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OPPORTUNITIES TO CONSTRAIN ASTROPHYSICAL REACTION RATES FOR THE s-PROCESS VIA DETERMINATION OF THE GROUND-STATE CROSS-SECTIONS

Modern models of s-process nucleosynthesis in stars require stellar reaction rates of high precision. Most neutron-capture cross-sections in the s-process have been measured, and for an increasing number of reactions the required precision is achieved. This does not necessarily mean, however, that the stellar rates are constrained equally well, because only the capture of the ground state of a target is measured in the laboratory. Captures of excited states can contribute considerably to stellar rates that are already at typical s-process temperatures. We show that the ground-state contribution X to a stellar rate is the relevant measure to identify reactions that are or could be well constrained by experiments and apply it to (n,{gamma}) reactions in the s-process. We further show that the maximum possible reduction in uncertainty of a rate via determination of the ground-state cross-section is given directly by X. An error analysis of X is presented, and it is found that X is a robust measure with mostly small uncertainties. Several specific examples (neutron capture of {sup 79}Se, {sup 95}Zr, {sup 121}Sn, {sup 187}Os, and {sup 193}Pt) are discussed in detail. The ground-state contributions for a set of 412 neutron-capture reactions around the s-process path are presented in a table. This allows identification of reactions that may be better constrained by experiments and that cannot be constrained solely by measuring ground-state cross-sections (and thus require supplementary studies). General trends and implications are discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Nuclear Data Sheets for A = 79

Nuclear spectroscopic information for known nuclides of mass number 79 (Ni,Cu,Zn,Ga,Ge,As,Se,Br,Kr,Rb, Sr,Y,Zr) has been evaluated and presented together with adopted energies, Jπ, and decay modes of levels in these nuclei. No data are yet available for excited states in {sup 79}Ni, {sup 79}Cu and {sup 79}Zr. The half–life of {sup 79}Se, a nuclide of importance in reactor–irradiated fuel composition has been measured by several independent groups and reported in a number of publications after 1995, and seems to be converging to a narrow margin of experimental values. These measurements were likely prompted by a recommendation made in the 1993 update of A = 79 nuclides (1993Si28), that since a 1949PaZZ report, there had been no measurement until 1993, and that based on simulation studies by 1993HeZW, the value listed in 1949PaZZ, and cited in all data tables and charts for 44 years, was quite likely in error, being too low by a factor of 10. According to conclusions in recent papers such as 2014Do20, there is still room for improvement in the measurement of this half–life, and further experiments are expected. This evaluation supersedes earlier Nuclear Data Sheets for A = 79 (2002Si13,1993Si28, 1982Si21,1975Ur03).

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Forbidden unique beta-decays and neutrino mass

The measurement of the electron spectrum in beta-decays provides a robust direct determination of the values of neutrino masses. The planned rhenium beta-decay experiment, called the “Microcalorimeter Arrays for a Rhenium Experiment” (MARE), might probe the absolute mass scale of neutrinos with the same sensitivity as the Karlsruhe tritium neutrino mass (KATRIN) experiment, which is expected to collect data in a near future. In this contribution we discuss the spectrum of emitted electrons close to the end point in the case of the first unique forbidden beta-decay of {sup 79}Se, {sup 107}Pd and {sup 187}Re. It is found that the p{sub 3/2}-wave emission dominates over the s{sub 1/2}-wave. It is shown that the Kurie plot near the end point is within a good accuracy linear in the limit of massless neutrinos like the Kurie plot of the superallowed beta-decay of {sup 3}H.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Radionuclide inventory of vitrified waste after spent nuclear fuel reprocessing at La Hague

The primary aim of the present work was to determine the inventories of the radionuclides and stable elements in vitrified high-level waste produced at La Hague and delivered to Germany, which are of importance for long-term safety assessment of final repositories for radioactive wastes. For a subset of these radionuclides and stable elements, the inventories were determined - either by direct measurements or by involving established correlations - and reported by AREVA. This allowed verification of the validity of application of a model approach utilizing the data of burnup and activation calculations and auxiliary information on the reprocessing and vitrification process operated at La Hague. Having proved that such a model approach can be applied for prediction of inventories of actinides, fission and activation products in vitrified waste, the present work estimated the minimum, average and maximum inventories of the radionuclides, which are of importance for long-term safety assessment of final repositories for radioactive waste but were not reported by AREVA for delivered CSD-V canisters. The average and maximum inventories in individual CSD-V canisters predicted in the present approach were compared to the inventories predicted by Nagra for canisters with vitrified waste delivered from La Hague to Switzerland [1]. This comparison revealed a number of differences between these inventories despite the fact that the canisters delivered to Switzerland were produced in essentially the same way and from the common reprocessing waste stock as CSD-V canisters delivered to Germany. Therefore, a further work is required in order to identify the reason for the discrepancy in the present estimation versus the Nagra estimation [1]. Such a work should also address the recommendation by the international peer review of the Safety Report of the Project Opalinus Clay to obtain estimates of the inventories of long-lived mobile radionuclides (such as {sup 14}C, {sup 36}Cl, {sup 79}Se, and {sup 129}I), which contribute most to the dose estimates in the radiological safety assessments, if possible, in agreement with other countries with similar waste streams in order for a coordinated set of data to be generated [2]. Since vitrified waste from reprocessing of spent nuclear fuel at La Hague was delivered to several countries - Belgium, France, Germany, Japan, Netherlands, and Switzerland - an international effort can be recommended. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Role of (n,2n) reactions in transmutation of long-lived fission products

The conditions under which (n,γ) and (n,2n) reactions can help or hinder each other in neutron transmutation of long-lived fission products (LLFPs) are considered. Isotopic and elemental transmutation for the main long-lived fission products, {sup 79}Se, {sup 93}Zr, {sup 99}Tc, {sup 107}Pd, {sup 126}Sn, {sup 129}I, and {sup 135}Cs, are considered. The effect of (n,2n) reactions on the equilibrium amount of nuclei of the transmuted isotope and the neutron consumption required for the isotope processing is estimated. The aim of the study is to estimate the influence of (n,2n) reactions on efficiency of neutron LLFP transmutation. The code TIME26 and the libraries of evaluated nuclear data ABBN-93, JEF-PC, and JANIS system are applied. The following results are obtained: (1) The effect of (n,2n) reactions on the minimum number of neutrons required for transmutation and the equilibrium amount of LLFP nuclei is estimated. (2) It is demonstrated that, for three LLFP isotopes ({sup 126}Sn, {sup 129}I, and {sup 135}Cs), (n,γ) and (n,2n) reactions are partners facilitating neutron transmutation. The strongest effect of (n,2n) reaction is found for {sup 126}Sn transmutation (reduction of the neutron consumption by 49% and the equilibrium amount of nuclei by 19%).

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Dry Pretreatment of Used Nuclear Fuel for Tritium Removal: A Review

Virtually all the elements in the periodic chart are generated as a result of atomic fission in nuclear fuel. Several of the elements are volatile or can readily react with other chemicals to form volatile molecules that can be released during the processing of used nuclear fuel for the recovery of the valuable products. Among the volatile fission products, {sup 129}I, {sup 14}C, {sup 3}H, {sup 85}Kr, and {sup 79}Se constitute the main environmental concern for uncontrolled release. Storage of used fuel allows the short-lived isotopes to decay significantly (e.g., {sup 3}H decays in half every 12.32 years and {sup 85}Kr every 10.76 years). However, depending on regulatory limits they may remain an environmental concern up to about 50-100 years of fuel storage. In contrast, the concern for environmental release of the highly mobile {sup 129}I and {sup 14}C remains for geological times (half-lives of 15.7 million years for {sup 129}I and 5730 years for {sup 14}C). Processing of used commercial nuclear fuel requires significant head-end operations to remove the fuel from the protective coverings (e.g., assemblies). The current industrial process includes cropping the end caps of the fuel assemblies, chopping of the fuel pins and/or bundles into short segments, and prolonged leaching of the segments using concentrated nitric acid (HNO{sub 3}). The infrastructure, processes, and waste treatment systems in the head-end operations, including the associated off-gas system, are some of the larger and more costly components of the entire plant. The bulk of the volatile fission products are released to the off-gas during the leaching and dissolution. However, a small but significant amount will transfer to the following steps of processing such as solvent extraction and will show up in many different waste streams. The effective capture of {sup 3}H and iodine throughout the different processes and disposition of associated waste streams is costly and complicated. Up-front removal and capture is highly desirable. Currently, at the U.S. Department of Energy national laboratories and internationally, several dry pretreatment technologies are being studied and developed with the potential to simplify and increase the safety of subsequent storage or chemical recycling processes. These studies include (1) alternative decladding methods, (2) oxidation of exposed fuel following either conventional shearing or chemical decladding, and (3) the collection and stabilization of released volatile radionuclides. Several dry processes are being developed for the up-front removal of tritium and other fission products. They can be combined with different decladding alternatives and, in general, produce a fine powder that can be fed to aqueous or pyrochemical separations processes. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Retention of Anionic Species on Granite: Influence of Granite Composition - 12129

Technetium (Tc-99, T{sub 1/2} = 2.1.10{sup 5} yrs) and selenium (Se-79, T{sub 1/2} = 6.5.10{sup 4} yrs) belong among fission products, being produced by fission of nuclear fuel. Both elements can significantly contribute to risk due to their complicated chemistry, long life times, high mobility and prevailing anionic character. Therefore, knowledge of migration behaviour under different conditions can significantly improve input into performance and safety assessment models. Granite is considered as a potential host rock for deep geological disposal of radioactive waste in many countries. Granitic rocks consist usually of quartz, feldspar, plagioclase (main components), mica, chlorite, kaolinite (minor components). The main feature of the rock is advection governed transport in fractures, complemented with diffusion process from fracture towards undisturbed rock matrix. The presented work is focused on interaction of anionic species (TcO{sub 4}{sup -}, SeO{sub 4}{sup 2-}, SeO{sub 3}{sup 2-}) with granitic rock. Furthermore, the importance of mineral composition on sorption of anionic species was also studied. The batch sorption experiments were conducted on the crushed granite from Bohemian Massive. Five fractions with defined grain size were used for static batch method. Mineral composition of each granitic fraction was evaluated using X-ray diffraction. The results showed differences in composition of granitic fractions, even though originating from one homogenized material. Sorption experiments showed influence of granite composition on adsorption of both TcO4{sup -} and SeO3{sup 2-} on granitic rock. Generally, Se(IV) showed higher retention than Tc(VII). Se(VI) was not almost sorbed at all. Fe containing minerals are pronounced as a selective Se and Tc sorbent, being reduced on their surface. As micas in granite are usually enriched in Fe, increased sorption of anionic species onto mica enriched fractions can be explained by this reason. On the other hand, fractions enriched in feldspar did not show increased sorption affinity to Tc and Se. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Prototype Performance Assessment Model for Generic Deep Borehole Repository for High-Level Nuclear Waste - 12132

A deep borehole repository is one of the four geologic disposal system options currently under study by the U.S. DOE to support the development of a long-term strategy for geologic disposal of commercial used nuclear fuel (UNF) and high-level radioactive waste (HLW). The immediate goal of the generic deep borehole repository study is to develop the necessary modeling tools to evaluate and improve the understanding of the repository system response and processes relevant to long-term disposal of UNF and HLW in a deep borehole. A prototype performance assessment model for a generic deep borehole repository has been developed using the approach for a mined geological repository. The preliminary results from the simplified deep borehole generic repository performance assessment indicate that soluble, non-sorbing (or weakly sorbing) fission product radionuclides, such as I-129, Se-79 and Cl-36, are the likely major dose contributors, and that the annual radiation doses to hypothetical future humans associated with those releases may be extremely small. While much work needs to be done to validate the model assumptions and parameters, these preliminary results highlight the importance of a robust seal design in assuring long-term isolation, and suggest that deep boreholes may be a viable alternative to mined repositories for disposal of both HLW and UNF. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DETECTION OF ELEMENTS AT ALL THREE r-PROCESS PEAKS IN THE METAL-POOR STAR HD 160617

We report the first detection of elements at all three r-process peaks in the metal-poor halo star HD 160617. These elements include arsenic and selenium, which have not been detected previously in halo stars, and the elements tellurium, osmium, iridium, and platinum, which have been detected previously. Absorption lines of these elements are found in archive observations made with the Space Telescope Imaging Spectrograph on board the Hubble Space Telescope. We present up-to-date absolute atomic transition probabilities and complete line component patterns for these elements. Additional archival spectra of this star from several ground-based instruments allow us to derive abundances or upper limits of 45 elements in HD 160617, including 27 elements produced by neutron-capture reactions. The average abundances of the elements at the three r-process peaks are similar to the predicted solar system r-process residuals when scaled to the abundances in the rare earth element domain. This result for arsenic and selenium may be surprising in light of predictions that the production of the lightest r-process elements generally should be decoupled from the heavier r-process elements.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

REACTION RATES OF {sup 64}Ge(p,γ){sup 65}As AND {sup 65}As(p,γ){sup 66}Se AND THE EXTENT OF NUCLEOSYNTHESIS IN TYPE I X-RAY BURSTS

The extent of nucleosynthesis in models of type I X-ray bursts (XRBs) and the associated impact on the energy released in these explosive events are sensitive to nuclear masses and reaction rates around the {sup 64}Ge waiting point. Using the well known mass of {sup 64}Ge, the recently measured {sup 65}As mass, and large-scale shell model calculations, we have determined new thermonuclear rates of the {sup 64}Ge(p,γ){sup 65}As and {sup 65}As(p,γ){sup 66}Se reactions with reliable uncertainties. The new reaction rates differ significantly from previously published rates. Using the new data, we analyze the impact of the new rates and the remaining nuclear physics uncertainties on the {sup 64}Ge waiting point in a number of representative one-zone XRB models. We find that in contrast to previous work, when all relevant uncertainties are considered, a strong {sup 64}Ge rp-process waiting point cannot be ruled out. The nuclear physics uncertainties strongly affect XRB model predictions of the synthesis of {sup 64}Zn, the synthesis of nuclei beyond A = 64, the energy generation, and the burst light curve. We also identify key nuclear uncertainties that need to be addressed to determine the role of the {sup 64}Ge waiting point in XRBs. These include the remaining uncertainty in the {sup 65}As mass, the uncertainty of the {sup 66}Se mass, and the remaining uncertainty in the {sup 65}As(p,γ){sup 66}Se reaction rate, which mainly originates from uncertain resonance energies.

79 ASTRONOMY AND ASTROPHYSICS↗

New detections of arsenic, selenium, and other heavy elements in two metal-poor stars

We use the Space Telescope Imaging Spectrograph on board the Hubble Space Telescope to obtain new high-quality spectra covering the 1900 ≤λ ≤ 2360 Å wavelength range for two metal-poor stars, HD 108317 and HD 128279. We derive abundances of Cu II, Zn II, As I, Se I, Mo II, and Cd II, which have not been detected previously in either star. Abundances derived for Ge I, Te I, Os II, and Pt I confirm those derived from lines at longer wavelengths. We also derive upper limits from the non-detection of W II, Hg II, Pb II, and Bi I. The mean [As/Fe] ratio derived from these two stars and five others in the literature is unchanged over the metallicity range –2.8 < [Fe/H] <–0.6, ([As/Fe]) = +0.28 ± 0.14 (σ = 0.36 dex). The mean [Se/Fe] ratio derived from these two stars and six others in the literature is also constant, ([Se/Fe]) = +0.16 ± 0.09 (σ = 0.26 dex). The As and Se abundances are enhanced relative to a simple extrapolation of the iron-peak abundances to higher masses, suggesting that this mass region (75 ≤A ≤ 82) may be the point at which a different nucleosynthetic mechanism begins to dominate the quasi-equilibrium α-rich freezeout of the iron peak. ([Cu II/Cu I]) = +0.56 ± 0.23 in HD 108317 and HD 128279, and we infer that lines of Cu I may not be formed in local thermodynamic equilibrium in these stars. The [Zn/Fe], [Mo/Fe], [Cd/Fe], and [Os/Fe] ratios are also derived from neutral and ionized species, and each ratio pair agrees within the mutual uncertainties, which range from 0.15 to 0.52 dex.

79 ASTRONOMY AND ASTROPHYSICS↗

A renewed search for short-lived 126 Sn in the early Solar System: Hydride generation MC-ICPMS for high sensitivity Te isotopic analysis

Although there is limited direct evidence for supernova input into the nascent Solar System many models suggest it formed by the gravitational collapse of a molecular cloud that was triggered by a nearby supernova. Existing lines of evidence mostly in the form of short lived radionuclidespresent in the early Solar System are potentially consistent with this hypothesis but still allow for alternative explanations. Since the natural production of Sn-126 is thought to occur only in supernovae and this isotope has a short half-life (Sn-126 -> Te-126 t(1/2) = 235 ky) the discovery of extant Sn-126 would provide unequivocal proof of supernova input to the early Solar System. Previous attempts to quantify the initial abundance of Sn-126 by examining Sn-Te systematics in early solids have been hampered by difficulties in precisely measuring Te isotope ratios in these materials. Thus here we describe a novel technique that uses hydride generation to dramatically increase the ionization efficiency of Te-an approximately 30-fold increase over previous work. This introduction system when coupled to a MC-ICPMS enables highprecision Te isotopic analyses on samples with < 10 ng of Te. We used this technique to analyze Te from a unique set of calcium-aluminum-rich inclusions (CAIs) that exhibit an exceptionally large range in Sn/Te ratios facilitating the search for the short-lived isotope Sn-126. This sample set shows no evidence of live Sn-126 implying at most minor input of supernova material during the time at which the CAIs formed. However based on the petrology of this sample set combined with the higher than expected concentrations of Sn and Te as well as the lack of nucleosynthetic anomalies in other isotopes of Te suggest that the bulk of the Sn and Te recovered from these particular refractory inclusions is not of primary origin and thus does not represent a primary signature of Sn-Te systematics of the protosolar nebula during condensation of CAIs or their precursors. Although no evidence of supernova input was found based on Sn-Te systematics in this sample set hydride generation represents a powerful tool that can now be used to further explore Te isotope systematics in less altered materials.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

THE ABUNDANCES OF LIGHT NEUTRON-CAPTURE ELEMENTS IN PLANETARY NEBULAE. III. THE IMPACT OF NEW ATOMIC DATA ON NEBULAR SELENIUM AND KRYPTON ABUNDANCE DETERMINATIONS

The detection of neutron(n)-capture elements in several planetary nebulae (PNe) has provided a new means of investigating s-process nucleosynthesis in low-mass stars. However, a lack of atomic data has inhibited accurate trans-iron element abundance determinations in astrophysical nebulae. Recently, photoionization (PI) and recombination data were determined for Se and Kr, the two most widely detected n-capture elements in nebular spectra. We have incorporated these new data into the photoionization code Cloudy. To test the atomic data, numerical models were computed for 15 PNe that exhibit emission lines from multiple Kr ions. We found systematic discrepancies between the predicted and observed emission lines that are most likely caused by inaccurate PI and recombination data. These discrepancies were removed by adjusting the Kr{sup +}–Kr{sup 3+} PI cross sections within their cited uncertainties and the dielectronic recombination rate coefficients by slightly larger amounts. From grids of models spanning the physical conditions encountered in PNe, we derive new, broadly applicable ionization correction factor (ICF) formulae for calculating Se and Kr elemental abundances. The ICFs were applied to our previous survey of near-infrared [Kr iii] and [Se iv] emission lines in 120 PNe. The revised Se and Kr abundances are 0.1–0.3 dex lower than former estimates, with average values of [Se/(O, Ar)] = 0.12 ± 0.27 and [Kr/(O, Ar)] = 0.82 ± 0.29, but correlations previously found between their abundances and other nebular and stellar properties are unaffected. We also find a tendency for high-velocity PNe that can be associated with the Galactic thick disk to exhibit larger s-process enrichments than low-velocity PNe belonging to the thin-disk population.

79 ASTRONOMY AND ASTROPHYSICS↗

THE IMPACT OF HELIUM-BURNING REACTION RATES ON MASSIVE STAR EVOLUTION AND NUCLEOSYNTHESIS

We study the sensitivity of presupernova evolution and supernova nucleosynthesis yields of massive stars to variations of the helium-burning reaction rates within the range of their uncertainties. The current solar abundances from Lodders are used for the initial stellar composition. We compute a grid of 12 initial stellar masses and 176 models per stellar mass to explore the effects of independently varying the {sup 12}C({alpha}, {gamma}){sup 16}O and 3{alpha} reaction rates, denoted R{sub {alpha},12} and R{sub 3{alpha}}, respectively. The production factors of both the intermediate-mass elements (A = 16-40) and the s-only isotopes along the weak s-process path ({sup 70}Ge, {sup 76}Se, {sup 80}Kr, {sup 82}Kr, {sup 86}Sr, and {sup 87}Sr) were found to be in reasonable agreement with predictions for variations of R{sub 3{alpha}} and R{sub {alpha},12} of {+-}25%; the s-only isotopes, however, tend to favor higher values of R{sub 3{alpha}} than the intermediate-mass isotopes. The experimental uncertainty (one standard deviation) in R{sub 3{alpha}}(R{sub {alpha},12}) is approximately {+-}10%({+-}25%). The results show that a more accurate measurement of one of these rates would decrease the uncertainty in the other as inferred from the present calculations. We also observe sharp changes in production factors and standard deviations for small changes in the reaction rates, due to differences in the convection structure of the star. The compactness parameter was used to assess which models would likely explode as successful supernovae, and hence contribute explosive nucleosynthesis yields. We also provide the approximate remnant masses for each model and the carbon mass fractions at the end of core-helium burning as a key parameter for later evolution stages.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Identification of Near-infrared [Se iii] and [Kr vi] Emission Lines in Planetary Nebulae

We identify [Se iii] 1.0994 μ m in the planetary nebula (PN) NGC 5315 and [Kr vi] 1.2330 μ m in three PNe from spectra obtained with the Folded-Port InfraRed Echellette (FIRE) spectrometer on the 6.5 m Baade Telescope. Se and Kr are the two most widely detected neutron-capture elements in astrophysical nebulae, and can be enriched by s -process nucleosynthesis in PN progenitor stars. The detection of [Se iii] 1.0994 μ m is particularly valuable when paired with observations of [Se iv] 2.2864 μ m, as it can be used to improve the accuracy of nebular Se abundance determinations, and allows Se ionization correction factor (ICF) schemes to be empirically tested for the first time. We present new effective collision strength calculations for Se{sup 2+} and Kr{sup 5+}, which we use to compute ionic abundances. In NGC 5315, we find that the Se abundance computed from Se{sup 3+}/H{sup +} is lower than that determined with ICFs that incorporate Se{sup 2+}/H{sup +}. We compute new Kr ICFs that take Kr{sup 5+}/H{sup +} into account, by fitting correlations found in grids of Cloudy models between Kr ionic fractions and those of more abundant elements, and use these to derive Kr abundances in four PNe. Observations of [Se iii] and [Kr vi] in a larger sample of PNe, with a range of excitation levels, are needed to rigorously test the ICF prescriptions for Se and our new Kr ICFs.

79 ASTRONOMY AND ASTROPHYSICS↗

HTO and selenate diffusion through compacted Na-, Na–Ca-, and Ca-montmorillonite

Radionuclide transport in smectite clay barrier systems used for nuclear waste disposal is controlled by diffusion, with adsorption significantly retarding transport rates. While a relatively minor component of spent nuclear fuel, 79 Se is a major driver of the safety case for spent fuel disposal due to its long half-life (3.3×10 5 yr) and its low adsorption to clay (K D < 10 L/kg), thus a thorough understanding of Se diffusion through clay is critical for understanding the long-term safety of spent fuel disposal systems. Through-diffusion experiments with tritiated water (HTO, conservative tracer) and Se(VI) were conducted with a well-characterized, purified montmorillonite source clay (SWy-2) under a constant ionic strength (0.1 M) and three different electrolyte compositions: Na + , Ca 2+ , and a Na + -Ca 2+ mixture at pH 6.5 in order to probe the effects of electrolyte composition and interlayer cation composition on clay microstructure, Se(VI) aqueous speciation, and ultimately diffusion. Further, the results were modeled using a reactive transport modeling approach to determine values of porosity (ε), D e (effective diffusion coefficient), and K D (distribution coefficient for adsorption). HTO diffusive flux was higher in Ca-montmorillonite (D e =1.68×10 -10 m 2 s -1 ) compared to Na-montmorillonite (De=7.83×10 -11 m 2 s -1 ). This increase in flux is likely due to a greater degree of clay layer stacking in the presence of Ca 2+ compared to Na + , which leads to larger inter-particle pores. Overall, the Se(VI) flux was much lower than the HTO flux due to anion exclusion, with Se(VI) flux following the order Ca (D e = 1.03×10 -11 m 2 s -1 ) > Na–Ca (D e = 2.12×10 -12 m 2 s -1 ) > Na (D e = 1.28×10 -12 m 2 s -1 ). These differences in Se(VI) flux are due to a combination of factors, including (1) larger accessible porosity in Ca-montmorillonite due to clay layer stacking and smaller electrostatic effects compared to Na-montmorillonite, (2) larger accessible porosity for neutral-charge CaSeO4 species which makes up 32% of aqueous Se(VI) in the pure Ca system, and (3) possibly higher Se(VI) adsorption for Ca-montmorillonite. Through a combination of experimental and modeling work, this study highlights the compounding effects that electrolyte and counterion compositions can have on radionuclide transport through clay. Diffusion models that neglect these effects are not transferable from laboratory experimental conditions to in situ repository conditions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗