A novel sample preparation procedure for highly sensitive concurrent analysis of 236U, 237Np, 239Pu and 240Pu from river and sea water samples with Accelerator Mass Spectrometry (AMS) was developed. A selective extraction chromatography resin, instead of Fe(OH)3 co-precipitation, is used to separate the actinides as a group from most of the matrix elements for "multi-actinide analysis" with AMS, as previously published [Quinto et al., Analytical Chemistry, 2015, 253, 451-458]. The new extraction method has been tested on two environmental water systems, which differ substantially in terms of salinity, namely, 2 L Rhine river water samples collected in the vicinity of the Fessenheim Nuclear Power Plant (NPP) and 250 mL surface sea water samples from the vicinity of the La Hague nuclear reprocessing plant (NRP). In addition, aliquots from the CRM IAEA-443 (Irish Sea water) are analysed for method validation. It is observed that extraction chromatography yields results that are consistent with the use of Fe(OH)3 co-precipitation for multi-actinide analysis and can increase the signal count rates of the AMS detector for sample systems where co-precipitation would concurrently precipitate significant amounts of sample matrix, diluting the analytes in the final AMS target material. The novel method can be applied to ultra-trace analysis of low-volume samples, such as environmental samples contaminated by global fallout and nuclear installations.

Background analysis of actinide and 99Tc tracers in the frame of an in-situ bentonite diffusion experiment at the Grimsel Test Site FRANCESCA QUINTO1, INGO BLECHSCHMIDT2, THOMAS FAESTERMANN3, KARIN HAIN4, DOMINIK KOLL5, GUNTHER KORSCHINEK3, STEPHANIE KRAFT1, JOHANNA PITTERS4, MARKUS PLASCHKE1, GEORG RUGEL6, THORSTEN SCHÄFER7, PETER STEIER4 AND HORST GECKEIS1 1Karlsruhe Institute of Technology (KIT), Institute for Nuclear Waste Disposal (INE) 2NAGRA (National Cooperative for the Disposal of Radioactive Waste) 3Technical University of Munich (TUM), Physics Department 4University of Vienna, Faculty of Physics, VERA Laboratory 5The Australian National University, Research School of Physics and Engineering, Department of Nuclear Physics 6Helmholtz-Zentrum Dresden-Rossendorf, Accelerator Mass Spectrometry and Isotope Research 7Friedrich Schiller University Jena Presenting Author: francesca.quinto@kit.edu

In the frame of studies on the safe disposal of nuclear waste, there is a great interest for understanding the migration behavior of 99Tc. 99Tc originating from nuclear energy production and global fallout shows environmental levels down to 107 atoms/g of soil (∼2 fg/g). Extremely low concentrations are also expected in groundwater after diffusion of 99Tc through the bentonite constituting the technical barrier for nuclear waste disposal. The main limitation to the sensitivity of the mass spectrometric analysis of 99Tc is the background of its stable isobar 99Ru. For ultratrace analysis, the Accelerator Mass Spectrometry (AMS) setup of the Technical University of Munich using a Gas-Filled Analyzing Magnet System (GAMS) and a 14 MV Tandem accelerator is greatly effective in suppressing this interference. In the present study, the GAMS setup is used for the analysis of 99Tc in samples of the seawater reference material IAEA-443, a peat bog lake, and groundwater from an experiment of in situ diffusion through bentonite in the controlled zone of the Grimsel Test Site (GTS) within the Colloid Formation and Migration (CFM) project. With an adapted chemical preparation procedure, measurements of 99Tc concentrations at the fg/g levels with a sensitivity down to 0.5 fg are accomplished in notably small natural water samples. The access to these low concentration levels allows for the long-term monitoring of in situ tracer tests over several years and for the determination of environmental levels of 99Tc in small samples.

Np and Pu are two important actinides of concern for the safe long-term disposal of nuclear waste. Both actinides are, in addition, constituents of global nuclear fallout. Investigation of their environmental behavior requires ultra-sensitive analytical methods, but current methods for a concurrent determination in clay minerals are lacking. In the present study, a Pu isotope was investigated for use as a non-isotopic yield tracer for Np in extraction, purification, and mass spectrometric determination of Np and Pu isotopes in clay materials. Inductively coupled plasma mass spectrometry was used in this developmental study, but the method is intended for future ultra-trace analysis of global-fallout Np and Pu in clay-rich soil materials by the more sensitive accelerator mass spectrometry. Another field of application may be the investigation of diffusion patterns of actinides in compacted clay liners and potential host rocks for radioactive waste disposal. The analytical procedure includes the following steps: (1) extraction of Np and Pu from clay samples; (2) adjustment of Np and Pu to Np(IV) and Pu(III); (3) pre-concentration of Np and Pu by co-precipitation with iron hydroxide; (4) adjustment of Pu to Pu(IV); (5) extraction chromatographic separation of Pu and Np from iron and matrix elements; and (6) determination of Np and Pu by mass spectrometry. The analytical procedure was applied successfully to spiked montmorillonite and illite test portions of up to 1 g. High chemical yields near 90% were obtained for both Np and Pu. The suitability of Pu as a non-isotopic tracer for Np was indicated by Np/Pu chemical yield ratios close to unity. Accurate pH adjustment during the reductive co-precipitation and short processing times are vital to obtain high chemical yields and Np/Pu yield ratios close to unity.

The multiactinide analysis with accelerator mass spectrometry (AMS) was applied to samples collected from the run 13-05 of the Colloid Formation and Migration (CFM) experiment at the Grimsel Test Site (GTS). In this in situ radionuclide tracer test, the environmental behavior of 233U, 237Np, 242Pu, and 243Am was investigated in a water conductive shear zone under conditions relevant for a nuclear waste repository in crystalline rock. The concentration of the actinides in the GTS groundwater was determined with AMS over 6 orders of magnitude from ∼15 pg/g down to ∼25 ag/g. Levels above 10 fg/g were investigated with both sector field inductively coupled plasma mass spectrometry (SF-ICPMS) and AMS. Agreement within a relative uncertainty of 50% was found for 237Np, 242Pu, and 243Am concentrations determined with the two analytical methods. With the extreme sensitivity of AMS, the long-term release and retention of the actinides was investigated over 8 months in the tailing of the breakthrough curve of run 13-05 as well as in samples collected up to 22 months after. Furthermore, the evidence of masses 241 and 244 u in the CFM samples most probably representing 241Am and 244Pu employed in a previous tracer test demonstrated the analytical capability of AMS for in situ studies lasting more than a decade.

A wide range of isoelectric points (IEPs) has been reported in the literature for sapphire-c (α-alumina), also referred to as basal plane, (001) or (0001), single crystals. Interestingly, the available data suggest that the variation of IEPs is comparable to the range of IEPs encountered for particles, although single crystals should be much better defined in terms of surface structure. One explanation for the range of IEPs might be the obvious danger of contaminating the small surface areas of single crystal samples while exposing them to comparatively large solution reservoirs. Literature suggests that factors like origin of the sample, sample treatment or the method of investigation all have an influence on the surfaces and it is difficult to clearly separate the respective, individual effects. In the present study, we investigate cause-effect relationships to better understand the individual effects. The reference IEP of our samples is between 4 and 4.5. High temperature treatment tends to decrease the IEP of sapphire-c as does UV treatment. Increasing the initial miscut (i.e. the divergence from the expected orientation of the crystal) tends to increase the IEP as does plasma cleaning, which can be understood assuming that the surfaces have become less hydrophobic due to the presence of more and/or larger steps with increasing miscut or due to amorphisation of the surface caused by plasma cleaning. Pre-treatment at very high pH caused an increase in the IEP. Surface treatments that led to IEPs different from the stable value of reference samples typically resulted in surfaces that were strongly affected by subsequent exposure to water. The streaming potential data appear to relax to the reference sample behavior after a period of time of water exposure. Combination of the zeta-potential measurements with AFM investigations support the idea that atomically smooth surfaces exhibit lower IEPs, while rougher surfaces (roughness on the order of nanometers) result in higher IEPs compared to reference samples. Two supplementary investigations resulted in either surprising or ambiguous results. On very rough surfaces (roughness on the order of micrometers) the IEP lowered compared to the reference sample with nanometer-scale roughness and transient behavior of the rough surfaces was observed. Furthermore, differences in the IEP as obtained from streaming potential and static colloid adhesion measurements may suggest that hydrodynamics play a role in streaming potential experiments. We finally relate surface diffraction data from previous studies to possible interpretations of our electrokinetic data to corroborate the presence of a water film that can explain the low IEP. Calculations show that the surface diffraction data are in line with the presence of a water film, however, they do not allow to unambiguously resolve critical features of this film which might explain the observed surface chemical characteristics like the dangling OH-bond reported in sum frequency generation studies. A broad literature review on properties of related surfaces shows that the presence of such water films could in many cases affect the interfacial properties. Persistence or not of the water film can be crucial. The presence of the water film can in principle affect important processes like ice-nucleation, wetting behavior, electric charging, etc.

236U, 237Np, and Pu isotopes and 243Am were determined in ground- and seawater samples at levels below ppq (fg/g) with a maximum sample size of 250 g. Such high sensitivity was possible by using accelerator mass spectrometry (AMS) at the Vienna Environmental Research Accelerator (VERA) with extreme selectivity and recently improved efficiency and a significantly simplified separation chemistry. The use of nonisotopic tracers was investigated in order to allow for the determination of 237Np and 243Am, for which isotopic tracers either are rarely available or suffer from various isobaric mass interferences. In the present study, actinides were concentrated from the sample matrix via iron hydroxide coprecipitation and measured sequentially without previous chemical separation from each other. The analytical method was validated by the analysis of the Reference Material IAEA 443 and was applied to groundwater samples from the Colloid Formation and Migration (CFM) project at the deep underground rock laboratory of the Grimsel Test Site (GTS) and to natural water samples affected solely by global fallout. While the precision of the presented analytical method is somewhat limited by the use of nonisotopic spikes, the sensitivity allows for the determination of ∼105 atoms in a sample. This provides, e.g., the capability to study the long-term release and retention of actinide tracers in field experiments as well as the transport of actinides in a variety of environmental systems by tracing contamination from global fallout.

This study was performed to obtain insight into the characteristics of contaminated cementitious materials which may result from a light water reactor core melt down accident. Such material arose in a huge amount from the Fukushima disaster. We analyzed the elemental and mineralogical composition of similar, heat-treated material and investigated its radionuclide retention properties.We present the radionuclide retention properties of concrete samples which originally were part of an experiment using a thick-walled concrete recipient that had been heated by simulating a reactor melt down. Batch sorption experiments have been performed with the elements Cs(I), Co(II), and Eu(III) in seawater under aerobic conditions. Sorption coefficients were measured: Rs(Eu) ∼5800mlg−1 and Rs(Co) ∼110mlg−1. A tentative value for Cs was determined, adulterated by the relatively high release of Cs from the concrete itself.

The purpose of this study is to examine the development and effectiveness of a persistent dissolved-phase treatment zone, created by injecting potassium permanganate solution, for mitigating discharge of contaminant from a source zone located in a relatively deep, low-permeability formation. A localized 1,1-dichloroethene (DCE) source zone comprising dissolved- and sorbed-phase mass is present in lower-permeability strata adjacent to sand/gravel units in a section of the Tucson International Airport Area (TIAA) Superfund Site. The results of bench-scale studies conducted using core material collected from boreholes drilled at the site indicated that natural oxidant demand was low, which would promote permanganate persistence. The reactive zone was created by injecting a permanganate solution into multiple wells screened across the interface between the lower-permeability and higher-permeability units. The site has been monitored for 9 years to characterize the spatial distribution of DCE and permanganate. Permanganate continues to persist at the site, and a substantial and sustained decrease in DCE concentrations in groundwater has occurred after the permanganate injection. These results demonstrate successful creation of a long-term, dissolved-phase reactive treatment zone that reduced mass discharge from the source. This project illustrates the application of in situ chemical oxidation as a persistent dissolved-phase reactive treatment system for lower-permeability source zones, which appears to effectively mitigate persistent mass discharge into groundwater.

Retention or release of radionuclides in a deep geological repository for radioactive wastes strongly depends on the geochemical environment and on the interaction with near-field components, e.g. waste packages and backfill materials. Deep geological disposal in rock salt is one of the concepts considered for cemented low- and intermediate-level wastes. Long-term experiments were performed to observe the evolution of full-scale cemented waste simulates (doped with (NH4)(2)U2O7) upon reaction with relevant salt brines, e.g. MgCl2-rich and saturated NaCl solutions, and to examine the binding mechanisms of uranium. Throughout the experiments, concentrations of major solution components, uranium and pH values were monitored regularly and compared to thermodynamic equilibrium calculations, which indicate that close-to-equilibrium conditions have been achieved after 13-14 years duration of the leaching experiments. Two of the full-scale cemented waste simulates were recovered from the solutions after 17-18 years and studied by different analytical methods to characterize the solids, especially with respect to uranium incorporation. In drill core fragments of various lateral and horizontal positions of the corroded monoliths, U-rich aggregates were detected and analyzed by means of space-resolved techniques. Raman, mu-XANES and mu-XRD analyses of several aggregates demonstrate that they consist of an amorphous diuranate-type solid. Within error, calculated U solubilities controlled by Na-diuranate (Na2U2O7.H2O) are consistent with measured U concentrations in both, the NaCl and the MgCl2-system. Since uranophane occurs also in the corroded monoliths, it is proposed that a transition towards the thermodynamic equilibrium U(VI) phase is kinetically hindered. (C) 2013 Elsevier Ltd. All rights reserved.

The objective of this study was to characterize the behavior of a groundwater contaminant (trichloroethene) plume after implementation of a source-containment operation at a site in Arizona. The plume resides in a quasi three-layer system comprising a sand/gravel unit bounded on the top and bottom by relatively thick silty clayey layers. The system was monitored for 60 months beginning at start-up in 2007 to measure the change in contaminant concentrations within the plume, the change in plume area, the mass of contaminant removed, and the integrated contaminant mass discharge. Concentrations of trichloroethene in groundwater pumped from the plume extraction wells have declined significantly over the course of operation, as have concentrations for groundwater sampled from 40 monitoring wells located within the plume. The total contaminant mass discharge associated with operation of the plume extraction wells peaked at 0.23 kg/d, decreased significantly within one year, and thereafter began an asymptotic decline to a current value of approximately 0.03 kg/d. Despite an 87% reduction in contaminant mass and a comparable 87% reduction in contaminant mass discharge for the plume, the spatial area encompassed by the plume has decreased by only approximately 50%. This is much less than would be anticipated based on ideal flushing and mass-removal behavior. Simulations produced with a simplified 3-D numerical model matched reasonably well to the measured data. The results of the study suggest that permeability heterogeneity, back diffusion, hydraulic factors associated with the specific well field system, and residual discharge from the source zone are all contributing to the observed persistence of the plume, as well as the asymptotic behavior currently observed for mass removal and for the reduction in contaminant mass discharge.

The objective of this study was to characterize the temporal behavior of contaminant mass discharge, and the relationship between reductions in contaminant mass discharge and reductions in contaminant mass, for a very heterogeneous, highly contaminated source-zone field site. Trichloroethene is the primary contaminant of concern, and several lines of evidence indicate the presence of organic liquid in the subsurface. The site is undergoing groundwater extraction for source control, and contaminant mass discharge has been monitored since system startup. The results show a significant reduction in contaminant mass discharge with time, decreasing from approximately 1 to 0.15kg/d over five years. Two methods were used to estimate the mass of contaminant present in the source area at the initiation of the remediation project. One was based on a comparison of two sets of core data, collected 3.5years apart, which suggests that a significant (~80%) reduction in aggregate sediment-phase TCE concentrations occurred between sampling events. The second method was based on fitting the temporal contaminant mass discharge data with a simple exponential source-depletion function. Relatively similar estimates, 784 and 993kg, respectively, were obtained with the two methods. These data were used to characterize the relationship between reductions in contaminant mass discharge (CMDR) and reductions in contaminant mass (MR). The observed curvilinear relationship exhibits a reduction in contaminant mass discharge essentially immediately upon the initiation of mass reduction. This behavior is consistent with a system wherein significant quantities of mass are present in hydraulically poorly accessible domains for which mass removal is influenced by rate-limited mass transfer. The results obtained from the present study are compared to those obtained from other field studies to evaluate the impact of system properties and conditions on mass-discharge and mass-removal behavior. The results indicate that factors such as domain scale, hydraulic-gradient status (induced or natural), and flushing-solution composition had insignificant impact on the CMDR–MR profiles and thus on underlying mass-removal behavior. Conversely, source-zone age, through its impact on contaminant distribution and accessibility, was implicated as a critical factor influencing the nature of the CMDR–MR relationship.

Two different gibbsites, one commercial and one synthesized according to a frequently applied recipe, were studied in an interlaboratory attempt to gain insight into the origin of widely differing reports on gibbsite acid-base surface properties. In addition to a thorough characterization of the two solids, several methods relevant to the interfacial charging were applied to the two samples: potentiometric titrations to obtain the "apparent" proton related surface charge density, zeta-potential measurements characterizing the potential at the plane of shear, and Attenuated Total Reflection Infrared Spectroscopy (ATR-IR) to obtain information on the variation of counter-ion adsorption with pH (using nitrate as a probe). Values of the IEP at 9-10 and 11.2-11.3 were found for the commercial and synthesized sample, respectively. The experimental observations revealed huge differences in the charging behavior between the two samples. Such differences also appeared in the titration kinetics. A detailed literature review revealed similar disparity with no apparent systematic trend. While previously the waiting time between additions had been advocated to explain such differences among synthesized samples, our results do not support such a conclusion. Instead, we find that the amount of titrant added in each aliquot appears to have a significant influence on the titration curves. While we can relate a number of observations to others, a number of open questions and contradictions remain. We suggest various processes, which can explain the observed behavior.

A tentative picture for the charging of the sapphire basal plane in dilute electrolyte solutions allows reconciliation of the available experimental observations within a dual charging model. It includes the MUltiSIte Complexation (MUSIC) model and auto-protolysis of interfacial water. The semi-empirical MUSIC model predicts protonation and deprotonation constants of individual surface functional groups based on crystal structure and bond-valence principles: on the ideal sapphire c-plane only doubly co-ordinated hydroxyl groups exist which cause quasi zero surface potential (defined as the potential in the plane of the surface hydroxyl groups) from pH 5 to 7 and rather weak charging beyond (compared to typical oxide behaviour). MUSIC predictions concur strikingly with recently published sum frequency data for the pH dependence of the so-called "ice-like" water band (interfacial water) and contact angle titrations. Zeta potential as well as second harmonic generation data reveal a sharp IEP of around 4 and a negative surface charge at the pristine point of zero charge predicted by the MUSIC model. New zeta-potential data corroborate (i) the low IEP and its insensitivity to salt concentration and (ii) the second harmonic results. We thus establish two groups of conflicting results arising from different techniques. A conventional model of the mineral electrolyte interface such as the MUSIC model is at odds with the negative zeta potentials in the pH range 5 to 7. Therefore an additional charging mechanism is invoked to explain all the observations. Enhanced auto-protolysis of interfacial water is the most probable candidate for this additional mechanism, in agreement with net water orientation observed with sum frequency generation and second harmonic generation. Our phenomenological explanation is further corroborated by the similarity of the zeta potential vs. pH curves of the c-plane with those of hydrophobic surfaces. Additional support comes from infrared spectroscopic data on thin water films on sapphire c-plane samples. Most stunningly, theoretical calculations on basal planes of this kind suggest a 2D water bilayer that makes such surfaces hydrophobic towards further adsorption of water. The proposed dual charging mode approach comprises the MUSIC model for protonation/deprotonation of the surface aluminols affecting the surface potential and the currently advocated enhanced auto-protolysis picture for hydrophobic surfaces controlling the zeta-potential and can explain the available information in a qualitative way. The respective contributions from the two components of this dual charging mechanism may be different for different single crystal cuts of alumina. Thus interplay between protonation/deprotonation of surface functional groups and auto-protolysis of interfacial water will cause the observed zeta potentials and isoelectric points. Repercussions of one mechanism on the other will result in the most favourable interfacial water structure, which can be followed by non-linear optic techniques like sum frequency generation.

Humic acids (HA) are chemically heterogeneous and structurally ill-defined biopolymers which are able to bind traces of actinides or lanthanides. Due to their dimensions in the colloidal size range they may affect transport of these elements in aquatic systems. Eu(III)- and UO(2)(2+)-HA aggregates have been investigated by Scanning Transmission X-ray Microscopy (STXM) and C 1s-NEXAFS under systematic variation of pH. In the Eu(III)- and UO(2)(2+)-HA systems aggregate morphologies at near neutral pH were similar to those observed in previous studies: optically dense zones (high absorption at the carbon K-edge) are embedded in a matrix of less dense material. C 1s-NEXAFS signatures observed in the different zones, i.e., the intensity of the characteristic complexation feature previously experimentally described and recently theoretically characterized, strongly depends on sample pH. In the alkaline regime (pH 9) with added carbonate, co-precipitation of Eu(III)-carbonate (or ternary carbonate/(oxo)hydroxide complexes) with the Eu(III)-HA majority fraction is observed but Eu(III) binding to HA over carbonate in the dense zones seems to be favoured. The UO(2)(2+)-HA system exhibits in alkaline solution more compact morphologies combined with a strong metal ion complexation effect in the NEXAFS. Eu(III) and UO(2)(2+) polyacrylic acid (PAA) aggregates used as HA model systems show similar spectral trends; these aggregates exhibit highly branched morphologies without segregation into zones with different NEXAFS signatures. The chemical environment such as pH or the type of metal cation strongly influences both HA aggregate morphologies and NEXAFS spectral signatures. These can, in turn, be used as indicators of the strength of lanthanide or actinide ion bound HA interaction.