Multi-spectral SWIR lidar for imaging and spectral discrimination through partial obscurations.

We have developed a multi-spectral SWIR lidar system capable of measuring simultaneous spatial-spectral information for imaging and spectral discrimination through partial obscurations. We employ objects in the presence and absence of a series of obscurants to evaluate the capability of the system in classifying the objects of interest based on spectral and range information. We employ a principal component analysis-based algorithm in classifying the objects and quantifying the accuracy of detection under various obscured scenarios. The merits of multi-spectral lidar over hyperspectral imaging are highlighted for target identification in the presence of obscurants.

Surface-Enhanced Raman Spectroscopy for Environmental Monitoring of Aerosols.

Surface-enhanced Raman spectroscopy (SERS) is conducted from single aerosol particles held in a linear electrodynamic quadrupole trap. SERS measurements from two representative types of ambient aerosol particles, semi-liquid and solid aerosols, are demonstrated; aerosol composed of adenine where the metallic nanoparticles (MNPs) are volume distributed throughout the particle and aerosol composed of polystyrene latex (PSL) beads where the MNPs are surface coated. An enhancement factor > 106 is demonstrated from 5 µm aerosols containing trace amounts of adenine (0.1% by mass), with a detection limit of 10-8 M corresponding to 5 × 105 molecules (equivalent to 100 ag in mass or a 50 nm diameter sphere), and a ratio of 100 adenine molecules per Ag NP. SERS signal intensities are linear with particle adenine concentration up to a saturation point. Both the linearity and enhancement factor were confirmed by SERS measurements of adenine as bulk suspensions. The SERS spectra of adenine as bulk suspensions were explored as a function of excitation wavelength ranging from 400 to 800 nm. The two main Raman peaks of adenine at 738 and 1336 cm-1 exhibit SERS maxima for excitation in the 450-500 nm range for commercially available 40 nm spherical Ag nanoparticles (NPs) used in this study, which shifts to longer wavelengths with the addition of NaCl. Shifts in SERS and spontaneous Raman shifts were observed between aqueous and dry adenine, in agreement with the literature, demonstrating the utility of SERS to possibly study water uptake of aerosols. SERS is measured from MNP surface-coated PSL beads with an enhancement factor of 30 for 5 µm PSLs. Theoretical extrapolation demonstrates that the enhancement factor will increase for decreasing particle size with an estimated enhancement factor of 140 for 1 µm PSLs.

Optical measurements from single levitated particles using a linear electrodynamic quadrupole trap.

We have recently made advancements in a linear electrodynamic quadrupole (LEQ) device for capturing and levitating either single or multiple micro-particles that provides significant improvements in capture efficiency, reliability, and optical measurement access. We have used our LEQ to trap particles ranging from 30 to less than 0.5 µm in size and provide a controlled environment to study particle physical/chemical dependencies on temperature, relative humidity, and gas constituents. To demonstrate this approach, we present data and analysis of liquid-droplet evaporation rates for two materials: glycerol and dibutyl sebacate. Droplet size was monitored as a function of time by two independent optical methods: direct imaging and fixed-angle light scattering. This new approach provides a means to rapidly characterize a wide range of aerosol particle properties and a platform for development of new aerosol optical-diagnostic measurements.

Metallic-nanoparticles-enhanced fluorescence from individual micron-sized aerosol particles on-the-fly.

Fluorescence spectra from individual aerosol particles that were either coated or embedded with metallic nanoparticles (MNPs) was acquired on-the-fly using 266 nm and 355 nm excitation. Using aqueous suspensions of MNPs with either polystyrene latex (PSL) spheres or dissolved proteins (tryptophan or ovalbumin), we generated PSL spheres coated with MNPs, or protein clusters embedded with MNPs as aerosols. Both enhanced and quenched fluorescence intensities were observed as a function of MNP concentration. Optimizing MNP material, size and spacing should yield enhanced sensitivity for specific aerosol materials that could be exploited to improve detection limits of single-particle, on-the-fly fluorescence or Raman based spectroscopic sensors.

Continuous flow, explosives vapor generator and sensor chamber.

A novel liquid injection vapor generator (LIVG) is demonstrated that is amenable to low vapor pressure explosives, 2,4,6-trinitrotoluene and hexahydro-1,3,5-trinitro-1,3,5-triazine. The LIVG operates in a continuous manner, providing a constant and stable vapor output over a period of days and whose concentration can be extended over as much as three orders of magnitude. In addition, a large test atmosphere chamber attached to the LIVG is described, which enables the generation of a stable test atmosphere with controllable humidity and temperature. The size of the chamber allows for the complete insertion of testing instruments or arrays of materials into a uniform test atmosphere, and various electrical feedthroughs, insertion ports, and sealed doors permit simple and effective access to the sample chamber and its vapor.

Generation and optical characterization of aerosol particles with controlled mixed composition.

A method for controlled generation of composite aerosol particles is achieved by coating a core particle material, such as glass or polymer beads, with a second (analyte) material on the core surface. The mass fraction of the analyte can be varied over a wide range to generate resultant composite aerosol particles, which for the low end of analyte mass fractions has little influence on the particle size, but can be varied up to mass fractions nearly equivalent to the core material, as demonstrated in this paper. Analysis of this method was carried out using fluorescent analyte and core particle materials in separable spectral bands to measure both particle size distributions and fluorescent emission distributions on individual particle basis.

Spectral characterization of biological aerosol particles using two-wavelength excited laser-induced fluorescence and elastic scattering measurements.

A two-wavelength laser-induced fluorescence (LIF) instrument has been developed and used to characterize individual biological aerosol particles, including biological warfare (BW) agent surrogates. Fluorescence in discrete spectral bands from widely different species, and also from similar species under different growth conditions were measured and compared. The two-wavelength excitation approach was found to increase discrimination among several biological materials, and especially with respect to diesel exhaust particles, a common interferent for LIF BW detection systems. The spectral characteristics of a variety of biological materials and ambient air components have been studied as a function of aerosol particle size and incident fluence.

Green and ultraviolet pulse generation with a compact, fiber laser, chirped-pulse amplification system for aerosol fluorescence measurements.

We use a compact chirped-pulse amplified system to harmonically generate ultrashort pulses for aerosol fluorescence measurements. The seed laser is a compact, all-normal dispersion, mode-locked Yb-doped fiber laser with a 1050 nm center wavelength operating at 41 MHz. Average powers of more than 1.2 W at 525 nm and 350 mW at 262 nm are generated with <500 fs pulse durations. The pulses are time-stretched with high-dispersion fiber, amplified by a high-power, large-mode-area fiber amplifier, and recompressed using a chirped volume holographic Bragg grating. The resulting high-peak-power pulses allow for highly efficient harmonic generation. We also demonstrate for the first time to our knowledge, the use of a mode-locked ultraviolet source to excite individual biological particles and other calibration particles in an inlet air flow as they pass through an optical chamber. The repetition rate is ideal for biofluorescence measurements as it allows faster sampling rates as well as the higher peak powers as compared to previously demonstrated Q-switched systems while maintaining a pulse period that is longer than the typical fluorescence lifetimes. Thus, the fluorescence excitation can be considered to be quasicontinuous and requires no external synchronization and triggering.

Classification and selective collection of individual aerosol particles using laser-induced fluorescence.

We describe the development and performance evaluation of a system for optical interrogation, subsequent selection, and collection of individual aerosol particles entrained in an inlet air stream. Elastic scatter and laser-induced fluorescence obtained from single particles on-the-fly provide compositional information for classification criteria. Individual particles could then be selectively electrically charged and captured to a conductive substrate with an electric potential. The optical subsystem also includes a novel two-beam velocimeter to provide accurate downstream timing. Good overall quantitative performance values are reported for particles in the size range of 1-8 microm at mean rates up to 4 kHz.

Multiple UV wavelength excitation and fluorescence of bioaerosols.

A two-wavelength laser-induced fluorescence technique is described for detecting and classifying biological aerosols. Single aerosols, smaller than 10 mm, are interrogated with 266 nm and 355 nm laser pulses separated in time by 400 ns. Fluorescence signals excited by these pulses are detected in three broad spectral bands centered at 350 nm, 450 nm and 550 nm. The results indicate that bacterial spores, vegetative bacterial cells and proteins can be differentiated based on the two wavelength excitation approach. Estimates of the fluorescence cross sections for 16 bioaerosol simulants and interferents are presented.

Tunable ultraviolet laser-induced fluorescence detection of trace plastics and dissolved organic compounds in water.

We developed a tunable (220-285-nm) UV and fixed 266-nm laser-induced fluorescence (LIF) system using a spectrometer and a cooled CCD imaging detector to measure the excitation-emission matrix spectra of various compounds in water, including quinine sulfate and plastic compound bisphenol-A. The LIF instrument was used for the fast, nonspecific determination of trace amounts of dissolved organic compounds present in natural water supplies and various brand name bottled distilled water and bottled drinking water. Plastic-related compounds that leached out of plastic utensils and containers were also detected with this instrument. The sensitivity of the system was approximately 1-2 orders of magnitude better than that for a commercial system.

Development and initial calibration of a portable laser-induced fluorescence system used for in situ measurements of trace plastics and dissolved organic compounds in seawater and the Gulf of Mexico.

A portable UV laser-induced fluorescence system that uses a high pulsed repetition frequency (8-kHz) microchip laser at 266 nm, 13 switchable optical filters, and a gated photomultiplier tube detector has been developed and tested successfully for the detection of leached plastics (possibly bisphenol-A) and trace dissolved organic compounds in seawater. The instrument is 100 times more sensitive than commercial portable spectrofluorometers and measures a complete fluorescence spectrum in a moderate time period of 1-2 min. The system was tested in the Gulf of Mexico over varying water masses. In addition, fluorescence lifetime, bleaching, and temporal flow characteristics were studied.