pi 1/2 and 2 Pi 3/2 manifolds have been observed at far-infrared wavelengths and rotational transitions between the two fine structure components have been detected at infrared wavelengths (10 microns). Signals have been observed for all five naturally occurring isotopes of germanium. Nuclear hyperfine structure for H-1 and Ge-73 has also been observed. The data for the dominant isotope (/Ge-74/H) have been fitted to within experimental error by an effective Hamiltonian to give a set of molecular parameters for the X 2 Pi state which is very nearly complete. In addition, the dipole moment of GeH in its ground state has been estimated from the relative intensities of electric and magnetic dipole transitions in the 10 micron spectrum to be 1.24(+ or - 0.10) D.

Brown, J. M.↗

Leveraging Calibration Transfer Techniques for Remote Monitoring of Samarium and Europium in LiCl Using Laser-Induced Florescence Spectroscopy for Radioisotope Production Applications

Radioisotope production relies on complex chemical processes that must be performed in radiological hot cells or glove boxes because of the radioactive and otherwise hazardous materials being used. In these situations, optical sensors can provide real-time monitoring to users, which is unobtainable by more traditional methods. This study explores the use of calibration transfer methods to train a model on one instrument and date and then transfer it to another instrument of the same or different configuration on a different date. By performing laser-induced fluorescence measurements of Eu(III) and Sm(III) in 10 M LiCl over the course of 6 months using two disparate spectrometers and two different training sets, a strategy for calibrating and deploying models for online monitoring was established. Three transfer techniques were compared: direct standardization (DS), piecewise direct standardization (PDS), and external parameter orthogonalization (EPO). DS and PDS outperformed EPO for day-to-day transfers, and EPO was not effective for instrument-to-instrument transfers. Transferring the initial date’s full factorial model provided better prediction performance compared with retraining models the day of measurements using a D-optimal designed calibration set. For both day-to-day and instrument-to-instrument transfers, five Kennard–Stone selected samples were sufficient. Based on this choice, the initial-date, high-resolution spectrometer model was transferred to a lower-resolution, compact spectrometer 6 months later to monitor a simulated, real-time demonstration. Here, the combined predictions of the DS and PDS transferred models were able to accurately track the anticipated concentration profiles, maintaining root-mean-square error of prediction values below 10 ppm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

TORONE: Total Characterisation by Remote Observation of Nuclear Environments - 20591

This paper describes the autonomous robotic systems developed in the TORONE project (Total Characterisation by Remote Observation of Nuclear Environments) for combined characterisation by remote techniques in nuclear environments. There are four main components to the system. Firstly, robot operation which uses a Robot Operating System (ROS) allowing ease of communication between hardware and software alongside robot vision systems such as Lidar and/or photogrammetry. Secondly, radiation detection instrumentation for gamma and neutron sources which is also collimated for spatial resolution. Thirdly, photonic characterisation instrumentation for remote material identification by means of Raman spectroscopy and Laser induced breakdown spectroscopy (LIBS). Finally, a data management system is described which contains the TORONE characterisation data with the ability to overlay material characterisation information onto 3D maps of the nuclear environment. Preliminary results are described alongside discussion of some of the synergies of the combined approach. There are many applications of such an autonomous system in nuclear decommissioning, waste management and asset management. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

An Overview of the Hybrid Illinois Device for Research and Applications Material Analysis Test-stand (HIDRA-MAT)

The Hybrid Illinois Device for Research and Applications (HIDRA) at the University of Illinois at Urbana-Champaign is a toroidal plasma device that enables fusion plasma-material interaction testing with both stellarator and tokamak plasmas. HIDRA’s long-pulse steady state stellarator plasmas provide a testbed for plasma facing component (PFC) plasma exposures. The HIDRA Material Analysis Test-stand (HIDRA-MAT) is a material characterization module attached to HIDRA that is being designed and fabricated to include thermal desorption spectroscopy and laser induced breakdown spectroscopy systems for in-vacuo PFC characterization. A specialized rotatable sample holder positions the sample for liquid metal droplet application from a liquid metal droplet injector on HIDRA-MAT. Early experiments look to investigate the effect liquid lithium has on porous tungsten samples’ retention of H, D, and He after plasma exposure. Preliminary results from a dual residual gas analyzer system show the ability to differentiate D2 and He in HIDRA-MAT. Finally, this work aims to advance the understanding of liquid metal PFCs and further the design and development of new fusion PFCs and technologies.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗