Deep-mantle krypton reveals Earth's early accretion of carbonaceous matter.

Establishing when, and from where, carbon, nitrogen and water were delivered to Earth is a fundamental objective in understanding the origin of habitable planets such as Earth. Yet, volatile delivery to Earth remains controversial1-5. Krypton isotopes provide insights on volatile delivery owing to their substantial isotopic variations among sources6-10, although pervasive atmospheric contamination has hampered analytical efforts. Here we present the full suite of krypton isotopes from the deep mantle of the Galápagos and Iceland plumes, which have the most primitive helium, neon and tungsten isotopic compositions11-16. Except for 86Kr, the krypton isotopic compositions are similar to a mixture of chondritic and atmospheric krypton. These results suggest early accretion of carbonaceous material by proto-Earth and rule out any combination of hydrodynamic loss with outgassing of the deep or shallow mantle to explain atmospheric noble gases. Unexpectedly, the deep-mantle sources have a deficit in the neutron-rich 86Kr relative to the average composition of carbonaceous meteorites, which suggests a nucleosynthetic anomaly. Although the relative depletion of neutron-rich isotopes on Earth compared with carbonaceous meteorites has been documented for a range of refractory elements1,17,18, our observations suggest such a depletion for a volatile element. This finding indicates that accretion of volatile and refractory elements occurred simultaneously, with krypton recording concomitant accretion of non-solar volatiles from more than one type of material, possibly including outer Solar System planetesimals.

A method for estimating (41)Ar, (85)(,88)Kr and (131m,133)Xe doses to non-human biota.

A method is presented for estimating (41)Ar, (85,88)Kr and (131m,133)Xe dose rates to terrestrial wildlife without having to resort to comparisons with analogue radionuclides. The approach can be used to calculate the dose rates arising from external exposures to given ambient air concentrations of these isotopes. Dose conversion coefficient (DCC) values for a range of representative organisms are calculated, using a Monte Carlo approach to generate absorbed fractions based on representing animals as reference ellipsoid geometries. Plume immersion is the main component of the total DCC. DCC values calculated for a human-sized organism are compared with human dose conversion factors from ICRP Publication 119, demonstrating the consistency of the biota approach with that for humans. An example of application is provided for hypothetical nuclear power plant atmospheric discharges with associated exposures to birds and insects. In this example, the dose rates appear to be dominated by (133)Xe and (88)Kr, respectively. The biota considered would be protected from the effects of noble gas radiation from a population protection perspective.

Krypton-81 in groundwater of the Culebra Dolomite near the Waste Isolation Pilot Plant, New Mexico.

The Waste Isolation Pilot Plant (WIPP) in New Mexico is the first geologic repository for disposal of transuranic nuclear waste from defense-related programs of the US Department of Energy. It is constructed within halite beds of the Permian-age Salado Formation. The Culebra Dolomite, confined within Rustler Formation evaporites overlying the Salado Formation, is a potential pathway for radionuclide transport from the repository to the accessible environment in the human-disturbed repository scenario. Although extensive subsurface characterization and numerical flow modeling of groundwater has been done in the vicinity of the WIPP, few studies have used natural isotopic tracers to validate the flow models and to better understand solute transport at this site. The advent of Atom-Trap Trace Analysis (ATTA) has enabled routine measurement of cosmogenic (81)Kr (half-life 229,000 yr), a near-ideal tracer for long-term groundwater transport. We measured (81)Kr in saline groundwater sampled from two Culebra Dolomite monitoring wells near the WIPP site, and compared (81)Kr model ages with reverse particle-tracking results of well-calibrated flow models. The (81)Kr model ages are ~130,000 and ~330,000 yr for high-transmissivity and low-transmissivity portions of the formation, respectively. Compared with flow model results which indicate a relatively young mean hydraulic age (~32,000 yr), the (81)Kr model ages imply substantial physical attenuation of conservative solutes in the Culebra Dolomite and provide limits on the effective diffusivity of contaminants into the confining aquitards.

Determination of gaseous radionuclide forms in the stack air of nuclear power plants.

The determination of gaseous forms of radionuclides in ventilation stacks utilising grab samples was performed as a part of independent monitoring of nuclear power plants in the Czech Republic. The activities of radionuclides (e.g. (41)Ar, (133)Xe, (135)Xe, (85m)Kr, (87)Kr, and (131m)Xe) were determined by semiconductor gamma-ray spectrometry in samples collected into pressure vessels. Radiochemical preparation of samples for determination of (14)CO(2), combustible (14)C forms, and (85)Kr was performed after the radioactive decay of radionuclides with short half-life.

[Effect of krypton-containing gas mixture on Japanese quail embryo development].

Investigated were effects of gas mixture with up to 3.0 kgs/cm2 of krypton on the embryonic development of domesticated Japanese quail (Coturnix coturnix japonica dom.). Results demonstrated absence of a serious krypton effect on Japanese quail embryos. Development of embryos proceeded in due course; morphometrically the experimental embryos were essentially similar to controls. It should be noted that despite exposure to acute hypoxic hypoxia during the initial 12 hours of development in the krypton-containing gas mixture, viability of quail embryos was high enough which can be ascribed to the krypton protective action. Besides, an additional experiment showed that krypton partial pressure of 5-5.5 kgs/cm2 produces the narcotic effect on adult Japanese quails.

Apparent 85Kr ages of groundwater within the Royal watershed, Maine, USA.

Specific 85Kr activity is mapped from 264 domestic and municipal wells sampled during 2002-2004 in the Royal watershed (361 km2), Maine. Gas samples are collected at 20 m, 40 m, and > 50 m interval depths within the unconfined aquifers. Gas extraction for 85Kr from wells is obtained directly via a wellhead methodology avoiding conventional collection of large sample volumes. Atmospheric 85Kr input to the recharge environment is estimated at 1.27 Bq m(-3) by time-series analyses of weighted monthly precipitation (2001-2004). Numerical simulation of Kr gas transport through the variable unsaturated zones to the water table suggests up to 12-year time lags locally, thus biasing the 85Kr groundwater ages. Apparent 85Kr ages suggest that approximately 70% of groundwater near 20 m depth was recharged less than 30 years BP (2004). Mass-age transport modeling suggests that post mid-1950s recharge penetrates to part of the basin's floor and that older groundwater seeps from the underlying fractured bedrock may occur.

Quadrupolar relaxation of hyperpolarized krypton-83 as a probe for surfaces.

This work reports the first systematic study of relaxation experienced by the hyperpolarized (hp) noble gas isotope (83)Kr (I=9/2) in contact with surfaces. The spin-lattice relaxation of (83)Kr is found to depend strongly on the chemical composition of the surfaces in the vicinity of the gas. This effect is caused by quadrupolar interactions during brief periods of surface adsorption that are the dominating source of longitudinal spin relaxation in the (83)Kr atoms. Simple model systems of closest packed glass beads with uniform but variable bead sizes are used for the relaxation measurements. The observed relaxation rates depend strongly on the chemical treatment of the glass surfaces and on the surface to volume ratio. Hp (83)Kr NMR relaxation measurements of porous polymers with pore sizes of 70-250 microm demonstrate the potential use of this new technique for material sciences applications.

Dissolved gases as partitioning tracers for determination of hydrogeological parameters.

In this study, dissolved Kr and SF6 gases were used to determine various hydrogeological parameters of laboratory columns under water-saturated and partially saturated conditions as a function of the flow velocity. The dissolved gases behaved conservatively in saturated columns but were significantly retarded in unsaturated conditions as a direct function of the Henry's law constant (KH) and the ratio of column pore spaces filled with air and water (Vg/Vw). Lower aqueous diffusion coefficients for SF6 compared to that for Kr also resulted in significant rate-limited mass transport across gas-water interface. This effect was exacerbated at higher flow velocities as was indicated by the asymmetric shape of breakthrough curves, more so in the case of SF6. A nonequilibrium advective-dispersive transport model accurately described tracer breakthrough and was used to estimate parameters such as final Vg/Vw under partially saturated conditions and partitioning rates. Internally consistent model results were obtained for both dissolved gases despite the wide range in physical properties (e.g., KH and aqueous diffusion coefficients), suggesting that dissolved Kr and SF6 may be used in conjunction to delineate and validate aquifer characteristics simultaneously from a single pulse injection of the tracer.

Sequential V(A)/Q distributions in the normal rabbit by micropore membrane inlet mass spectrometry.

We developed micropore membrane inlet mass spectrometer (MMIMS) probes to rapidly measure inert-gas partial pressures in small blood samples. The mass spectrometer output was linearly related to inert-gas partial pressure (r(2) of 0.996-1.000) and was nearly independent of large variations in inert-gas solubility in liquid samples. We infused six inert gases into five pentobarbital-anesthetized New Zealand rabbits and used the MMIMS system to measure inert-gas partial pressures in systemic and pulmonary arterial blood and in mixed expired gas samples. The retention and excretion data were transformed into distributions of ventilation-to-perfusion ratios (V(A)/Q) with the use of linear regression techniques. Distributions of V(A)/Q were unimodal and broad, consistent with prior reports in the normal rabbit. Total blood sample volume for each VA/Q distribution was 4 ml, and analysis time was 8 min. MMIMS provides a convenient method to perform the multiple inert-gas elimination technique rapidly and with small blood sample volumes.

An experimental study of the isotopic enrichment in Ar, Kr, and Xe when trapped in water ice.

The isotopic enrichment of argon, krypton, and xenon, when trapped in water ice, was studied experimentally. The isotopes were found to be enriched according to their (m1/m2)1/2 ratio. These enrichment factors could be useful for comparison among the uncertain cosmic or solar isotopic ratios, the hopeful in situ cometary ratio, and those in Earth's atmosphere, in the context of cometary delivery of volatiles to Earth.

Countercurrent extraction of sparingly soluble gases for membrane introduction mass spectrometry.

Membrane introduction mass spectrometry has been applied to inert gas measurements in blood and tissue, but gases with low blood solubility are associated with reduced sensitivity. Countercurrent extraction of inert gases from a blood sample into a water carrier phase has the potential to extract most of the gas sample while avoiding dependence of signal on blood solubility. We present the design of a membrane countercurrent exchange (CCE) device coupled with a conventional direct insertion membrane probe to measure partial pressure of low solubility inert gases in aqueous samples. A mathematical model of steady-state membrane CCB predicts that countercurrent extraction with appropriate selection of carrier and sample flow rates can provide a mass spectrometer signal nearly independent of variations in solubility over a specified range, while retaining a linear response to changes in gas partial pressure over several orders of magnitude. Experimental data are presented for sulfur hexafluoride and krypton in water samples. Optimal performance is dependent on adequate equilibration between the sample and carrier streams, and the large resistance to diffusion in the aqueous phase for insoluble gases presents a substantial challenge to the application of this principle.

Fractionated martian atmosphere in the nakhlites?

Considerable evidence points to a martian origin of the SNC meteorites. Noble gas isotopic compositions have been measured in most SNC meteorites. The 129Xe/132Xe vs, 84Kr/132Xe ratios in Chassigny, most shergottites, and lithology C of EETA 79001 define a linear array. This array is thought to be a mixing line between martian mantle and martian atmosphere. One of the SNC meteorites, Nakhla, contains a leachable component that has an elevated 129Xe/132Xe ratio relative to its 84Kr/132Xe ratio when compared to this approximately linear array. The leachable component probably consists in part of iddingsite, an alteration product produced by interaction of olivine with aqueous fluid at temperatures lower than 150 degrees C. The elevated Xe isotopic ratio may represent a distinct reservoir in the martian crust or mantle. More plausibly, it is elementally fractionated martian atmosphere. Formation of sediments fractionates the noble gases in the correct direction. The range of sediment/atmosphere fractionation factors is consistent with the elevated 129Xe/132Xe component in Nakhla being contained in iddingsite, a low temperature weathering product. The crystallization age of Nakhla is 1.3 Ga. Its low-shock state suggests that it was ejected from near the surface of Mars. As liquid water is required for the formation of iddingsite, these observations provide further evidence for the near surface existence of aqueous fluids on Mars more recently than 1.3 Ga.

The origin of inner planet atmospheres.

NASA: A comet-impact model for Mars uses the current atmosphere with argon as the index volatile and assumes a surface pressure of about 40 mb. The model also allows for changes in surface pressure. The model is based on analysis of gases trapped in Shergottite and Nakhlite meteorites. Tests of the model include the identification of noble gases in comets and the presence of nitrogen compounds in Jupiter identified by the Galileo probe.^ieng

Simulations of the Viking Gas Exchange Experiment using palagonite and Fe-rich montmorillonite as terrestrial analogs: implications for the surface composition of Mars.

Simulations of the Gas Exchange Experiment (GEX), one of the Viking Lander Biology Experiments, were run using palagonite and Fe-rich montmorillonite as terrestrial analogs of the Martian soil. These terrestrial analogs were exposed to a nutrient solution of the same composition as that of the Viking Landers under humid (no contact with nutrient) and wet (intimate contact) conditions. The headspace gases in the GEX sample cell were sampled and then analyzed by gas chromatography under both humid and wet conditions. Five gases were monitored: CO2, N2, O2, Ar, and Kr. It was determined that in order to simulate the CO2 gas changes of the Viking GEX experiment, the mixture of soil analog mineral plus nutrient medium must be slightly (pH = 7.4) to moderately basic (pH = 8.7). This conclusion suggests constraints upon the composition of terrestrial analogs to the Mars soil; acidic components may be present, but the overall mixture must be basic in order to simulate the Viking GEX results.

Xenon fractionation in porous planetesimals.

The distinctively fractionated Xe on Mars and Earth may have its root in a common source from which both planets accreted. We begin with Ozima and Nakazawa's hypothesis that terrestrial Xe fractionation was caused by gravitational separation of adsorbed solar nebular gases inside large porous planetesimals. We point out that Xe would have been trapped as the planetesimal grew and pores were squeezed shut by lithostatic pressure. We show that enough fractionated Xe to supply the Earth could have been trapped this way. The degree of fractionation is controlled by the lithostatic pressure at the pore-closing front and so would have been roughly the same for all large planetesimals. The predicted degree of fractionation agrees well with that preserved in terrestrial and martian Xe. Relative to Xe, this source is strongly depleted in other noble gases. In contrast to the original Ozima and Nakazawa hypothesis, our hypothesis predicts the observed fractionation, and it allows planetary accretion to occur after the dissipation of the solar nebula. The required planetesimals are large, representing a class of object now extinct in the solar system.

S-process krypton of variable isotopic composition in the Murchison meteorite.

Current theories on the origin of the chemical elements explain the abundance of medium-heavy and heavy nuclides to be due to the capture by pre-existing lighter nuclides of free neutrons on either a slow timescale (s-process) or a rapid timescale (r-process). Experimental evidence in support of these theories comes from the analysis of carbonaceous chondrites. In acid-resistant residues of these meteorites a kind of xenon has been found, the isotopic composition of which matches almost perfectly that predicted for s-process xenon. We report data that allow us, for the first time, to derive with reasonable precision the full isotopic spectrum of s-process krypton as well. We show that this s-Kr in a residue from Murchison meteorite did not originate in one single s-process but rather is a mixture of contributions from stellar environments where the density of free neutrons was not the same. The astrophysical conditions under which this Krypton has been produced were distinct from those that have been invoked to explain the Solar System s-process abundance. Similar to the 13C-rich carbon component in an aliquot of the same residue, the s-process Kr from different astrophysical sites has retained its identity during the accumulation and subsequent history of the meteorite.

Evaluation of radiation monitor effectiveness for the detection of 85Kr.

As part of the preparations for the purging of TMI Unit-2, the 85Kr sensitivity of 12 radiation detector systems or system combinations was determined. Eleven of these were evaluated using a cube-shaped polyethylene-walled room containing a volume of 5.6 m3 (200 ft3). Krypton-85 gas was added to produce a concentration of 6.7 x 10(-6) muCi/ml in the test room. It was found that none of the ion chambers and scintillation detector systems were able to detect this concentration of 85Kr. Detectors employing thin window GM pancake probes were found to be sensitive enough to monitor this gas down to the unrestrictive area maximum permissible concentration level (MPC) of 3 x 10(-5) muCi/ml, while a large window gas flow proportional counter was found to be sensitive enough to monitor down to about 09.1 MPC. At the end of this experiment, 2.3 m3 (80 ft3) of the gas in the test room was pumped into a compressed air cylinder (scuba bottle) and was used to calibrate The Pennsylvania State University (PSU) Noble Gas Monitor. The sensitivity of this system, which employs gas compression and Ge(Li) spectroscopy, was demonstrated to be between 0.1 and 0.03 times MPC, depending on the counting time employed.