Reika Yokochi

Fast chemical and isotopic exchange of nitrogen during reaction with hot molybdenum

Molybdenum crucibles are commonly used to extract nitrogen from geological samples by induction heating. Because nitrogen is known to be reactive with certain metals (e.g., Ti and Fe), we have tested the reactivity of gaseous nitrogen with a Mo crucible held at 1800°C. The consumption of nitrogen, determined by monitoring the N2/40Ar ratio of the gas phase, varied between 25 and 100%, depending on the reaction duration. Nitrogen of the reacted gas was found to be systematically enriched in 15N relative to 14N by 10‰ compared to the initial isotopic composition, without any correlation with nitrogen consumption. We propose that a rapid isotopic exchange occurs between nitrogen originally trapped in the crucible and nitrogen from the gas phase, which modifies the isotopic composition of the reacted gas. This process can significantly bias the isotopic determination of nitrogen in rocks and minerals when a Mo furnace is used for gas extraction. Meanwhile, the rate of N-Mo chemical bonding may be controlled by the formation of nitride (rather than solid solution), a process slower than the isotopic exchange. The use of a Mo furnace for the extraction of trace nitrogen from rocks and minerals should therefore be avoided.

Method for Purification of Krypton from Environmental Samples for Analysis of Radiokrypton Isotopes

Radiokrypton isotopes ((81)Kr and (85)Kr) are ideal tracers and chronometers of various environmental processes. Atom trap trace analysis (ATTA) is capable of determining the ultralow isotopic abundances of radiokryptons (<10(-12)) provided that 50 microL of pure Kr is available. The analysis by using ATTA of (81)Kr in naturally occurring gases of interest, e.g., dissolved gases in hydrological reservoirs, requires separation of parts-per-million (ppm) level Kr from chemically airlike bulk gas. A newly developed Kr purification system is based on conventional cryogenic distillation and gas chromatography to which continuous monitoring of gas effluent composition using a quadrupole mass spectrometer brings significant advantages. Simple cryogenic distillation is controlled based on the evolution of N2/Ar ratio that is relatively constant in naturally occurring, inorganic gas. Gas chromatographic separation of parts-per-million by volume (ppmv) level Kr from up to a few liters of bulk gas can be achieved by concentrating the Kr under the chromatographic tails of major components. The system described here is capable of extracting Kr of >98% purity from 5-125 L STP (standard temperature and pressure) of bulk gas with >90% yield within several hours. This system is generally useful for separation of microliter amounts of unreactive trace volatile compounds from large-volume gas samples.

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.

Spectroscopic study of the cycling transition 4s[3/2]{sub 2}-4p[5/2]{sub 3} at 811.8 nm in {sup 39}Ar: Hyperfine structure and isotope shift

Doppler-free saturated absorption spectroscopy is performed on an enriched radioactive {sup 39}Ar sample. The spectrum of the 3s{sup 2}3p{sup 5}4s[3/2]{sub 2}-3s{sup 2}3p{sup 5}4p[5/2]{sub 3} cycling transition at 811.8 nm is recorded, and its isotope shift between {sup 39}Ar and {sup 40}Ar is derived. The hyperfine coupling constants A and B for both the 4s[3/2]{sub 2} and 4p[5/2]{sub 3} energy levels in {sup 39}Ar are also determined. The results partially disagree with a recently published measurement of the same transition. Based on earlier measurements as well as the current work, the isotope shift and hyperfine structure of the corresponding transition in {sup 37}Ar are also calculated. These spectroscopic data are essential for the realization of laser trapping and cooling of {sup 37,39}Ar.