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Surface-Enhanced Raman Spectroscopy (SERS) for Venus Atmospheric Characterization and Trace Organics Identification

The chemical composition of Venus’ clouds has attracted considerable attention since the first atmospheric probes entered the planet in the early 1980s. We know from these early studies that cloud aerosols consist of micron and submicron droplets of sulfuric acid (~85%) and water (~15%), but outstanding questions still exist regarding their trace chemical composition, especially the identity of the unknown UV absorber(s) and the possible presence of organic material (Spacek & Benner, 2021). Veritas and DaVinci will launch at the end of the decade to advance our understanding of Venus’ surface and atmosphere, however these missions are not designed to sample and analyze cloud aerosols at trace levels. Raman spectroscopy is an ideal candidate for characterizing aerosols and has a track record in studies of Earth’s atmosphere. Raman provides broad chemical screening of organic and inorganic molecules within seconds, and Raman instrumentation can be miniaturized to meet the stringent size, weight, and power (SWaP) constraints of an atmospheric probe while retaining sensitivity and specificity that allow spectral fingerprinting of compounds and functional groups. Raman alone is insufficient to characterize trace constituents however, as limits of detection are typically in the 10s to 100s of ppm at best for planetary Raman spectrometers. Surface-Enhanced Raman Spectroscopy (SERS), a method that utilizes nanoscale materials interacting with a sample to enhance weak Raman signals by orders of magnitude when probed by a laser, has the potential to drastically improve the sensitivity of a Raman instrument while adding little-to-no SWaP nor complexity to a scientific payload. We aim to de-risk SERS technology for rapid infusion in future planetary science missions by developing custom SERS substrates tailored towards Venus atmospheric exploration. We have developed SERS substrates consisting of nanotextured silver films and tested them on potential Venus-relevant organic compounds, with preliminary results indicating sub-ppm sensitivity. Additionally, we have planned tests to investigate durability, longevity, and other key characteristics that impact SERS substrate performance to prepare SERS technology for flight.

Venus↗
NASA NTRS2015

Thermally-Resilient, Broadband Optical Absorber from UV-to-IR Derived from Carbon Nanostructures and Method of Making the Same

A monolithic optical absorber and methods of making same. The monolithic optical absorber uses an array of mutually aligned carbon nanotubes that are grown using a PECVD growth process and a structure that includes a conductive substrate, a refractory template layer and a nucleation layer. Monolithic optical absorbers made according to the described structure and method exhibit high absorptivity, high site densities (greater than 10.sup.9 nanotubes/cm.sup.2), very low reflectivity (below 1%), and high thermal stability in air (up to at least 400.degree. C.). The PECVD process allows the application of such absorbers in a wide variety of end uses.

Kaul, Anupama B.↗
NASA NTRS2001

Far Ultraviolet Spectroscopic Explorer Observations of the Seyfert 1.5 Galaxy NGC 5548 in a Low State

We present far-ultraviolet spectra of the Seyfert 1.5 galaxy NGC 5548 obtained in 2000 June with the Far Ultraviolet Spectroscopic Explorer (FUSE). Our data span the observed wavelength range 915-1185 A at a resolution of approximately 20 km s(exp -1). The spectrum shows a weak continuum and emission from O VI (lambda)(lambda)1032, 1038, C III (lambda)977, and He II (lambda)1085. The FUSE data were obtained when the AGN (Active Galactic Nuclei) was in a low state, which has revealed strong, narrow O VI emission lines. We also resolve intrinsic, associated absorption lines of O VI and the Lyman series. Several distinct kinematic components are present, spanning a velocity range of approximately 0 to -1300 km s(exp -1) relative to systemic, with kinematic structure similar to that seen in previous observations of longer wavelength ultraviolet (UV) lines. We explore the relationships between the far-UV (ultraviolet) absorbers and those seen previously in the UV and X-rays. We find that the high-velocity UV absorption component is consistent with being low-ionization, contrary to some previous claims, and is consistent with its non-detection in high-resolution X-ray spectra. The intermediate velocity absorbers, at -300 to -400 km s(exp -1), show H I and O VI column densities consistent with having contributions from both a high-ionization X-ray absorber and a low-ionization UV absorber. No single far-UV absorbing component can be solely identified with the X-ray absorber.

Brotherton, M. S.↗
NASA NTRS2000

Response of Two Legumes to Two Ultraviolet-B Radiation Regimes

Depletion of the stratospheric ozone layer has been directly linked to increased levels of UV radiation at the earth's surface. The purpose of this study was to evaluate the responses of soybean (Glycine max) and alfalfa (Medicago sativa) to increased UV-B radiation (280-320 nm). Soybean and alfalfa were grown successively in a growth chamber that provided UV-B intensities 45% above nominal summer field levels. Mylar-D (UVB opaque) and mono-acetate (UV-B transparent) films were used to establish the two UV-B treatments. Soybean grown under increased UV showed 21% smaller internodal lengths and higher concentrations of UV-B absorbing pigments (i.e. flavonoids) compared to plants grown under no UV. Significant results for alfalfa included 22% greater leaf flavonoid concentration under increased UV, 14% greater leaf chlorophyll concentration under no UV, and 32% greater above-ground biomass with no UV. These leguminous species possess mechanisms that protect against UV-B damage as indicated by increases in foliar concentrations of UV-B absorbing compounds. Alfalfa appears to be more sensitive to UV-B damage than soybean. Remote sensing of chlorophyll fluorescence may offer a means of monitoring UV-induced plant stress and damage.

Levy, Daniel L.↗
NASA NTRS2000

A High Signal-To-Noise Ultraviolet Spectrum of NGC 7469: New Support for Reprocessing of Continuum Radiation

From 1996 June 10 to 1996 July 29, the International AGN Watch monitored the Seyfert 1 galaxy NGC 7469 using the International Ultraviolet Explorer, the Rossi X-Ray Timing Explorer, and a network of ground-based observatories. On 1996 June 18, in the midst of this intensive monitoring period, we obtained a high signal-to-noise snapshot of the UV spectrum from 1150 to 3300 A, using the Faint Object Spectrograph (FOS) on the Hubble Space Telescope. This spectrum allows us to disentangle the UV continuum more accurately from the broad wings of the emission lines, to identify clean continuum windows free of contaminating emission and absorption, and to deblend line complexes such as Ly(alpha) + N V, C IV + He II + O III], Si III] + C III], and Mg II + Fe II. Using the FOS spectrum as a template, we have fitted and extracted line and continuum fluxes from the IUE monitoring data. The cleaner continuum extractions c o n h the discovery of time delays between the different UV continuum bands by Wanders et al. Our new measurements show delays increasing with wavelength for continuum bands centered at 1485, 1740, and 1825 A, relative to 1315 A with delays of 0.09, 0.28, and 0.36 days, respectively. Like many other Seyfert I galaxies, the UV spectrum of NGC 7469 shows intrinsic, blue-shifted absorption in Ly(alpha), N V, and C IV. Soft X-ray absorption is also visible in archival ASCA X-ray spectra. The strength of the UV absorption, however, is not compatible with a single-zone model in which the same material absorbs both the UV and X-ray light. Similar to other Seyfert galaxies, such as NGC 3516, the UV-absorbing gas in NGC 7469 has a lower ionization parameter and column density than the X-ray-absorbing material. While the UV and X-ray absorption does not arise in the same material, the frequent occurrence of both associated UV absorption and X-ray warm absorbers in the same galaxies suggests that the gas supply for each has a common origin.

Kriss, Gerard A.↗
NASA NTRS1998

Discovery of Associated Absorption Lines in an X-Ray Warm Absorber: Hubble Space Telescope Observations of PG 1114+445

The unified picture of X-ray/UV absorbers offers a unique opportunity to probe the nuclear environment of active galactic nuclei. To test the unified absorber scenario and to understand the physical properties of the absorber, we obtained the first UV spectrum of PG 1114+445 using the Hubble Space Telescope (HST) Faint Object Spectrograph. PG 1114+445 is known to have an X-ray ionized ('warm') absorber,so that UV absorption is predicted. The HST spectrum clearly shows strong UV absorption lines due to Lyalpha, C iv, and N v, blueshifted by approximately 530 km s(exp -1) with respect to the quasar redshift. Since both X-ray and UV absorbers are rare in radio-quiet quasars, these observations argue strongly that the X-ray and UV absorbers are closely physically related. perhaps identical. We place constraints on the parameters of the absorber and conclude that the mass outflow rate is comparable to the accretion rate in PG 1114+445.

Mathur, Smita↗
NASA NTRS1996

Mechanism of cyanoacetylene photochemistry at 185 and 254 nm

The role of cyanoacetylene (HC3N) in the atmospheric photochemistry of Titan and its relevance to polymer formation are discussed. Investigation of the relative light absorption of HC3N, acetylene (C2H2), and diacetylene (C4H2) revealed that HC3N is an important absorber of UV light in the 205- to 225-nanometer wavelength region in Titan's polar regions. Laboratory studies established that photolysis of C2H2 initiates the polymerization of HC3N even though the HC3N is not absorbing the UV light. Quantum yield measurements establish that HC3N is 2-5 times as reactive as C2H2 for polymer formation. Photolysis of HC3N with 185-nanometer light in the presence of N2, H2, Ar, or CF4 results in a decrease in the yield of 1,3,5-tricyanobenzene (1,3,5-tcb), while photolysis in the presence of CH4, C2H6, or n-C4H10 results in an increase in 1,3,5-tcb. The rate of loss of HC3N is increased by all gases except H2, where it is unchanged. It was not possible to detect 1,3,5-tcb as a photoproduct when the partial pressure of HC3N was decreased to 1 torr. Photolysis of HC3N with 254-nanometer light in the presence of H2 or N2 results in the formation of 1,2,4-tcb, while photolysis in the presence of CH4, C2H6, or n-C4H10 results in the formation of increasing amounts of 1,3,5-tcb. Mechanisms for the formation of polymers are presented.

Non-NASA Center↗
NASA NTRS2010

Hybrid AlGaN-SiC Avalanche Photodiode for Deep-UV Photon Detection

The proposed device is capable of counting ultraviolet (UV) photons, is compatible for inclusion into space instruments, and has applications as deep- UV detectors for calibration systems, curing systems, and crack detection. The device is based on a Separate Absorption and Charge Multiplication (SACM) structure. It is based on aluminum gallium nitride (AlGaN) absorber on a silicon carbide APD (avalanche photodiode). The AlGaN layer absorbs incident UV photons and injects photogenerated carriers into an underlying SiC APD that is operated in Geiger mode and provides current multiplication via avalanche breakdown. The solid-state detector is capable of sensing 100-to-365-nanometer wavelength radiation at a flux level as low as 6 photons/pixel/s. Advantages include, visible-light blindness, operation in harsh environments (e.g., high temperatures), deep-UV detection response, high gain, and Geiger mode operation at low voltage. Furthermore, the device can also be designed in array formats, e.g., linear arrays or 2D arrays (micropixels inside a superpixel).

Aslam, Shahid↗
NASA NTRS2003

The Nature of the UV/X-ray Absorber In PG 2302+029

We present Chandra X-ray observations of the radio-quiet QSO PG 2302+029. This quasar has a rare system of ultra-high velocity (-56,000 km s(exp -1) UV absorption lines that form in an outflow from the active nucleus. The Chandra data indicate that soft X-ray absorption is also present. We perform a joint UV and X-ray analysis, using photoionization calculations, to determine the nature of the absorbing gas. The UV and X-ray datasets were not obtained simultaneously. Nonetheless, our analysis suggests that the X-ray absorption occurs at high velocities in the same general region as the UV absorber. There are not enough constraints to rule out multi-zone models. In fact, the distinct broad and narrow UV line profiles clearly indicate that multiple zones are present. Our preferred estimates of the ionization and total column density in the X-ray absorber (logU = 1.6, N(sub eta) = 10(exp 22.4) cm (exp -2) over predict the O VI lambda lambda1032,1038 absorption unless the X-ray absorber is also outflowing at approximately 56,000 km s(exp-l), but they over predict the Ne VIII lambda lambda 770,780 absorption at all velocities. If we assume that the X-ray absorbing gas is outflowing at the same velocity of the UV-absorbing wind and that the wind is radiatively accelerated, then the outflow must be launched at a radius of less than or equal to 10(exp 15) cm from the central continuum source. The smallness of this radius casts doubts on the assumption of radiative acceleration.

Sabra, Bassem M.↗
NASA NTRS1971

Radiation heat transfer calculations for the uranium fuel-containment region of the nuclear light bulb engine.

Calculation results are reviewed of the radiant heat transfer characteristics in the fuel and buffer gas regions of a nuclear light bulb engine based on the transfer of energy by thermal radiation from gaseous uranium fuel in a neon vortex, through an internally cooled transparent wall, to seeded hydrogen propellant. The results indicate that the fraction of UV energy incident on the transparent walls increases with increasing power level. For the reference engine power level of 4600 megw, it is necessary to employ space radiators to reject the UV radiated energy absorbed by the transparent walls. This UV energy can be blocked by employing nitric oxide and oxygen seed gases in the fuel and buffer gas regions. However, this results in increased UV absorption in the buffer gas which also requires space radiators to reject the heat load.

Rodgers, R. J.↗
NASA NTRS1978

Organic chemistry on Titan

Observations of nonequilibrium phenomena on the Saturn satellite Titan indicate the occurrence of organic chemical evolution. Greenhouse and thermal inversion models of Titan's atmosphere provide environmental constraints within which various pathways for organic chemical synthesis are assessed. Experimental results and theoretical modeling studies suggest that the organic chemistry of the satellite may be dominated by two atmospheric processes: energetic-particle bombardment and photochemistry. Reactions initiated in various levels of the atmosphere by cosmic ray, Saturn wind, and solar wind particle bombardment of a CH4 - N2 atmospheric mixture can account for the C2-hydrocarbons, the UV-visible-absorbing stratospheric haze, and the reddish color of the satellite. Photochemical reactions of CH4 can also account for the presence of C2-hydrocarbons. In the lower Titan atmosphere, photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. Hot H-atom reactions initiated by photo-dissociation of NH3 can couple the chemical reactions of NH3 and CH4 and produce organic matter.

Chang, S.↗
NASA NTRS1979

Organic chemistry on Titan

Features taken from various models of Titan's atmosphere are combined in a working composite model that provides environmental constraints within which different pathways for organic chemical synthesis are determined. Experimental results and theoretical modeling suggest that the organic chemistry of the satellite is dominated by two processes: photochemistry and energetic particle bombardment. Photochemical reactions of CH4 in the upper atmosphere can account for the presence of C2 hydrocarbons. Reactions initiated at various levels of the atmosphere by cosmic rays, Saturn 'wind', and solar wind particle bombardment of a CH4-N2 atmospheric mixture can account for the UV-visible absorbing stratospheric haze, the reddish appearance of the satellite, and some of the C2 hydrocarbons. In the lower atmosphere photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. It is concluded that the surface of Titan may contain ancient or recent organic matter (or both) produced in the atmosphere.

Chang, S.↗
NASA NTRS1987

Extremely Luminous Far-infrared Sources (ELFS)

The Infrared Astronomical Satellite (IRAS) survey uncovered a class of Extremely Luminous Far Infrared Sources (ELFS), exhibiting luminosities up to and occasionally exceeding 10 to the 12th power L sub 0. Arguments are presented to show that sources with luminosities L equal to or greater than 3 x 10 to the 10th power L sub 0 may represent gas rich galaxies in collision. The more conventional explanation of these sources as sites of extremely active star formation fails to explain the observed low optical luminosities of ELFS as well as their high infrared excess. In contrast, a collisional model heats gas to a temperature of approx. 10 to the 6th power K where cooling takes place in the extreme ultraviolet. The UV is absorbed by dust and converted into far infrared radiation (FIR) without generation of appreciable optical luminosity. Gas recombination as it cools generates a Lyman alpha photon only once for every two extreme ultraviolet approx. 50eV photons emitted by the 10 to the 6th power gas. That accounts for the high infrared excess. Finally, the model also is able to explain the observed luminosity distribution of ELFS as well as many other traits.

Harwit, Martin↗
NASA NTRS1999

Ozone Depletion, UVB and Atmospheric Chemistry

The primary constituents of the Earth's atmosphere are molecular nitrogen and molecular oxygen. Ozone is created when ultraviolet light from the sun photodissociates molecular oxygen into two oxygen atoms. The oxygen atoms undergo many collisions but eventually combine with a molecular oxygen to form ozone (O3). The ozone molecules absorb ultraviolet solar radiation, primarily in the wavelength region between 200 and 300 nanometers, resulting in the dissociation of ozone back into atomic oxygen and molecular oxygen. The oxygen atom reattaches to an O2 molecule, reforming ozone which can then absorb another ultraviolet photon. This sequence goes back and forth between atomic oxygen and ozone, each time absorbing a uv photon, until the oxygen atom collides with and ozone molecule to reform two oxygen molecules.

Stolarski, Richard S.↗
NASA NTRS1999

Ozone Depletion, UVB and Atmospheric Chemistry

The primary constituents of the Earth's atmosphere are molecular nitrogen and molecular oxygen. Ozone is created when ultraviolet light from the sun photodissociates molecular oxygen into two oxygen atoms. The oxygen atoms undergo many collisions but eventually combine with a molecular oxygen to form ozone (O3). The ozone molecules absorb ultraviolet solar radiation, primarily in the wavelength region between 200 and 300 nanometers, resulting in the dissociation of ozone back into atomic oxygen and molecular oxygen. The oxygen atom reattaches to an O2 molecule, reforming ozone which can then absorb another ultraviolet photon. This sequence goes back and forth between atomic oxygen and ozone, each time absorbing a uv photon, until the oxygen atom collides with and ozone molecule to reform two oxygen molecules.

Stolarski, Richard S.↗
NASA NTRS1994

Plant Responses to Increased UV-B Radiation: A Research Project

Ozone decrease implies more ultraviolet-B (UV-B) radiation reaching the surface of the Earth. Increased UV-B radiation triggers responses by living organisms. Despite the large potential impacts on vegetation, little is known about UV-B effects on terrestrial ecosystems. Long-term ecological studies are needed to quantify the effects of increased UV radiation on terrestrial ecosystems, asses the risks, and produce reliable data for prediction. Screening pigments are part of one of the protective mechanism in plants. Higher concentrations of screening pigments in leaves may be interpreted as a response to increased UV radiation. If the screening effect is not sufficient, important molecules will be disturbed by incoming radiation. Thus, genetics, photosynthesis, growth, plant and leaf shape and size, and pollen grains may be affected. This will have an impact on ecosystem dynamics, structure and productivity. It is necessary to monitor selected terrestrial ecosystems to permit detection and interpretation of changes attributable to global climate change and depleted ozone shield. The objectives of this project are: (1) To identify and measure indicators of the effects of increased solar UV-B radiation on terrestrial plants; (2) to select indicators with the greatest responses to UV-B exposure; (3) to test, adapt or create ecosystem models that use the information gathered by this project for prediction and to enhance our understanding of the effects of increased UV-B radiation on terrestrial ecosystems. As a first step to achieve these objectives we propose a three-year study of forest and steppe vegetation on the North slope of the Brooks Range (within the Arctic circle, in Alaska), in the Saguaro National Monument (near Tucson, Arizona) and in the forests and steppes of Patagonia (Argentina). We selected (1) vegetation north of the Polar Circle because at 70N there is 8% risk of plant damage due to increased UV-B radiation; (2) the foothills of Catalina Mountains because there is anecdotal evidence of plant damage on the saguaros that has been linked to increased UV radiation, and (3) the forests of Nothofagus spp. and the steppe of Patagonia where the risk of plant damage at 35S is 5% and increases to as much as 15% at 55S due to increased UV-B radiation. Measurements of UV-B radiation impinging on the surface at 55S largely exceed the predicted UV-B radiation values at 50 latitude and 0% ozone depletion. Preliminary HPLC analyses of UV-B absorbing compounds in Nothofagus antartica, N. pumilio, N. betuloides and Rumex sp. in natural conditions show species-specific patterns. The spectrum of N. antartica grown at 38S differs significantly from that of N. antartica in natural conditions in Ushuaia (55S). These results suggest that the selected main area (Patagonia) is appropriate for assessing the problem and its magnitude and that Nothofagus is appropriate for our study.

DAntoni, H. L.↗