Search

Background Fire models use pyrolysis data from ground samples and environments that differ from wildland conditions. Two analytical methods successfully measured oxidative pyrolysis gases in wind tunnel and field fires: Fourier transform infrared (FTIR) spectroscopy and gas chromatography with flame-ionisation detector (GC-FID). Compositional data require appropriate statistical analysis. Aims To determine if oxidative pyrolysis gas composition differed between analytical methods and locations (wind tunnel and field). Methods Oxidative pyrolysis gas sample composition collected in wind tunnel and prescribed fires was determined by FTIR and GC/FID. Proportionality between gases was tested. Analytical method and location effects on composition were tested using permutational multivariate analysis of variance and the Kruskal–Wallis test. Key results Gases proportional to each other were identified. The FTIR composition differed between locations. The subcomposition of common gases differed between analytical methods but not between locations. Relative amount of the primary fuel gases (CO, CH4) was not significantly affected by location. Conclusions Composition of trace gases differed between the analytical methods; however, each method yielded a comparable description of the primary fuel gases. Implications Both FTIR and GC/FID methods can be used to quantify primary pyrolysis fuel gases for physically-based fire models. Importance of the trace gases in combustion models remains to be determined.

The spectra of C1 molecules are confounding in that each of the fundamental vibrational modes transform as the same irreducible representation (A) and hence each band consists of a seemingly random distribution of a-, b-, and c-type transitions. This is in contrast to higher symmetry molecules for which band types are readily deduced by simple symmetry rules. Herein, we present a method to simulate the convoluted rotational contours in the gas-phase spectra of C1 molecules by combining existing ab initio calculations with Colin Western’s pgopher rotational contour program. Specifically, ab initio calculations in the NWChem suite of programs were employed to predict the components of the dipole moment derivatives along the principal axes of the moments of inertia. This information was then input into pgopher to model the fundamental band contours as a sum of a-, b-, and c-type transitions. This method was applied to simulate the rotational contour spectra of a series of representative C1 molecules which were then compared against both ab initio stick spectra and experimentally measured broadband IR spectra from the Pacific Northwest National Laboratory infrared gas-phase database. In addition to providing further insight beyond what is revealed in a typical stick spectrum, the simulated contours showed good agreement with the measured spectra.

We document an artifact associated with the back reflection from samples or sampling accessories in Fourier transform spectrometers. Samples oriented normal to the incoming modulated beam can reflect light back to the interferometer and this light (the percentage dependent on the sample’s refractive index) is modulated by the interferometer a second time resulting in light erroneously appearing at twice its true frequency. The phenomenon occurs across the spectrum but is most apparent when positive-going narrow absorption peaks at 1 f display as negative-going peaks at 2 f. We have redressed the artifact by implementing a rotation stage directly beneath the sample holder: As the stage is rotated through small angles relative to beam normal, the back-reflected light does not enter the interferometer and the artifact disappears. The observation is relevant to several IR sampling methods: gas/liquid cells, alkali halide pellets, reflectance accessories, etc.

This paper investigates the accuracy of deriving the composite optical constants of binary mixtures from only the complex indices of refraction of the neat materials. These optical constants enable the reflectance spectra of the binary mixtures to be modeled for multiple scenarios (

The Pacific Northwest National Laboratory (PNNL) gas-phase database is a compilation of quantitative experimental (5, 25, and 50 °C) infrared spectra of ca. 500 molecules, designed for in situ, standoff or remote sensing of gases and vapors at or near atmospheric pressure. The data are characterized by calibration on both the wavenumber and intensity axes. Recent papers have called into question the PNNL intensity values for isobutane, [2-methylpropane, HC(CH3)3], suggesting discrepancies of 30-40%. In this study, we remeasure and re-examine the intensity values of isobutane using both similar and alternate methods to those used to generate the original PNNL database spectra. Indirect confirmation from literature data of homologous molecules and direct confirmation from new results confirm that for many band integrals across the isobutane spectrum, the original PNNL data are indeed accurate to within the reported 3% experimental uncertainty.

A spectral analysis tool has been developed to interactively identify and quantify individual gas-phase species from complex infrared absorbance spectra obtained from laboratory or field data. The SpecQuant program has an intuitive graphical interface that accommodates both reference and experimental data with varying resolution and instrumental lineshape, as well as algorithms to readily align the wavenumber axis of a sample spectrum with the raster of a reference spectrum. Using a classical least squares model in conjunction with reference spectra such as those from the Pacific Northwest National Laboratory (PNNL) gas-phase infrared database or simulated spectra derived from the HITRAN line-by-line database, the mixing ratio of each identified species is determined along with its associated estimation error. After correcting the wavelength and intensity of the field data, SpecQuant displays the calculated mixing ratio versus the experimental data for each analyte along with the residual spectrum with any or all analyte fits subtracted for visual inspection of the fit and residuals. The software performance for multianalyte quantification was demonstrated using moderate resolution (0.5 cm–1) infrared spectra that were collected during the time-resolved infrared photolysis of methyl iodide.

In combination with other parameters, the real, n([Formula: see text]), and imaginary, k([Formula: see text]), components of the complex refractive index, [Formula: see text] = n + i k, can be used to simulate the optical properties of a material in different forms, e.g., its infrared spectra. Ultimately, such n/k values can be used to generate a database of synthetic reflectance spectra for the different morphologies to which experimental data can be compared. But obtaining reliable values of the optical constants n/k for solid materials is challenging due to the lack of optical quality specimens, usually crystals, large enough to measure. An alternative to crystals is to press the powder into a uniform disk. We have produced pellets from ammonium sulfate, (NH4)2SO4, powder and derived the pellets' n and k values via single-angle reflectance using a specular reflectance device in combination with a Fourier transform infrared spectrometer. The single-angle technique measures amplitude of light reflected from the material as a function of wavelength over a wide spectral domain; the optical constants are determined from the reflectance data using the Kramers–Kronig relationship. We investigate several parameters associated with the pellets and pellet formation and their effects upon delivering the most reliable n/k values. Parameters studied include pellet diameter, mass, and density (void space), drying, grinding, sieving, and particle size in the pellet formation, as well as pressing pressure and duration. Of these parameters, using size-selected mixtures of dried, small (4)2SO4 both as crystal reflectance as well as extinction spectra of aerosols measured in a flow tube shows reasonable agreement, but suggests the present values, as confirmed from two independent techniques, represent a substantial improvement for n/k values for (NH4)2SO4, also demonstrating promise to measure the optical constants of other materials.

Infrared reflectance analysis is facilitated via the comparison of spectra recorded in situ to a databank of actual or synthetic infrared reflectance spectra. It has recently been shown that reference spectra corresponding to the many different morphological forms of the same chemical can be generated synthetically using the imaginary, k, and real, n, components of the complex refractive index, [Formula: see text] = n + i k. One method to obtain the n and k vectors is infrared ellipsometry, which measures the changes in amplitude, tan Ψ, and phase, Δ, of polarized light reflected from the sample both as a function of wavenumber and angle of incidence. The method requires specularly reflected light, so best results are usually obtained with polished planar samples of large surface area. Due to the difficulties of obtaining such samples, however, we investigate the possibility of pressing powders of neat materials and obtaining the corresponding optical constants from the pellets. In this paper, variability in the sample pellet and preparation method is investigated, as is variability in the fitting procedure for the derived optical constants. The n/k vectors are derived from the measured ellipsometric parameters, tan ψ and Δ, as they are fit by an oscillator model which yield n([Formula: see text]) and k([Formula: see text]) vectors as a function of wavenumber, [Formula: see text]. Construction of the oscillator model is not automatic and depends on significant input from the analyst as well as the sample’s physical characteristics. For pellet pressing, the experimental variability was found to be minimized for size-selected powdered samples as gauged by the minimal variance in ψ and Δ for three different pellets; similarly, the analytical precision for multiple measurements of the same pellet was also quite good, suggesting that a pressed pellet is a viable sample preparation method. Experimental variabilities were comparatively small; the greatest variability came in the analytic fitting procedure with differences in the k-peak values up to 10% for only the sharpest bands arising from four different fits to the same data set. The final ellipsometric n/k data are compared to literature values obtained from crystalline ammonium sulfate ((NH4)2SO4) samples as well as single-angle reflectance measurements that also used pressed pellets. Comparison with the previous literature values shows generally good agreement, although larger k-values are observed for the independent sets of data derived from pressed pellets. These data are suggested as an improved set of optical constants for (NH4)2SO4.

Pyrolysis products from wildland fuels are typically measured under tightly controlled conditions using fuels which have been processed to remove water content and physical shape. Different instruments can be used to identify and quantify the composition of these gases. Measurement of pyrolysis gases under conditions typical of wildland fires has seldom occurred. We used FTIR spectroscopy and GC/FID analysis to measure pyrolysis gases produced in wind tunnel experiments and small prescribed burns in longleaf pine needle fuel beds with live shrubs. Use of compositional data techniques on the 8 common gases measured by both methods showed that the compositions were affected by the measurement method and interaction between method and location was significant.

To support stand-off detection, spectral libraries are being developed that include the optical constants, n(ν) and k(ν). Variable angle spectroscopic ellipsometry and single-angle reflectance are used to derive these data, enabling the reference spectra to be modeled for different parameters.

This paper updates recent work to populate spectral databases for (near-) infrared sensing of solids in different modalities including passive and active sensing of minerals, ores and other mining chemicals and minerals.

Much is still unknown about the mechanisms and rates of environmental degradation of organophosphorous pesticides and agents. In this study we focus on the degradation of one organophosphorous compound, namely solid methylphosphonic anhydride [CH3P(O)OHOP(O)OHCH3, MPAN] and its rate of conversion to methylphosphonic acid (MPA) via heterogeneous hydrolysis. Pure MPAN was synthesized and loaded in open sample cups placed inside exposure chambers containing saturated salt solutions to control the relative humidity (RH). The reaction was monitored in the sample cup at various times using both infrared hemispherical reflectance (HRF) spectroscopy and Raman spectroscopy. Calibrated HRF and Raman spectra of both pure reagents as well as gravimetrically prepared mixtures were used to quantify the concentrations of MPAN and MPA throughout the reaction. Results show both HRF and Raman spectroscopies are convenient non-invasive methods for detection of solid chemicals as long as a large area is sampled to average out any spatial inhomogeneities that occur on the sample surface and minimal phase changes occur during the course of the reaction. The samples for the 54 and 75% RH studies showed significant deliquescence, and the liquid water had to be removed prior to measurement; this effect led to differences in the sample form, such that the calibration spectra were no longer valid for quantitative analysis using HRF spectroscopy. Raman spectroscopy, on the other hand, proved to be less sensitive to these effects and provided better estimation of the MPAN and MPA concentrations. The MPAN degradation rate displayed a very strong dependence on relative humidity: at room temperature the reaction showed 50% conversion of the MPAN in 761 ± 54 h at 33% RH, 33 ± 4 h at 43% RH, 17 ± 2 h at 54% RH and just 7 ± 1 h at 75% RH.

In this study we capture and identify pyrolysis gases from prescribed burns conducted in pine forests with a shrub understory using a manual extraction device. The device selectively sampled emissions ahead of the flame front, minimizing collection of oxidized gases, with the captured gases analyzed in the laboratory using infrared absorption spectroscopy. Results show that emission ratios (ER) relative to CO for ethene, and acetylene were significantly greater than previous fire studies, suggesting that the sample device was able to collect gases prior to ignition. Further evidence that ignition had not begun was corroborated by novel infrared detections of several species, in particular naphthalene. With regards to oxygenated species, several aldehydes (acrolein, furaldehyde, acetaldehyde, formaldehyde) and the carboxylic acids (formic, acetic) were all observed; results show that ERs for acetaldehyde were noticeably greater while ERs for formaldehyde and acetic acid were lower compared to other studies. The acetylene-to-furan ratio also suggests that high temperature pyrolysis was the dominant process generating the collected gases. This hypothesis is further supported by the presence of HCN and the absence of NH3.

Volatile organic compounds (VOCs) are emitted from many sources, including wildland fire. VOCs have received heightened emphasis due to such gases' influential role in the atmosphere, as well as possible health effects. We have used extractive infrared (IR) spectroscopy on recent prescribed burns in longleaf pine stands and herein report the first detection of five compounds using this technique. The newly reported IR detections include naphthalene, methyl nitrite, allene, acrolein and acetaldehyde. We discuss the approaches used for detection, particularly the software methods needed to fit the analyte and multiple (interfering) spectral components within the selected spectral micro-window(s). We also discuss the method's detection limits and related parameters such as spectral resolution.

Binary mixtures of liquids may be encountered in industrial or remote sensing scenarios and present challenges to positive identification compared to neat single-component liquids. Our investigation examines whether one can predict the optical properties of the mixture, i.e. its complex index of refraction, by assuming a linear superposition of the real and imaginary components of the index of refraction in proportion to the ratio of each constituent. To investigate this hypothesis various liquid mixtures were created using mass ratios. The mixtures were then characterized as to their complex index of refraction and used in numerical modeling calculations of thin liquid mixture films on surfaces and compared with composed mixtures using linear n and k synthetic mixtures where the n and k components of the complex index of refraction were combined in similar ratios. The comparison of modeling and experimental results is presented with recommendations for further investigation.

Knowledge of the bulk optical constants n and k of solids or liquids allows researchers to accurately predict the absorption, reflection, and scattering properties of materials for different physical forms. Indeed, chemically complex materials such as minerals can have an almost limitless variety of morphologies, particle sizes, shapes, and compositions, and the optical properties of such species can be predicted if the optical constants are known. For species such as minerals, there can be additional challenges due to e.g. hydration or dehydration during the course of the optical constants measurement. Here, we describe the protocols to obtain the bulk optical constants n and k of uranium-bearing minerals and ores such as uraninite or autunite. If quality n and k data are at hand, the (infrared) reflectance spectra can be predicted for different particle sizes and morphologies and the modeling results for various scenarios can be derived.

A method for deriving the optical constants of organic powdered materials in the mid-infrared spectral range is introduced using both variable angle spectroscopic ellipsometry and transmission spectroscopy. The approach uses pressed pellets of the powder and is applied to organic solids, which have both strong and weak infrared absorption features. Many powders have significant voids and do not press into smooth, homogenous pellets. To account for pellet non-idealities and to accurately measure both n and k, three different forms of pellets were pressed and measured: A pure analyte pellet, a mixed analyte/KBr pellet with a large analyte percentage, and a KBr transmission pellet with only a small analyte percentage. Using all three pellets in a multi-sample analysis involving both ellipsometric and transmission data, the complex refractive index (n/k) values can be derived for many organic compounds. This method is illustrated to calculate the optical constants for anhydrous lactose from 6000-400 cm-1. The transmission measurements improve the spectral fitting of weak absorption features, and the multi-sample analysis enables a better determination of the significant void space that is present in the pure pellet, leading to lower values for both n and k if not properly accounted for in the multi-oscillator model used to fit the ellipsometric data.

Detecting chemical agents in outdoor environments such as a battlefield is made challenging by not only the spurious signatures from background chemicals and surfaces (e.g. asphalt, dirt, concrete), but also by the chemical transformation of the actual agents. The change of CW agents to other species can be catalyzed by other chemicals present in the scene, by different substrates, as well as by local weather conditions. Some of the final environmental transformation products are known (e.g. for the G agents methylphosphonic acid), but many of the intermediate chemical states are not, nor are the rates of transformation to the other intermediates or the end products. In this study we have made preliminary optical investigations into the degradation products of a G-agent intermediate, namely methylphosphonic anhydride and its rate of conversion to the more stable methylphosphonic acid. Using infrared and Raman spectroscopies, we have found that the relative humidity greatly affects the rate of change and we report first results from these studies.

This paper presents the methods for developing synthetic spectral libraries using the real n(λ) and imaginary k(λ) parts of the complex refractive index for sensors, including hyperspectral sensors, and presents results for solid materials.

We present an overview of solids reflectance spectra that report quantitative reflectance spectra between 1.3 and 16 µm of both natural and anthropogenic materials. The spectra can be used for myriad applications.

Pyrolysis is the first step in a series of chemical and physical processes that produce flammable organic gases from wildland fuels that can result in a wildland fire. We report results using a new time-resolved Fourier transform infrared method that correlates the measured FTIR spectrum to an infrared thermal image sequence enabling identification and quantification of gases within different phases of the fire process. The flame from burning fuel beds composed of pine needles (Pinus palustris) and mixtures of sparkleberry, fetterbush and inkberry plants was the natural heat source for pyrolysis. Extractive gas samples were analyzed and identified in both static and dynamic modes synchronized to thermal infrared imaging: A total of 29 gases were identified including small alkanes, alkenes, aldehydes, nitrogen compounds and aromatics, most previously measured by FTIR in wildland fires. This study presents one of the first identifications of phenol associated with both pre-combustion and combustion phases, using ca. 1 Hz resolution. Preliminary results indicate ~ 2.5× greater phenol emission from sparkleberry and inkberry compared to fetterbush, with differing temporal profiles.

Infrared reflectance spectra can be influenced by many factors, e.g. the substrate and the thickness of the layer for liquids or the surface micromorphology, the form (powder, crystal) and the particle size for solids. All these parameters can have an effect on the appearance of the measured spectrum. To avoid collecting multitudes of spectra to cover all such scenarios, the optical constants n and k, which are intrinsic properties of a material, can instead be used to model the reflectance spectrum. For solids, two techniques are commonly used to derive optical constants: ellipsometry and single-angle reflectance spectroscopy. For both methods, best results are usually obtained from single crystals. We have recently demonstrated for ammonium sulfate (a relatively soft material) that by optimizing certain conditions, high quality pellets with specularly reflective surfaces can be used in lieu of crystals. This was confirmed by the excellent agreement between the optical constants derived by these two methods. This work focuses on the possible extension of these methods to harder materials, starting with sodium sulfate. The first step is to see if high quality pellet surfaces can be obtained as for ammonium sulfate. The reflectance values and the associated optical constants can also be obtained.

In combination with other parameters, the real

Infrared reflectance analysis is facilitated via the comparison of spectra recorded in situ to a databank of actual or synthetic infrared reflectance spectra. It has recently been shown that reference spectra corresponding to the many different morphological forms of the same chemical can be generated synthetically using the imaginary

We report on recent work on spectral databases that can be used for (near-) infrared sensing of solids and liquids relevant to both passive/active sensing of materials related to mining, oil and gas exploration.

Uranium dioxide (UO2) is a material with historical and emerging applications in numerous areas such as photonics, nuclear energy, and aerospace electronics. While often grown synthetically as single-crystal UO2, the mineralogical form of UO2 called uraninite is of interest as a precursor to various chemical processes involving uranium-bearing chemicals. Here, we investigate the optical and chemical properties of a series of three UO2 specimens: synthetic single-crystal UO2, uraninite ore of relatively high purity, and massive uraninite mineral containing numerous impurities. An optical technique called single-angle reflectance spectroscopy was used to derive the optical constants n and k of these uranium specimens by measuring the specular reflectance spectra of a polished surface across the mid- and far-infrared spectral domains (ca. 7000-50 cm-1). X-ray diffractometry, scanning electron microscopy, and energy-dispersive X-ray spectroscopy were further used to analyze the surface composition of the mineralogical forms of UO2. Most notably, the massive uraninite mineral was observed to contain significant deposits of calcite and quartz in addition to UO2 (as well as other metal oxides and radioactive decay products). Knowledge of the infrared optical constants for this series of uranium chemicals facilitates nondestructive, noncontact detection of UO2 under a variety of conditions.

The identification of minerals, including uranium-bearing species, is often a labor-intensive process using X-ray diffraction (XRD), fluorescence, or other solid-phase or wet chemical techniques. While handheld XRD and fluorescence instruments can aid in field applications, handheld infrared (IR) reflectance spectrometers can now also be used in industrial or field environments, with rapid, nondestructive identification possible via analysis of the solid’s reflectance spectrum providing information not found in other techniques. In this paper, we report the use of laboratory methods that measure the IR hemispherical reflectance of solids using an integrating sphere and have applied it to the identification of mineral mixtures (i.e., rocks), with widely varying percentages of uranium mineral content. We then apply classical least squares (CLS) and multivariate curve resolution (MCR) methods to better discriminate the minerals (along with two pure uranium chemicals U3O8 and UO2) against many common natural and anthropogenic background materials (e.g., silica sand, asphalt, calcite, K-feldspar) with good success. Ground truth as to mineral content was attained primarily by XRD. Identification is facile and specific, both for samples that are pure or are partially composed of uranium (e.g., boltwoodite, tyuyamunite, etc.) or non-uranium minerals. The characteristic IR bands generate unique (or class-specific) bands, typically arising from similar chemical moieties or functional groups in the minerals: uranyls, phosphates, silicates, etc. In some cases, the chemical groups that provide spectral discrimination in the longwave IR reflectance by generating upward-going (reststrahlen) bands can provide discrimination in the midwave and shortwave IR via downward-going absorption features, i.e., weaker overtone or combination bands arising from the same chemical moieties.

We have re-investigated the optical constants n and k for the homologous series of inorganic salts barium fluoride (BaF2) and calcium fluoride (CaF2) using a single-angle near-normal incidence reflectance device in combination with a calibrated Fourier transform infrared (FTIR) spectrometer. Our results are in good qualitative agreement with most previous works. However, certain features of the previously published data near the reststrahlen band exhibit distinct differences in spectral characteristics. Notably, our measurements of BaF2 do not include a spectral feature in the ∼250 cm−1 reststrahlen band that was previously published. Additionally, CaF2 exhibits a distinct wavelength shift relative to the model derived from previously published data. We confirmed our results with recently published works that use significantly more modern instrumentation and data reduction techniques.

Reflectance (emittance) spectroscopy, especially at infrared wavelengths, continues to grow in utility as an analytical technique for contact, standoff, and remote sensing. The reflectance spectra of solids, however, are complex, depending on many parameters, even for the same material. Granule or powder particle size, crystal morphology, layer thickness, and substrate material all affect the spectral distribution of reflected light. However, such phenomena can all be modeled if the optical constants n(ν) and k(ν) are available. If the quantitative absorption coefficient K(ν) is known, the k value can be obtained via the relation k(ν) = 2.303K(ν)/4πν. The absorption coefficient can in turn be derived from a simple KBrpellet infrared absorption measurement, provided the pellet mass ratio is prepared quantitatively. The method requires the pellet’s mass and diameter, along with the analyte mass fraction and density. In this paper we demonstrate the requisite experimental details in preparing the pellets, as well as methods to reduce light scattering in order to obtain more quantitative values. Theoretical methods to derive the related optical constants will also be detailed, in particular the assumptions used to obtain the scalar refractive index n. Ideally, this value is known or measured separately, but in some cases we have found that it can be approximated (first approximation) for most organic chemicals by n~1.5 at the shortest wavelength. The results are presented for a couple of species.

Other than open bodies of water, bulk liquids are rarely encountered in the environment. Rather, liquids are typically found as aerosols, liquid droplets, or liquid layers on sundry substrates: glass, concrete, metals, etc. The layers can be of varying thicknesses, from micron-level to millimeter thick deposits. The infrared (IR) reflectance spectra of such deposits vary greatly, approximating the bulk reflectance for thicker deposits and for thinner layers on reflective surfaces, producing “transflectance” spectra that more closely replicate simple transmission of the IR light twice traversing the absorptive medium. Rather than recording large numbers of such spectra to serve as endmembers of a spectral reflectance library, we have recognized that the spectra can be modeled so long as the complex optical constants n(ν) and k(ν) are known as a function of frequency, ν. Here n is the real (dispersion) part and k is the imaginary (absorption) component of the complex index of refraction. However, in many cases the bands in the longwave IR (7 to 13 μm) can become saturated, and better signal-to-noise and specificity can be realized at shorter wavelengths. In earlier studies, we obtained the n/k values from 1.28 to 25 μm for a series of liquids, but are now expanding those measurements to include additional liquid species and extending the spectral range to lower wavelengths. In this paper we describe the methodologies for compiling and fusing the two data sets collected to provide better and more complete spectral coverage from 1 to 25 μm (10,000 to 400 cm-1 ). The broad spectral range means that one needs to account for both strong and weak spectral features, all of which can be useful for detection, depending on the scenario. To account for the large dynamic range, both long and short path length transmission cells are required for accurate measurements.

Fixed-angle reflectance spectroscopy using a commercial Fourier transform infrared (FTIR) spectrometer was employed to derive the optical constants n and k of several uranium compounds. This technique relies upon measurement of the quantitative reflectance R(ν) spectra from a polished surface across a broad spectral range (in this case, the mid- and far-IR covering ca. 7500 to 50 cm-1 ) followed by application of the Kramers-Kronig transformation (KKT). Near-normal fixed-angle measurements as used in this technique require continuous reflectance spectra to as low a wavenumber value as possible. Here, we discuss some of the many challenges in measuring the far-IR and very far-IR (terahertz) spectra using an interferometric instrument, particularly those stemming from small sample sizes, typically just millimeters on a face for crystalline samples, as well as limitations due to optical components and diffraction. We apply this method to single-crystal UO2 and its mineralogical form uraninite, as well as other Ubearing minerals such as autunite [Ca(UO2)2(PO4)2·8-12H2O] and the dehydrated form of autunite, meta-autunite. In addition to the specular reflectance spectra, x-ray diffractometry was used as a confirmatory technique to analyze the surface composition of the species. Deriving the infrared optical constants for such U-bearing species (as well as other solids) will enable nondestructive detection under a variety of environmental and compositional conditions.

Halogen-bearing compounds are known to photolyze under UV radiation; analysis of degradation products is of interest for both safety and environmental considerations. Time-resolved infrared spectroscopy was used in the laboratory to study the UV-photolysis of methyl iodide. Photolysis products methanol (CH3OH) and formaldehyde (HCHO) were clearly identified in a time-resolved manner. Preliminary kinetic models predict the formation of both CH3OH and HCHO.

A method for deriving the optical constants ( n / k ) of organic powdered materials using pressed pellets in the mid-infrared spectral range is introduced that combines variable angle spectroscopic ellipsometry and transmission spectroscopy. The approach is applied to anhydrous lactose, in which three different forms of pellets were pressed and measured: a pure lactose pellet and a mixed lactose/potassium bromide (KBr) pellet with a large analyte percentage were used for ellipsometric measurements, and a KBr transmission pellet with only a small analyte percentage was used for transmission measurements. The transmittance data provide an initial set of oscillators and improve the spectral fitting of weak absorption features ( k < 0.01 ). Ellipsometric data for the pure and mixed pellets are then fit simultaneously to derive the final n / k values for lactose from 6000 − 400 c m − 1 . An alternative method just using the ellipsometric data from the mixed pellet and the transmittance data is also presented and shows good agreement with the multi-sample analysis, providing a simpler method for powders that do not press easily into pure pellets. Finally, the derived optical constants were used to model the reflectance data, demonstrating a good match with the measured reflectance spectra if non-idealities are included.

Since solids are only sometimes seen en masse in a pure bulk form, and for liquids other than water almost never, a capability to model reflectance spectra from analytes deposited on various substrates would be highly advantageous. If available, the real, n ( ν ) , and imaginary, k ( ν ) , components of the complex refractive index, n∼ = n + ik, can be used to simulate infrared spectra, accounting for reflection, refraction, and absorption phenomena as a function of wavelength. We focus on using the Pacific Northwest National Laboratory (PNNL) derived n / k vectors for solid and liquid analytes deposited as thin layers on different types of substrates including conductors, such as aluminum, and inorganic dielectrics, such as glass. The model is an adaptation of the Monte Carlo ray trace modeling program, TracePro, extended through the use of its macrolanguage. The model is tested using thin films of organic liquids including silicone oil and no. 2 diesel fuel, as well as organic solids such as caffeine and acetaminophen on aluminum and glass. The predicted spectra for the solid films were compared to experimental hemispherical reflectance data measured using a Fourier transform spectrometer with an integrating sphere. The thickness of the calculated layer is a parameter for predicting the (transflectance) spectra and is obtained using the areal density measured from gravimetric methods to generate the thin-layer samples. Comparison of the calculated spectra with experimental hemispherical reflectance data shows excellent agreement, indicating promise for the use of measured n / k data to synthesize reference spectral data. In particular, accounting for the inhomogeneity of the deposits greatly improved the match with experimental data. Finally, the theoretical modeling shows that for thicker layers (ca. 20 to 100 μm) of typical organics possessing moderately strong k values, the longwave infrared features are often saturated and better spectral contrast is obtained from the overtone/combination bands in the shortwave infrared.

Broadband high-speed absorption spectroscopy using swept-wavelength external cavity quantum cascade lasers (ECQCLs) is applied to measure multiple pyrolysis and combustion gases in biomass burning experiments. Two broadly-tunable swept-ECQCL systems were used, with the first tuned over a range of 2089-2262 cm−1 (4.42–4.79 µm) to measure spectra of CO2, H2O, and CO. The second was tuned over a range of 920-1150 cm−1 (8.70–10.9 µm) to measure spectra of ammonia (NH3), ethene (C2H4), and methanol (MeOH). Absorption spectra were measured continuously at a 100 Hz rate throughout the burn process, including inhomogeneous flame regions, and analyzed to determine time-resolved gas concentrations and temperature. The results provide in-situ, dynamic information regarding gas-phase species as they are generated, close to the biomass fuel source.

Volatile organic compounds (VOCs) are emitted from many sources, including wildland fire; VOCs have received heightened emphasis due to such gases' influential role in the atmosphere, as well as possible health effects. We have used extractive infrared (IR) spectroscopy on recent prescribed burns in longleaf pine stands and herein report seminal detection of five compounds using this technique. The newly reported IR detections include naphthalene, methyl nitrite, allene, acrolein and acetaldehyde. We discuss the approaches used for detection, particularly the software methods needed to fit the analyte and multiple (interfering) spectral components within the selected spectral micro-window(s). We also discuss the method's detection limits and individual species' context in terms of atmospheric chemistry.

Pyrolysis of intact wildland fuels in the southern United States is being measured at bench, wind tunnel, and field scales as part of a larger research project to measure and model pyrolysis of wildland fuels to improve models used to predict prescribed fire behavior. Traditional pyrolysis experiments typically use dried, ground samples in either an inert or oxidizing environment subject to uniform heating and heat transfer. Fletcher and others are presenting results of pyrolysis experiments using a flat-flame burner to heat intact foliage from 14 species of plants native to the southern U.S. at this conference. The fuel beds in prescribed burns in southern pine forests are composed of a mixture of dead pine needles and a large variety of herbaceous and woody plants. We have burned 73 fuel beds composed of Pinus palustris needles and mixtures of Lyonia lucida, Ilex glabra, and Vaccinium darrowii plants in a wind tunnel facility with and without a moderate wind speed of ~ 1 m s-1. The flame from the spreading fire is the heat source for the pyrolysis experiment. Canister samples of pyrolysis and flaming combustion gases within the fuel bed have been collected for offline analysis. Open path spectrometers nonintrusively measured composition of pyrolysis gases in real-time. Thermocouples, a Schmidt-Boelter heat flux sensor, a nadir thermal IR camera, and background-oriented Schlieren photography estimated heat transfer and air flow around the plants. This presentation will present results of this ongoing work.

Other than water, pure bulk liquids and solids are rarely encountered in the environment, but more commonly exist as layers on various substrates, e.g. concrete, metals, glass, etc. Unlike gas-phase transmission spectra, condensed-phase reflectance spectra depend not only on absorption, but also on the material’s refraction and reflection at interfaces. Providing reference spectra to account for the plethora of morphological conditions (e.g. substrate, layer thickness, particle or droplet size) that may be encountered under different scenarios is a daunting challenge. An alternative approach is to derive the complex optical constants, n and k, which can be used to model the optical phenomena in media and at interfaces, minimizing the need for a vast number of laboratory measurements. The current status of obtaining such optical constants for both solids and liquids is briefly summarized.

The morphology, size, and media surrounding a solid material can all influence its optical properties, such as scattering, absorption, and reflection of light. While it is possible to measure the optical properties of hundreds of individual surface or particle configurations, it is impractical. Conversely, knowledge of the bulk optical constants n and k of a pure solid facilitates computation of arbitrarily sized particles, shapes, surrounding media, etc. As we describe here, single-angle reflectance spectroscopy is one such method used to obtain the bulk optical constants of solids. In particular, solid crystalline materials typically have responses in the mid- and far-infrared arising from phenomena such as lattice (phonon) vibrations as well as stretching or bending vibrations, among others. These vibrational modes in the mid- and far-infrared often present unique experimental challenges as the wavelength of light across such a wide spectral range varies greatly and can dimensionally approach the magnitude of specimens and even optical apertures used to limit the illumination area. Here we describe challenges and solutions, with an emphasis on optical instrumentation and far-infrared spectra, related to measuring realistic-sized mineralogical samples (down to ca. 2 mm) where sample purity, exposed surface area, cost, and rarity can all play important roles in obtaining the optical constants n and k.

Uranium dioxide (UO

We present the rationale, methods, and results of modeling of thin film organic liquids on various substrates. These liquids may coat surfaces (substrates) either as a result of their production, dispersal via aerosols or spills. Identification of unknown coated surfaces using either reflectance or emittance spectroscopy cannot be accomplished simply through reference to reflectance signature libraries since neither the thickness of the liquid layer nor the substrate type is known beforehand and both contribute to the signature. Liquid spectral libraries offer the complex index of refraction (n,k) as a function of wavelength which by itself is useful only for thick (bulk) liquid layers via computation of reflectance and transmittance coefficients using the Fresnel equations. Thin liquid layers both reflect and refract incident light in combination with reflectance from the substrate. We show modeling of various organic liquids on substrates using commercial thin film design and modeling software, as well as Monte Carlo ray tracing software to demonstrate the variety of potential signatures encountered that depend on the thickness of the liquid layer as well as the characteristics of the substrate (metal or dielectric). These substrates give rise to transflectance behavior, while many dielectric substrates have rich absorption features that provide complex signatures that combine attributes of both the liquid and the substrate. Knowledge of the complex index of refraction of both target liquids and substrates is essential in order to synthesize spectra necessary in the application of target identification algorithms.

We present accurate measurements for the optical constants for a series of organic liquids, including organophosphorous compounds. Bulk liquids are rarely encountered in the environment, but more commonly are present as droplets of liquids or thin layers on various substrates. Providing reference spectra to account for the plethora of morphological conditions that may be encountered under different scenarios is a challenge. An alternative approach is to provide the complex optical constants, n and k, which can be used to model the optical phenomena in media and at interfaces, minimizing the need for a vast number of laboratory measurements. In this work, we present improved protocols for measuring the optical constants for a series of liquids that span from 7800 to 400 cm-1. The broad spectral range means that one needs to account for both strong and weak spectral features that are encountered, all of which can be useful for detection, depending on the scenario. To span this dynamic range, both long and short cells are required for accurate measurements. These protocols are presented along with experimental and modeling results for thin layers of silicone oil on aluminum.

We have developed methods to measure the directional-hemispherical (ρ) and diffuse (ρd) reflectances of powders, liquids, and disks of powders and solid materials using a commercially available, matte gold-coated integrating sphere and Fourier transform infrared spectrometer. To determine how well the sphere and protocols produce quantitative reflectance data, measurements were made of three diffuse and two specular standards prepared by the National Institute of Standards and Technology (NIST), LabSphere Infragold and Spectralon standards, hand-loaded sulfur and talc powder samples, and water. Relative to the NIST measurements of the NIST standards, our directional hemispherical reflectance values are within ±4% for four of the standards and within ±7% for a low reflectance diffuse standard. For the three diffuse reflectance NIST standards, our diffuse reflectance values are within ±5% of the NIST values. For the two specular NIST standards, our diffuse reflectance values are an order of magnitude larger than those of NIST, pointing to a systematic error in the manner in which diffuse reflectance measurements are made for specular samples using our methods and sphere. Sources of uncertainty are discussed in the paper.

We demonstrate a sensor based on tunable diode laser absorption spectroscopy for the detection of hydrogen fluoride (HF) gas at ambient pressure. Absorption from the HF R(1) ro-vibrational peak at ν = 4038.962 cm−1 (2.476 µm) in the fundamental (Δν = 1) band is measured. A quantitative spectral fit based on HITRAN data is used to account for overlapping spectral peaks of HF and water vapor, with an rms residual noise of 5 × 10−4 absorbance units. The sensor is optimized for the detection of transient variations in HF concentration. We measure noise-equivalent concentrations for HF of 38 parts-per-trillion by volume (ppt) for 1-s integration times and 2.3 ppt for 10-min integration times.