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NASA NTRS2014

Distribution of Amino Acids in Lunar Regolith

One of the most eagerly studied questions upon initial return of lunar samples was whether significant amounts of organic compounds, including amino acids, were present. Analyses during the 1970s produced only tentative and inconclusive identifications of indigenous amino acids. Those analyses were hampered by analytical difficulties including relative insensitivity to certain compounds, the inability to separate chiral enantiomers, and the lack of compound-specific isotopic measurements, which made it impossible to determine whether the detected amino acids were indigenous to the lunar samples or the results of contamination. Numerous advances have been made in instrumentation and methodology for amino acid characterization in extraterrestrial samples in the intervening years, yet the origin of amino acids in lunar regolith samples has been revisited only once for a single lunar sample, (3) and remains unclear. Here, we present initial data from the analyses of amino acid abundances in 12 lunar regolith samples. We discuss these abundances in the context of four potential amino acid sources: (1) terrestrial biological contamination; (2) contamination from lunar module (LM) exhaust; (3) derivation from solar windimplanted precursors; and (4) exogenous delivery from meteorites.

Elsila, J. E.↗
NASA NTRS2014

Radioelements on Vesta: An Update

The main-belt asteroid 4 Vesta is the putative parent body of the howardite, eucrite, and diogenite (HED) meteorites. Because these achondrites have similar petrology, geochemistry, chronology, and O-isotope compositions, it is thought that most HEDs originated from a single parent body. The connection to Vesta is supported by a close spectroscopic match between Vesta and the HEDs and a credible mechanism for their delivery to Earth. Studies of the HEDs show that Vesta underwent igneous differentiation, forming a Fe-rich core, ultramafic mantle, and basaltic crust. Here we present the results of peak analyses applied to a gamma ray difference spectrum to determine the absolute abundances of K and Th. Data are compared to meteorite whole-rock compositions and other inner solar system bodies. The results, while preliminary, represent our present best estimates for these elements. Because the element signatures are near detection limits and not fully resolved, further analysis (e.g. using spectral unmixing) will be required for improved accuracy and to characterize systematic errors.

Prettyman, T. H.↗
NASA NTRS2020

Abundant Extraterrestrial Amino Acids in the Primitive CM Carbonaceous Chondrite Asuka 12236

The Asuka (A)-12236 meteorite has recently been classified as a CM carbonaceous chondrite of petrologic type 3.0/2.9 and is among the most primitive CM meteorites studied to date. Here, we report the concentrations, relative distributions, and enantiomeric ratios of amino acids in water extracts of the A-12236 meteorite and another primitive CM chondrite Elephant Moraine(EET) 96029 (CM2.7) determined by ultra-high-performance liquid chromatography time-of-flight mass spectrometry. EET 96029 was highly depleted in amino acids and dominated by glycine, while a wide diversity of two- to six-carbon aliphatic primary amino acids were identified in A-12236, which had a total amino acid abundance of 360 ± 18 nmol g-1, with most amino acids present without hydrolysis (free). The amino acid concentrations of A-12236 were double those previously measured in the CM2.7 Paris meteorite, consistent with A-12236 being a highly primitive and unheated CM chondrite. The high relative abundance of α-amino acids in A-12236 are consistent with formation by a Strecker-cyanohydrin dominated synthesis during a limited early aqueous alteration phase on the CM meteorite parent body. The presence of predominantly free glycine, a near racemic mixture of alanine (D/L ~0.93 to 0.96), and elevated abundances of several terrestrially rare non-protein amino acids including α-amino isobutyric acid (α-AIB) and racemic isovaline, indicate that these amino acids in A-12236 are extraterrestrial in origin. Given a lack of evidence for biological amino acid contamination in A-12236, it is possible that some of the L-enantiomeric excesses (Lee ~34 to 64%) of the protein amino acids aspartic and glutamic acids and serine are indigenous to the meteorite; however, isotopic measurements are needed for confirmation. In contrast to more aqueously altered CMs of petrologic types ≤ 2.5, no L-isovaline excesses were detected in A-12236. This observation strengthens the hypothesis that extensive parent body aqueous activity is required to produce or amplify the large L-isovaline excesses that cannot be explained solely by exposure to circularly polarized radiation or other chiral symmetry breaking mechanisms prior to incorporation into the asteroid parent body.

Daniel P Glavin↗
NASA NTRS1993

Live Iron-60 in the early solar system

Isotopic analyses of nickel in samples from the differentiated meteorite Chervony Kut revealed the presence of relative excesses of Ni-60 ranging from 2.4 up to 50 parts per 10 exp 4. These isotopic excesses are from the decay of the now extinct short-lived nuclide Fe-60 and provide clear evidence for the existence of Fe-60 over large scales in the early solar system. Not only was Fe-60 present at the time of melting and differentiation (that is, Fe-Ni fractionation) of the parent body of Chervony Kut but also later at the time when basaltic magma solidified at or near the surface of the planetesimal. The inferred abundance of Fe-60 suggests that its decay alone could have provided sufficient heat to melt small (diameters of several hundred kilometers) planetary bodies shortly after their accretion.

Shukolyukov, A.↗
NASA NTRS1996

In Situ Mineralogical Analysis of Planetary Materials Using X-Ray Diffraction and X-Ray Fluorescence

Remote observations of Mars have led scientists to believe that its early climate was similar to that of the early Earth, having had abundant liquid water and a dense atmosphere. One of the most fascinating questions of recent times is whether simple bacterial life developed on Mars (as it did on the Earth) during this early element period. Analyses of SNC meteorites have broadened considerably our knowledge of the chemistry of certain types of Martian rocks, underscoring the tantalizing possibility of early hydrothermal systems and even of ancient bacterial life. Detailed analyses of SNC meteorites in Terrestrial laboratories utilize the most sophisticated organic, isotopic and microscopic techniques in existence. Indeed; it is unlikely that the key biogenic indicators used in McKay et al (ibid) could be identified by a remote instrument on the surface of Mars. As a result, it is probable that any robotic search for evidence of an ancient Martian biosphere will have as its focus the identification of key minerals in likely host rocks rather than the direct detection of organic or isotopic biomarkers. Even on a sample return mission, mineralogical screening will be utilized to choose the most likely candidate rocks. X-ray diffraction (XRD) is the only technique that can provide a direct determination of the crystal structures of the phases present within a sample. When many different crystalline phases are present, quantitative analysis is better constrained if used in conjunction with a determination of elemental composition, obtainable by X-ray fluorescence (XRF) using the same X-ray source as for XRD. For planetary surface analysis, a remote instrument combining XRD and XRF could be used for mineralogical characterization of both soils and rocks. We are designing a remote XRD/XRF instrument with this objective in mind. The instrument concept pays specific attention to constraints in sample preparation, weight, volume, power, etc. Based on the geometry of a pinhole camera (transmission geometry, flat two-dimensional detector perpendicular to the direct beam), the instrument (which we call CHEMIN, for Chemistry and Mineralogy) uses an X-ray sensitive CCD detector which will allow concurrent positional and energy-dispersive analysis of collected photons. Thus XRF (energy) and XRD (geometry) analysis of transmitted X-rays will be performed at the same time. Tests performed with single minerals and simple mixtures give promising results. Refinements of the prototype promise interpretable results on complex samples.

Sarrazin, P.↗
NASA NTRS2019

Measuring the D/H Ratios of Exoplanets and Brown Dwarfs

The relative abundance of deuterium and hydrogen is a potent tracer of planet formation and evolution. Jupiter and Saturn have protosolar atmospheric D/H ratios, a relic of substantial gas accretion from the nebula, while the atmospheres of Neptune and Uranus are enhanced in D by accretion of ices into their envelopes. For terrestrial planets, D/H ratios are used to determine the mechanisms of volatile delivery and subsequent atmosphere loss over the lifetime of the planet. Planets and brown dwarfs more massive than ~13 M(J) quickly fuse their initial D reservoir. Here, we simulate spectra for giant exoplanets and brown dwarfs (2 M(Neptune) to ~10 M(Jupiter)) from T(eff) = 200–1800 K including both CH3D and HDO to determine the observability of these dominant deuterium isotopologues in mid-infrared thermal emission spectra. Colder objects have stronger molecular features in their spectra, due to the temperature dependence of molecular cross sections. CH3D is easier to observe than HDO at all temperatures considered, due to the strength of its absorption bands and locations of features at wavelengths with few other strong absorption features. We predict that for nearby cool brown dwarfs, the CH3D abundance can be measured at high signal to noise with the James Webb Space Telescope (JWST); for objects from 200 to 800 K closer than 10 pc, a protosolar D/H ratio would be readily observable in 2.5 hr. Moderately young Jupiter-mass planets (100–300 Myr) and young Neptunes (10 Myr) may be discovered with JWST and provide the best targets for detecting deuterium on an exoplanet in the coming decade. Future telescope designs should consider the importance of isotopes for understanding the formation and evolution of planetary atmospheres.

Caroline V. Morley↗
NASA NTRS2018

The Diversity of Refractory Organic Material in Comets

Organic matter exists in comets (most notably in 81P/Wild 2 [Stardust], 67P/Churyomov- Gerasimenko (67P/C-G) [Rosetta], chondritic porous IDPS, and UCAMMs) and in primitive carbonaceous chondrites that likely retain some chemistry that reflects an origin in the prenatal cold molecular cloud (Alexander+2017). Heavy isotopic enrichments, 15N/14N and possibly D/H, signify preserved molecular cloud organics. In the cold outer disk, if grains are lofted above the disk mid-plane then organics likely experience significant UV processing (Ciesla+2012). In remote sensing of comet comae, organics in the dust are considered refractory or semirefractory. Semi-refractory organics have limited comae lifetimes and produce distributed sources of molecules (H2CO and CO). Rosetta's close passes of 67P/C-G's nucleus (10-15 km) reveals a distributed source of glycine, methyl amine and ethylamine (Altwegg+2016). Cometary samples and primitive meteorites have two types of organic matter: (1) acid-insoluble organic matter (IOM), which is a macromolecular polymer with a mixture of aromatic and aliphatic moieties, and (2) labile, soluble organics, which includes the amino acids, such as glycine (Stardust, Elsila+2009). Meteoritic IOM is robust, withstanding experimental temperatures of 1200 K (Dobrica+2011, Cody+2008). Nanoglobules are a type of IOM; they have a distinct physical structure, but often share the same chemistry as the other IOM from the same meteorite. Moderate-sized PAHs (20 C-atoms) are detected in Stardust samples (Clemett+2010). Refractory organic IOM is ubiquitous yet has a great diversity of abundances between cometary samples. IOM is in primitive chondrites, 67P/C-G (Rosetta), 81P/Wild 2 (Stardust), 1P/Halley, 26P/Grigg-Skjellerup, UCAMMs, anhydrous IDPs, and in chondritic porous IDPs (CP IDPs) and larger cluster IDPs (e.g., Fray+2016, Fomenkova+94, Busemann+ 09, Dobrica+2011, Dobrica+2012). 81P's refractory organic matter is of two types (De Gregorio+2011): nanoglobules of highly aromatic refractory organic matter and polyaromatic carbonyl-containing organic matter, which is similar to IOM in primitive meteorites and IDPs. Fray+2017 estimate that 50% of carbon in 67P/C-G is in IOM. 67P/C-G's organics appear to lack the soluble organic matter, aliphatic carbon, amino acids, and PAHs (Fray+2016). Other notable aspects of the diversity in IOM in cometary samples are the ranges of atomic ratios of N/C, O/C, and H/C, and the range of isotopic enrichments of 15N/14N and D/H. Aqueous and thermal processing on asteroids changes the balance of soluble to insoluble organics, and may be important for diversifying the range of OM delivered to Earth.

Wooden, Diane↗
DOE OSTI2023

Metagenomic stable isotope probing reveals bacteriophage participation in soil carbon cycling

Soil viruses are important components of the carbon (C) cycle, yet we still know little about viral ecology in soils. We added diverse 13 C-labelled carbon sources to soil and we used metagenomic-SIP to detect 13 C assimilation by viruses and their putative bacterial hosts. These data allowed us to link a 13 C-labelled bacteriophage to its 13 C-labelled Streptomyces putative host, and we used qPCR to track the dynamics of the putative host and phage in response to C inputs. Following C addition, putative host numbers increased rapidly for 3 days, and then more gradually, reaching maximal abundance on Day 6. Viral abundance and virus:host ratio increased dramatically over 6 days, and remained high thereafter (8.42 ± 2.94). From Days 6 to 30, virus:host ratio remained high, while putative host numbers declined more than 50%. Putative host populations were 13 C-labelled on Days 3–30, while 13 C-labelling of phage was detected on Days 14 and 30. This dynamic suggests rapid growth and 13 C-labelling of the host fueled by new C inputs, followed by extensive host mortality driven by phage lysis. Furthermore, these findings indicate that the viral shunt promotes microbial turnover in soil following new C inputs, thereby altering microbial community dynamics, and facilitating soil organic matter production.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Atomic-scale mechanism of carbon nucleation from a deep crustal fluid by replica exchange reactive molecular dynamics simulation

Here we present a mechanistic model of carbon nucleation and growth from a fluid at elevated temperature (T) and pressure conditions, typical of those found in the shallow Earth’s lithosphere. Our model uses a replica exchange reactive molecular dynamics framework in which molecular configurations are swapped between adjacent T replica at regular intervals according to underlying statistical mechanics. This framework allows predicting complex molecular structures and thermodynamics while remaining computationally efficient. Here we simulate the reactivity of an unstable mixture of CO 2 and CH 4 at 1000 K and 1 GPa. We find that the path to thermodynamic equilibrium is initially entropy-driven, producing a diversity of short-lived species, including various alcohols with intermediate carbon oxidation states. Cyclic and polycyclic radicals that are sometimes resonance-stabilized form next and set the stage for carbon nucleation. The carbon exsolution process releases abundant water, is exothermic and starts with the nucleation of a large aggregate of hydrogenated graphene flakes from covalently bonded polycyclic units. The carbon backbone of this nucleus subsequently grows into a hydrogen-depleted fullerene-like structure, before evolving toward a partially bilayered graphene layer. Overall, our results show that the mechanism of graphitic C formation is certainly not bimolecular, and that it may involve a combination of key condensation and radical chain reactions. This will help understand the isotopic, and reactive characteristics of carbon-bearing fluids during their upward transit through the Earth’s mantle and crust. Moreover, the mechanistic insights outlined here present intriguing similarities with the process of soot and interstellar dust formation, which suggests that the widespread distribution of abiotic polyaromatic and graphitic material on Earth and beyond may reflect the prevalence of a fundamental chemical pathway.

58 GEOSCIENCES↗
DOE OSTI2024

Mid-infrared trace detection with parts-per-quadrillion quantitation accuracy: Expanding frontiers of radiocarbon sensing

Detection sensitivity is a critical characteristic to consider during selection of spectroscopic techniques. However, high sensitivity alone is insufficient for spectroscopic measurements in spectrally congested regions. Two-color cavity ringdown spectroscopy (2C-CRDS), based on intra-cavity pump–probe detection, simultaneously achieves high detection sensitivity and selectivity. This combination enables mid-infrared detection of radiocarbon dioxide ( 14 CO 2 ) molecules in room-temperature CO 2 samples, with 1.4 parts-per-quadrillion (ppq, 10 − 15 ) sensitivity (average measurement precision) and 4.6-ppq quantitation accuracy (average calibrated measurement error for 21 samples from four separate trials) demonstrated on samples with 14 C/C up to ∼ 1.5 × natural abundance ( ∼ 1,800 ppq). These highly reproducible measurements, which are the most sensitive and quantitatively accurate in the mid-infrared, are accomplished despite the presence of orders-of-magnitude stronger, one-photon signals from other CO 2 isotopologues. This is a major achievement in laser spectroscopy. A room-temperature-operated, compact, and low-cost 2C-CRDS sensor for 14 CO 2 benefits a wide range of scientific fields that utilize 14 C for dating and isotope tracing, most notably atmospheric 14 CO 2 monitoring to track CO 2 emissions from fossil fuels. The 2C-CRDS technique significantly enhances the general utility of high-resolution mid-infrared detection for analytical measurements and fundamental chemical dynamics studies.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS1993

Planetary noble gases

An overview of the history and current status of research on planetary noble gases is presented. The discovery that neon and argon are vastly more abundant on Venus than on earth points to the solar wind rather than condensation as the fundamental process for placing noble gases in the atmospheres of the terrestrial planets; however, solar wind implantation may not be able to fully reproduce the observed gradient, nor does it obviously account for similar planetary Ne/Ar ratios and dissimilar planetary Ar/Kr ratios. More recent studies have emphasized escape rather than accretion. Hydrodynamic escape, which is fractionating, readily accounts for the difference between atmospheric neon and isotopically light mantle neon. Atmospheric cratering, which is nearly nonfractionating, can account for the extreme scarcity of nonradiogenic noble gases (and other volatiles) on Mars.

Zahnle, Kevin↗
NASA NTRS2002

Shergottite Impact Melt Glasses Contain Soil from Martian Uplands

Martian meteorite (shergottite) impact melt glasses that contain high concentrations of martian atmospheric noble gases and show significant variations in Sr-87/Sr-86 isotopic ratios are likely to contain Martian surface fines mixed with coarser regolith materials. The mixed soil constituents were molten due to shock at the time of meteoroid impact near the Martian surface and the molten glass got incorporated into the voids and cracks in some shergottite meteorites. Earlier, Rao et al. found large enrichments of sulfur (sulfate) during an electron-microprobe study of several impact melt glass veins and pods in EET79001,LithC thin sections. As sulfur is very abundant in Martian soil, these S excesses were attributed to the mixing of a soil component containing aqueously altered secondary minerals with the LithC precursor materials prior to impact melt generation. Recently, we studied additional impact melt glasses in two basaltic shergottites, Zagami and Shergotty using procedures similar to those described by Rao et al. Significant S enrichments in Zagami and Shergotty impact melt glass veins similar to the EET79001, LithC glasses were found. In addition, we noticed the depletion of the mafic component accompanied by the enrichment of felsic component in these impact melt glass veins relative to the bulk host rock in the shergottites. To explain these observations, we present a model based on comminution of basaltic rocks due to meteroid bombardment on martian regolith and mechanical fractionation leading to enrichment of felsics and depletion of mafics in the fine grained dust which is locally mobilized as a result of saltation and deflation due to the pervasive aeolian activity on Mars.

Rao, M. N.↗
NASA NTRS2002

Shergottite Impact Melt Glasses Contain Soil from Martian Uplands

Martian meteorite (shergottite) impact melt glasses that contain high concentrations of martian atmospheric noble gases and show significant variations in Sr-87/Sr-86 isotopic ratios are likely to contain Martian surface fines mixed with coarser regolith materials. The mixed soil constituents were molten due to shock at the time of meteoroid impact near the Martian surface and the molten glass got incorporated into the voids and cracks in some shergottite meteorites. Earlier, Rao et al. found large enrichments of sulfur (sulfate) during an electron-microprobe study of several impact melt glass veins and pods in EET79001,LithC thin sections. As sulfur is very abundant in Martian soil, these S excesses were attributed to the mixing of a soil component containing aqueously altered secondary minerals with the LithC precursor materials prior to impact melt generation. Recently, we studied additional impact melt glasses in two basaltic shergottites, Zagami and Shergotty using procedures similar to those described. Significant S enrichments in Zagami and Shergotty impact melt glass veins similar to the EET79001, LithC glasses were found. In addition, we noticed the depletion of the mafic component accompanied by the enrichment of felsic component in these impact melt glass veins relative to the bulk host rock in the shergottites. To explain these observations, we present a model based on comminution of basaltic rocks due to meteoroid bombardment on martian regolith and mechanical fractionation leading to enrichment of felsics and depletion of mafics in the fine grained dust which is locally mobilized as a result of saltation and deflation due to the pervasive aeolian activity on Mars.

Rao, M. N.↗
NASA NTRS2012

A Propensity for n-omega-Amino Acids in Thermally-Altered Antarctic Meteorites

Carbonaceous meteorites are known to contain a wealth of indigenous organic molecules, including amino acids, which suggests that these meteorites could have been an important source of prebiotic organic material during the origins of life on Earth and possibly elsewhere. We report the detection of extraterrestrial amino acids in thermally-altered type 3 CV and CO carbonaceous chondrites and ureilites recovered from Antarctica. The amino acid concentrations of the thirteen Antarctic meteorites were generally less abundant than in more amino acid-rich CI, CM, and CR carbonaceous chondrites that experienced much lower temperature aqueous alteration on their parent bodies. In contrast to low-temperature aqueously-altered meteorites that show complete structural diversity in amino acids formed predominantly by Strecker-cyanohydrin synthesis, the thermally-altered meteorites studied here are dominated by small, straight-chain, amine terminal (n-omega-amino) amino acids that are not consistent with Strecker formation. The carbon isotopic ratios of two extraterrestrial n-omega-amino acids measured in one of the CV chondrites are consistent with C-13-depletions observed previously in hydrocarbons produced by Fischer-Tropsch type reactions. The predominance of n-omega-amino acid isomers in thermally-altered meteorites hints at cosmochemical mechanisms for the preferential formation and preservation of a small subset of the possible amino acids.

Burton, Aaron S.↗
NASA NTRS1994

Inter-Agency Consultative Group for Space Science (IACG): Handbook of Missions and Payloads

The ACE spacecraft design is based on the Charge Composition Explorer (CCE) built by Johns Hopkins University (JHU) and the Applied Physics Lab (APL) for the AMPTE program. ACE is designed as a spinning spacecraft with its spin axis aligned to the Earth-Sun axis. The ACE launch weight will be approx. 633 kg, including 105 kg of scientific instruments and 184 kg of propellant. Using a Delta-class expendable launch vehicle, ACE will be launched into an L1 libration point (240 R(sub e)) orbit. Telemetry will be 6.7 kbps average, using tape recorder storage with daily readout to DSN. The experiment power requirement is approximately 76 W nominal and 96 W peak. The prime objective of the ACE mission is: (1) to determine accurate elemental and isotropic abundances including solar matter, local interstellar matter and local galactic matter; (2) to study the origin of elements and evolutionary processing in galactic nucleosynthesis, galactic evolution, origin and evolution of the solar system; (3) to study coronal formation and solar-wind acceleration processes; and (4) to study particle acceleration and transport, including coronal shock acceleration, stochastic flare acceleration, interplanetary shock acceleration, and interstellar acceleration and propagation. To accomplish this objective, ACE will perform comprehensive and coordinated determinations of the elemental and isotopic composition of energetic nuclei accelerated on the Sun, in interplanetary space, and from galactic sources. These observations will span five decades in energy, from solar wind to galactic cosmic ray energies, and will cover the element range from H-1 to Zr-40. Comparison of these samples of matter will be used to study the origin and subsequent evolution of both solar system and galactic material by isolating the effects of fundamental processes that include nucleosynthesis, charged and neutral particle separation, bulk plasma acceleration, and the acceleration of suprathermal and high-energy particles.

Source record↗
NASA NTRS2004

Yamato 980459: The Most Primitive Shergottite?

The Antarctic Research Center of the Japanese National Institute of Polar Research (NIPR) recently announced the discovery of a new Martian shergottite, Y98(0459). This sample is a member of the subgroup of basaltic shergottites that contain abundant olivine phenocrysts, and are thus olivine- phyric. Y98 may have special significance among the basaltic shergottites because (1) it appears to have been the most magnesian Martian magma yet found, and thus can provide valuable clues to magma petrogenesis on Mars; (2) it contains no late-crystallizing phases, but instead contains approx. 30% interstitial glass, which can provide unambiguous incompatible element patterns of the parent melt; and (3) it carries an LREE-depleted signature similar to QUE 94201, whose isotopic characteristics are the most primitive of all basaltic shergottites.

McKay, G.↗
NASA NTRS1993

Research program on the Manson impact structure, Iowa

At or near the end of the Cretaceous, at least two large impact events occurred in the western hemisphere. One impact formed the 180-km diameter Chicxulub crater on the northern tip of the Yucatan peninsula. Another formed the 35-km diameter Manson structure in western Iowa. Several lines of evidence, including the chemical and isotopic composition of glass found in the K/T boundary layer at sites in the Gulf of Mexico and Caribbean region, the regional variation in thickness and the size of spherules in the K/T boundary layer, and indications at and near the boundary of disturbance and deposition of beds by giant waves in the Gulf of Mexico, point to Chicxulub as a major source of K/T boundary material, including a lower layer of clay at K/T boundary sites in western North America. The size, abundance, and mineral and lithic composition of shocked grains from an upper K/T boundary layer found at western North American sites, on the other hand, point to Manson as a possible source crater. More than one impact seems to be indicated by the K/T boundary stratigraphy in western North America, and present constraints on the age of the Manson structure suggest that it, as well as Chicxulub, may be a K/T boundary crater. Multiple craters produced over a relatively short interval of time are much more likely to have been formed by impact of comets rather than by impact of asteroids. Among likely mechanisms that could have produced multiple craters at or near the time of the K/T boundary are as follows: (1) splitting of a comet shortly before impact with Earth (impacts may have been spaced over about an hour), (2) fragmentation of a very large, Sun-grazing, periodic comet to form a compact stream of comets that intercepted the Earth's orbit (impacts may have been spread over about a century), and (3) perturbation of the Oort comet cloud by a passing massive object to form a comet shower in the inner solar system (impacts may have been spread over about a million years). Only in the first two cases are the impacts likely to have been close enough in time to contribute to the observed K/T boundary layers. All mechanisms could have produced many more than two craters.

Shoemaker, E. M.↗
DOE OSTI2026

Volatilized Ammonia Supports Subterranean Ecosystems with Unusual Nitrogen Isotopic Signatures

The Frasassi cave system hosts a robust subterranean ecosystem based on microbial lithoautotrophy. Curiously, acidic biofilms forming above degassing sulfidic cave streams, and the invertebrates that feed on them, are extremely depleted in nitrogen-15 (δ 15 N values less than −20‰). In this study, we tested the hypothesis that these low δ 15 N values result from the volatilization, trapping, and uptake of ammonia degassed from circumneutral streams. We found that dissolved ammonium in the streams had δ 15 N values near +3‰, whereas NH 3(g) in the cave atmosphere above streams exhibited δ 15 N values as low as −27‰, consistent with fractionation by NH 3 volatilization. Extremely acidic condensation droplets on cave walls efficiently trapped airborne NH 3 , accumulating up to 4 mM NH 4 + with δ 15 N values as low as −29‰, thereby confirming volatilized and trapped ammonia as the primary N source to cave wall biofilms and the extensive subsurface ecosystem they support. Airborne ammonia trapping represents a novel mechanism for biological N acquisition and provides abundant N for growth in an extreme subsurface environment that otherwise receives very limited nutrient input.

Nitrogen↗