This PDF file contains the front matter associated with SPIE Proceedings Volume 9455, including the Title Page, Copyright information, Table of Contents, Invited Panel Discussion, and Conference Committee listing.

The feasibility of a hydrogen implanted, direct band gap III-V semiconductors as new scintillators for fast neutron spectroscopy using the proton-recoil technique has been investigated. Direct band gap semiconductors have high radiative efficiency and have the potential of high photon yield per unit energy deposited, which are desirable features for a scintillator used for pulse height analysis. In this paper we present our computational results obtained using SRIM software for select materials. The expected depth profiles of implanted hydrogen ions have been applied to the n-p elastic recoil process in both InP and GaN. It is shown that, under ideal conditions, neutron irradiation of hydrogen implanted InP and GaN creates proton recoil scintillation with photon output being directly proportional to incoming neutron energy. It has been found that for the desirable dynamic range of neutron energies, loss to phonon creation in the lattice is negligible compared to energy used in electron excitation which results in the linear response in energy versus pulse height spectrum.

We present optical subwavelength nanostructure architecture suitable for standoff radiation dosimetry with remote optical readout in the visible or infrared spectral regions. To achieve this, films of subwavelength structures are fabricated over several square inches via the creation of a 2D non-close packed (NCP) array template of radiationsensitive polymeric nanoparticles, followed by magnetron sputtering of a metallic coating to form a 2D array of separated hemispherical nanoscale metallic shells. The nanoshells are highly reflective at resonance in the visible or infrared depending on design. These structures and their behavior are based on the open ring resonator (ORR) architecture and have their analog in resonant inductive-capacitive (LC) circuits, which display a resonance wavelength that is inversely proportional to the square root of the product of the inductance and capacitance. Therefore, any modification of the nanostructure material properties due to radiation alters the inductive or capacitive behavior of the subwavelength features, which in turn changes their optical properties resulting in a shift in the optical resonance. This shift in resonance may be remotely interrogated actively using either laser illumination or passively by hyperspectral or multispectral sensing with broadband illumination. These structures may be designed to be either anisotropic or isotropic, which can also offer polarization-sensitive interrogation. We present experimental measurements of a radiation induced shift in the optical resonance of a subwavelength film after exposure to an absorbed dose of gamma radiation from 2 Mrad up to 62 Mrad demonstrating the effect. Interestingly the resonance shift is non-monotonic for this material system and possible radiation damage mechanisms to the nanoparticles are discussed.

Uranyl nitrate is a key species in the nuclear fuel cycle, but is known to exist in different states of hydration, including the hexahydrate [UO₂(NO₃)₂(H₂O)₆] (UNH) and the trihydrate [UO₂(NO₃)₂(H₂O)₃] (UNT) forms. Their stabilities depend on both relative humidity and temperature. Both phases have previously been studied by infrared transmission spectroscopy, but the data were limited by both instrumental resolution and the ability to prepare the samples as pellets without desiccating it. We report time-resolved infrared (IR) measurements using an integrating sphere that allow us to observe the transformation from the hexahydrate to the trihydrate simply by flowing dry nitrogen gas over the sample. Hexahydrate samples were prepared and confirmed via known XRD patterns, then measured in reflectance mode. The hexahydrate has a distinct uranyl asymmetric stretch band at 949.0 cm^-1 that shifts to shorter wavelengths and broadens as the sample dehydrates and recrystallizes to the trihydrate, first as a blue edge shoulder but ultimately resulting in a doublet band with reflectance peaks at 966 and 957 cm^-1. The data are consistent with transformation from UNH to UNT since UNT has two non-equivalent UO2²⁺ sites. The dehydration of UO₂(NO₃)₂(H₂O)₆ to UO₂(NO₃)₂(H₂O)₃ is both a morphological and structural change that has the lustrous lime green crystals changing to the dull greenish yellow of the trihydrate. Crystal structures and phase transformation were confirmed theoretically using DFT calculations and experimentally via microscopy methods. Both methods showed a transformation with two distinct sites for the uranyl cation in the trihydrate, as opposed to a single crystallographic site in the hexahydrate.

While reflectance spectroscopy is a useful tool for identifying molecular compounds, laboratory measurement of solid (particularly powder) samples often is confounded by sample preparation methods. For example, both the packing density and surface roughness can have an effect on the quantitative reflectance spectra of powdered samples. Recent efforts in our group have focused on developing standard methods for measuring reflectance spectra that accounts for sample preparation, as well as other factors such as particle size and provenance. In this work, the effect of preparation method on sample reflectivity was investigated by measuring the directional-hemispherical spectra of samples that were hand-loaded as well as pressed into pellets using an integrating sphere attached to a Fourier transform infrared spectrometer. The results show that the methods used to prepare the sample can have a substantial effect on the measured reflectance spectra, as do other factors such as particle size.

A new scintillator crystal, now known as CLYC (Cs₂LiYCl₆:Ce), has been under development for over 15 years ⁽¹⁾. It was primarily of interest for radiation detection applications because of its good energy resolution for gamma rays (< 4% for 662 keV gamma rays) and its capability for detection of thermal neutrons. The pulse shapes of the signals from the two radiations are different, which allow them to be separated electronically, permitting simultaneous detection of gamma rays and neutrons. The crystal is now commercially available. Early investigations of the neutron response by the current authors ⁽²⁾ revealed that CLYC also responds to fast neutrons. In fact, the good energy resolution of the response under monoenergetic neutron irradiations showed that CLYC was an excellent high-energy neutron spectrometer. This discovery has great impact on the field of neutron spectroscopy, which has numerous, although often specialized, applications. This presentation focuses on applications in counter-terrorism scenarios where neutrons may be involved. The relative importance of the fast neutron response of CLYC, compared to the thermal and gamma-ray response, will be discussed for these scenarios.

Biological warfare agents (BWAs) represent the current menace of the asymmetric war. The early detection of BWAs, especially in the form of bioaerosol, is a challenging task for governments all around the world. Label-free quartz crystal microbalance (QCM) immunosensor and electrochemical immunosensor were developed and tested for rapid detection of BWA surrogate (E. coli) in the form of bioaerosol. Two immobilization strategies for the attachment of antibody were tested; the gold sensor surface was activated by cysteamine and then antibody was covalently linked either using glutaraldehyde, or the reduced antibodies were attached via Sulfo-SMCC. A portable bioaerosol chamber was constructed and used for safe manipulation with aerosolized microorganisms. The dissemination was done using a piezoelectric humidifier, distribution of bioaerosol inside the chamber was ensured using three 12-cm fans. The whole system was controlled remotely using LAN network. The disseminated microbial cells were collected and preconcentrated using the wetted-wall cyclone SASS 2300, the analysis was done using the on-line linked immunosensors. The QCM immunosensor had limit of detection 1×10⁴ CFU·L⁻¹ of air with analysis time 16 min, the whole experiment including dissemination and sensor surface regeneration took 40 min. In case of blank (disseminated sterile buffer), no signal change was observed. The electrochemical immunosensor was able to detect 150 CFU·L⁻¹ of air in 20 min; also in this case, no interferences were observed. Reference measurements were done using particle counter Met One 3400 and by cultivation method on agar plates. The sensors have proved to be applicable for rapid screening of microorganisms in air.

The high and still increasing number of attacks by hazardous bioorganic materials makes enormous demands on their detection. A very high detection sensitivity and differentiability are essential, as well as a rapid identification with low false alarm rates. One single technology can hardly achieve this. Point sensors can collect and identify materials, but finding an appropriate position is time consuming and involves several risks. Laser based standoff detection, however, can immediately provide information on propagation and compound type of a released hazardous material. The coupling of both methods may illustrate a solution to optimize the acquisition and detection of hazardous substances.

At DLR Lampoldshausen, bioorganic substances are measured, based on laser induced fluorescence (LIF), and subsequently classified. In this work, a procedure is presented, which utilizes lots of information (time-dependent spectral data, local information) and predicts the presence of hazardous substances by statistical data analysis. For that purpose, studies are carried out on a free transmission range at a distance of 22m at two different excitation wavelengths alternating between 280nm and 355 nm. Time-dependent fluorescence spectra are recorded by a gated intensified CCD camera (iCCD). An automated signal processing allows fast and deterministic data collection and a direct subsequent classification of the detected substances. The variation of the substance parameters (physical state, concentration) is included within this method.

We present results obtained by a detection system designed to measure laser-induced fluorescence from individual aerosol particles using dual excitation wavelengths. The aerosol is sampled from ambient air and via a 1 mm diameter nozzle, surrounded by a sheath air flow, confined into a particle beam. A continuous wave blue laser at 404 nm is focused on the aerosol beam and two photomultiplier tubes monitor the presence of individual particles by simultaneous measuring the scattered light and any induced fluorescence. When a particle is present in the detection volume, a laser pulse is triggered from an ultraviolet laser at 263 nm and the corresponding fluorescence spectrum is acquired with a spectrometer based on a diffraction grating and a 32 channel photomultiplier tube array with single-photon sensitivity. The spectrometer measures the fluorescence spectra in the wavelength region from 250 to 800 nm. In the present report, data were measured on different monodisperse reference aerosols, simulants of biological warfare agents, and different interference aerosol particles, e.g. pollen. In the analysis of the experimental data, i.e., the time-resolved scattered and fluorescence signals from 404 nm c.w. light excitation and the fluorescence spectra obtained by a pulsed 263 nm laser source, we use multivariate data analysis methods to classify each individual aerosol particle.

In today’s fast-paced world, a new biological threat could emerge at any time, necessitating a prompt, reliable, inexpensive detection reagent in each case. Combined with magnetic-activated cell sorting (MACS), bacterial display technology makes it possible to isolate selective, high affinity peptide reagents in days to weeks. Utilizing the eCPX display scaffold is also a rapid way to screen potential peptide reagents. Peptide affinity reagents for protective antigen (PA) of the biothreat Bacillus anthracis were previously discovered using bacterial display. Bioinformatics analysis resulted in the consensus sequence WXCFTC. Additionally, we have discovered PA binding peptides with a WW motif, one of which, YGLHPWWKNAPIGQR, can pull down PA from 1% human serum. The strength of these two motifs combined, to obtain a WWCFTC consensus, is assessed here using Fluorescence Activated Cell Sorting (FACS). While monitoring binding to PA, overall expression of the display scaffold was assessed using the YPet Mona expression control tag (YPet), and specificity was assessed by binding to Streptavidin R-Phycoerythrin (SAPE). The importance of high YPet binding is highlighted as many of the peptides in one of the three replicate experiments fell below our 80% binding threshold. We demonstrate that it is preferable to discard this experiment, due to questionable expression of the peptide itself, than to try to normalize for relative expression. The peptides containing the WWCFTC consensus were of higher affinity and greater specificity than the peptides containing the WW consensus alone, validating further investigation to optimize known PA binders.

Lab-on-a-chip systems are very promising approach for a decentralized continuous pathogen monitoring. The overall presented system consisting of a microtiter plate sized consumable and the respective instrument allows for the detection of airborne biological pathogen. The target pathogens to be detected are Yersinia pestis, Francisella tularensis, Burkholderia mallei, Burkholderia pseudomallei, Brucella melitensis, Brucella abortis, Coxiella burnetti, and Bacillus anthracis. Important to stress that the technical platform can be easily expanded to further pathogens. In this paper the development of a fully integrated system for the 8-plex detection of bacterial pathogens will be presented. Two exceptional features are combined in this device: The overall system allows for the permanent sampling and analysis of airborne biological pathogens and combines the detection of the respective bacteria on molecular and immunological level. The overall system consisting of chip and instrument and the biological procedures embedded on chip will be presented.

Countries are trying to equip their public transportation infrastructure with fixed radiation portals and detectors to detect radiological threat. Current works usually focus on neutron detection, which could be useless in the case of dirty bomb that would not use fissile material. Another approach, such as gamma dose rate variation monitoring is a good indication of the presence of radionuclide. However, some legitimate products emit large quantities of natural gamma rays; environment also emits gamma rays naturally. They can lead to false detections. Moreover, such radio-activity could be used to hide a threat such as material to make a dirty bomb. Consequently, radionuclide identification is a requirement and is traditionally performed by gamma spectrometry using unique spectral signature of each radionuclide. These approaches require high-resolution detectors, sufficient integration time to get enough statistics and large computing capacities for data analysis. High-resolution detectors are fragile and costly, making them bad candidates for large scale homeland security applications. Plastic scintillator and NaI detectors fit with such applications but their resolution makes identification difficult, especially radionuclides mixes. This paper proposes an original signal processing strategy based on artificial spiking neural networks to enable fast radionuclide identification at low count rate and for mixture. It presents results obtained for different challenging mixtures of radionuclides using a NaI scintillator. Results show that a correct identification is performed with less than hundred counts and no false identification is reported, enabling quick identification of a moving threat in a public transportation. Further work will focus on using plastic scintillators.

CELiS (Compact Eyesafe Lidar System) is an elastic backscatter light detection and ranging (lidar) system developed for monitoring air quality environmental compliance regarding particulate matter (PM_k) generated from off-road use of wheeled and tracked vehicles as part of the SERDP (Strategic Environmental Research and Development Program) Measurement and Modeling of Fugitive Dust Emission from Off-Road DoD Activities program. CELiS is small, lightweight and easily transportable for quick setup and measurement of PM_k concentration and emissions. CELiS operates in a biaxial configuration at the 1.5μm eyesafe wavelength with a working range of better than 6 km and range resolution of 5 m. In this paper, we describe an algorithm that allows for semi-quantitative PM_k determination under a set of guiding assumptions using a single wavelength lidar. Meteorological and particle measurements are used to estimate the total extinction (α) and backscatter (β) at a calibration point located at the end range of the lidar. These α and β values are used in conjunction with the Klett inversion to estimate α and β over the lidar beam path. A relationship between β, α and PM_k mass concentrations at calibration points is developed, which then allows the β and α values derived to be converted to PM_k at each lidar bin over the lidar beam path. CELiS can be used to investigate PM_k concentrations and emissions over a large volume, a task that is very difficult to accomplish with typical PM_k sensors.

A method of classifying signatures that are very nearly identical is described. In this instance, slight template errors can result in poor classification performance even in a high signal-to-noise ratio environment. To ameliorate the uncertainty in the signature templates a new approach is proposed. It involves processing only the maximum discrimination frequency bands. A computer simulation using actual chemical signatures illustrates the approach and demonstrates its improved performance over traditional techniques.

Non-specific chemical sensor arrays have been the subject of considerable research efforts over the past thirty years with the idea that, by analogy to vertebrate olfaction, they are potentially capable of rendering complex chemical assessments with relatively modest logistical footprints. However, the actual implementation of such devices in challenging "real world" scenarios has arguably continued to fall short of these expectations. This work examines the inherent limitations of such devices for complex chemical sensing scenarios, placing them on a continuum between simple univariate sensors and complex multivariate analytical instrumentation and analyzing their utility in general-purpose chemical detection and accurate chemical sensing in the presence of unknown "unknowns." Results with simulated and acquired data sets are presented with discussion of the implications in development of chemical sensor arrays suitable for complex scenarios.

Multiplex coherent anti-Stokes Raman spectroscopy (MCARS) has been used to create a complete Raman spectrum of a material of interest in milliseconds. However, these MCARS spectra often embedded in a nonresonant background that reduces the ability to use those spectra to positively identify the material of interest. There are a number of techniques that are used experimentally to reduce the nonresonant background when taking the MCARS spectrum. However, there are situations where these experimental nonresonant background reduction techniques may result in a loss of the desired MCARS signal. In an effort to maintain the signal strength of the MCARS spectrum, analytical methods of background removal are employed. There are a number of analytical techniques for nonresonant background removal from MCARS signals. However, many of them either make blanket assumptions about the nonresonant background that sacrifice accuracy of the technique or require knowledge of the material of interest before removing the nonresonant background. We will be reporting on an analytical method to remove the nonresonant background that utilizes a combination of the maximum entropy method to reproduce the spectrum as well as complex spectral filtering to remove the nonresonant background and accurately determine the CARS spectrum interest without prior knowledge of the material of interest.

We are developing a technology for stand-off detection based on photo-thermal infrared imaging spectroscopy (PT-IRIS). In this approach, one or more infrared (IR) quantum cascade lasers are tuned to strong absorption bands in the analytes and directed at the sample while an IR focal plane array is used to image the subsequent thermal emissions. In this paper we present recent advances in the theory and numerical modeling of photo-thermal imaging and spectroscopy of particulates on flat substrates. We compare the theoretical models with experimental data taken on our mobile cart-based PT-IRIS system. Synthetic data of the photo-thermal response was calculated for a wide range of analytes, substrates, particle sizes, and analyte mass loadings using their known thermo-physical and optical properties. These synthetic data sets can now be generated quickly and were used to accelerate the development of detection algorithms. The performance of detection algorithms will also be discussed.

With progress in nanofabrication, new strategies have become available that allow precise control of nanoscale optical fields using metallic nanostructures. Here we review recent progress in the control of optical resonances in metal nanostructures for applications in sensing and spectroscopy. We discuss the use of new techniques, such as helium-ion beam milling, which allow precise sculpting of nanometer-scale gaps; new materials such as metal oxides, which have a response somewhere inbetween that of conventional dielectrics and noble metals; and new designs such as L-shaped gap antennas which allow controlling the polarization state of light through near-field interactions between closely spaced antennas.

Widely tunable quantum cascade lasers (QCLs) spanning the long-wave infrared (LWIR) atmospheric transmission window and an HgCdTe detector were incorporated into a transceiver having a 50-mm-diameter transmit/receive aperture. The transceiver was used in combination with a 50-mm-diameter hollow retro-reflector for the open-path detection of chemical clouds. Two rapidly tunable external-cavity QCLs spanned the wavelength range of 7.5 to 12.8 m. Open-path transmission measurements were made over round-trip path-lengths of up to 562 meters. Freon-132a and other gases were sprayed into the beam path and the concentration-length (CL) product was measured as a function of time. The system exhibited a noise-equivalent concentration (NEC) of 3 ppb for Freon-132a given a round-trip path of 310 meters. Algorithms based on correlation methods were used to both identify the gases and determine their CLproducts as a function of time.

Over the past two years we have developed a new approach for detecting and identifying the presence of liquid chemical contamination on surfaces using hyperspectral imaging data. This work requires an algorithm for unmixing the data to separate the liquid contamination component of the data from all other possible spectral effects, such as the illumination and reflectance spectra of the pure background. The contamination components from S and P polarized reflectance data are then used to estimate the complex refractive index. We retain the index estimates within spectral windows chosen for each of a set of candidate contaminant materials based on their optical extinction. Spectral estimates within those windows are characteristic of the liquid material, and can be passed on to an algorithm for chemical detection and identification. The resulting algorithm is insensitive to the composition of the surface material, and requires no prior measurements of the uncontaminated surface. In a series of field tests, data from the Telops Hyper-Cam sensor were used to develop and validate our approach. We discuss our hyperspectral unmixing and index estimation approaches, and show results from tests conducted at the Telops facility in Québec under a contract with the U.S. Army Edgewood Chemical Biological Center.

Raman spectroscopy is a valuable tool for the investigation and analysis of explosive and biological analytes because it provides a unique molecular fingerprint that allows for unambiguous target identification. Raman can be advantageous when utilized with deep UV excitation, but typical deep UV Raman systems have numerous limitations that hinder their performance and make their potential integration onto a field portable platform difficult. These systems typically offer very low throughput, are physically large and heavy, and can only probe an area the size of a tightly focused laser, severely diminishing the ability of the system to investigate large areas efficiently. The majority of these limitations are directly related to a system’s spectrometer, which is typically dispersive grating based and requires a very narrow slit width and long focal length optics to achieve high spectral resolution. To address these shortcomings, ChemImage Sensor Systems (CISS), teaming with the University of South Carolina, are developing a revolutionary wide-field Raman hyperspectral imaging system capable of providing wide-area, high resolution measurements with greatly increased throughput in a small form factor, which would revolutionize the way Raman is conducted and applied. The innovation couples a spatial heterodyne spectrometer (SHS), a novel slit-less spectrometer that operates similar to Michelson interferometer, with a fiber array spectral translator (FAST) fiber array, a two-dimensional imaging fiber for hyperspectral imagery. This combination of technologies creates a novel wide-field, high throughput Raman hyperspectral imager capable of yielding very high spectral resolution measurements using defocused excitation, giving the system a greater area coverage and faster search rate than traditional Raman systems. This paper will focus on the need for an innovative UV Raman system, provide an overview of spatial heterodyne Raman spectroscopy, and discuss the development of the system.

Proliferation of chemical and explosive threats as well as illicit drugs continues to be an escalating danger to civilian and military personnel. Conventional means of detecting and identifying hazardous materials often require the use of reagents and/or physical sampling, which is a time-consuming, costly and often dangerous process. Stand-off detection allows the operator to detect threat residues from a safer distance minimizing danger to people and equipment. Current fielded technologies for standoff detection of chemical and explosive threats are challenged by low area search rates, poor targeting efficiency, lack of sensitivity and specificity or use of costly and potentially unsafe equipment such as lasers. A demand exists for stand-off systems that are fast, safe, reliable and user-friendly. To address this need, ChemImage Sensor Systems™ (CISS) has developed reagent-less, non-contact, non-destructive sensors for the real-time detection of hazardous materials based on widefield shortwave infrared (SWIR) and Raman hyperspectral imaging (HSI). Hyperspectral imaging enables automated target detection displayed in the form of image making result analysis intuitive and user-friendly. Application of the CISS’ SWIR-HSI and Raman sensing technologies to Homeland Security and Law Enforcement for standoff detection of homemade explosives and illicit drugs and their precursors in vehicle and personnel checkpoints is discussed. Sensing technologies include a portable, robot-mounted and standalone variants of the technology. Test data is shown that supports the use of SWIR and Raman HSI for explosive and drug screening at checkpoints as well as screening for explosives and drugs at suspected clandestine manufacturing facilities.

We present preliminary results on the performance of a basic stand-off Raman spectroscopy setup using coded apertures compared to a setup using a round-to-slit fiber for light collection. Measurements were performed using single 5 ns laser shots at 355 nm with a target distance of 5.4 meters on ammonium nitrate powder. The results show an increase in signal-to-noise ratio of 3-8 times when using coded aperture multiplexing compared to the fiber setup.

When handling explosives, or related surfaces, the hands routinely become contaminated with particles of explosives and related materials. Subsequent contact with a solid surface results in particle crushing and deposition. These particles provide an evidentiary trail which is useful for security applications. As such, the opto-physico-chemical characteristics of these particles are critical to trace explosives detection applications in DOD or DHS arenas. As the persistence of these particles is vital to their forensic exploitation, it is important to understand which factors influence their persistence. The longevity or stability of explosives particles on a substrate is a function of several environmental parameters or particle properties including: Vapor pressure, particle geometry, airflow, particle field size, substrate topography, humidity, reactivity, adlayers, admixtures, particle areal density, and temperature. In this work we deposited particles of 2,4-dinitrotoluene on standard microscopy glass slides by particle sieving and studied their sublimation as a function of airflow velocity, areal particle density and particle field size. Analysis of 2D microscopic images was used to compute and track particle size and geometrical characteristics. The humidity, temperature and substrate type were kept constant for each experiment. A custom airflow cell, using standard microscopy glass slide, allowed in-situ photomicroscopy. Areal particle densities and airflow velocities were selected to provide relevant loadings and flow velocities for a range of potential applications. For a chemical of interest, we define the radial sublimation velocity (RSV) for the equivalent sphere of a particle as the parameter to characterize the sublimation rate. The RSV is a useful parameter because it is independent of particle size. The sublimation rate for an ensemble of particles was found to significantly depend on airflow velocity, the areal density of the particles, and the particle field size. To compare sublimation studies these parameters must be known.

Laser induced Raman scattering from the commonly used chemical warfare agent simulants dimethyl sulfoxide, tributyl phosphate, triethyl phosphonoacetate was measured at excitation wavelengths ranging from 210 to 410 nm using a pulsed laser based spectrometer system with a probing distance of 1.4 m and with a field of view on the target of less than 1mm. For the purpose of comparison with well explored reference liquids the Raman scattering from simulants was measured in the form of an extended liquid surface layer on top of a silicon wafer. This way of measuring enabled direct comparison to the Raman scattering strength from cyclohexane. The reference Raman spectra were used to validate the signal strength of the simulants and the calibration of the experimental set up. Measured UV absorbance functions were used to calculate Raman cross sections. Established Raman cross sections of the simulants make it possible to use them as reference samples when measuring on chemical warfare agents in droplet form.

Photoacoustic spectroscopy (PAS) is a versatile tool that is well suited for the ranged interrogation of layered samples. We have previously demonstrated standoff photoacoustic (PA) chemical detection of condensed phase samples at one meter distance using an interferometric sensing platform. Current research investigates layered solid samples constructed from a thin layer of energetic material deposited on a substrate. The PA signal from the system, as measured by the interferometer, changes based on the differing optical and mechanical properties of the substrate. This signal variance must be understood in order to develop a sensor capable of detecting trace quantities of hazardous materials independent of the surface. Optical absorption and modal excitation are the two biggest sources of PA signal generated in the sample/substrate system. Finally, the mode of operation of the excitation source is investigated. Most PA sensing paradigms use a quantum cascade laser (QCL) operating in either pulsed or modulated CW mode. We will discuss photoacoustic signal generation with respect to these different operating modes.

The defense of the US armed forces against chemical and biological (CB) attack is transitioning from a focus on standoff detection of these threats to the concept of Early Warning (EW). In this approach an array of dual-use and low-burden dedicated use sensor capabilities are used to replace longer-range single use sensors to detect a CB attack. In this paper we discuss the use of passive broadband thermal imaging to detect chemical vapor clouds as well as a developing suite of compact UAV-borne chemical and radiological sensors for the investigation of threats detected by these indirect approaches. The sensors include a colorimetric ammonia sensor, a chemical sensor based on ion mobility spectrometry, and a radiation detector based on gamma ray scintillation. The implementation and initial field tests of each of these sensor modalities is discussed and future plans for the further development of the capability is presented.

Raman spectroscopy is a powerful tool for obtaining molecular structure information of a sample. While Raman spectroscopy is a common laboratory based analytical tool, miniaturization of opto-electronic components has allowed handheld Raman analyzers to become commercially available. These handheld systems are utilized by Military and First Responder operators tasked with rapidly identifying potentially hazardous chemicals in the field. However, one limitation of many handheld Raman detection systems is strong interference caused by fluorescence of the sample or underlying surface which obscures the characteristic Raman signature of the target analyte. Munitions grade chemical warfare agents (CWAs) are produced and stored in large batches and typically have more impurities from the storage container, degradation, or unreacted precursors. In this work, Raman spectra of munitions grade CWAs were collected using a handheld Raman spectrometer with a 1064 nm excitation laser. While Raman scattering generated by a 1064 nm laser is inherently less efficient than excitation at shorter wavelengths, high quality spectra were easily obtained due to significantly reduced fluorescence of the munitions grade CWAs. The spectra of these less pure, but more operationally relevant, munitions grade CWAs were then compared to spectra of CASARM grade CWAs, as well as Raman spectra collected using the more common 785 nm excitation laser.

Recently, microcantilever-based technology has emerged as a viable sensing platform due to its many advantages such as small size, high sensitivity, and low cost. However, microcantilevers lack the inherent ability to selectively identify hazardous chemicals (e.g., explosives, chemical warfare agents). The key to overcoming this challenge is to functionalize the top surface of the microcantilever with a receptor material (e.g., a polymer coating) so that selective binding between the cantilever and analyte of interest takes place. Molecularly imprinted polymers (MIPs) can be utilized as artificial recognition elements for target chemical analytes of interest. Molecular imprinting involves arranging polymerizable functional monomers around a template molecule followed by polymerization and template removal. The selectivity for the target analyte is based on the spatial orientation of the binding site and covalent or noncovalent interactions between the functional monomer and the analyte. In this work, thin films of sol-gel-derived xerogels molecularly imprinted for TNT and dimethyl methylphosphonate (DMMP), a chemical warfare agent stimulant, have demonstrated selectivity and stability in combination with a fixed-fixed beam microelectromechanical systems (MEMS)-based gas sensor. The sensor was characterized by parametric bifurcation noise-based tracking.

There is a need for rapid and accurate detection and identification of complex aerosol particles in a number of fields for countless applications. Full identification of these particles has been hampered by the inability to use an information-rich spectroscopic method such as Raman scattering in a flowing aerosol environment due to the time needed to generate a Raman spectrum. Multiplex coherent anti-Stokes Raman spectroscopy (MCARS) has been shown to generate a complete Raman spectrum from the material of interest using a single ultrabroadband pulse to coherently drive multiple molecular vibrations simultaneously. When used in conjunction with a narrow probe pulse, a complete Raman spectrum is created that can be detected in milliseconds. We will report on the MCARS spectra obtained from materials of interest at a distance of 1 m from the sample location. A limit of detection study of the MCARS spectrum of various materials of interest will be also reported in with the nonresonant background both present and removed. Additionally, a limit of detection study as a function of the number of pulses used to comprise the CARS spectrum of the materials of interest will be presented.

Differential Excitation Spectroscopy (DES) is a new pump-probe detection technique (patent-pending) which characterizes molecules based on a multi-dimensional parameterization of the rovibrational excited state structure, pump and probe interrogation frequencies, as well as the lifetimes of the excited states. Under appropriate conditions, significant modulation of the ground state can result. DES results provide a unique, simple mechanism to probe various molecules. In addition, the DES multi-dimensional parameterization provides an identification signature that is highly unique and has demonstrated high levels of immunity from interferents, providing significant practical value for highspecificity material identification. Dimethyl methylphosphonate (DMMP) is used as a simulant for G series nerve agents and thiodiglycol as a simulant for sulfur mustard (HD). Ab initio calculations were performed on DMMP for various rovibrational states up to J’ ≤ 3 and validated experimentally, demonstrating good agreement between theory and experiment and the very specific responses generated. Thiodiglycol was investigated empirically. Optimal detection parameters were determined and mixtures of the two materials were used to demonstrate the immunity of the DES technique to interference from other materials, even those whose IR spectra show significant overlap.

Over the past several years we have developed a photo-acoustic spectroscopic (PAS) technique for trace gas detection that is capable of parts per trillion (ppt) detection limits. The desire to reduce the size of the system has led to several efforts that have reduced the size of the various components of the system. We have reduced the dimensions of the resonant cell to micrometer scale (MEMS). We have worked with Daylight Solutions to reduce the size of the tunable quantum cascade laser (QCL) used in the system. In this paper we demonstrate the reduction in size of the entire system to a 12” x 12” footprint. We do this by implementing the lock-in amplifier on a field programmable gate array (FPGA) demonstration board that is also capable of acting as the system controller and data output device. We briefly describe the digital lock-in amplifier and sketch our implementation on the FPGA. We go on to compare the spectroscopic data we collected using this system with data we collected using a large rack mounted Stanford Research Systems SR830 lock-in amplifier and a PC.