OrganiCam: a lightweight time-resolved laser-induced luminescence imager and Raman spectrometer for planetary organic material characterization.

OrganiCam is a laser-induced luminescence imager and spectrometer designed for standoff organic and biosignature detection on planetary bodies. OrganiCam uses a diffused laser beam (12° cone) to cover a large area at several meters distance and records luminescence on half of its intensified detector. The diffuser can be removed to record Raman and fluorescence spectra from a small spot from 2 m standoff distance. OrganiCam's small size and light weight makes it ideal for surveying organics on planetary surfaces. We have designed and built a brassboard version of the OrganiCam instrument and performed initial tests of the system.

Remote Raman spectroscopy of natural rocks.

We report the remote Raman spectra of natural igneous, metamorphic, and sedimentary rock samples at a standoff distance of 5 m. High-quality remote Raman spectra of unprepared rocks are necessary for accurate and realistic analysis of future Raman measurements on planetary surfaces such as Mars. Our results display the ability of a portable compact remote Raman system (CRRS) to effectively detect and isolate various light- and dark-colored mineral phases in natural rocks. The CRRS easily detected plagioclase and potassium feldspar end members, quartz, and calcite in rocks with high fluorescence backgrounds. Intermediate feldspars and quartz, when found in rocks with complex mineralogies, exhibited band shifts and broadening in the ${504{-}510}\,\,{{\rm cm}^{ - 1}}$504-510cm-1 and ${600{-}1200}\,\,{{\rm cm}^{ - 1}}$600-1200cm-1 regions. A good approximation of intermediate plagioclase feldspars was possible by using overall Raman spectral shape and assigning other minor Raman peaks in addition to the $ 504{-}510\,\,{{\rm cm}^{ - 1}}$504-510cm-1 peaks. Detection of olivine and pyroxene in mafic rocks allowed for compositional characterization.

Standoff ultracompact micro-Raman sensor for planetary surface explorations.

We report the development of an innovative standoff ultracompact micro-Raman instrument that would solve some of the limitations of traditional micro-Raman systems to provide a superior instrument for future NASA missions. This active remote sensor system, based on a 532 nm laser and a miniature spectrometer, is capable of inspection and identification of minerals, organics, and biogenic materials within several centimeters (2-20 cm) at a high 10 µm resolution. The sensor system is based on inelastic (Raman) light scattering and laser-induced fluorescence. We report on micro-Raman spectroscopy development and demonstration of the standoff Raman measurements by acquiring Raman spectra in daylight at a 10 cm target distance with a small line-shaped laser spot size of 17.3 µm (width) by 5 mm (height).

Remote Raman measurements of minerals, organics, and inorganics at 430 m range.

Raman spectroscopy is a characterization technique that is able to analyze and detect water or water-bearing minerals, minerals, and organic materials that are of special interest for planetary science. Using a portable pulsed remote Raman system with a commercial 8 in. (203.2 mm) telescope, a frequency doubled Nd-YAG-pulsed laser, and a spectrometer equipped with an intensified CCD camera, we acquired good quality Raman spectra of various materials from a 430 m standoff distance during daylight with detection times of 1-10 s, in a realistic context in which both the exciting source and the detector are part of the same measurement system. Remote Raman spectra at this distance provided unambiguous detection of compounds such as water and water ice, dry ice, sulfur, sulfates, various minerals and organics, and atmospheric gases. This research work demonstrates significant improvement in the remote Raman technique as well as its suitability for solar system exploration.

Mineralogy and astrobiology detection using laser remote sensing instrument.

A multispectral instrument based on Raman, laser-induced fluorescence (LIF), laser-induced breakdown spectroscopy (LIBS), and a lidar system provides high-fidelity scientific investigations, scientific input, and science operation constraints in the context of planetary field campaigns with the Jupiter Europa Robotic Lander and Mars Sample Return mission opportunities. This instrument conducts scientific investigations analogous to investigations anticipated for missions to Mars and Jupiter's icy moons. This combined multispectral instrument is capable of performing Raman and fluorescence spectroscopy out to a >100 m target distance from the rover system and provides single-wavelength atmospheric profiling over long ranges (>20 km). In this article, we will reveal integrated remote Raman, LIF, and lidar technologies for use in robotic and lander-based planetary remote sensing applications. Discussions are focused on recently developed Raman, LIF, and lidar systems in addition to emphasizing surface water ice, surface and subsurface minerals, organics, biogenic, biomarker identification, atmospheric aerosols and clouds distributions, i.e., near-field atmospheric thin layers detection for next robotic-lander based instruments to measure all the above-mentioned parameters.

High-sensitivity Raman spectrometer to study pristine and irradiated interstellar ice analogs.

We discuss the novel design of a sensitive, normal-Raman spectrometer interfaced to an ultra-high vacuum chamber (5 × 10(-11) Torr) utilized to investigate the interaction of ionizing radiation with low temperature ices relevant to the solar system and interstellar medium. The design is based on a pulsed Nd:YAG laser which takes advantage of gating techniques to isolate the scattered Raman signal from the competing fluorescence signal. The setup incorporates innovations to achieve maximum sensitivity without detectable heating of the sample. Thin films of carbon dioxide (CO2) ices of 10 to 396 nm thickness were prepared and characterized using both Fourier transform infrared (FT-IR) spectroscopy and HeNe interference techniques. The ν+ and ν- Fermi resonance bands of CO2 ices were observed by Raman spectroscopy at 1385 and 1278 cm(-1), respectively, and the band areas showed a linear dependence on ice thickness. Preliminary irradiation experiments are conducted on a 450 nm thick sample of CO2 ice using energetic electrons. Both carbon monoxide (CO) and the infrared inactive molecular oxygen (O2) products are readily detected from their characteristic Raman bands at 2145 and 1545 cm(-1), respectively. Detection limits of 4 ± 3 and 6 ± 4 monolayers of CO and O2 were derived, demonstrating the unique power to detect newly formed molecules in irradiated ices in situ. The setup is universally applicable to the detection of low-abundance species, since no Raman signal enhancement is required, demonstrating Raman spectroscopy as a reliable alternative, or complement, to FT-IR spectroscopy in space science applications.

Biofinder detects biological remains in Green River fish fossils from Eocene epoch at video speed.

The "Search for life", which may be extinct or extant on other planetary bodies is one of the major goals of NASA planetary exploration missions. Finding such evidence of biological residue in a vast planetary landscape is an enormous challenge. We have developed a highly sensitive instrument, the "Compact Color Biofinder", which can locate minute amounts of biological material in a large area at video speed from a standoff distance. Here we demonstrate the efficacy of the Biofinder to detect fossils that still possess strong bio-fluorescence signals from a collection of samples. Fluorescence images taken by the Biofinder instrument show that all Knightia spp. fish fossils analysed from the Green River formation (Eocene, 56.0-33.9 Mya) still contain considerable amounts of biological residues. The biofluorescence images support the fact that organic matter has been well preserved in the Green River formation, and thus, not diagenetically replaced (replaced by minerals) over such a significant timescale. We further corroborated results from the Biofinder fluorescence imagery through Raman and attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopies, scanning electron microscopy, energy dispersive X-ray spectroscopy (SEM-EDS), and fluorescence lifetime imaging microscopy (FLIM). Our findings confirm once more that biological residues can survive millions of years, and that using biofluorescence imaging effectively detects these trace residues in real time. We anticipate that fluorescence imaging will be critical in future NASA missions to detect organics and the existence of life on other planetary bodies.

Enhancement of the Anti-Stokes Fluorescence of Hollow Spherical Carbon Nitride Nanostructures by High Intensity Green Laser.

Fluorescence spectra of graphitic (g-C3N4) and spherical (s-C3N4) modifications of carbon nitride were measured as a function of green pulsed (6 ns-pulse) laser intensity. It was found that the intensity of the laser increases the maximum of the fluorescence shifts towards the anti-Stokes side of the fluorescence for s-C3N4 spherical nanoparticles. This phenomenon was not observed for g-C3N4 particles. The maximum of the anti-Stokes fluorescence in s-C3N4 nanoparticles was observed at 480 nm. The ratio of the intensity of the anti-Stokes peak (centered at 480 nm) to that of the Stokes peak (centered at 582 nm) was measured to be I484/582 = 6.4 × 10-3 at a low level of intensity (5 mW) of a green pulsed laser, whereas it rose to I484/582 = 2.27 with a high level of laser intensity (1500 mW).

Detecting Minerals and Organics Relevant to Planetary Exploration Using a Compact Portable Remote Raman System at 122 Meters.

Raman spectroscopy is a technique that can detect and characterize a range of molecular compounds such as water, water ice, water-bearing minerals, and organics of particular interest to planetary science. The detection and characterization of these molecular compounds, which are indications of habitability on planetary bodies, have become an important goal for planetary exploration missions spanning the solar system. Using a compact portable remote Raman system consisting of a 532 nm neodymium-doped yttrium aluminum garnet- (Nd:YAG-) pulsed laser, a 3-in. (7.62 cm) diameter mirror lens and a compact spectrograph with a miniature intensified charge coupled device (mini-ICCD), we were able to detect water (H2O), water ice (H2O-ice), CO2-ice, hydrous minerals, organics, nitrates, and an amino acid from a remote distance of 122 m in natural lighting conditions. To the best of our knowledge, this is the longest remote Raman detection using a compact system. The development of this uniquely compact portable remote Raman system is applicable to a range of solar system exploration missions including stationary landers for ocean worlds and lunar exploration, as they provide unambiguous detection of compounds indicative of life as well as resources necessary for further human exploration.

Underwater Time-Gated Standoff Raman Sensor for In Situ Chemical Sensing.

We describe the fabrication of an underwater time-gated standoff Raman sensor, consisting of a custom Raman spectrometer, custom scanner, and commercial diode-pumped pulsed 532 nm laser all located inside a pressure housing. The Raman sensor was tested in the laboratory with samples in air, a tank containing tap water and seawater, and in the coastal Hawaiian harbor. We demonstrate our new system by presenting standoff Raman spectra of some of the chemicals used in homemade explosive devices and improvised explosive devices, including sulfur, nitrates, chlorates, and perchlorates up to a distance of ∼6 m in seawater and tap water. Finally, the Raman spectra of these hazardous chemicals sealed inside plastic containers submersed in the Hawaiian Harbor water are also presented.

Compact Color Biofinder (CoCoBi): Fast, Standoff, Sensitive Detection of Biomolecules and Polyaromatic Hydrocarbons for the Detection of Life.

We have developed a compact instrument called the "COmpact COlor BIofinder", or CoCoBi, for the standoff detection of biological materials and organics with polyaromatic hydrocarbons (PAHs) using a nondestructive approach in a wide area. The CoCoBi system uses a compact solid state, conductively cooled neodymium-doped yttrium aluminum garnet (Nd:YAG) nanosecond pulsed laser capable of simultaneously providing two excitation wavelengths, 355 and 532 nm, and a compact, sensitive-gated color complementary metal-oxide-semiconductor camera detector. The system is compact, portable, and determines the location of biological materials and organics with PAHs in an area 1590 cm2 wide, from a target distance of 3 m through live video using fast fluorescence signals. The CoCoBi system is highly sensitive and capable of detecting a PAH concentration below 1 part per billion from a distance of 1 m. The color images provide the simultaneous detection of various objects in the target area using shades of color and morphological features. We demonstrate that this unique feature successfully detected the biological remains present in a 150-million-year-old fossil buried in a fluorescent clay matrix. The CoCoBi was also successfully field-tested in Hawaiian ocean water during daylight hours for the detection of natural biological materials present in the ocean. The wide-area and video-speed imaging capabilities of CoCoBi for biodetection may be highly useful in future NASA rover-lander life detection missions.

Remote Raman Detection of Chemicals from 1752 m During Afternoon Daylight.

The detection and identification of materials from a distance is highly desirable for applications where accessibility is limited or there are safety concerns. Raman spectroscopy can be performed remotely and provides a very high level of confidence in detection of chemicals through vibrational modes. However, the remote Raman detection of chemicals is challenging because of the very weak nature of Raman signals. Using a remote Raman system, we performed fast remote detection of various solid and liquid chemicals from 1752 m during afternoon hours on a sunny day in Hawaii. Remote Raman systems with kilometer target range could be useful for chemical detection of volcanic gases, methane clathrate icebergs or fire ice, toxic gas clouds and toxic waste, explosives, and hazardous chemicals. With this successful test, we demonstrate the feasibility of developing future mid-size remote Raman systems suitable for long range chemical detection using helicopters and light airplanes.

Novel micro-cavity substrates for improving the Raman signal from submicrometer size materials.

A novel and simple method for improving the detection limit of conventional Raman spectra using a micro-Raman system and picoliter volumes is presented. A micro-cavity in a reflecting metal substrate uses various mechanisms that collectively improve the entire Raman spectrum from the sample. A micro-cavity with a radius of several micrometers acts as a very effective device that provides multiple excitation of the sample with the laser and couples the forward-scattered Raman photons toward the collection optics in the back-scattered Raman geometry. One of the important features of the micro-cavity substrate is that it enhances the entire Raman spectrum of the molecules under investigation and maintains the relative intensity ratios of the various Raman bands. This feature of maintaining the overall integrity of the Raman features during signal enhancement makes the micro-cavity substrate ideal for forensic science applications for chemical detection of residual traces and other applications requiring low sample concentrations. The spectra measured in these cavities are also observed to be highly reproducible and reliable. A simple method for fabricating micro-cavity substrates with precise sizes and shapes is described. It is further shown that micro-cavities coated with nanofilms of gold take advantage of both surface-enhanced Raman scattering (SERS) and micro-cavity methods and also significantly improve sample detection limits.

A Two Components Approach for Long Range Remote Raman and Laser-Induced Breakdown (LIBS) Spectroscopy Using Low Laser Pulse Energy.

The remote detection of chemicals using remote Raman spectroscopy and laser-induced breakdown spectroscopy (LIBS) is highly desirable for homeland security and NASA planetary exploration programs. We recently demonstrated Raman spectra with high signal-to-noise ratio of various materials from a 430 m distance during daylight with detection times of 1-10 s, utilizing a 203 mm diameter telescopic remote Raman system and 100 mJ/pulse laser energy at 532 nm for excitation. In this research effort, we describe a simple two-components approach that helps to obtain remote Raman and LIBS spectra of targets at distance of 246 m with 3 mJ/pulse in daytime. The two components of the method are: (1) a small spectroscopy system utilizing 76 mm diameter collection optics; and (2) a small remote lens near the target. Remote Raman spectra of various chemicals are presented here with detection time of 1 s. Remote LIBS spectra of minerals using single laser pulse of 3 mJ/pulse energy from a distance of 246 m are also presented. This research work demonstrates a simple approach that significantly improves remote Raman and LIBS capabilities for long range chemical detection with compact low laser power Raman and LIBS systems.

Remote Raman Efficiencies and Cross-Sections of Organic and Inorganic Chemicals.

We determined Raman cross-sections of various organic liquids and inorganic polyatomic ions in aqueous solutions with a 532 nm pulsed laser using remote Raman systems developed at the University of Hawaii. Using a calibrated integrating sphere as a light source, we converted the intensity counts in the spectrum of the light from the integrating sphere measured with UH remote Raman instrument to spectral radiance. From these data, a response function of the remote Raman instrument was obtained. With the intensity-calibrated instrument, we collected remote Raman data from a standard 1 mm path length fused silica spectrophotometer cell filled with cyclohexane. The measured value of the differential Raman cross-section for the 801 cm-1 vibrational mode of cyclohexane is 4.55 × 10-30 cm2 sr-1 molecule-1 when excited by a 532 nm laser, in good agreement with the values reported in the literature. Using the measured cyclohexane Raman cross-section as a reference and relative Raman mode intensities of the various ions and organic liquids, we calculated the Raman cross-sections of the strongest Raman lines of nitrate, sulfate, carbonate, phosphate ions, and organic liquids by maintaining same experimental conditions for remote Raman detection. These relative Raman cross-section values will be useful for estimating detection capabilities of remote Raman systems for planetary exploration.

Remote Raman spectroscopic detection of minerals and organics under illuminated conditions from a distance of 10 m using a single 532 nm laser pulse.

Raman spectra of several minerals and organics were obtained from a small portable instrument at a distance of 10 m in a well-illuminated laboratory with a single 532 nm laser pulse with energy of 35 mJ/pulse. Remote Raman spectra of common minerals (dolomite, calcite, marble, barite, gypsum, quartz, anatase, fluorapatite, etc.) obtained in a short period of time (1.1 mus) clearly show Raman features that can be used as fingerprints for mineral identification. Raman features of organics (benzene, cyclohexane, 2-propanol, naphthalene, etc.) and other chemicals such as oxides, silicates, sulfates, nitrates, phosphates, and carbonates were also easily detected. The ability to identify minerals from their Raman spectra obtained from a single laser pulse has promise for future space missions where power consumption is critical. Such a system could be reduced in size by minimizing the cooling requirements for the laser unit. The remote Raman system is also capable of performing time-resolved measurements. Data indicate that further improvement in the performance of the system is possible by reducing the gate width of the detector (ICCD) from 1.1 mus to approximately 20 ns, which would significantly reduce the background signal from daylight or a well-illuminated laboratory. The 1.1 mus signal gating was effective in removing nearly all background fluorescence with 532 nm excitation, indicating that the fluorescence in most minerals is probably from long-lifetime inorganic phosphorescence.

"Standoff Biofinder" for Fast, Noncontact, Nondestructive, Large-Area Detection of Biological Materials for Planetary Exploration.

UNLABELLED: We developed a prototype instrument called the Standoff Biofinder, which can quickly locate biological material in a 500 cm(2) area from a 2 m standoff distance with a detection time of 0.1 s. All biogenic materials give strong fluorescence signals when excited with UV and visible lasers. In addition, the luminescence decay time of biogenic compounds is much shorter (<100 ns) than the micro- to millisecond decay time of transition metal ions and rare-earth ions in minerals and rocks. The Standoff Biofinder takes advantage of the short lifetime of biofluorescent materials to obtain real-time fluorescence images that show the locations of biological materials among luminescent minerals in a geological context. The Standoff Biofinder instrument will be useful for locating biological material during future NASA rover, lander, and crewed missions. Additionally, the instrument can be used for nondestructive detection of biological materials in unique samples, such as those obtained by sample return missions from the outer planets and asteroids. The Standoff Biofinder also has the capacity to detect microbes and bacteria on space instruments for planetary protection purposes. KEY WORDS: Standoff Biofinder-Luminescence-Time-resolved fluorescence-Biofluorescence-Planetary exploration-Planetary protection-Noncontact nondestructive biodetection. Astrobiology 16, 715-729.

Portable remote Raman system for monitoring hydrocarbon, gas hydrates and explosives in the environment.

We report our initial efforts to use a small portable Raman system for stand-off detection and identification of various types of organic chemicals including benzene, toluene, ethyl benzene and xylenes (BTEX). Both fiber-optic (FO) coupled and a directly coupled f/2.2 spectrograph with the telescope have been developed and tested. A frequency-doubled Nd:YAG pulsed laser (20 Hz, 532 nm, 35 mJ/pulse) is used as the excitation source. The operational range of the FO coupled Raman system was tested to 66 m, and the directly coupled system was tested to a distance of 120 m. We have also measured remote Raman spectra of compressed methane gas and methane gas hydrate. The usefulness of the remote Raman system for identifying unknown compounds is demonstrated by measuring stand-off spectra of two plastic explosives, e.g. tri-amino tri-nitrobenzene (TATB) and beta-HMX at 10 m stand-off distance. The remote Raman system will be useful for terrestrial applications such as monitoring environmental pollution, in identifying unknown materials in public places in 10s or less, and for detecting hydrocarbon plumes and gas hydrates on planetary surfaces such as Mars.

Remote Raman and fluorescence studies of mineral samples.

In the present study, we investigated remote laser-induced fluorescence (LIF), at a distance of 4.8 m, of a variety of natural minerals and rocks, and Hawaiian Ti (Cordyline terminalis) plant leaves. These minerals included calcite cleavage, calcite onex and calcite travertine, gypsum, fluorapatite, Dover flint and chalk, chalcedony and nephelene syenite, and rubies containing rock. Pulsed laser excitation of the samples at 355 and 266 nm often resulted in strong fluorescence. The LIF bands in the violet-blue region at approximately 413 and approximately 437 nm were observed only in the spectrum of calcite cleavage. The green LIF bands with band maxima in the narrow range of approximately 501-504 nm were observed in the spectra of all the minerals with the exception of the nephelene syenite and ruby rocks. The LIF red bands were observed in the range approximately 685-711 nm in all samples. Excitation with 532 nm wavelength laser gave broad but relatively low fluorescence background in the low-frequency region of the Raman spectra of these minerals. One microsecond signal gating was effective in removing nearly all background fluorescence (with peak at approximately 610 nm) from calcite cleavage Raman spectra, indicating that the fluorescence was probably from long-lifetime inorganic phosphorescence.

Pulsed remote Raman system for daytime measurements of mineral spectra.

A remote Raman system has been developed utilizing a 532nm pulsed laser and gated intensified charged couple device (ICCD) detector in the oblique geometry. When the system is set for 50m sample distance it is capable of measuring Raman spectra of minerals located at distances in the range of 10-65m from the telescope. Both daytime and nighttime operations are feasible and the spectra of minerals can be measured in a short period of time, of the order of a few seconds. In oblique geometry, measured sampling depth is more than 30m, during which the system maintains very high performance without any adjustments. Much longer sampling depth (0.1-120m) has been observed when the system is configured in the coaxial geometry. Clear advantages of using a gated detection mode over the continuous (CW) mode of operation in reducing the background signal and eliminating long-lived fluorescence signals from the Raman spectra are presented. The performance of the pulsed Raman system is demonstrated by measuring spectra of Raman standards including benzene (C(6)H(6)) and naphthalene (C(10)H(8)), a low Raman cross section silicate mineral muscovite (KAl(2)(Si(3)Al)O(10)(OH)(2)), and a medium Raman cross section mineral calcite (CaCO(3)).