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NASA NTRS2003

AGE (Argon Geochronology Experiment): An Instrument for Geochronology on the Surface of Mars

As our knowledge of the planet Mars continues to grow, one parameter that remains elusive is the absolute chronology of the planet s geological history. Although crater counts have provided a robust relative chronology, impactor fluxes are poorly enough known that there are places on Mars where the absolute age is uncertain by a factor of two or more. To resolve these uncertainties, it will be necessary to either analyze well-documented samples returned to the Earth from the Martian surface or to perform in situ measurements with sufficient precision. Sample return is still at least a decade away, and even then it might be from a biologically interesting area that might be geologically complex. Hence an in situ measurement, within an uncertainty of 20% or better, could greatly improve our knowledge of the history of Mars. With funding from the Planetary Instrument Definition and Development Program (PIDDP), we have been working on an instrument to perform potassium-argon (K-Ar) and cosmic-ray exposure (CRE) dating in situ on the surface of Mars. For either of these techniques, it is necessary to measure the abundance of one or more major or minor elements (K in the case of KAr; all majors and minors in the case of CRE) and the abundance and isotopes composition of a noble gas (Ar in the case of K-Ar; He, Ne and Ar for CRE dating). The technology for either of these types of measurements exists, but has never before been integrated for a spacecraft. We refer to the instrument as AGE, the Argon Geochronology Experiment (although we will measure the noble gases He and Ne as well for CRE ages). We report here on the basic components that go into such an instrument, both those that use existing technology and those that had to be developed to create the integrated package.

Swindle, T. D.↗

NASA NTRS2016

Continued Development of in Situ Geochronology for Planetary Using KArLE (Potassium-Argon Laser Experiment)

Geochronology is a fundamental measurement for planetary samples, providing the ability to establish an absolute chronology for geological events, including crystallization history, magmatic evolution, and alteration events, and providing global and solar system context for such events. The capability for in situ geochronology will open up the ability for geochronology to be accomplished as part of lander or rover complement, on multiple samples rather than just those returned. An in situ geochronology package can also complement sample return missions by identifying the most interesting rocks to cache or return to Earth. The K-Ar radiometric dating approach to in situ dating has been validated by the Curiosity rover on Mars as well as several laboratories on Earth. Several independent projects developing in situ rock dating for planetary samples, based on the K-Ar method, are giving promising results. Among them, the Potassium (K)-Argon Laser Experiment (KArLE) at MSFC is based on techniques already in use for in planetary exploration, specifically, Laser-induced Breakdown Spectroscopy (LIBS, used on the Curiosity Chemcam), mass spectroscopy (used on multiple planetary missions, including Curiosity, ExoMars, and Rosetta), and optical imaging (used on most missions).

In SITU Geochronology↗

NASA NTRS2012

Development of the Potassium-Argon Laser Experiment (KArLE) Instrument for In Situ Geochronology

Absolute dating of planetary samples is an essential tool to establish the chronology of geological events, including crystallization history, magmatic evolution, and alteration. Traditionally, geochronology has only been accomplishable on samples from dedicated sample return missions or meteorites. The capability for in situ geochronology is highly desired, because it will allow one-way planetary missions to perform dating of large numbers of samples. The success of an in situ geochronology package will not only yield data on absolute ages, but can also complement sample return missions by identifying the most interesting rocks to cache and/or return to Earth. In situ dating instruments have been proposed, but none have yet reached TRL 6 because the required high-resolution isotopic measurements are very challenging. Our team is now addressing this challenge by developing the Potassium (K) - Argon Laser Experiment (KArLE) under the NASA Planetary Instrument Definition and Development Program (PIDDP), building on previous work to develop a K-Ar in situ instrument [1]. KArLE uses a combination of several flight-proven components that enable accurate K-Ar isochron dating of planetary rocks. KArLE will ablate a rock sample, determine the K in the plasma state using laser-induced breakdown spectroscopy (LIBS), measure the liberated Ar using quadrupole mass spectrometry (QMS), and relate the two by the volume of the ablated pit using an optical method such as a vertical scanning interferometer (VSI). Our preliminary work indicates that the KArLE instrument will be capable of determining the age of several kinds of planetary samples to +/-100 Myr, sufficient to address a wide range of geochronology problems in planetary science.

Cohen, Barbara A.↗

NASA NTRS2014

Updates of the KArLE Experiment: New Libs Calibration Under High Vacuum for the Quantification of Potassium in Basalt for In Situ Geochronology

In planetary exploration, in situ absolute geochronology is one of the main important measurements that needs to be accomplished. Until now, on Mars, the age of the surface is only determined by crater density counting, which gives relative ages. These ages can have a lot of uncertainty as they depend on many parameters. More than that, the curves must be ties to absolute ages. Thus far, only the lost lander Beagle 2 was designed to conduct absolute geochronology measurements, though some recent attempts using MSL Curiosity show that this investigation is feasible and should be strongly encouraged for future flight. Experimental: The Potassium (K)-Argon Laser Experiment (KArLE) is being developed at MSFC through the NASA Planetary Instrument Definition and Development Program (PIDDP). The goal of this experiment is to provide in situ geochronology based on the K-Ar method. A laser ablates a rock under high vacuum, creating a plasma which is sensed by an optical spectrometer to do Laser Induced Breakdown Spectroscopy (LIBS). The ablated material frees gases, including radiogenic 40Ar,which is measured by a mass spectrometer (MS). As the potassium is a content and the 40Ar is a quantity, the ablated mass needed in order to relate them. The mass is given by the product of the ablated volume by the density of this material. So we determine the mineralogy of the ablated material with the LIBS spectra and images and calculate its density. The volume of the pit is measured by using microscopy. LIBS measurement of K under high vacuum: Three independant projects [1, 2, 3] including KArLE, are developing geochronological instruments based on this LA-LIBS-MS method. Despite several differences in their setup, all of them have validated the methods with analyses and ages. However, they all described difficulties with the LIBS measurements of K [3,4]. At ambient pressure, the quantification of K by LIBS on geological materials can be accurate [5]. However the protocol of the LA-LIBS-MS experiment required hundreds of shots under high vacuum in order to free enough 40Ar* to be measured by the QMS. This long duration of ablation may induces significant changes in the LIBS spectra. The pressure may increases by orders of magnitudewithin the chamber and the laser pit geometry can change the effectiveness of ablation and intensity of plasma light received. These effects introduce variation between the first and last spectra and so the quantification of K is more complex. The ablation of one crater can give, depending on the protocol of acquisition, from tens to hundreds of spectra. Protocol and results: We are in the process of further characterizing the variation introduced into LIBS spectra by the use of hundreds of laser shots, and definining a protocol that can be used to ensure accuracy and reporoducibility in the results.We are using natural rock powder standards fused in a furnace, as well as mars analog samples with known K content. We will show the result of the calibration and some new statistical approaches in order to apprehend the effects of the long time ablation on rocks under high vacuum.

Devismes, D.↗

NASA NTRS2014

The Potassium-Argon Laser Experiment (KARLE): In Situ Geochronology for Planetary Robotic Missions

Isotopic dating is an essential tool to establish an absolute chronology for geological events, including crystallization history, magmatic evolution, and alteration events. The capability for in situ geochronology will open up the ability for geochronology to be accomplished as part of lander or rover complement, on multiple samples rather than just those returned. An in situ geochronology package can also complement sample return missions by identifying the most interesting rocks to cache or return to Earth. The K-Ar Laser Experiment (KArLE) brings together a novel combination of several flight-proven components to provide precise measurements of potassium (K) and argon (Ar) that will enable accurate isochron dating of planetary rocks. KArLE will ablate a rock sample, measure the K in the plasma state using laser-induced breakdown spectroscopy (LIBS), measure the liberated Ar using mass spectrometry (MS), and relate the two by measuring the volume of the ablated pit by optical imaging. Our work indicates that the KArLE instrument is capable of determining the age of planetary samples with sufficient accuracy to address a wide range of geochronology problems in planetary science. Additional benefits derive from the fact that each KArLE component achieves analyses useful for most planetary surface missions.

Cohen, B. A.↗

NASA NTRS2016

The Potassium-Argon Laser Experiment (karle): In Situ Geochronology for Planetary Missions

Isotopic dating is an essential tool to establish an absolute chronology for geological events. It enables a planet's crystallization history, magmatic evolution, and alteration to be placed into the framework of solar system history. The capability for in situ geochronology will open up the ability for this crucial measurement to be accomplished as part of lander or rover complement. An in situ geochronology package can also complement sample return missions by identifying the most interesting rocks to cache or return to Earth. Appropriate application of in situ dating will enable geochronology on more terrains than can be reached with sample-return missions to the Moon, Mars, asteroids, outer planetary satellites, and other bodies that contain rocky components. The capability of flight instruments to conduct in situ geochronology is called out in the NASA Planetary Science Decadal Survey and the NASA Technology Roadmap as needing development to serve the community's needs. Beagle 2 is the only mission launched to date with the explicit aim to perform in situ K-Ar isotopic dating [1], but it failed to communicate and was lost. The first in situ K-Ar date on Mars, using SAM and APXS measurements on the Cumberland mudstone [2], yielded an age of 4.21 +/- 0.35 Ga and validated the idea of K-Ar dating on other planets, though the Curiosity method is not purpose-built for dating and requires many assumptions that degrade its precision. To get more precise and meaningful ages, multiple groups are developing dedicated in situ dating instruments.

planetary↗

NASA NTRS2022

Identifying Shocked Feldspar on Mars Using Perseverance Spectroscopic Instruments: Implications for Geochronology Studies on Returned Samples

The Perseverance rover (Mars 2020) mission, the first step in NASA’s Mars Sample Return (MSR) program, will select samples for caching based on their potential to improve understanding Mars’ astrobiological, geological, geochemical, and climatic evolution. Geochronologic analyses will be among the key measurements planned for returned samples. Assessing a sample’s shock history will be critical because shock metamorphism could influence apparent sample age. Shock effects in one Mars-relevant mineral class, plagioclase feldspar, have been well- documented using various spectroscopy techniques (thermal infrared reflectance, emission, and transmission spectroscopy, Raman, and luminescence). A subset of these data will be obtained with the SuperCam and SHERLOC (Scanning Habitable Environments with Raman & Luminescence for Organics & Chemicals) instruments onboard Perseverance to inform caching decisions for MSR. Here, we review shock indicators in plagioclase feldspar as revealed in Raman, luminescence, and IR spectroscopy lab data, with an emphasis on Raman spectroscopy. We consider how this information may inform caching decisions for selecting optimal samples for geochronology measurements. We then identify challenges and make recommendations for both in situ measurements performed with SuperCam and SHERLOC and for supporting lab studies to enhance the success of geochronologic analyses after return to Earth.

mars↗

NASA NTRS2014

Relationship between LIBS Ablation and Pit Volume for Geologic Samples: Applications for in situ Absolute Geochronology

In planetary sciences, in situ absolute geochronology is a scientific and engineering challenge. Currently, the age of the Martian surface can only be determined by crater density counting. However this method has significant uncertainties and needs to be calibrated with absolute ages. We are developing an instrument to acquire in situ absolute geochronology based on the K‐Ar method. The protocol is based on the laser ablation of a rock by hundreds of laser pulses. Laser Induced Breakdown Spectroscopy (LIBS) gives the potassium content of the ablated material and a mass spectrometer (quadrupole or ion trap) measures the quantity of 40Ar released. In order to accurately measure the quantity of released 40Ar in cases where Ar is an atmospheric constituent (e.g., Mars), the sample is first put into a chamber under high vacuum. The 40Arquantity, the concentration of K and the estimation of the ablated mass are the parameters needed to give the age of the rocks. The main uncertainties with this method are directly linked to the measures of the mass (typically some μg) and of the concentration of K by LIBS (up to 10%). Because the ablated mass is small compared to the mass of the sample, and because material is redeposited onto the sample after ablation, it is not possible to directly measure the ablated mass. Our current protocol measures the ablated volume and estimates the sample density to calculate ablated mass. The precision and accuracy of this method may be improved by using knowledge of the sample's geologic properties to predict its response to laser ablation, i.e., understanding whether natural samples have a predictable relationship between laser energy deposited and resultant ablation volume. In contrast to most previous studies of laser ablation, theoretical equations are not highly applicable. The reasons are numerous, but the most important are: a) geologic rocks are complex, polymineralic materials; b) the conditions of ablation are unusual (for example, variable vacuum pressure), and c) the ablation is made with hundreds of successive laser pulses. In this work, we aim to understand the effects that occur on LIBS spectra when a homogeneous rock or a mineral is ablated under high vacuum. Understanding these effects is important to define best practices for LIBS measurements and may lead to improved measurement (or possibly prediction) of the ablated volume. We will describe our laboratory approach and first results, and discuss its utility for situ absolute geochronology campaigns.

Devismes, D.↗

NASA NTRS1988

Present status of the geochronology of the early Precambrian of South India

The present status of Precambrian geochronology of South India was summarized. Support was offered for Raith's conclusion of an extensive 3.3 to 3.4-Ga tonalite-forming event. Evidence that the Sargur supracrustal sequence predates this event, however, remains equivocal. The only reliably dated supracrustal rocks are the similar to 3.0-Ga Chitradurga acid volcanics, and these are separated from the older Bababudan supracrustals by a major gneiss-forming event. A major unsolved problem relates to the timing of the Sargur supracrustals in relation to the basal units of the Dharwar succession. An appeal was made for more geochronological work on South Indian samples.

Gopalan, K.↗

NASA NTRS2004

Ar-40 - Ar-39 Geochronology on Apollo 12 Regolith

The Apollo 12 landing site in Oceanus Procellarum is located about 400 km south of the rim of Copernicus. The geochemical and petrographical characterization of the Apollo 12 lunar samples have been extensively studied. The site is characterized by a high proportion of nonmare material with KREEP composition and mare basalts low in Th. Recent studies have focused on the geochemistry of the nonmare material and on inferring the origin of these materials. Previous geochronological investigations of Apollo 12 mare basalts have yielded ages ranging from 3.1 to 3.3 Ga. On the other hand, nonmare materials have yielded older ages between 3.8 to 4.0 Ga; with the sole exception of a single lunar granite fragment from sample 12033. This granite sample has an Ar-40 - Ar-39 age of 800 +/- 15 Ma. This resetting age has been interpreted as the age of the Copernicus crater since a ray from this crater crosses the landing site. Here we present new 40Ar-39Ar geochronological data on three samples of nonmare material from the Apollo 12 regolith in order to further constrain the age and source of this material.

Barra, F.↗

NASA NTRS2006

The Argon Geochronology Experiment (AGE)

This viewgraph presentation reviews the Argon Geochronology Experiment (AGE). Potassium-Argon dating is shown along with cosmic ray dating exposure. The contents include a flow diagram of the Argon Geochronology Experiment, and schematic diagrams of the mass spectrometer vacuum system, sample manipulation mechanism, mineral heater oven, and the quadrupole ion trap mass spectrometer. The Laser-Induced Breakdown Spectroscopy (LIBS) Operation with elemental abundances is also described.

age dating↗

NASA NTRS2012

Developement of the Potassium-Argon Laser Experiment (KArLE) for In Situ Geochronology

Absolute dating of planetary samples is an essential tool to establish the chronology of geological events, including crystallization history, magmatic evolution, and alteration. Thus far, radiometric geochronology of planetary samples has only been accomplishable in terrestrial laboratories on samples from dedicated sample return missions and meteorites. In situ instruments to measure rock ages have been proposed, but none have yet reached TRL 6, because isotopic measurements with sufficient resolution are challenging. We have begun work under the NASA Planetary Instrument Definition and Development Program (PIDDP) to develop the Potassium (K) - Argon Laser Experiment (KArLE), a novel combination of several flight-proven components that will enable accurate KAr isochron dating of planetary rocks. KArLE will ablate a rock sample, measure the K in the plasma state using laser-induced breakdown spectroscopy (LIBS), measure the liberated Ar using quadrupole mass spectrometry (QMS), and relate the two by measuring the volume of the abated pit using a optical methods such as a vertical scanning interferometer (VSI). Our preliminary work indicates that the KArLE instrument will be capable of determining the age of several kinds of planetary samples to 100 Myr, sufficient to address a wide range of geochronology problems in planetary science. Additional benefits derive from the fact that each KArLE component achieves analyses common to most planetary surface missions.

Cohen, Barbara A.↗

NASA NTRS2014

In-situ Geochronology on the Mars 2020 Rover with KArLE (The Potassium-Argon Laser Experiment)

A successful Mars exploration program has revealed chapters of Mars history, but in this book, the pages are ripped out of the binding and scattered across the surface. An examination of each page reveals interesting information, but there is no way to read the book in a logical order. Geochronology is the tool that puts page number onto the individual pages, and allows the book of Martian history to be read in its proper order. The KArLE experiment performs the first dedicated in situ geochronology investigation on Mars, bringing clarity to Mars 2020 samples and context to its landing site.

Cohen, Barbara A.↗

NASA NTRS2016

The Potassium-Argon Laser Experiment (KArLE): In Situ Geochronology for Planetary Robotic Missions

The Potassium (K) - Argon (Ar) Laser Experiment (KArLE) will make in situ noble-gas geochronology measurements aboard planetary robotic landers and roverss. Laser-Induced Breakdown Spectroscopy (LIBS) is used to measure the K abun-dance in a sample and to release its noble gases; the evolved Ar is measured by mass spectrometry (MS); and rela-tive K content is related to absolute Ar abundance by sample mass, determined by optical measurement of the ablated volume. KArLE measures a whole-rock K-Ar age to 10% or better for rocks 2 Ga or older, sufficient to resolve the absolute age of many planetary samples. The LIBS-MS approach is attractive because the analytical components have been flight proven, do not require further technical development, and provide complementary measurements as well as in situ geochronology.

KArLE↗

NASA NTRSDate not supplied

In Situ Geochronology for the Next Decade

Geochronology, or determination of absolute ages for geologic events, underpins many inquiries into the formation and evolution of planets and our Solar System. The bombardment chronology inferred from lunar samples has played a significant role in the development of models of early Solar System and extrasolar planet dynamics, as well as the timing of volatile, organic, and siderophile element delivery. Absolute ages of ancient and recent magmatic products provide strong constraints on the dynamics of magma oceans and crustal formation, and the longevity and evolution of interior heat engines and distinct mantle/crustal source regions. Absolute dating also relates habitability markers to the timescale of evolution of life on Earth. The number of geochronologically-significant terrains across the inner Solar System far exceeds our ability to conduct sample return to all of them. Therefore NASA has invested in the development of in situ dating techniques; several such instruments will be TRL 6 by the time of the next Decadal Survey. We formulated a set of medium-class (New Frontiers) mission concepts to three different locations (the Moon, Mars, and Vesta) with a notional payload consisting of the CDEX and KArLE instruments to measure radiometric ages, an imaging spectrometer and optical cameras to provide site geologic context and sample characterization, an ICP-MS to augment sample contextualization, and a sample acquisition and handling system. A Vesta hopper and single-site lunar and Mars landers to advance Solar System chronology fit into the New Frontiers cost cap in our study. Such missions would also enable a broad suite of geologic investigations such as basic geologic characterization, geomorphologic analysis, establishing ground truth for remote sensing analyses, analyses of major, minor, trace, and volatile elements, atmospheric and other long-lived monitoring, organic molecule analyses, and soil and geotechnical properties.

Barbara A Cohen↗

NASA NTRS2012

In-Situ Geochronology as a Mission-Enabling Technology

Although there are excellent estimates of ages of terrains on Mars from crater counting, even a few absolute ages would serve to validate the calibration. Results with uncertainties, although much larger than those that could be achieved in labs on Earth, would be extremely valuable. While there are other possibilities for in-situ geochronology instruments, we describe here to alternative technologies, being developed in JPL. There are two common features of both. The first is analysis by means of miniature mass spectrometer. The second is use of laser sampling to reduce or avoid sample handling, preparation and pre-treatment and equally importantly, to allow analysis of individual, textually resolved minerals in coarse-grained rocks. This textural resolved minerals in coarse-grained rocks. This textural resolution will aid in selection of grains more or less enriched in the relevant elements and allow construction of isochrons for more precise dating. Either of these instruments could enable missions to Mars and other planetary bodies.

geochronology↗

NASA NTRS1977

A critical evaluation of the application of amino acid racemization to geochronology and geothermometry

Attempts have been made to determine the age of biological samples by measuring the racemization of amino acids in protein samples. The pitfalls and inherent complications in diagenetic racemization studies are reviewed, and recent advances in improving techniques are outlined. Methodological topics include isolation of amino acids from geological samples, resolution of amino acid enantiomers, and the effects of acid hydrolysis. The theory and kinetics of amino acid racemization are discussed with attention to the derivation of the rate expression for amino acid racemization, isoleucine and the equilibrium constant, the mechanism of amino acid racemization, the racemization of 'bound' versus 'free' amino acids, and factors affecting the racemization rates of free amino acids in aqueous solution. Applications of amino acid racemization kinetics to geochronology is considered with reference to shells, marine sediments, and bones. Potential complications include heating and diagenesis, diagenetic formation of amino acids, the effect of clays, species effect, and contamination.

Williams, K. M.↗

NASA NTRS1988

Geochronological and lead-isotope evidences for rapid crust formation in middle-proterozoic time: The Labrador example

Extensive U-Pb geochronological studies in the Grenville and Makkovik provinces have shown that eastern Labrador is underlain by two distinct crustal blocks. In order to substantiate the juvenile character of the middle-Proterozoic crustal block, the isotopic compositon of lead in leached k-feldspars from the same rocks were analyzed. The results of the analysis are briefly discussed.

Schaerer, Urs↗