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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
NASA NTRS2001

Advanced Methods for Aircraft Engine Thrust and Noise Benefits: Nozzle-Inlet Flow Analysis

Three connected sub-projects were conducted under reported project. Partially, these sub-projects are directed to solving the problems conducted by the HU/FM&AL under two other NASA grants. The fundamental idea uniting these projects is to use untraditional 3D corrugated nozzle designs and additional methods for exhaust jet noise reduction without essential thrust lost and even with thrust augmentation. Such additional approaches are: (1) to add some solid, fluid, or gas mass at discrete locations to the main supersonic gas stream to minimize the negative influence of strong shock waves forming in propulsion systems; this mass addition may be accompanied by heat addition to the main stream as a result of the fuel combustion or by cooling of this stream as a result of the liquid mass evaporation and boiling; (2) to use porous or permeable nozzles and additional shells at the nozzle exit for preliminary cooling of exhaust hot jet and pressure compensation for non-design conditions (so-called continuous ejector with small mass flow rate; and (3) to propose and analyze new effective methods fuel injection into flow stream in air-breathing engines. Note that all these problems were formulated based on detailed descriptions of the main experimental facts observed at NASA Glenn Research Center. Basically, the HU/FM&AL Team has been involved in joint research with the purpose of finding theoretical explanations for experimental facts and the creation of the accurate numerical simulation technique and prediction theory for solutions for current problems in propulsion systems solved by NASA and Navy agencies. The research is focused on a wide regime of problems in the propulsion field as well as in experimental testing and theoretical and numerical simulation analysis for advanced aircraft and rocket engines. The F&AL Team uses analytical methods, numerical simulations, and possible experimental tests at the Hampton University campus. We will present some management activity and theoretical numerical simulation results obtained by the FM&AL Team in the reporting period in accordance with the schedule of the work.

Morgan, Morris H.↗
NASA NTRS2007

Aerospace Toxicology and Microbiology

Toxicology dates to the very earliest history of humanity with various poisons and venom being recognized as a method of hunting or waging war with the earliest documentation in the Evers papyrus (circa 1500 BCE). The Greeks identified specific poisons such as hemlock, a method of state execution, and the Greek word toxos (arrow) became the root of our modern science. The first scientific approach to the understanding of poisons and toxicology was the work during the late middle ages of Paracelsus. He formulated what were then revolutionary views that a specific toxic agent or "toxicon" caused specific dose-related effects. His principles have established the basis of modern pharmacology and toxicology. In 1700, Bernardo Ramazzini published the book De Morbis Artificum Diatriba (The Diseases of Workers) describing specific illnesses associated with certain labor, particularly metal workers exposed to mercury, lead, arsenic, and rock dust. Modern toxicology dates from development of the modern industrial chemical processes, the earliest involving an analytical method for arsenic by Marsh in 1836. Industrial organic chemicals were synthesized in the late 1800 s along with anesthetics and disinfectants. In 1908, Hamilton began the long study of occupational toxicology issues, and by WW I the scientific use of toxicants saw Haber creating war gases and defining time-dosage relationships that are used even today.

James, John T.↗
NASA NTRS1998

Inverse Compton Scattering in Mildly Relativistic Plasma

We investigated the effect of inverse Compton scattering in mildly relativistic static and moving plasmas with low optical depth using Monte Carlo simulations, and calculated the Sunyaev-Zel'dovich effect in the cosmic background radiation. Our semi-analytic method is based on a separation of photon diffusion in frequency and real space. We use Monte Carlo simulation to derive the intensity and frequency of the scattered photons for a monochromatic incoming radiation. The outgoing spectrum is determined by integrating over the spectrum of the incoming radiation using the intensity to determine the correct weight. This method makes it possible to study the emerging radiation as a function of frequency and direction. As a first application we have studied the effects of finite optical depth and gas infall on the Sunyaev-Zel'dovich effect (not possible with the extended Kompaneets equation) and discuss the parameter range in which the Boltzmann equation and its expansions can be used. For high temperature clusters (k(sub B)T(sub e) greater than or approximately equal to 15 keV) relativistic corrections based on a fifth order expansion of the extended Kompaneets equation seriously underestimate the Sunyaev-Zel'dovich effect at high frequencies. The contribution from plasma infall is less important for reasonable velocities. We give a convenient analytical expression for the dependence of the cross-over frequency on temperature, optical depth, and gas infall speed. Optical depth effects are often more important than relativistic corrections, and should be taken into account for high-precision work, but are smaller than the typical kinematic effect from cluster radial velocities.

Molnar, S. M.↗
NASA NTRS1991

Flow analysis and design optimization methods for nozzle afterbody of a hypersonic vehicle

This report summarizes the methods developed for the aerodynamic analysis and the shape optimization of the nozzle-afterbody section of a hypersonic vehicle. Initially, exhaust gases were assumed to be air. Internal-external flows around a single scramjet module were analyzed by solving the three dimensional Navier-Stokes equations. Then, exhaust gases were simulated by a cold mixture of Freon and Argon. Two different models were used to compute these multispecies flows as they mixed with the hypersonic airflow. Surface and off-surface properties were successfully compared with the experimental data. In the second phase of this project, the Aerodynamic Design Optimization with Sensitivity analysis (ADOS) was developed. Pre and post optimization sensitivity coefficients were derived and used in this quasi-analytical method. These coefficients were also used to predict inexpensively the flow field around a changed shape when the flow field of an unchanged shape was given. Starting with totally arbitrary initial afterbody shapes, independent computations were converged to the same optimum shape, which rendered the maximum axial thrust.

Baysal, Oktay↗
NASA NTRS2021

Experimental and Computational Investigation of Flow Boiling in Microgravity

This study explores use of Computational Fluid Dynamics (CFD) to predict near-saturated flow boiling of FC-72 in microgravity. The computational method employs transient analysis to predict detailed interfacial behavior and heat transfer characteristics along a rectangular channel heated along two opposite walls. Predicted results are validated against experimental temperature measurements and high-speed video images captured during a series of parabolic aircraft maneuvers for three sets of operating conditions which include variations of both mass velocity and wall heat flux. The computational method is based on the multi-phase volume of fluid (VOF) model, which is combined with appropriate phase change and turbulence models, and accounts for both shear-lift force on bubbles and conjugate heat transfer along the heating walls. A key advantage of the CFD method is ability to capture details that are very difficult to measure experimentally, including detailed spatial variations of bubble shape, void fraction, mixture fluid temperature, liquid velocity, and vapor velocity, results for which are presented for each of the three test cases. Different flow regimes predicted along the heated length exhibit a number of dominant mechanisms including bubble nucleation, bubble growth, coalescence, vapor blankets, interfacial waviness, and residual liquid sub-layer, all of which agree well with experiment. Vapor velocity is shown to increase appreciably along the heated length because of increased void fraction, while liquid velocity experiences large fluctuations. Non-equilibrium effects are accentuated with increasing mass velocity, contributing minor deviations of fluid temperature from simulations compared to those predicted by the analytical method. Predicted wall temperature is fairly uniform in the middle of the heated length but increases in the entrance region, due to sensible heat transfer in the subcooled liquid, and decreases toward the exit, mostly because of flow acceleration resulting from increased void fraction.

two-phase cooling; flow boiling; CFD; microgravity↗
NASA NTRS2016

Monte Carlo Simulation of a Knudsen Effusion Mass Spectrometer Sampling System

Knudsen flow is easily simulated with a Monte Carlo method. In this study we develop a Visual Basic for Excel (VBA) code to simulate the molecular beam from a vaporizing solid. The system at NASA Glenn uses the restricted collimation method of Chatillon and colleagues, which consists of two apertures between the effusion cell and the ionizer. The diameter of the first aperture is smaller than the diameter of the effusion cell orifice, so the ionizer effectively only sees inside the effusion cell. The code is able to calculate the transmission coefficient through the cell orifice, through the cell orifice and the first aperture, and through the cell orifice and first and second aperatures. Calculated transmission coefficients through the cell orifice are compared to tabulated values to validate the code. Then transmission coefficients are calculated through the cell orifice and both apertures to the ionizer. This allows the geometry (aperture spacing and diameters) of the sampling system the sampling system to be optimized. Calculated transmission factors are also compared to literature values calculated via an analytic method.

Radke, Michael J.↗
NASA NTRS2020

An Overview of the Null-Field Method. II: Convergence and Numerical Stability

In this paper we provide an analysis of the convergence and numerical stability of the null-field method with discrete sources. We show that (i) if the null-field scheme is numerically stable then we can decide whether or not convergence can be achieved; (ii) if the null-field scheme is numerically unstable then we cannot draw any conclusion about the convergence issue; and (iii) the numerical stability is closely related to the property of a tangential system of radiating discrete sources to form a Riesz basis. Our numerical analysis indicates that for prolate spheroids and localized vector spherical wave functions, the null-field scheme is numerically unstable (this system of vector functions does not form a Riesz basis), while for distributed vector spherical wave functions, the numerical instability is not so pronounced (this system of discrete sources almost possesses the property of being a Riesz basis). We also describe an analytical method for computing the surface integrals in the framework of the conventional null-field method with localized vector spherical wave functions which increases the stability of the numerical scheme.

Null-field method↗
NASA NTRS1992

Resin transfer molding of textile preforms for aircraft structural applications

The NASA LaRC is conducting and supporting research to develop cost-effective fabrication methods that are applicable to primary composite aircraft structures. One of the most promising fabrication methods that has evolved is resin transfer molding (RTM) of dry textile material forms. RTM has been used for many years for secondary structures, but has received increased emphasis because it is an excellent method for applying resin to damage-tolerant textile preforms at low cost. Textile preforms based on processes such as weaving, braiding, knitting, stitching, and combinations of these have been shown to offer significant improvements in damage tolerance compared to laminated tape composites. The use of low-cost resins combined with textile preforms could provide a major breakthrough in achieving cost-effective composite aircraft structures. RTM uses resin in its lowest cost form, and storage and spoilage costs are minimal. Near net shape textile preforms are expected to be cost-effective because automated machines can be used to produce the preforms, post-cure operations such as machining and fastening are minimized, and material scrap rate may be reduced in comparison with traditional prepreg molding. The purpose of this paper is to discuss experimental and analytical techniques that are under development at NASA Langley to aid the engineer in developing RTM processes for airframe structural elements. Included are experimental techniques to characterize preform and resin behavior and analytical methods that were developed to predict resin flow and cure kinetics.

Hasko, Gregory H.↗
NASA NTRS1994

Accretion disk coronae in high-luminosity systems

We present the results of self-consistent models of Compton-heated accretion disk coronae. The models are calculated using a new method for computing monochromatic radiative transfer n two dimensions. The method splits the radiation into direct and scattered components. The direct radiation is computed by calculating the optical depth along rays, while transfer of the scattered radiation is approximated by flux-limited diffusion. The resulting code agrees with more accurate treatments to within 50%, and is highly efficient, making it practical for use in large hydrodynamic simulations. The coronal models are used to confirm the results of earlier work, and to extend it to higher luminosities. In contrast to earlier work, which found the outer disks to be shadowed by the inner corona at high luminosities, we find our results to form an almost continuous extension of the models at lower luminosities. This is due to the presence of multiply scattered radiation, which acts to partially offset the loss of direct radiation from the central source. Although the analytic methods derived at lower luminosities cannot be used to derive the coronal structure for L/L(sub Edd) approx. greater than 0.1, the results of the models are amenable to semiempirical fits. We also discuss possible observational consequences of the results for coronal veiling and line fluorescence from the disk.

Murray, Stephen D.↗
NASA NTRS2010

SSME - Materials and Methods for Addressing High-Pressure Hydrogen Embrittlement

From the humid, corrosion-friendly atmosphere of KSC, to the extreme heat of ascent, to the cold vacuum of space, the Space Shuttle faced one hostile environment after another. One of those harsh environments the hydrogen environment existed within the shuttle itself. Liquid hydrogen was the fuel that powered the shuttle s complex, powerful, and reusable main engine. Hydrogen provided the high specific impulse the bang per pound of fuel needed to perform the shuttle s heavy lifting duties. Hydrogen, however, was also a potential threat to the very metal of the propulsion system that used it. The diffusion of hydrogen atoms into a metal can make it more brittle and prone to cracking a process called hydrogen embrittlement. This effect can reduce the toughness of carefully selected and prepared materials. A concern that exposure to hydrogen might encourage crack growth was present from the beginning of the Space Shuttle Program, but the rationale for using hydrogen was compelling. This paper outlines the material characterization, anomaly resolution, and path to understanding of hydrogen embrittlement on superalloys through the course of the SSME program. Specific examples of nickel alloy turbine housings and single crystal turbine blades are addressed. The evolution of fracture mechanics analytical methods is also addressed.

Matejczk, Daniel↗
NASA NTRS1994

Computation of iodine species concentrations in water

During an evaluation of the use of iodine as a water disinfectant and the development of methods for measuring various iodine species in water onboard Space Freedom, it became necessary to compute the concentration of the various species based on equilibrium principles alone. Of particular concern was the case when various amounts of iodine, iodide, strong acid, and strong base are added to water. Such solutions can be used to evaluate the performance of various monitoring methods being considered. The authors of this paper present an overview of aqueous iodine chemistry, a set of nonlinear equations which can be used to model the above case, and a computer program for solving this system of equations using the Newton-Raphson method. The program was validated by comparing results over a range of concentrations and pH values with those previously presented by Gottardi for a given pH. Use of this program indicated that there are multiple roots to many cases and selecting an appropriate initial guess is important. Comparison of program results with laboratory results for the case when only iodine is added to water indicates the program gives high pH values for the iodine concentrations normally used for water disinfection. Extending the model to include the effects of iodate formation results in the computer pH values being closer to those observed, but the model with iodate does not agree well for the case in which base is added in addition to iodine to raise the pH. Potential explanations include failure to obtain equilibrium conditions in the lab, inaccuracies in published values for the equilibrium constants, and inadequate model of iodine chemistry and/or the lack of adequate analytical methods for measuring the various iodine species in water.

Schultz, John R.↗
DOE OSTI2025

A Synchrotron-Based Vacuum Ultraviolet Photoionization Mass Spectrometer-Coupled Microreactor To Probe Thermocatalysis

Vacuum ultraviolet photoionization (VUV-PI) mass spectrometry offers an isomer-selective and universal ionization with minimal fragmentation detection of organics in complex chemical systems such as pyrolysis and combustion. Here, in this study, we report a state-of-the-art experimental setup of a universal catalytic microreactor combined with a molecular beam to investigate the thermocatalytic oxidation of a heterogeneous system relevant for probing reactions at gas–solid interfaces. In strong contrast to traditional off-line analytical methods, this technique is capable of identifying and quantifying short-lived species (radicals) as well as stable products to decipher initial reaction steps via the detection of nascent products. The thermocatalytic oxidative degradation of exo-tetrahydrodicyclopentadiene (JP-10), a high energy-density hydrocarbon fuel, over solid titanium–aluminum–boron reactive mixed metal nanopowder (Ti-Al-B RMNP) is exploited to showcase potential applications. Overall, some 59 nascent gas-phase products are identified via photoionization efficiency (PIE) curves, including oxygenated species and hydrocarbons comprising closed-shell molecules and radicals. The critical temperature for complete oxidative decomposition of JP-10 was lowered by 450 K from 1400 K to 950 K, indicating an efficient thermocatalytic action of Ti-Al-B nanoparticles on JP-10. The enabling of a universal chemical microreactor along with VUV-PI mass spectrometry broadens the applicability of this technique to hydrocarbon fuel oxidation and pyrolysis characterization. This isomer-selective sensitive probing along with the detection of radical transients makes the aforementioned technique superior to other conventional analytical techniques such as microflow tube and pyrolysis-gas chromatography coupled with mass spectrometry for investigating similar pyrolysis reactions and comprehensive quantification.

Paul, Dababrata [Univ. of Hawaii at Manoa, Honolul↗
NASA NTRSDate not supplied

Improving the Fidelity of Capability & Resource Weighting in A Probalistic Risk Assessment Model for Spaceflight

INTRODUCTION NASA’s Informing Mission Planning via Analysis of Complex Tradespaces (IMPACT) tool uses Probabilistic Risk Assessment (PRA) to provide an evidence-based, data-driven estimate of how medical system capabilities affect mission outcomes. IMPACT maps condition incidence to available resources thereby facilitating the calculation of outcome metrics that allow the estimation of mission medical risk. Conditions can be nominally categorized as either treated or untreated depending on the availability of necessary diagnostic and therapeutic capabilities. This categorization enables IMPACT to estimate the effect of various medical system configurations on mission outcomes such as crew mortality, disability, crew member down-time, return to duty/recovery, and need for evacuation. IMPACT currently employs an equal weighting, “partial credit” approach to define treatment in which each of the capabilities associated with a given condition contributes an equal amount to management of the condition. This feature enables IMPACT to report values in between “fully untreated” and “fully treated” based on the proportion of capabilities available within the model. However, as is normal in medical/clinical practice, not all individual capabilities contribute equally to medical care. For example, the ability to provide intramuscular epinephrine during an anaphylactic episode contributes more likelihood of overall management success than does the administration of oral diphenhydramine. We hypothesize that weighting the relative contribution of each capability to each specific condition will improve outcome prediction and therefore will better provide mission planners with more nuanced and accurate options when designing space medical systems. METHODS Using a five-point Fibonacci scaling sequence (1, 2, 3, 5, 8) subject matter experts from NASA’s Exploration Medical Capabilities (ExMC) element assigned relative contribution weighting values to each identified capability within IMPACT. Since the relative importance of each capability varies depending on the specific condition, the resulting “partial” weighting was completed for more than 1,600 individual weighting assignments for 666 capabilities across 121 conditions. Each assignment required three-physician concurrence based on the overall importance of the capability to the diagnosis and management of the condition being considered and the difficulty with which it could be improvised by the crew. Once complete, 100,000 IMPACT simulations were run for a 6-month Lunar mission with a 30-day surface stay to evaluate the effect of this modification of the model. RESULTS Partial weighting significantly decreased predicted task time loss (TTL), evacuation, and loss of crew life without causing significant changes to the recommended medical system design. CONCLUSIONS The paucity of real-world referent data to support long-duration space missions of this type limits the ability to judge one predictive analytics method as superior to another. However, since the proposed method significantly reduces and optimizes outcome risks—without changing the medical system design—incorporating a partial weighting methodology is likely to provide a more accurate and operationally-relevant representation of medical risk without compromising IMPACTs ability to inform overarching medical system requirements.

Steller JG↗
NASA NTRS1999

Sonic Boom Prediction and Minimization of the Douglas Reference OPT5 Configuration

Conventional CFD methods and grids do not yield adequate resolution of the complex shock flow pattern generated by a real aircraft geometry. As a result, a unique grid topology and supersonic flow solver was developed at Northrop Grumman based on the characteristic behavior of supersonic wave patterns emanating from the aircraft. Using this approach, it was possible to compute flow fields with adequate resolution several body lengths below the aircraft. In this region, three-dimensional effects are diminished and conventional two-dimensional modified linear theory (MLT) can be applied to estimate ground pressure signatures or sonic booms. To accommodate real aircraft geometries and alleviate the burdensome grid generation task, an implicit marching multi-block, multi-grid finite-volume Euler code was developed as the basis for the sonic boom prediction methodology. The Thomas two-dimensional extrapolation method is built into the Euler code so that ground signatures can be obtained quickly and efficiently with minimum computational effort suitable to the aircraft design environment. The loudness levels of these signatures can then be determined using a NASA generated noise code. Since the Euler code is a three-dimensional flow field solver, the complete circumferential region below the aircraft is computed. The extrapolation of all this field data from a cylinder of constant radius leads to the definition of the entire boom corridor occurring directly below and off to the side of the aircraft's flight path yielding an estimate for the entire noise "annoyance" corridor in miles as well as its magnitude. An automated multidisciplinary sonic boom design optimization software system was developed during the latter part of HSR Phase 1. Using this system, it was found that sonic boom signatures could be reduced through optimization of a variety of geometric aircraft parameters. This system uses a gradient based nonlinear optimizer as the driver in conjunction with a computationally efficient Euler CFD solver (NIIM3DSB) for computing the three-dimensional near-field characteristics of the aircraft. The intent of the design system is to identify and optimize geometric design variables that have a beneficial impact on the ground sonic boom. The system uses a simple wave drag data format to specify the aircraft geometry. The geometry is internally enhanced and analytic methods are used to generate marching grids suitable for the multi-block Euler solver. The Thomas extrapolation method is integrated into this system, and hence, the aircraft's centerline ground sonic boom signature is also automatically computed for a specified cruise altitude and yields the parameters necessary to evaluate the design function. The entire design system has been automated since the gradient based optimization software requires many flow analyses in order to obtain the required sensitivity derivatives for each design variable in order to converge on an optimal solution. Hence, once the problem is defined which includes defining the objective function and geometric and aerodynamic constraints, the system will automatically regenerate the perturbed geometry, the necessary grids, the Euler solution, and finally the ground sonic boom signature at the request of the optimizer.

Siclari, Michael J.↗
DOE OSTI2024

Determining sulfur speciation in oxidatively crosslinked degradable polymers using sulfur K-edge X-ray absorption spectroscopy

A new family of water-degradable elastic polymers prepared by oxidative crosslinking of the parent polythionolactones shows promise in a broad range of applications, but the compositions of these materials elude conventional analytical methods. Here, in this work, we use sulfur K-edge X-ray absorption spectroscopy to quantify the amounts of thioether, disulfide, sulfone, sulfate ester, and thionoester in each polymer and to rule out the presence of several other functional groups, including sulfonate, thiosulfonate, sulfate, and sulfoxide. We rationalize this speciation as a function of linker flexibility in the context of sulfinyl cycloaddition reactions and propose a mechanism of aggregation for the oxidized polymers. Our results correlate with swelling ratios but not with porosity nor crosslink density measurements, demonstrating the importance of pairing mechanical and chemical techniques when characterizing heterogeneous organic polymers. Finally, we take advantage of the proximity of the gold M 4,5 -edges to the sulfur K-edge to analyze the binding and reactivity of Au(III) with the crosslinked polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Direct Measurements of Dimethyl Sulfide Oxidation Chemistry: Uncovering the Primary Pathways from Gas Phase to Sulfate Aerosols

We report experimental measurements of dimethyl sulfide oxidation, focusing on a major chemical intermediate, hydroperoxymethyl thioformate (HPMTF). The (photo)chemistry and transport properties of HPMTF, which are critical to accurate modeling of tropospheric sulfur, are not known, partly because current analytical methods are not optimized for elusive chemical intermediates. We investigated dimethyl sulfide oxidation using a custom time-resolved photoionization mass spectrometer, interfaced with pulsed laser photolysis, continuous photolysis, and liquid droplet reactors. We detected and characterized HPMTF (along with other reaction intermediates), quantified its yield, and measured its formation rate coefficient. We also developed a clean, intense, online HPMTF source, suitable for further experimental investigations. Lastly, we measured the mass accommodation coefficient of HPMTF on water droplets – a critical quantity for modeling its atmospheric partitioning between the gas and condensed phases. The experimental platform we developed here enables the exploration of other critical elusive reaction intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Diffusion power spectra as a window into dynamic materials architecture

Chemical recycling of commodity and specialty polymers presents a multifaceted challenge for industrial societies. On one hand, macromolecular architectures must be engineered to yield durable products that, on the other hand, rapidly deconstruct to recyclable monomers under pre-determined conditions. Polymer deconstruction is a chemical process that requires deep understanding of molecular reactivity in heterogeneous media, where porous material architectures evolve in both space and time. To build this understanding, we develop herein experimental and analytical methods describing sets of diffusive eigenmodes that exist within time-varying, non-Euclidean boundary conditions, a situation commonly encountered in the reactive deconstruction of polymers where chain fragments splay, alter their local dynamics, and evolve in their confinement of reacting media. Diffusion power spectra, discerned experimentally by NMR, yield polymer and solvent frequency-domain velocity autocorrelation functions that are analyzed in the context of physical models for chemical reactions parameterized with fractal mathematics. The results connect local motion in polymers to chemical reactivity during acidolysis of circular elastomers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Use of carbonyldiimidazole as a derivatization agent for the detection of pinacolyl alcohol, a forensic marker for Soman, by EI-GC–MS and LC-HRMS in official OPCW proficiency test matrices

Pinacolyl alcohol (PA), a key forensic marker for the nerve agent Soman (GD), is a particularly difficult analyte to detect by various analytical methods. In this work, we have explored the reaction between PA and 1,1'-carbonyldiimidazole (CDI) to yield pinacolyl 1H-imidazole-1-carboxylate (PIC), a product that can be conveniently detected by gas chromatography–mass spectrometry (GC–MS) and liquid chromatography-high-resolution mass spectrometry (LC-HRMS). Regarding its GC–MS profile, this new carbamate derivative of PA possesses favorable chromatographic features such as a sharp peak and a longer retention time (RT = 16.62 min) relative to PA (broad peak and short retention time, RT = 4.1 min). Additionally, the derivative can also be detected by LC-HRMS, providing an avenue for the analysis of this chemical using this technique where PA is virtually undetectable unless present in large concentrations. From a forensic science standpoint, detection of this low molecular weight alcohol signals the past or latent presence of the nerve agent Soman (GD) in a given matrix (i.e., environmental or biological). The efficiency of the protocol was tested separately in the analysis and detection of PA by EI-GC–MS and LC-HRMS when present at a 10 μg/mL in a soil matrix featured in the 44th PT and in a glycerol-rich liquid matrix featured in the 48th Official Organization for the Prohibition of Chemical Weapons (OPCW) Proficiency Test when present at a 5 μg/mL concentration. In both scenarios, PA was successfully transformed into PIC, establishing the protocol as an additional tool for the analysis of this unnatural and unique nerve agent marker by GC–MS and LC-HRMS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗