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).

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.

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.

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.

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.

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.

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.

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.

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 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.

"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.

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.

Next generation laser-based standoff spectroscopy techniques for Mars exploration.

In the recent Mars 2020 Rover Science Definition Team Report, the National Aeronautics and Space Administration (NASA) has sought the capability to detect and identify elements, minerals, and most importantly, biosignatures, at fine scales for the preparation of a retrievable cache of samples. The current Mars rover, the Mars Science Laboratory Curiosity, has a remote laser-induced breakdown spectroscopy (LIBS) instrument, a type of quantitative elemental analysis, called the Chemistry Camera (ChemCam) that has shown that laser-induced spectroscopy instruments are not only feasible for space exploration, but are reliable and complementary to traditional elemental analysis instruments such as the Alpha Particle X-Ray Spectrometer. The superb track record of ChemCam has paved the way for other laser-induced spectroscopy instruments, such as Raman and fluorescence spectroscopy. We have developed a prototype remote LIBS-Raman-fluorescence instrument, Q-switched laser-induced time-resolved spectroscopy (QuaLITy), which is approximately 70 000 times more efficient at recording signals than a commercially available LIBS instrument. The increase in detection limits and sensitivity is due to our development of a directly coupled system, the use of an intensified charge-coupled device image detector, and a pulsed laser that allows for time-resolved measurements. We compare the LIBS capabilities of our system with an Ocean Optics spectrometer instrument at 7 m and 5 m distance. An increase in signal-to-noise ratio of at least an order of magnitude allows for greater quantitative analysis of the elements in a LIBS spectrum with 200-300 µm spatial resolution at 7 m, a Raman instrument capable of 1 mm spatial resolution at 3 m, and bioorganic fluorescence detection at longer distances. Thus, the new QuaLITy instrument fulfills all of the NASA expectations for proposed instruments.

Planetary geochemical investigations using Raman and laser-induced breakdown spectroscopy.

An integrated Raman spectroscopy and laser-induced breakdown spectroscopy (LIBS) instrument is a valuable geoanalytical tool for future planetary missions to Mars, Venus, and elsewhere. The ChemCam instrument operating on the Mars Curiosity rover includes a remote LIBS instrument. An integrated Raman-LIBS spectrometer (RLS) based on the ChemCam architecture could be used as a reconnaissance tool for other contact instruments as well as a primary science instrument capable of quantitative mineralogical and geochemical analyses. Replacing one of the ChemCam spectrometers with a miniature transmission spectrometer enables a Raman spectroscopy mineralogical analysis to be performed, complementing the LIBS chemical analysis while retaining an overall architecture resembling ChemCam. A prototype transmission spectrometer was used to record Raman spectra under both Martian and Venus conditions. Two different high-pressure and high-temperature cells were used to collect the Raman and LIBS spectra to simulate surface conditions on Venus. The resulting LIBS spectra were used to generate a limited partial least squares Venus calibration model for the major elements. These experiments demonstrate the utility and feasibility of a combined RLS instrument.

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.

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.

Time-resolved remote Raman study of minerals under supercritical CO2 and high temperatures relevant to Venus exploration.

We report time-resolved (TR) remote Raman spectra of minerals under supercritical CO(2) (approx. 95 atm pressure and 423 K) and under atmospheric pressure and high temperature up to 1003 K at distances of 1.5 and 9 m, respectively. The TR Raman spectra of hydrous and anhydrous sulphates, carbonate and silicate minerals (e.g. talc, olivine, pyroxenes and feldspars) under supercritical CO(2) (approx. 95 atm pressure and 423 K) clearly show the well-defined Raman fingerprints of each mineral along with the Fermi resonance doublet of CO(2). Besides the CO(2) doublet and the effect of the viewing window, the main differences in the Raman spectra under Venus conditions are the phase transitions, the dehydration and decarbonation of various minerals, along with a slight shift in the peak positions and an increase in line-widths. The dehydration of melanterite (FeSO(4).7H(2)O) at 423 K under approximately 95 atm CO(2) is detected by the presence of the Raman fingerprints of rozenite (FeSO(4).4H(2)O) in the spectrum. Similarly, the high-temperature Raman spectra under ambient pressure of gypsum (CaSO(4).2H(2)O) and talc (Mg(3)Si(4)O(10)(OH)(2)) indicate that gypsum dehydrates at 518 K, but talc remains stable up to 1003 K. Partial dissociation of dolomite (CaMg(CO(3))(2)) is observed at 973 K. The TR remote Raman spectra of olivine, alpha-spodumene (LiAlSi(2)O(6)) and clino-enstatite (MgSiO(3)) pyroxenes and of albite (NaAlSi(3)O(8)) and microcline (KAlSi(3)O(8)) feldspars at high temperatures also show that the Raman lines remain sharp and well defined in the high-temperature spectra. The results of this study show that TR remote Raman spectroscopy could be a potential tool for exploring the surface mineralogy of Venus during both daytime and nighttime at short and long distances.