David E. Bates

Single-pulse standoff Raman detection of chemicals from 120 m distance during daytime.

The capability to analyze and detect the composition of distant samples (minerals, organics, and chemicals) in real time is of interest for various fields including detecting explosives, geological surveying, and pollution mapping. For the past 10 years, the University of Hawaii has been developing standoff Raman systems suitable for measuring Raman spectra of various chemicals in daytime or nighttime. In this article we present standoff Raman spectra of various minerals and chemicals obtained from a distance of 120 m using single laser pulse excitation during daytime. The standoff Raman system utilizes an 8-inch Meade telescope as collection optics and a frequency-doubled 532 nm Nd: YAG laser with pulse energy of 100 mJ/pulse and pulse width of 10 ns. A gated intensified charge-coupled device (ICCD) detector is used to measure time-resolved Raman spectra in daytime with detection time of 100 ns. A gate delay of 800 ns (equivalent to target placed at 120 m distance) was used to minimize interference from the atmospheric gases along the laser beam path and near-field scattering. Reproducible, good quality single-shot Raman spectra of various inorganic and organic chemicals and minerals such as ammonium nitrate, potassium perchlorate, sulfur, gypsum, calcite, benzene, nitrobenzene, etc., were obtained through sealed glass vials during daytime. The data indicate that various chemicals could easily be identified from their Raman fingerprint spectra from a far standoff distance in real time using single-shot laser excitation.

Remote-Raman spectroscopic study of minerals under supercritical CO2 relevant to Venus exploration.

The authors have utilized a recently developed compact Raman spectrometer equipped with an 85 mm focal length (f/1.8) Nikon camera lens and a custom mini-ICCD detector at the University of Hawaii for measuring remote Raman spectra of minerals under supercritical CO(2) (Venus chamber, ∼102 atm pressure and 423 K) excited with a pulsed 532 nm laser beam of 6 mJ/pulse and 10 Hz. These experiments demonstrate that by focusing a frequency-doubled 532 nm Nd:YAG pulsed laser beam with a 10× beam expander to a 1mm spot on minerals located at 2m inside a Venus chamber, it is possible to measure the remote Raman spectra of anhydrous sulfates, carbonates, and silicate minerals relevant to Venus exploration during daytime or nighttime with 10s integration time. The remote Raman spectra of gypsum, anhydrite, barite, dolomite and siderite contain fingerprint Raman lines along with the Fermi resonance doublet of CO(2). Raman spectra of gypsum revealed dehydration of the mineral with time under supercritical CO(2) at 423 K. Fingerprint Raman lines of olivine, diopside, wollastonite and α-quartz can easily be identified in the spectra of these respective minerals under supercritical CO(2). The results of the present study show that time-resolved remote Raman spectroscopy with a compact Raman spectrometer of moderate resolution equipped with a gated intensified CCD detector and low power laser source could be a potential tool for exploring Venus surface mineralogy both during daytime and nighttime from a lander.

Compact remote Raman and LIBS system for detection of minerals, water, ices, and atmospheric gases for planetary exploration

At the University of Hawaii, we have developed a compact, portable remote Raman and Laser-Induced Breakdown Spectroscopy (LIBS) system with a 532 nm pulsed laser for planetary exploration under the Mars Instrument Development Program. The compact time-resolved remote Raman and LIBS system consists of (i) a regular 85 mm Nikon (F/1.8) camera lens with clear aperture of 50 mm as collection optics, (ii) a miniature spectrograph that occupies 1/14th the volume of a comparable commercial spectrograph from Kaiser Optical Systems Inc., (iii) a custom mini-ICCD detector, and (iv) a small frequency-doubled 532 nm Nd:YAG pulsed laser (30 mJ/pulse, 20 Hz) with a 10x beam expander. In the standoff Raman mode the system is capable of measuring various minerals, water, ices, and atmospheric gases from a 50 meter range with a 10 s integration time. At shorter distances of 10 m or less, good quality Raman spectra can be obtained within 1 s. The time-gated system is capable of detecting both the target mineral as well as the atmospheric gases before the target using their Raman fingerprints. Various materials can easily be identified through glass, plastic, and water media. The time-gating capability makes the system insensitive to window material, which is highly desirable for future missions to Venus where instruments are expected to be within the lander. The standoff LIBS range is 10 m and LIBS spectra of various minerals can be obtained with single laser pulse excitation. The standoff LIBS capability provides additional elemental verification of the targeted material.

Compact standoff Raman system for detection of homemade explosives

We present data on standoff detection of chemicals used in synthesis of homemade explosives (HME) using a compact portable standoff Raman system developed at the University of Hawaii. Data presented in this article show that good quality Raman spectra of various organic and inorganic chemicals, including hazardous chemicals such as ammonium nitrate, potassium nitrate, potassium perchlorate, sulfur, nitrobenzene, benzene, acetone, and gasoline, can be easily obtained from remote distances with a compact standoff Raman system utilizing only a regular 85 mm Nikon camera lens as collection optics. Raman spectra of various chemicals showing clear Raman fingerprints obtained from targets placed at 50 m distance in daylight with 1 to 10 second of integration time are presented in this article. A frequency-doubled mini Nd:YAG pulsed laser source (532 nm, 30 mJ/pulse, 20 Hz, pulse width 8 ns) is used in an oblique geometry to excite the target located at 50 m distance. The standoff Raman system uses a compact spectrograph of size 10 cm (length) × 8.2 cm (width) × 5.2 cm (height) with spectral coverage from 100 to 4500 cm-1 Stokes-Raman shifted from 532 nm laser excitation and is equipped with a gated thermo-electrically cooled ICCD detector. The system is capable of detecting both the target as well as the atmospheric gases before the target. Various chemicals could be easily identified through glass, plastic, and water media. Possible applications of the standoff Raman system for homeland security and environmental monitoring are discussed.

Portable standoff Raman system for fast detection of homemade explosives through glass, plastic, and water

The University of Hawaii has been developing portable remote Raman systems capable of detecting chemicals in daylight from a safe standoff distance. We present data on standoff detection of chemicals used in the synthesis of homemade explosives (HME) using a portable standoff Raman system utilizing an 8-inch telescope. Data show that good-quality Raman spectra of various hazardous chemicals such as ammonium nitrate, potassium nitrate, potassium perchlorate, sulfur, nitrobenzene, benzene, acetone, various organic and inorganic chemicals etc. could be easily obtained from remote distances, tested up to 120 meters, with a single-pulse laser excitation and with detection time less than 1 μs. The system uses a frequency-doubled Nd:YAG pulsed laser source (532 nm, 100 mJ/pulse, 15 Hz, pulse width 10 ns) capable of firing a single or double pulse. The double-pulse configuration also allows the system to perform standoff LIBS (Laser-Induced Breakdown Spectroscopy) at 50 m range. In the standoff Raman detection, the doublepulse sequence simply doubles the signal to noise ratio. Significant improvement in the quality of Raman spectra is observed when the standoff detection is made with 1s integration time. The system uses a 50-micron slit and has spectral resolution of 8 cm-1. The HME chemicals could be easily detected through clear and brown glass bottles, PP and HDPE plastic bottles, and also through fluorescent plastic water bottles. Standoff Raman detection of HME chemical from a 10 m distance through non-visible concealed bottles in plastic bubble wrap packaging is demonstrated with 1 s integration time. Possible applications of the standoff Raman system for homeland security and environmental monitoring are discussed.

Scanning time-resolved standoff Raman instrument for large-area mineral detection on planetary surfaces

A S canning St andoff R aman S pectroscopy (SSTRS) system has been developed to map out the spatial distributions of selected minerals at long distances (10–100 m). The SSTRS is based on a standoff Raman system, which is mounted inside a custom pan and tilt scanner. Computer software is used to control the direction of the pan-tilt scanner and to point the laser beam onto the distant samples. Measurements are made in an x-y grid pattern on a target area defined by the user. The Raman spectra collected at each grid point are processed to identify the distribution of minerals present from their respective Raman fingerprints. In the initial experiment, the Raman spectra of barite (BaSO 4 ), gypsum (CaSO 4 ·2H 2 O), plagioclase feldspar (solid solution of NaAlSi 3 O 8 -CaAl 2 Si 2 O 8 ), α -quartz ( α -SiO 2 ) rocks, and silica glass were measured at 30 m distance. The Raman spectra at the grid points are measured and processed to obtain a Raman mineral image of the distant minerals by selecting respective Raman fingerprints of α -quartz, gypsum and plagioclase feldspar. The ability to provide interpolated Raman images of distant mineral species is illustrated. The new SSTRS system works well and now offers the ability to obtain spatial distribution maps of distant mineral species from their Raman fingerprints.

Lidar, sun photometer and polar nephelometer measurements: Remote sensing of aerosol size distribution properties

We are developing new sensors to measure aerosols using lidar, automated Sun photometers, and in situ polar nephelometers. The lidar measurements are based on a ground system using a 532 nm laser. The sun photometer are based on a custom Sun tracking design. The aerosol phase function measurements are based on a custom polar nephelometer system developed at the University of Hawaii. Results from our first joint field experiment using these new systems will be discussed.

Raman discrimination of bacterial strains using multilayered microcavity substrates

Surface-enhanced Raman scattering (SERS) utilizing colloidal silver and gold has been demonstrated to provide a rapid means of measuring the Raman spectra of microorganisms in the fingerprint region. In this study, we have introduced microcavity substrates coated with alternating layers of silver and gold thin films for measuring the Raman spectra of four strains of E. coli. These microcavitiy substrates have been prepared by placing glass microspheres between two polished aluminum substrates and pressing them together using a standard lab press. After removing the glass microspheres from the substrates, the substrates have been coated with 15 to 70 nm thick films of chromium, silver and gold in a precise order. The cavities were evaluated for SERS enhancement by measuring Raman spectra of dilute rhodamine 6G (R6G) down to 10-8 M. With these microcavities, we have investigated the SERS spectra of four chemically competent strains of E. coli (One Shot OmniMAX 2-T1, Mach1-T1, Stbl3, and TOP10). Replicate SERS spectra of all the four e-coli strains show excellent reproducibility. Visual examination of the spectra, however, reveals differences in the spectra of these strains. To confirm this observation, we have used multivariate analysis for positive identification and discrimination between the strains.