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Isotopic analysis of sub-nanogram neodymium loads using new ATONA™ amplifiers

The long-term gains of the ATONA™ amplifiers are shown to have less than 1 ppm variability. Repeat measurements of the JNdi-1 reference material demonstrate the ability of the ATONA™ amplification technology to make measurements of 143 Nd/ 144 Nd ratios with 23 ppm external reproducibility on 100-pg loads. The effect of increasing integration time on analytical reproducibility is also displayed as increasing integration time from 10 to 30s reduced the external measurement uncertainty from 37 to 23 ppm. These measurements represent an improvement of more than a factor of 3 in external measurement reproducibility relative to previously published 143 Nd/ 144 Nd measurements of 100-pg loads. Furthermore, this new technology will allow for the measurement of smaller samples for precise isotope ratios and open new avenues of research in the geological and nuclear forensic communities.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Heavy ozone distribution in the stratosphere from far-infrared observations

The distribution of isotopically heavy ozone in the stratosphere has been obtained from analysis of balloon-based high-resolution thermal emission spectra in the far infrared. The mixing ratio profiles of (O-16)(O-16)(O-18) and (O-16)(O-18)(O-16), retrieved from inversion of several limb sequences of a number of spectral lines in the 39-76/cm region, indicate enhancements over the expected values in the 25- to 37-km altitude range. The ratio of total heavy isotopic ozone (10-50)3 to normal (O-48)3 shows enhancements of about 45 percent at 37 km, decreasing to a minimum of about 13 percent at 29 km, and increasing to about 18 percent at 25 km. The results from this work are compared with Mauersberger's (1987) in situ mass spectrometer measurements.

Abbas, M. M.↗

Stardust in STARDUST - the C, N, and O Isotopic Compositions of Wild 2 Cometary Matter in Al foil Impacts

In January 2006, the STARDUST mission successfully returned dust samples from the tail of comet 81P/Wild 2 in two principal collection media, low density silica aerogel and Al foil. While hypervelocity impacts at 6.1 km/s, the encounter velocity of STARDUST, into Al foils are generally highly disruptive for natural, silicate-dominated impactors, previous studies have shown that many craters retain sufficient residue to allow a determination of the elemental and isotopic compositions of the original projectile. We have used the NanoSIMS to perform C, N, and O isotope imaging measurements on four large (59-370 microns diameter) and on 47 small (0.32-1.9 microns diameter) Al foil impact craters as part of the STARDUST Preliminary Examination. Most analyzed residues in and around these craters are isotopically normal (solar) in their C, N, and O isotopic compositions. However, the debris in one large crater shows an average 15N enrichment of approx. 450 %, which is similar to the bulk composition of some isotopically primitive interplanetary dust particles. A 250 nm grain in another large crater has an O-17 enrichment with approx. 2.65 times the solar O-17/O-16 ratio. Such an O isotopic composition is typical for circumstellar oxide or silicate grains from red giant or asymptotic giant branch stars. The discovery of this circumstellar grain clearly establishes that there is authentic stardust in the cometary samples returned by the STARDUST mission. However, the low apparent abundance of circumstellar grains in Wild 2 samples and the preponderance of isotopically normal material indicates that the cometary matter is a diverse assemblage of presolar and solar system materials.

Stadermann, Frank J.↗

Recovery of Neptunium-236g from Photon and Proton-Irradiated Actinide Targets

Neptunium-236g is a rare radionuclide used as a tracer for neptunium-237 analyses. The availability of 236gNp is limited and the viable production routes are costly, time consuming, and only produce trace quantities of the desired product. For this work, two known production methods were tested to determine product recovery, purity, and viability for use as a tracer. The first method utilizes a photon-irradiated 237Np target to produce 236gNp by the 237Np(?,n)?236Np reaction. The second method utilizes the 238U(d,4n) ?236Np reaction. These production routes were evaluated previously, and the former was considered ineffective without isotope separation and the latter was not well-characterized for the 236mNp/236gNp production ratio. Recent resurgence of electromagnetic isotope separation technology has enabled at least partial recovery of 236gNp from part-per-million abundance feeds produced by the photonuclear reaction. To address the lack of production data for the second method, a deuteron-irradiated depleted uranium target was chemically processed to recover and purify the Np for abundance and ratio analyses. The status and current analytical results for each production method are presented.

07 ISOTOPE AND RADIATION SOURCES↗

Stardust in STARDUST - the C, N, and O Isotopic Compositions of Wild 2 Cometary Matter in Al Foil Impacts

In January 2006, the Stardust mission successfully returned dust samples from the tail of comet 81P/Wild 2 in two principal collection media, low density silica aerogel and Al foil. While hypervelocity impacts at the Stardust encounter velocity of 6.1 kilometers per second into Al foils are generally highly disruptive for natural, silicate-dominated impactors, previous studies have shown that many craters retain sufficient residue to allow a determination of the elemental and isotopic compositions of the original projectile. We have used two NanoSIMS ion microprobes to perform C, N, and O isotope imaging measurements on four large (59-295 micrometer diameter) and on 47 small (0.32-1.9 micrometer diameter) Al foil impact craters as part of the Stardust Preliminary Examination. Most analyzed residues in and around these craters are isotopically normal (solar) in their C, N, and O isotopic compositions. However, the debris in one large crater shows an average N-15 enrichment of approx. 450%o, which is similar to the bulk composition of some isotopically primitive interplanetary dust particles and to components of some primitive meteorites. A 250 nm grain in another large crater has an O-17 enrichment with approx. 2.65 times the solar O-17/O-16 ratio. Such an O isotopic composition is typical for circumstellar oxide or silicate grains from red giant or asymptotic giant branch stars. The discovery of this circumstellar grain clearly establishes that there is authentic stardust in the cometary samples returned by the Stardust mission. However, the low apparent abundance of circumstellar grains in Wild 2 samples and the preponderance of isotopically normal material indicates that the cometary matter is a diverse assemblage of presolar and solar system materials.

Stadermann, Frank J.↗

Constraints on the Formation of the Moon from High-Precision ND-Isotopic Measurements of Lunar Basalts

The most widely accepted theory for the formation of the Earth-Moon system proposes a giant impact model, where Earth collided in its later stages of accretion with a body of the approximate size of Mars [1, 2]. In this model, the Moon ultimately formed from hot debris generated during this giant impact. Short-lived radioisotopes such as Sm-146 (t(sub 1/2) = 103 Ma) may be useful in determining the chronology of the events that formed the Earth-Moon system and for how these terrestrial bodies evolved following accretion. New high-precision samarium-neodymium data showed that chondritic meteorites are on average 20 ppm lower in 142Nd/144Nd than terrestrial samples [3]. These data suggest that if the bulk silicate Earth (BSE) has a Sm/Nd ratio within the range measured for chondrites, the higher-than-chondritic Nd-142/Nd-144 ratio of terrestrial materials requires that the silicate Earth experienced a global chemical differentiation during the lifetime of Sm-146. If the Moon has super-chondritic Nd-142/Nd-144 identical to the Earth, as suggested by available data [4], then the giant impact must have occurred into an already differentiated Earth, predominantly sampling the Nd-depleted reservoir. In order to test this hypothesis, high-precision Nd-isotope ratios were obtained on a Thermo-Finnigan Triton TIMS for six lunar basalts that span the compositional range of lavas from the Moon: Samples 15555 and LAP 02205 represent low-Ti basalts; 70017 and 74275 are high-Ti basalts; 15386 and SAU 169 are KREEP basalts.

Rankenburg, K.↗

The ratios of carbon and non-radiogenic helium and argon isotopes in the mantle and crustal rocks

The studies of the relations of carbon and primary isotopes of noble gases were carried out on the natural gases and on the mantle rocks from the mantle M-type sources, which represent the degassed mantle reservoir (MORB's). These works has the aim of estimation of the values of the C/3He ratios in the deep mantle fluids to determine the flux of the mantle CO2 on the basis of known flux of primary mantle 3He. It was found, that in the natural gases the values of the C/3He ratios fall into the range from 1 times E plus 6 to 1 times E plus 15, and in the fluids of MORB's are constant near 2 times E plus 9. We have studied the mantle rocks from the relatively undergassed mantle P minus type sources: continental; Baikal Rift (Siberia), Mongolia, Catalonia (Spain), Pannonia Depression (central Europe) and ocean; Spietzbergen isl., Hawaii isl., Canarian isl. It ws found, that in mantle xenolites and the host alkaline basalts from the continental rifts and ocean islands, the values of the C/3He ratios fall into the range from E plus 11 to E plus 15 (and this result needed to be explained; the higher carbon to helium ratios is relatively undergassed mantle reservoir compared with the degassed one, requires whether hilly compatibility of helium compared with carbon, whether additional flux of 3He to the degassed mantle reservoir). From the other hand it was found that in the mantle rocks from the sources of P minus and M minus types, continental carbonatites, the values of the C/36Ar ratios are constant in the range from E plus 9 to E plus 10, the close values have the MORB's also.

Lokhov, K.↗

Fission Product Quantification and Burnup Analysis via Gamma Spectrometry of the AGR-5/6/7 TRISO Fuel Experiment

Five capsules containing varying configurations of TRISO fuel compacts were irradiated in the most recent Advanced Gas Reactor (AGR) TRISO test campaign, AGR-5/6/7. As part of the post-irradiation examination (PIE) of this work all the fuel compacts and capsule graphite holders were measured with the Precision Gamma Scanner (PGS) to determine isotopic activities and locations using gamma spectrometry. Measuring the compacts allowed for the comparison of physics model depletion calculations with the measured compact activity to validate models. These measurements also are used to find compacts of interest with low fission product retention that may be tested in subsequent PIE. Measurements of the holders can confirm fission product distribution and migration. Of the isotopes measured, Cs-137 and Cs-134 were used to estimate location of failed particles as well as determine a measured burnup estimation. Results from Capsule 1 compacts and the holder indicate many fuel particle failures occurred. There are high amounts of cesium in the holder near Stack 9 of Capsule 1 that corresponds to low fractions?measured-to-calculated (M/C) ratio?of cesium remaining in those compacts. All other capsules had cesium retention ratios near 1. The isotope 110mAg had less consistent results. Capsule 2 compacts exhibited a M/C of 0.20, much lower than anticipated for the temperatures these compacts underwent. Capsule 3 experienced much higher temperatures, >1300C and had an average M/C of 0.75. These are the opposite results than what was predicted by past AGR experiments for the relationship between temperature and isotope retention. Capsule 4 and 5 showed good fission product retention and agreement with the physics model predictions. The burnup results from the PGS measurements showed strong agreement between the physics models and the measured values. Using a ratio of Cs-134/Cs-137 to calculate the burnup match closely with the physics models. Additionally, the Cs-137 burnup results were less accurate but extremely close to the model results.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The charge and isotopic composition of Z = 6-14 cosmic ray nuclei at their source

Using data from a cosmic ray charge-isotope telescope flown on balloons, both the charge and isotopic composition are determined of Z = 6-14 cosmic ray nuclei. A low abundance for the elements N and Ne in the cosmic ray source relative to solar cosmic rays is observed. For the isotopes, a cosmic ray source ratio Ne-22/Ne-20 is found that is 3.52 plus or minus 0.67 times the solar ratio, this enhancement being due in part to an enhancement of Ne-22 and in part to an underabundance of Ne-20. Also observed are possible enhancements of the Mg-26/Mg-24 ratio, which is 1.40 plus or minus 0.24 times the solar t ratio, and the C-13/C-12 ratio, which is 2.90 plus or minus 0.93 times the solar ratio. For Ne, the underabundance of this element, coupled with the overabundnace of the isotope Ne-22, is seen as providing an important new clue to the nucleosynthesis processes producing these differences.

Webber, W. R.↗

Application of Fe Isotopes to the Search for Life and Habitable Planets

The relatively new field of Fe isotope geochemistry can make important contributions to tracing the geochemical cycling of Fe, which bears on issues such as metabolic processing of Fe, surface redox conditions, and development of planetary atmospheres and biospheres. It appears that Fe isotope fractionation in nature and the lab spans about 4 per mil (%) in Fe-56/Fe-54, and although this range is small, our new analytical methods produce a precision of +/- 0.05% on sample sizes as small as 100 ng (10(exp -7) g); this now provides us with a sufficient "signal-to-noise" ratio to make this isotope system useful. We review our work in three areas: 1) the terrestrial and lunar rock record, 2) experiments on inorganic fractionation, and 3) experiments involving biological processing of Fe. Additional information is contained in the original extended abstract.

Johnson, Clark M.↗

Detection of Cometary Amines in Samples Returned by the Stardust Spacecraft

The delivery of amino acids to the early Earth by comets and their fragments could have been a significant source of the early Earth's prebiotic organic inventory that led to the emergence of life (Chyba and Sagan, 1992). Over 20 organic molecules including methane, ethane, ammonia, cyanic acid, formaldehyde, formamide, acetaldehyde, acetonitrile, and methanol have been identified by radio spectroscopic observations of the comae of comets Hale-Bopp and Hyakutake (Crovisier et al. 2004). These simple molecules could have provided the organic reservoir to allow the formation of more complex prebiotic organic compounds such as amino acids. After a 7-year mission, the Stardust spacecraft returned to Earth samples from comet Wild 2 on January 15, 2006 providing the opportunity to analyze the organic composition and isotopic distribution of cometary material with state-of-the-art laboratory instrumentation. The Preliminary Examination Team analyses of organics in samples returned by Stardust were largely focused on particles that impacted the collector aerogel and aluminum foil (Sandford et al. 2006). However, it is also possible that Stardust returned a "diffuse" sample of gas-phase organic molecules that struck the aerogel directly or diffused away from the grains after impact. To test this possibility, samples of Stardust flight aerogel and foil were carried through a hot water extraction and acid hydrolysis procedure to see if primary amine compounds were present in excess of those seen in controls. Here we report highly sensitive liquid chromatography time-of-flight mass spectrometry measurements of amino acids and amines in samples returned from a comet (Glavin et al. 2008). A suite of amino acids and amines including glycine, L-alanine, methylamine (MA), and ethylamine (EA) were identified in the Stardust bulk aerogel. With the exception of MA and EA, all other primary amines detected in comet-exposed aerogels were also present in the aerogel witness tile that was not exposed to Wild 2, suggesting that most amines are terrestrial in origin. However, the enhanced abundances of MA, EA, and possibly glycine in comet-exposed aerogel compared to controls, coupled with MA to EA ratios (1 to 2) that are distinct from preflight aerogels (7 to 10), suggest that these amines were captured from Wild 2. It is possible that MA and EA were formed on energetically processed icy grains containing methane, ethane, and ammonia. The presence of cometary amines in Stardust material supports the hypothesis that comets were an important source of prebiotic organics on the early Earth. To better understand their origin, a systematic compound specific carbon isotopic analysis (C-CSIA) via gas chromatography quadrupole mass spectrometry in with parallel with combustion isotope ratio mass spectrometry (GCQMS/ IRMS) is being conducted. We will discuss our latest C-CSIA measurements and what they indicate about the origin of amino acids extracted from Stardust samples.

Glavin, Daniel P.↗

Detection of Cometary Amines in Samples Returned by the Stardust Spacecraft

The delivery of amino acids to the early Earth by comets and their fragments could have been a significant source of the early Earth's prebiotic organic inventory that led to the emergence of life (Chyba and Sagan, 1992). Over 20 organic molecules including methane, ethane, ammonia, cyanic acid, formaldehyde, formamide, acetaldehyde, acetonitrile, and methanol have been identified by radio spectroscopic observations of the comae of comets Hale-Bopp and Hyakutake (Crovisier et al. 2004). These simple molecules could have provided the organic reservoir to allow the forn1ation of more complex prebiotic organic compounds such as amino acids. After a 7 -year mission, the Stardust spacecraft returned to Earth samples from comet Wild 2 on January 15, 2006 providing the opportunity to analyze the organic composition and isotopic distribution of cometary material with state-of-the-art laboratory instrun1entation. The Preliminary Examination Team analyses of organics in samples returned by Stardust were largely focused on particles that impacted the collector aerogel and aluminum foil (Sandford et al. 2006). However, it is also possible that Stardust returned a "diffuse" sample of gas-phase organic molecules that struck the aerogel directly or diffused away from the grains after impact. To test this possibility, samples of Stardust flight aerogel and foil were carried through a hot water extraction and acid hydrolysis procedure to see if primary amine compounds were present in excess of those seen in controls. Here we report highly sensitive liquid chromatography time-of-flight mass spectron1etry measurements of amino acids and amines in samples returned from a comet (Glavin et al. 2008). A suite of amino acids and amines including glycine, L-alanine, methylamine (MA), and ethylamine (EA) were identified in the Stardust bulk aerogel. With the exception of MA and EA, all other primary amines detected in comet-exposed aerogels were also present in the aerogel witness tile that was not exposed to Wild 2, suggesting that most amines are terrestrial in origin. However, the enhanced abundances of MA, EA, and possibly glycine in comet-exposed aerogel compared to controls, coupled with MA to EA ratios (1 to 2) that are distinct from preflight aerogels (7 to 10), suggest that these amines were captured from Wild 2. It is possible that MA and EA were formed on energetically processed icy grains containing methane, ethane, and ammonia. The presence of cometary amines in Stardust material supports the hypothesis that comets were an important source of pre biotic organics on the early Earth. To better understand their origin, a systematic compound specific carbon isotopic analysis (C-CSIA) via gas chromatography quadrupole mass spectrometry in with parallel with combustion isotope ratio mass spectrometry (GC-QMS/IRMS) is being conducted. We will discuss our latest C-CSIA measurements and what they indicate about the origin of amino acids extracted from Stardust samples.

Glavin, Daniel P.↗

Bulk Composition of Vesta as Constrained by the Dawn Mission and the HED Meteorites

Of the objects in the main asteroid belt, Vesta is of particular interest as it is large enough to have experienced internal differentiation (520 km diameter), and it is known to have a basaltic surface dominated by FeO-bearing pyroxenes. Furthermore, visible-IR spectra of Vesta and associated Vestoids are remarkably similar to laboratory spectra of Howardite-Eucrite-Diogenite (HED) meteorites, leading to the paradigm that the HEDs ultimately came from Vesta. Geochemical and petrological studies of the HEDs confirm the differentiated nature of the near-surface region of their parent body, and imply that crust extraction occurred well within the first 10 Ma of solar system history Vesta is therefore a prime target for studies that aim to constrain the earliest stages of planet building, and it is within this context that the NASA Dawn spacecraft orbited Vesta from July 2011 to September 2012. The results of the Dawn mission so far have significantly reinforced the HED-Vesta connection, confirming a significant degree of internal differentiation, a surface mineralogy compatible with that of the HEDs, and near-surface ratios of Fe/O and Fe/Si consistent with HED lithologies. The combination of data from the HED meteorites and the Dawn mission thus presents an unprecedented opportunity to use Vesta as a natural laboratory of early differentiation processes in the early solar system. However, the bulk composition of Vesta remains a significant unknown parameter, but one that plays a key role on the physical and chemical properties of the internal and surface reservoirs (core, mantle, crust). Several attempts have been made to constrain the bulk composition of the eucrite parent body, early endeavours relying on petrological or cosmochemical constraints. More recently, individual chondrite class compositions, or mixtures thereof, have been considered, constrained by considerations such as O-isotopes, trace-element ratios and siderophile element concentrations of the eucrites. The work presented here builds upon these latter studies, with the primary aims of: i) illustrating the potential diversity of the geochemical and geophysical properties of a fully differentiated Vesta-sized parent body, and ii) assessing which, if any, of the known chondritic bulk compositions are plausible analogues for proto-Vesta.

Toplis, M. J.↗

The isotopic composition of cosmic-ray helium from 123 to 279 MeV per nucleon - A new measurement and analysis

A description is given of an experiment which was designed to measure the spectra and composition of cosmic-ray hydrogen and helium isotopes in the interval 120-280 MeV per nucleon to compare with the recent values observed at low energies and also with the only earlier measurement in this high-energy regime. The results presented were obtained during a high-altitude balloon flight from Thompson, Manitoba, in 1973 August. This flight occurred during the period in which the presence of the anomalous component in the helium spectrum became apparent, and provides the opportunity of determining whether this component extends to higher energies than those studied by satellite experiments. The results place an upper limit on the flux of 'anomalous' He-4 (which appeared at low energy in 1972) of at most 15% in the energy range of this experiment, and combined with the low-energy observations of the Chicago group, show an energy dependence of the average ratio of the helium isotopes in the modulated cosmic rays which is difficult to reconcile with current modulation models.

Leech, H. W.↗

Rare earth element transport in the western North Atlantic inferred from Nd isotopic observations

The relationship between the Nd isotopic composition in the Atlantic waters and the origin and circulation of the water masses was investigated. Samples were collected in the western North Atlantic between 7 and 54 deg N. The isotopic composition (Nd-143/Nd-144 ratios) showed extensive vertical structure at all locations. In regions where a thermocline was well-developed, large isotopic shifts were observed across the base of the thermocline, while regions without a thermocline were characterized by much more gradual shifts in isotopic composition with depth. The data reveal an excellent correlation between the Nd isotopic distribution in the western North Atlantic water column and the distribution of water masses identified from temperature and salinity measurements.

Piepgras, D. J.↗

The Timing of Potential Last Nucleosynthetic Injections into the Protosolar Molecular Cloud Inferred from 41 Ca– 26 Al Systematics of Bulk CAIs

Short-lived radionuclides (SLRs) provide important information about the chronology of the early solar system. Among them, 41 Ca, due to its decay to 41 K with a half-life of only 0.1 Ma, is particularly valuable in constraining the timescales and origins of both SLRs and the formation of the oldest solar system materials, the Ca–Al-rich inclusions (CAIs). The initial abundance of 41Ca in the solar system, expressed as the ( 41 Ca/ 40 Ca)I ratio, is the key to unveiling the origin of this nuclide. Here, we report a new solar system ( 41 Ca/ 40 Ca)I ratio of 2.0 × 10 −8 derived from the K isotope compositions of two CAIs. This new ratio is about four times higher than the previous value inferred from a mineral isochron. Such a high ( 41 Ca/ 40 Ca)I ratio in the CAIs exceeds that expected for the protosolar molecular cloud by ∼1000×, implying very late injection of the 41 Ca (and possibly other SLRs) into the protosolar molecular cloud. The correlated enrichments of 41 Ca and 26 Al in the bulk CAI samples hint at a common stellar origin of both SLRs. The injection time estimated from our new data depends on the stellar source—it ranges from 0.6 Ma for a Wolf–Rayet wind to 1.0 Ma for a TP-AGB star ejecta.

79 ASTRONOMY AND ASTROPHYSICS↗

First observation of 28 O

Subjecting a physical system to extreme conditions is one of the means often used to obtain a better understanding and deeper insight into its organization and structure. In the case of the atomic nucleus, one such approach is to investigate isotopes that have very different neutron-to-proton ($N/Z$) ratios than in stable nuclei. Light, neutron-rich isotopes exhibit the most asymmetric $N/Z$ ratios and those lying beyond the limits of binding, which undergo spontaneous neutron emission and exist only as very short-lived resonances (about 10 -21 s), provide the most stringent tests of modern nuclear-structure theories. Here we report on the first observation of 28 O and 27 O through their decay into 24 O and four and three neutrons, respectively. The 28 O nucleus is of particular interest as, with the $Z$ = 8 and $N$ = 20 magic numbers, it is expected in the standard shell-model picture of nuclear structure to be one of a relatively small number of so-called ‘doubly magic’ nuclei. Furthermore, both 27 O and 28 O were found to exist as narrow, low-lying resonances and their decay energies are compared here to the results of sophisticated theoretical modelling, including a large-scale shell-model calculation and a newly developed statistical approach. In both cases, the underlying nuclear interactions were derived from effective field theories of quantum chromodynamics. Finally, it is shown that the cross-section for the production of 28 O from a 29 F beam is consistent with it not exhibiting a closed $N$ = 20 shell structure.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Detection of C-13O radio emission from C-13-rich carbon stars

A high ratio of C-13O radio emission in the J = 1-0 rotational line has been detected from three mass-losing carbon stars which optical data indicate have high C-13/C12 ratios. Since chemical fractionation, isotope-dependent photodissociation and opacity in the rotational and vibrational lines may not raise significantly the C-13O ratio above the actual C-13/C-12 ratio in these circumstellar envelopes, the relative abundance of C-13 in these stars might be even greater by perhaps a factor of two than previously believed. About 15 percent of all luminous carbon stars are C-13-rich, and these stars may play a significant role in the enhancement in the C-13/C12 ratio that has occurred during the past 4.6 billion years since the formation of the sun.

Jura, M.↗