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At least 19 records

Rn-222 tracing and stable isotope measurements of biogenic gas fluxes from methane saturated sediments

Transport of reduced biogenic gases from anoxic sediments and soils to the atmosphere can be quantitatively studied through measurement of radon-222/radium-226 disequilibrium. In previous work, seasonal variations in biogenic gas transport mechanisms, net fluxes and overall composition were documented. Now presented are direct field measurements of radon-222 activity in gases exiting organic rich sediments which show their usefulness for tracing of the stripping of dissolved biogenic gases from within the sediment column and transport via bubble ebullition. Methane is depleted in deuterium during the summer as compared with winter months and is in general lighter than in most marine sediments signaling the probable importance of acetate as an important precursor molecule. The significant seasonal isotopic variations observed illustrate the importance of understanding mechanisms and rates of biogenic gas production in order to interpret observed tropospheric isotopic data.

Martens, Christopher S.↗

Atmospheric Trace Gas Abundances and Stable Isotope Ratios via IR-LIF

We propose to develop new technologies with support provided by PIDDP that will enable the in situ measurements of abundances and stable isotope ratios in important radiatively and biogenically active gases such as carbon dioxide, carbon monoxide, water, methane, nitrous oxide, and hydrogen sulfide to very high precision (0.1 per mil or better for the isotopic ratios, for example). Such measurements, impossible at present, could provide pivotal new constraints on the global (bio)geochemical budgets of these critical species, and could also be used to examine the dynamics of atmospheric transport on Mars, Titan, and other solar system bodies. We believe the combination of solid state light sources with imaging of the IR laser induced fluorescence (IR-LIF) via newly available detector arrays will make such in situ measurements possible for the first time. Even under ambient terrestrial conditions, the LIF yield from vibrational excitation of species such as water and carbon dioxide should produce emission measures well in excess of ten billion photons/sec from samples volumes of order 1 c.c. These count rates can, in principle, yield detection limits into the sub-ppt range that are required for the in situ isotopic study of atmospheric trace gases. While promising, such technologies are relatively immature, but developing rapidly, and there are a great many uncertainties regarding their applicability to in situ IR-LIF planetary studies. We therefore feel PIDDP support will be critical to developing these new tools, and propose a three-year program to combine microchip near-IR lasers with low background detection axes and state-of-the-art HgCdTe detectors developed for astronomical spectroscopy to investigate the sensitivity of IR-LIF under realistic planetary conditions, to optimize the optical pumping and filtering schemes for important species, and to apply the spectrometer to the non-destructive measurement of stable isotopes in a variety of test samples. These studies form the necessary precursors to the development of compact, lightweight stable isotope/trace gas sensors for future planetary missions.

Blake, Geoffrey A.↗

Trace element and isotope geochemistry of Cretaceous-Tertiary boundary sediments: identification of extra-terrestrial and volcanic components

Trace element and stable isotope analyses were performed on a series of sediment samples crossing the Cretaceous-Tertiary (K-T) boundary from critical sections at Aumaya and Sopelano, Spain. The aim is to possibly distinguish extraterrestrial vs. volcanic or authigenic concentration of platinum group and other elements in K-T boundary transitional sediments. These sediments also have been shown to contain evidence for step-wise extinction of several groups of marine invertebrates, associated with negative oxygen and carbon isotope excursions occurring during the last million years of the Cretaceous. These isotope excursions have been interpreted to indicate major changes in ocean thermal regime, circulation, and ecosystems that may be related to multiple events during latest Cretaceous time. Results to date on the petrographic and geochemical analyses of the Late Cretaceous and Early Paleocene sediments indicate that diagenesis has obviously affected the trace element geochemistry and stable isotope compositions at Zumaya. Mineralogical and geochemical analysis of K-T boundary sediments at Zumaya suggest that a substantial fraction of anomalous trace elements in the boundary marl are present in specific mineral phases. Platinum and nickel grains perhaps represent the first direct evidence of siderophile-rich minerals at the boundary. The presence of spinels and Ni-rich particles as inclusions in aluminosilicate spherules from Zumaya suggests an original, non-diagenetic origin for the spherules. Similar spherules from southern Spain (Caravaca), show a strong marine authigenic overprint. This research represents a new approach in trying to directly identify the sedimentary mineral components that are responsible for the trace element concentrations associated with the K-T boundary.

Margolis, S. V.↗

The Effects of Experimentally Induced Zircon Annealing on Melt Inclusion-Zircon Geochemistry: A Case Study of Archean Zircon From the Barberton Complex

Crystalline melt inclusions (MIs) in Archean zircons can potentially constrain the evolution of magmatic processes. However, to obtain a homogeneous glassy MI representative of the parent melt, devitrified MIs must be heated at temperatures above the liquidus. Although, it is well known that radiation damaged domains in MI-host zircon undergo temperature-time dependent annealing, the effects of annealing on zircon stable isotope and trace element compositions has received less attention. In this study, we heated multiple aliquots of low-magnetism zircons with relatively low levels of radiation damage (Deff<9.6x1014 α-events/mg) from a 3.304 Ga tonalite gneiss xenolith from the Barberton greenstone belt (sample B87-18; Kamo and Davis, 1994) in an internally-heated pressure vessel at 0.4GPa and 1000–1200°C. Zircons were imaged by SEM (CL, BSE) to determine the zoning patterns around the MIs. The radiation damage preserved in the heated and unheated zircons was determined by measuring broadening of the 3(SiO4) Raman stretching band of zircon (FWHM). Oxygen isotope ratios (δ18O), OH/O ratios, and trace and rare earth element (TREE) concentrations were measured in the zircons and MIs using SIMS. The FWHM and Raman shift of the zircon 3(SiO4) band show a systematic increase of zircon crystallinity with increasing experimental temperature. Despite increasing crystallinity, the 3(SiO4) FWHM is not correlated with δ18O(Zrn) values in the heated or unheated zircons, suggesting that δ18O was not altered by laboratory heating in these low initial radiation damage zircons. FWHM and OH/O are positively correlated in both heated and unheated zircons. The unheated zircons have the largest FWHM and OH/O (OH/OMAX=3.5×10-4) suggesting that H2O was lost during experimental heating due to the progressive annealing of radiation-damaged domains in the zircons. Zircon TREE concentrations and FWHM values are not correlated despite the presence of TREE altered domains in both the heated and unheated zircons. Our results demonstrate that pre-experimental zircon TREE concentrations and δ18O(Zrn) remain intact during laboratory heating of crystalline MIs in zircon, while secondary H2O hosted in radiation damaged domains is partially lost. Thus, MIs in low initial radiation damage Archean zircon are a potentially viable tool for constraining melt compositions.

Joseph P. Gonzalez↗

Macrofossil records of West Antarctic Ice Sheet retreat during the Holocene

Marine macrofossils in emerged beaches around Antarctica represent a geochemical framework for interpreting meltwater signatures associated with variations in the adjacent ice sheet margins during the last 10,000 years. In particular, mollusc species provide ideal experimental templates for assessing hydrochemical variations in Antarctic coastal marine environments because of their excellent preservation, high abundances, circumpolar distributions, and carbonate shells, which incorporate trace elements and stable isotopes. Modern samples of the bivalve Adamussium colbecki, which were collected across a depth gradient in the vicinity of a glacial meltwater stream in West McMurdo Sound, revealed shell trace element concentrations that were significantly higher above 10 meters because of their exposure to meltwater runoff. This meltwater signature also was reflected by the shell oxygen isotopic composition, which was in equilibrium with the ambient seawater, as demonstrated by the overlap between the predicted and actual O-(delta-18)sub w values. These modern samples provide analogs for interpreting the geochemical records in their fossils, which were based solely on molluscan fossils, complement the above geochemical data by suggesting that the rate of beach emergence fluctuated around Antarctica during the mid-Holocene. Paleoenvironmental analysis of macrofossils from emerged beaches represents a new direction in Antarctic research that can be used to assess changes in the margins of the ice sheets since the Last Glacial Maximum. The resolution of these analyses will be enhanced by collaborations that are developing with scientists who are conducting comparable studies in other coastal regions around the continent.

Berkman, Paul Arthur↗

Revealing the Mysteries of Venus: The DAVINCI Mission

The Deep Atmosphere Venus Investigation of Noble gases, Chemistry, and Imaging (DAVINCI) mission described herein has been selected for flight to Venus as part of the NASA Discovery Program. DAVINCI will be the first mission to Venus to incorporate science driven flybys and an instrumented descent sphere into a unified architecture. The anticipated scientific outcome will be a new understanding of the atmosphere, surface, and evolutionary path of Venus as a possibly once-habitable planet and analog to hot terrestrial exoplanets. The primary mission design for DAVINCI as selected features a preferred launch in summer/fall 2029, two flybys in 2030, and descent sphere atmospheric entry by the end of 2031. The in situ atmospheric descent phase subsequently delivers definitive chemical and isotopic composition of the Venus atmosphere during an atmospheric transect above Alpha Regio. These in situ investigations of the atmosphere and near infrared descent imaging of the surface will complement remote flyby observations of the dynamic atmosphere, cloud deck, and surface near infrared emissivity. The overall mission yield will be at least 60 Gbits (compressed) new data about the atmosphere and near surface, as well as the first unique characterization of the deep atmosphere environment and chemistry, including trace gases, key stable isotopes, oxygen fugacity, constraints on local rock compositions, and topography of a tessera.

James B Garvin↗

The Frasnian-Famennian mass killing event(s), methods of identification and evaluation

The absence of an abnormally high number of earlier Devonian taxa from Famennian sediments was repeatedly documented and can hardly be questioned. Primary recognition of the event(s) was based on paleontological data, especially common macrofossils. Most paleontologists place the disappearance of these common forms at the gigas/triangularis contact and this boundary was recently proposed as the Frasnian-Famennian (F-F) boundary. Not unexpectedly, alternate F-F positions were suggested caused by temporary Frasnian survivors or sudden post-event radiations of new forms. Secondary supporting evidence for mass killing event(s) is supplied by trace element and stable isotope geochemistry but not with the same success as for the K/T boundary, probably due to additional 300 ma of tectonic and diagenetic overprinting. Another tool is microfacies analysis which is surprisingly rarely used even though it can explain geochemical anomalies or paleontological overlap not detectable by conventional macrofacies analysis. The combination of microfacies analysis and geochemistry was applied at two F-F sections in western Canada and showed how interdependent the two methods are. Additional F-F sections from western Canada, western United States, France, Germany and Australia were sampled or re-sampled and await geochemical/microfacies evaluation.

Geldsetzer, H. H. J.↗

The Chemical and Isotopic Signatures of the Hibonite-rich FUN Inclusion "HIDALGO" in Dar al Gani 027 (CO3)

Refractory Ca-Al-rich Inclusions (CAIs) with FUN (Fractionation with Unidentified Nuclear effects) characteristics are peculiar samples among all high-temperature components in chondritic meteorites. They are generally characterized by strong mass-dependent isotopic fractionations in several elements (e.g., O, Mg, Ca, Ti), large (~5-20‰) enrichments or depletions in neutron-rich isotopes (e.g., 48 Ca, 50 Ti, 54 Cr), and low inferred abundances of 26 Al ( 26 Al/ 27 Al < 1×10 −5 ). Understanding the origins of these features in FUN CAIs can shed light on the astrophysical environment and chemical processes that took place in the early Solar System. A large fraction (slightly less than 50%) of the ~20 FUN CAIs discovered so far are hibonite-rich (such as HAL, SHAL and DH-H1, collectively called HAL-type inclusions hereafter). According to their elemental and isotopic signatures and the results of evaporation experiments, HAL-type inclusions are thought to have formed as a distillation residue. However, questions regarding the timing of the formation of HAL-type inclusions (or FUN inclusions in general) relative to those of regular CAIs and the decoupling between the 26 Al abundances and nucleosynthetic anomalies remain poorly understood. In 2021, we reported the discovery of a new HAL-type inclusion, HIDALGO (Hibonite in Dar al Gani CO3) in the CO3 chondrite Dar al Gani 027 (DaG027), based on its (fractionated) oxygen isotopic compositions and low inferred 26 Al/ 27 Al ratio of (1.50±0.02)×10 −5 . Since then, more work on other short-lived and stable isotope systems and trace element abundances has been conducted. Here we report these new results and discuss the implications for the possible formation history of HIDALGO and origins of shortlived radionuclides (SLRs).

Meteorite↗

Neutral Mass Spectrometry for Venus Atmosphere and Surface

The assignment is to make precise (better than 1 %) measurements of isotope ratios and accurate (5-10%) measurements of abundances of noble gas and to obtain vertical profiles of trace chemically active gases from above the clouds all the way down to the surface. Science measurement objectives are as follows: 1) Determine the composition of Venus atmosphere, including trace gas species and light stable isotopes; 2) Accurately measure noble-gas isotopic abundance in the atmosphere; 3) Provide descent, surface, and ascent meteorological data; 4) Measure zonal cloud-level winds over several Earth days; 5) Obtain near-IR descent images of the surface from 10-km altitude to the surface; 6) Accurately measure elemental abundances & mineralogy of a core from the surface; and 7) Evaluate the texture of surface materials to constrain weathering environment.

Mahaffy, Paul↗

Winds, Water Budgets and Stable Isotopes in Tropical Cyclones using TRMM and QUICKSCAT

Water vapor is the most abundant greenhouse gas in the atmosphere. Changes in its concentration and distribution are controlled by the hydrologic cycle. Because of its capacity to absorb and emit long wave radiation, release latent heat during condensation in storms and reflect short wave radiation when clouds form it has a major impact on Global climate change. The stable isotope ratios of water are H20 H2l6O and H0 H2l6O. These ratios change whenever water undergoes a phase change. They also change in both rain and water vapor whenever an air parcel is exposed to rain. In addition the relative changes in the two ratios differ as a &nction of the relative humidity. In short, the stable isotope ratios in water vapor in the atmosphere contain an integrated history of the processes affecting the concentration and distribution of water vapor in the atmosphere. Therefore the measurement and interpretation of changes in these stable isotope ratios are a powerful tool matched by no other method in tracing the transport history of water in the atmosphere. Our initial studies under this grant focused on the changes of the stable isotope ratios of precipitation and water vapor in tropical cyclones. The changes in time and space were found to be very large and to trace the transport of water in the storms reflecting changes in basic structural features. Because the stable isotope ratios of rains from tropical cyclones are so low flooding associated with land falling tropical cyclones introduces a negative isotopic spike into the coastal surface waters. In addition the stable isotope ratios of water vapor in the vicinity of tropical cyclones is anomalously low. This suggests that carbonate shelled organisms such as ostracoda living in coastal waters have the potential to record the isotopic spike and thereby provide a long term record of tropical storm activity in sediment cores containing fossil shells. Likewise, tree rings in coastal environments offer a similar potential. We have analyzed the oxygen isotopic composition of ostrcoda shells formed in the floodwaters of Tropical Storm Allison (2001) and discovered the negative isotopic 1 16 spike. Because we had learned that storm activity has a major impact on the stable isotope ratios of water vapor in the tropics and sub-tropics we decided to analyze the isotopic compositions of water vapor in different locations in the tropics. We did this in Puerto Escondido, Mexico in July 1998, near Kwajalein Island in the Pacific in 1999 as part of a TRMM summer field program and in 2001 in Key West, Florida as part of the CAMEX 4 summer field program. Our isotopic studies along with our earlier tropical cyclone studies showed that the low isotopic ratios in water vapor induced by exposure to rains the storms persisted for 48 hours often far away from the original storm site. We also noted that positive isotopic spikes were introduced into atmospheric water vapor if winds were high and extensive sea spray was present. These findings have a significant impact on the interpretation of the stable isotope studies of tropical ice cores found in the high mountain regions of the tropics. The assumption made in interpreting the ice core record is that the source water vapor evaporated from the sea surface is in near isotopic equilibrium with the seawater and undergoes a decrease during its transport that reflects the change in temperature from the sea surface to the site of the ice core. Because an additional isotopic depletion occurs at the sea surface source area that depends on the intensity, duration and size of the tropical rain system the isotopic variations found in the ice cores must take into account changes in past storm activity in the tropics. These systems must be an important source of water vapor to the ice cores because they charge the troposphere with water vapor to a far greater vertical height than evaporation in quiescent regions. Finally, an interest in increased heat transfer in thnterior of tropical cyclones resulting from greater amounts of sea spray is a topic of considerable interest to the research community. Increases in sea spray may be related to rapid changes in the intensity of hurricanes, a feature of hurricanes that currently is very poorly forecast. Project CBLAST of the Hurricane Research Division of NOAA is an active program that uses P3 research aircraft to evaluate this problem. An instrument has been designed and built at the University of Houston that will be placed on the P3 research aircraft during the 2004 hurricane season. It continuously measures the salt content of rain in hurricanes. Changes in the salt content of the rains should reflect the abundance of sea spray at the sea surface. In this way maps of sea spray intensity in hurricanes may be forthcoming. This should help computer modelers who simulate hurricanes to better understand the potential of changes in sea spray to change the intensity of hurricanes. The cost of designing, building and installing this instrument was borne largely by funding from this NASA grant. A list of presentations at national meetings and publications that were as the result of funding from this NASA grant are found in the report.

Lawrence, James R.↗

Chlorine stable isotopes in sedimentary systems: does size matter?

Stable isotope abundances vary because of size differences. The chlorine stable isotope system was one of the first described theoretically, but had a slow, disappointment strewn development, relative to other elements. Method improvement gave only small, but significant, differences in compositions of geological materials. Eventually, brines and groundwater chlorides gave larger differences. Physical processes like diffusion and adsorption, probably are the main controls of groundwater compositions. Recent work on anthropogenic groundwater contaminants shows variations resulting from manufacturing processes; implying possibilities of tracing sources.

chlorine stable isotopes↗

Bulk and Stable Isotopic Compositions of Carbonate Minerals in Martian Meteorite Allan Hills 84001: No Proof of High Formation Temperature

Understanding the origin of carbonate minerals in the Martian meteorite Allan Hills (ALH) 84001 is crucial to evaluating the hypothesis that they contain traces of ancient Martian life. Using arguments based on chemical equilibria among carbonates and fluids, an origin at greater than 650 C (inimical to life) has been proposed. However, the bulk and stable isotopic compositions of the carbonate minerals are open to multiple interpretations and so lend no particular support to a high-temperature origin. Other methods (possibly less direct) will have to be used to determine the formation temperature of the carbonates in ALH 84001.

Treiman, Allan H.↗

Lunar and Planetary Science XXXV: Impacts on Mars and Earth

The session "Impacts on Mars and Earth" included the following reports:A Timescale for Major Events in Early Mars Crustal Evolution; Impact Craters in Arabia Terra, Mars; Ancient Giant Basin/Aquifer System in the Arabia Region, Mars; Small Crater Morphology Within Gusev Crater and Isidis Planitia: Evidence for Widespread Secondaries on Mars; Martian Surface Properties: Inferences from Resolved Differences in Crater Geometries; Asymmetric Ramparts of Secondary Craters in Cerberus, Mars: Interpretation and Implications for Local Stratigraphy; Depth to Diameter Relationships of Craters in the High Latitudes (70 -80 ) of Mars: Implications for Geologic History of Those Areas; Impact Cratering on Mars: Search for Target Influence on Morphology; Starting Conditions for Hydrothermal Systems Underneath Martian Craters: Hydrocode Modeling; Impact-induced Hydrothermal System at the Sudbury Crater: Duration, Temperatures, Mechanics, and Biological Implications; Major and Trace Element Variations in Impact Crater Clay from Chicxulub, Lonar, and Mistastin, Implications for the Martian Soil; Stable Isotopes and Hydrothermal Fluid Source in the Yaxcopoil-1 Borehole, Chicxulub Impact Structure, Mexico; and Chicxulub Impact Melts: Geochemical Signatures of Target Lithology Mixing and Post-Impact Hydrothermal Fluid Processes.

Source record↗

Geochemical aspects of some Japanese lavas.

K, Rb, Sr, Ba and rare-earth concentrations in some Japanese lavas have been determined by mass-spectrometric stable-isotope dilution. The samples fall into three rare-earth groups corresponding to tholeiitic, high alumina and alkali basalts. Japanese tholeiites have trace element characteristics similar to those of oceanic ridge tholeiites except for distinctly higher relative concentrations of Ba. Japanese lavas may result from various degrees of partial fusion of amphibole eclogite.

Philpotts, J. A.↗

Precision Subsampling System for Mars Surface Missions

The ability to analyze heterogeneous rock samples at fine spatial scales would represent a powerful addition to our planetary in situ analytical toolbox. This is particularly true for Mars, where the signatures of past environments and, potentially, habitability are preserved in chemical and morphological variations across sedimentary layers and among mineral pr.ases in a given rock specimen. On Earth, microbial life often associates with surfaces at the interface of chemical nutrients, and ultimately retains sub-millimeter to millimeter-scale layer confinement in fossilization. On Mars, and possibly other bodies, trace chemical markers (elemental, organic/molecular, isotopic, chiral, etc.) and fine-scale morphological markers (e.g., micro-fossils) may he too subtle, degraded, or ambiguous to be detected, using miniaturized instrumentation, without some concentration or isolation. This is because (i) instrument sensitivity may not be high enough to detect trace markers in bulk averages; and (ii) instrument s~lectiviry may not be sufficient to distinguish such markers from interfering/counteracting signals from the bulk. Moreover from a fundamental chemostratigraphic perspective there would be a great benefit to assessing specific chemical and stable isotopic gradients, over millimeter-to-centimeter scales and beyond, with higher precision than currently possible in situ. We have developed a precision subsampling system (PSS) that addresses this need while remaining relatively flexible to a variety of instruments that may take advantage of the capability on future missions. The PSS is relevant to a number of possible lander/rover missions, especially Mars Sample Return. Our specific PSS prototype is undergoing testing under Mars ambient conditions, on a variety of natural analog rocks and rock drill cores, using a set of complementary flight-compatible measurement techniques. The system is available for testing with other contact instruments that may benefit from precision sampling.

Mahaffy, P. R.↗

Light stable isotope analysis of meteorites by ion microprobe

The main goal was to develop the necessary secondary ion mass spectrometer (SIMS) techniques to use a Cameca ims-4f ion microprobe to measure light stable isotope ratios (H, C, O and S) in situ and in non-conducting mineral phases. The intended application of these techniques was the analysis of meteorite samples, although the techniques that have been developed are equally applicable to the investigation of terrestrial samples. The first year established techniques for the analysis of O isotope ratios (delta O-18 and delta O-17) in conducting mineral phases and the measurement of S isotope ratios (delta S-34) in a variety of sulphide phases. In addition, a technique was developed to measure delta S-34 values in sulphates, which are insulators. Other research undertaken in the first year resulted in SIMS techniques for the measurement of wide variety of trace elements in carbonate minerals, with the aim of understanding the nature of alteration fluids in carbonaceous chondrites. In the second year we developed techniques for analyzing O isotope ratios in nonconducting mineral phases. These methods are potentially applicable to the measurement of other light stable isotopes such as H, C and S in insulators. Also, we have further explored the analytical techniques used for the analysis of S isotopes in sulphides by analyzing troilite in a number of L and H ordinary chondrites. This was done to see if there was any systematic differences with petrological type.

Mcsween, Harry Y., Jr.↗