Nanoscale characterization (TEM on FIB-SEM-prepared foils) was undertaken on feldspars undergoing transformation from early post-magmatic (deuteric) to hydrothermal stages in granites hosting the Olympic Dam Cu-U-Au-Ag deposit, and from the Cu-Au skarn at Hillside within the same iron-oxide copper-gold (IOCG) province, South Australia. These include complex perthitic textures, anomalously Ba-, Fe-, or REE-rich compositions, and REE-flourocarbonate + molybdenite assemblages which pseudomorph pre-existing feldspars. Epitaxial orientations between cryptoperthite (magmatic), patch perthite (dueteric) and replacive albite (hydrothermal) within vein perthite support interface-mediated reactions between pre-existing alkali-feldspars and pervading fluid, irrespective of micro-scale crystal morphology. Such observations are consistent with a coupled dissolution-reprecipitation reaction mechanism, which assists in grain-scale element remobilization via the generation of transient interconnected microporosity. Micro-scale aggregates of hydrothermal hyalophane (Ba-rich K-feldspar), crystallizing within previously albitized areas of andesine, reveal a complex assemblage of calc-silicate, As-bearing fluorapatite and Fe oxides along reaction boundaries in the enclosing albite-sericite assemblage typical of deuteric alteration. Such inclusions are good REE repositories and their presence supports REE remobilization at the grain-scale during early hydrothermal alteration. Iron-metasomatism is recognized by nanoscale maghemite inclusions within ‘red-stained’ orthoclase, as well as by hematite in REE-fluorocarbonates, which reflect broader-scale zonation patterns typical for IOCG systems. Potassium-feldspar from the contact between alkali-granite and skarn at Hillside is characterized by 100–1000 ppm REE, attributable to pervasive nanoscale inclusions of calc-silicates, concentrated along microfractures, or pore-attached. Feldspar replacement by REE-fluorcarbonates at Olympic Dam and nanoscale calc-silicate inclusions in feldspar at Hillside are both strong evidence for the role of feldspars in concentrating REE during intense metasomatism. Differences in mineralogical expression are due to the availability of associated elements. Lattice-scale intergrowths of assemblages indicative of Fe-metasomatism, REE-enrichment and sulfide deposition at Olympic Dam are evidence for a spatial and temporal relationship between these processes.

The Kabwe Zn-Pb deposit (central Zambia) consists of a cluster of mixed sulfide and non-sulfide orebodies. The sulfide ores comprise sphalerite, galena, pyrite, chalcopyrite and accessory Ge-sulfides (±Ga and In). The non-sulfide ores comprise: (1) willemite-dominated zones encasing massive sulfide orebodies and (2) oxide-dominated alteration bands, overlying both the sulfide and Zn-silicate orebodies. This study focuses on the Ge, In and Ga distribution in the non-sulfide mineralization, and was carried out on a suite of Kabwe specimens, housed in the Natural History Museum Ore Collection (London). Petrography confirmed that the original sulfides were overprinted by at least two contrasting oxidation stages dominated by the formation of willemite (W1 and W2), and a further event characterized by weathering-related processes. Oxygen isotopic analyses have shown that W1 and W2 are unrelated genetically and furthermore not related to supergene Zn-Pb-carbonates in the oxide-dominated assemblage. The δ18O composition of 13.9–15.7‰ V-SMOW strongly supports a hydrothermal origin for W1. The δ18O composition of W2 (−3.5‰ to 0‰ V-SMOW) indicates that it precipitated from groundwaters of meteoric origin in either a supergene or a low-T hydrothermal environment. Gallium and Ge show a diversity of distribution among the range of Zn-bearing minerals. Gallium has been detected at the ppm level in W1, sphalerite, goethite and hematite. Germanium occurs at ppm levels in W1 and W2, and in scarcely detectable amounts in hemimorphite, goethite and hematite. Indium has low concentrations in goethite and hematite. These different deportments among the various phases are probably due to the different initial Ga, In and Ge abundances in the mineralization, to the different solubilities of the three elements at different temperatures and pH values, and finally to their variable affinities with the various minerals formed.

Evidence of crystallization by particle attachment in synthetic materials is described in numerous contributions. However, efforts to establish the contribution of the particle attachment mechanism to inorganic crystallization in natural environments have barely begun. Here, we show, for the first time, evidence that confirms oriented particle attachment as a crystal growth mechanism that is relevant in sedimentary environments. In these natural settings, oriented particle attachment operates during the formation of highly anisotropically structured clay minerals, which constitute one of the most extensively distributed groups of minerals in the Earth's crust. High-resolution transmission electron microscopy images show that the clay minerals aggregation process occurs in different manners. Smectites aggregate by semi-oriented attachment, while kaolinite, sepiolite and palygorskite aggregate by oriented attachment.

The crystal structure of the mineral mertieite-II from the Kaarreoja River, Inari commune, Finnish Lapland, Finland, was refined to R1 = 0.0222 (I) and 0.0228 (II) on the basis of X-ray diffraction data collected from two single crystals. The mineral is trigonal, space group is $R\bar 3c$. The unit-cell parameters for the two crystals are determined as: a = 7.5172(3), c = 43.037(2) Å, V = 2106.1(2) Å3 (I); a = 7.5135(4), c = 43.003(3) Å, V = 2102.4(3) Å3 (II) with Z = 12. The occupancies of the Sb and As position in the structure were refined according to the Sb:As ratio of each crystal. The position As1 (Wyckoff 6b) is completely filled by As atoms. Any excess of As is distributed together with Sb on structural position M1 (Wyckoff 12c). The crystal chemical formulae are defined as Pd8Sb1.5(Sb0.94As0.06)As0.5 (crystal I) and Pd8Sb1.5(Sb0.88As0.12)As0.5 (crystal II). As → Sb substitution of up to 4.50 wt% of As does not affect the main structural topology of mertieite-II. Mertieite-II, Pd8Sb2.5As0.5 and synthetic Pd8Sb3 are isotypic compounds. The crystal structures of synthetic Pd8Sb3 and natural mertieite-II, Pd8Sb2.5As0.5, can be derived from the hexagonal close packing by filling additional layers between the close-packed 36 layers. The structure consists of Sb and (Sb,As) triangular 36, Pd triangular 36 and Pd pentagonal-triangular 5.33 layers. Stacking of Sb-, (Sb,As)- and Pd-nets along the z axis caused extension of the unit cell. It contains a total of 36 layers: six Sb1-nets, six (M1,As1)-nets, 12 Pd1-nets and 12 (Pd1,Pd3,Pd4)-nets.

Heavy mineral concentrates from rivers and river terraces near York, Freetown Peninsula, Sierra Leone have been examined for their platinum-group mineral (PGM) content. The alluvial PGM are 0.1 to 1.5 mm in size and include Cu-bearing isoferroplatinum (Pt3Fe) and disordered Pt3–xFe (x ≤ 0.38), tulameenite (Pt2FeCu), hongshiite (PtCu), cooperite–vysotskite (PtS–PdS), laurite (RuS2), erlichmanite (OsS2), Os-Ir alloy, Os-Ru alloy and native copper.

Are the alluvial nuggets primary or a neoformation? Comparison of the PGM mineralogy of fresh rocks, weathered rocks and the saprolite, with the alluvial suite shows strongly contrasting features highlighted by the mineral assemblage. Cooperite in the fresh rocks is rare in the alluvium whilst Pt-Fe alloys become more abundant. Oxidized PGM are a feature only of the weathering process and disordering of the Pt-Fe alloys develops during weathering. Palladium is much less abundant in the alluvial suite than in the primary minerals whereas Cu, present as Cu-sulfides in the fresh rocks, occurs in the alluvium as a minor component of the Pt-Fe alloys and as hongshiite alteration to the Pt-Fe alloys. The size difference is striking; the primary mineralogy is micrometre-sized whereas the alluvial PGM are three orders of magnitude larger. Delicate PGM with alteration textures are seen only in the weathered rocks whilst delicate dendritic PGM are reported only from the alluvial suite. An organic coating to the alluvial PGM may be indicative of an organic or bacterial involvement. Some alluvial PGM occur in a drainage basin devoid of outcrops of PGE-bearing horizons.

Together these contrasting features of the primary and placer PGM support the proposal that the Freetown nuggets developed as a result of breakdown of the primary PGM during weathering, movement of the PGE in solution, and growth of new PGM in placers with a different mineral assemblage, mineralogy and mineral chemistry.

A new member of the gadolinite supergroup, gadolinite-(Nd), IMA2016-013, ideally Nd2FeBe2Si2O10, was found in the Malmkärra mine, ~3.5 km WSW of Norberg, south-central Sweden, where it occurs in association with fluorbritholite-(Ce), västmanlandite-(Ce), dollaseite-(Ce), bastnäsite-(Ce) and tremolite. Gadolinite-(Nd) forms anhedral grains up to 150 µm in size, commonly occurring as aggregates of olive green colour. The crystals are transparent with vitreous to adamantine lustre. Gadolinite-(Nd) is brittle with conchoidal fracture, no cleavage or parting was observed. It has a white streak, the Mohs hardness is 6.5–7 and the calculated density is 4.86 g cm–3. Optically, the mineral is weakly pleochroic in shades of olive green, biaxial (–), nα = 1.78(1), nβ(calc.) = 1.80, nγ = 1.81(1) measured in white light, 2V(meas.) = 62(3)°. Electron-microprobe and laser ablation inductively coupled plasma mass spectrometry analysis [in wt.%] provided SiO2 21.77, Y2O3 5.49, La2O3 2.78, Ce2 O3 14.04, Pr2O3 3.28, Nd2O3 19.27, Sm2O3 5.30, Eu2O3 0.24, Gd2O3 4.10, Tb2O3 0.36, Dy2O3 1.32, Ho2O3 0.18, Er2O3 0.38, MgO 0.51, CaO 0.14, MnO 0.10, FeO 10.62, B2O3 0.10, BeOcalc. 8.99, H2Ocalc. 0.55 and total 99.52 giving the following empirical formula (based on 2 Si): (Nd0.632 Ce0.472Y0.268Sm0.168Gd0.125Pr0.110La0.094Dy0.039Ca0.014Er0.011Tb0.011Eu0.008Ho0.008)∑1.957(Fe0.816Mg0.070Mn0.008)∑0.894(Be1.984B0.016)∑2.000Si2O9.660OH0.337. A weak Raman vibration band at ~3525 cm–1 confirms the presence of water in the structure. Gadolinite-(Nd) is monoclinic, P21/c, with a = 4.8216(3) Å, b = 7.6985(4) Å, c = 10.1362(6) Å, β = 90.234(4)°, V = 376.24(6) Å3 and Z = 2. The strongest X-ray diffraction lines are [dobs in Å (hkl) Irel]: 4.830 (100) 72, 3.603 (021) 37, 3.191(-112) 52, 3.097 (013) 35, 2.888 (121) 100, 2.607(113) 49, 2.412 (200) 24. Along with the Malmkärra mine, gadolinite-(Nd) was also recorded also at Johannagruvan and Nya Bastnäs. The minerals of the gadolinite subgroup together with fluorbritholite-(Ce) incorporate the highest fraction of medium-to-heavy rare-earth elements among associated rare-earth element minerals in the Malmkärra mine and possibly in all Bastnäs-type deposits.

Several gold deposits hosted mainly by Variscan granites and Precambrian to Palaeozoic metasediments occur in the northwestern part of Portugal. Most of these deposits were mined by the Romans (in the period I BC to II AD) as open pits and surface galleries. The Castromil-Serra da Quinta gold deposit is an important example of such a mined site; it occurs in the Dúrico-Beirã Au province located in the Central Iberian Zone (CIZ) in the western branch of European Variscan belt, mainly on the eastern flank of the Valongo anticline. Open pits and underground galleries at Castromil-Serra da Quinta exploited the gossan formed from the weathering of primary mineralization. The gossan is composed essentially of goethite, scorodite and clay minerals. A recent drilling campaign at Castromil-Serra da Quinta has provided samples of the primary mineralization below the oxidation level. Different modes of gold occurrence are defined based on metallographic studies of both the gossan and drill cores. Gold I occurs encapsulated in primary sulfide minerals, mainly arsenopyrite and pyrite; Gold II is also associated with the main primary sulfides, but occurs along grain boundaries and in microfractures of the sulfides or in associated quartz veins; and Gold III occurs as free gold particles in iron oxides within the gossan. In the gossan samples, it is difficult to distinguish whether the gold particles hosted in oxides correspond to Gold I, Gold II, or both, so these particles are described as Gold I–II and they are commonly surrounded by very much smaller particles of Gold III. Scanning electron microscope (SEM) and electron probe microanalysis (EPMA) data for the different gold particles reveal that Gold I is poorer in Ag (~15.5–39.76%) than Gold II (37.46–51.45%), whereas Gold III corresponds to native gold (<16.11% Ag). Gold III is thought to reflect gold enrichment in the upper level of the deposit, resulting from weathering processes that affected the primary Au (Bi) mineralization.

High concentrations of indium (In) and selenium (Se) have been reported in the Neves-Corvo volcanic-hosted massive sulfide deposit, Portugal. The distribution of these ore metals in the deposit is complex as a result of the combined effects of early ore-forming processes and late tectonometamorphic remobilization. The In and Se contents are higher in Cu-rich ore types, and lower in Zn-rich ore types. At the deposit scale, both In and Se correlate positively with Cu, whereas their correlations with Zn are close to zero. This argues for a genetic connection between Cu, In and Se in terms of metal sourcing and precipitation. However, re-distribution and re-concentration of In and Se associated with tectonometamorphic deformation are also processes of major importance for the actual distribution of these metals throughout the whole deposit. Although minor roquesite and other In-bearing phases were recognized, it is clear that most In within the deposit is found incorporated within sphalerite and chalcopyrite. When chalcopyrite and sphalerite coexist, the In content in sphalerite (avg. 1400 ppm) is, on average, 2–3 times higher than in chalcopyrite (avg. 660 ppm). The In content in stannite (avg. 1.3 wt.%) is even higher than in sphalerite, but the overall abundance of stannite is subordinate to either sphalerite or chalcopyrite. Selenium is dispersed widely between many different ore minerals, but galena is the main Se-carrier. On average, the Se content in galena is ~50 times greater than in either chalcopyrite (avg. 610 ppm) or sphalerite (avg. 590 ppm). The copper concentrate produced at Neves-Corvo contains very significant In (+Se) content, well above economic values if the copper smelters recovered it. Moreover, the high In content of sphalerite from some Cu-Zn ores, or associated with shear structures, could possibly justify, in the future, a selective exploitation strategy for the production of an In-rich zinc concentrate.

The UK has published a generic Disposal System Safety Case for a geological disposal facility (NDA, 2010) and is planning to update this in 2016. However, it is a challenge to present a meaningful safety case when the location and hence the design of a geological disposal facility are not known. Consequently, this paper describes our aim to present a narrative, explaining how we can have confidence in the long-term safety of a geological disposal facility. This narrative is based on an understanding of the environmental safety functions of a geological disposal facility and the features, events and processes (FEPs) that support them. The highest level environmental safety functions required for a geological disposal facility are isolation and containment. By isolation we mean removal of the wastes from people and the surface environment. By containment we mean retaining the radioactivity from the wastes within various parts of the disposal facility for as long as required to achieve safety. Beneath these top-level environmental safety functions we have identified generic environmental safety functions associated with each of the key safety barriers within a geological disposal facility, namely: the wasteform, the container, the local buffer or backfill, the mass backfill (in the access tunnels and service ways), the plugs and seals and the geosphere. This paper discusses the application of environmental safety functions and FEPs to building a safety narrative and explains how it is proposed to use such an approach to develop a generic environmental safety case for the UK to provide confidence in the longterm safety of a geological disposal facility after it has been sealed and closed.

Large quantities of irradiated graphite will arise from the decommissioning of the UK's Magnox power stations. Irradiated graphite contains 14C as well as other longer lived radionuclides (e.g. 36Cl). The potential use of magnetic sector secondary ion mass spectrometry (MS-SIMS) to examine the distribution of the 14C within trepanned graphite samples from a Magnox nuclear power station has been investigated. This work indicates that the methodology proposed has the potential to be used to analyse irradiated graphite samples with preliminary results highlighting a possible 14C enrichment in the carbonaceous deposit found on a channel wall sample. 14C concentrations in samples without this deposit were below the limits of detection of the instrument. The methodology used for these determinations ensured that possible mass interferences between 14C species and oxygen-bearing or nitrogen-bearing species were eliminated from the analysis. Future work will utilize the methodology proposed in this work on a larger number of samples.

Carbon-14 is an important radionuclide in the inventory of radioactive waste and is considered to be a key radionuclide in performance assessment. In Switzerland, the 14C inventory in a cement-based repository for low- and intermediate-level radioactive waste is mainly associated with activated steel (∼85%). Anaerobic corrosion of the activated steel will determine the time-dependent release of 14C-bearing compounds from the cementitious near field into the host rock. The present study was carried out to provide an overview on the current state of the art knowledge regarding the carbon speciation during the anaerobic corrosion of activated and non-activated iron/steel and to critically assess the capability of thermodynamic modelling to predict 14C speciation in anoxic alkaline conditions. Previous experimental work showed the presence of oxidized and reduced hydrocarbons during corrosion in iron-water systems in anoxic (near neutral to alkaline) conditions which appears to be inconsistent with the negative redox potential of the system. The capability of thermodynamic modelling to predict the carbon speciation in these conditions was found to be limited due to uncertainties associated with the concept of metastability in the C–H–O system.

A detailed understanding of the response of mineral phases to the radiation fields experienced in a geological disposal facility (GDF) is currently poorly constrained. Prolongued ion irradiation has the potential to affect both the physical integrity and oxidation state of materials and therefore may alter a structure's ability to react with radionuclides. Radiohalos (spheres of radiation damage in minerals surrounding radioactive (α-emitting) inclusions) provide useful analogues for studying long term α-particle damage accumulation. In this study, silicate minerals adjacent to Th- and U-rich monazite and zircon were probed for redox changes and long/short range disorder using microfocus X-ray absorption spectroscopy (XAS) and high resolution X-ray diffraction (XRD) at Beamline I18, Diamond Light Source. Fe3+ → Fe2+ reduction has been demonstrated in an amphibole sample containing structural OH– groups – a trend not observed in anhydrous phases such as garnet. Coincident with the findings of Pattrick et al. (2013), the radiolytic breakdown of OH– groups is postulated to liberate Fe3+ reducing electrons. Across all samples, high point defect densities and minor lattice aberrations are apparent adjacent to the radioactive inclusion, demonstrated by micro-XRD.

A new protocol for the quantitative determination of zeolite-group mineral compositions by electron probe microanalysis (wavelength-dispersive spectrometry) under ambient conditions, is presented. The method overcomes the most serious challenges for this mineral group, including new confidence in the fundamentally important Si-Al ratio. Development tests were undertaken on a set of natural zeolite candidate reference samples, representing the compositional extremes of Na, K, Cs, Mg, Ca, Sr and Ba zeolites, to demonstrate and assess the extent of beam interaction effects on each oxide component for each mineral. These tests highlight the variability and impact of component mobility due to beam interaction, and show that it can be minimized with recommended operating conditions of 15 kV, 2 nA, a defocused, 20 μm spot size, and element prioritizing with the spectrometer configuration. The protocol represents a pragmatic solution that works, but provides scope for additional optimization where required. Vital to the determination of high-quality results is the attention to careful preparations and the employment of strict criteria for data reduction and quality control, including the monitoring and removal of non-zeolitic contaminants from the data (mainly Fe and clay phases). Essential quality criteria include the zeolite-specific parameters of R value (Si/(Si + Al + Fe3+), the 'E%' charge-balance calculation, and the weight percent of non-hydrous total oxides. When these criteria are applied in conjunction with the recommended analytical operating conditions, excellent inter-batch reproducibility is demonstrated. Application of the method to zeolites with complex solid-solution compositions is effective, enabling more precise geochemical discrimination for occurrence-composition studies. Phase validation for the reference set was conducted satisfactorily with the use of X-ray diffraction and laser-ablation inductively-coupled plasma mass spectroscopy.

The generation and stability of inorganic colloids have been studied under hyperalkaline conditions. For the generation of colloids, intact cores of Bromsgrove Sandstone were flushed with simulated cement leachates, and the eluates were ultrafiltered sequentially (12 μm, 1 μm, 0.1 μm and 30 kDa) for the separation of any colloids found. No colloid formation was observed during the experiments; however the analysis by ICPMS of the eluates showed significant increases in Si and Al, indicating silicate mineral dissolution, as well as reduction of the concentration of Ca in the leachates indicating precipitation of secondary Ca-rich phases. Flow experiments with cement leachates spiked with tritiated water showed a noticeable reduction of the porosity of the sandstone as well as changes in the pore distribution. Additional stability experiments were carried out using model silica and Fe2O3 colloids. The experiments indicated that the stability of the colloids was mainly controlled by the concentration of Ca in solution and that both types were unstable under the chemical conditions in the alkaline disturbed zone. The presence of cement additives such as superplasticisers could enhance the stability of the colloids.

Bulk rock geochemistry and major- and trace-element compositions of clinopyroxene have been determined for three suites of peridotitic mantle xenoliths from the North Atlantic Craton (NAC) in northern Scotland, to establish the magmatic and metasomatic history of subcontinental lithospheric mantle (SCLM) below this region. Spinel lherzolites from the southernmost locality (Streap Com'laidh) have non-NAC mantle compositions, while the two northern xenolith suites (Loch Roag and Rinibar) are derived from the thinned NAC marginal keel. Clinopyroxene compositions have characteristic trace-element signatures which show both 'primary' and 'metasomatic' origins. We use Zr and Hf abundances to identify ancient cryptic refertilization in 'primary' clinopyroxenes. We suggest that Loch Roag and Rinibar peridotite xenoliths represent an ancient Archaean-Palaeoproterozoic SCLM with original depleted cratonic signatures which were overprinted by metasomatism around the time of intrusion of the Scourie Dyke Swarm (∼2.4 Ga). This SCLM keel was preserved during Caledonian orogenesis, although some addition of material and/or metasomatism probably also occurred, as recorded by Rinibar xenoliths. Rinibar and Streap xenoliths were entrained in Permo-Carboniferous magmas and thus were isolated from the SCLM ∼200 Ma before Loch Roag xenoliths (in an Eocene dyke). Crucially, despite their geographical location, lithospheric mantle peridotite samples from Loch Roag show no evidence of recent melting or refertilization during the Palaeogene opening of the Atlantic.

Due to its favourable properties, in particular, low permeability and swelling capacity, bentonite has been favoured as an engineered-barrier and backfill material for the geological storage of radioactive waste. To ensure its safe long-term performance it is important to understand any changes in these properties when the material is subject to heat-emitting waste. As such, this study investigates the hydraulic response of bentonite under multi-step thermal loading subject to a constant-volume boundary condition, to represent a barrier system used in a crystalline or other hard-rock host rock. The experimental set up allows continuous measurement of the hydraulic and mechanical responses during each phase of the thermal cycle. After the initial hydration of the bentonite, the temperature was raised in 20°C increments from 20 to 80°C followed by a final step to reach 120°C. Each temperature was held constant for at least 7–10 days to allow the hydraulic transients to equilibrate. The data suggest that the permeability of bentonite appears to be sensitive to changes in temperature which may extend beyond those explained by simple changes in water viscosity. However, permeability may be boundary-condition dependent and this should be considered when designing experiments or applying these results to other repository host rocks. Either way, the magnitude of the change in permeability observed in this study is minor and its impact on the hydraulic performance of the barrier is negligible.

ENTRAP comprises a pan-European cooperation of leading scientific institutions and regulatory bodies in the field of nuclear-waste characterization and its quality assurance for the safe disposal of radioactive waste. Here, the scope of this cooperation is presented and explained and links or interfaces for a potential collaboration with partners fulfilling tasks of IDG-TP are pursued.

Under the alkaline conditions expected in an intermediate-level waste repository, cellulosic material will undergo chemical hydrolysis. This will produce hydrolysis products, some of which can form soluble complexes with some radionuclides. Analyses of samples containing autoclaved tissue and cotton wool incubated in a saturated solution of Ca(OH)2 ( pH > 12) confirmed previous reports that isosaccharinic acid (ISA) is produced from these cellulose polymers at high pH. However, when inoculated with a sediment sample from a hyperalkaline site contaminated with lime-kiln waste, microbial activity was implicated in the enzymatic hydrolysis of cellulose and the subsequent production of acetate. This in turn led to acidification of the microcosms and a marked decrease in ISA production from the abiotic alkali hydrolysis of cellulose. DNA analyses of microbial communities present in the microcosms further support the hypothesis that bacterial activities can have a controlling influence on the formation of organic acids, including ISA, via an interplay between direct and indirect mechanisms. These and previous results imply that microorganisms could have a role in attenuating the mobility of some radionuclides in and around a geological disposal facility, via either the direct biodegradation of ISA or by catalysing cellulose fermentation and therefore preventing the formation of ISA.

Ternary systems of 152Eu(III), bulk bentonite and ethylenediaminetetraacetic acid (EDTA) ([Eu] = 7.9 × 10–10 M; pH = 6.0–7.0) have been studied. Without EDTA, there was slow uptake in a two-stage process, with initial rapid sorption of Eu(III) (96%), followed by slower uptake of a much smaller fraction (3.0% over a period of one month). The reversibility of Eu(III) binding was tested by allowing Eu(III) to sorb to bentonite for 1–322 days. EDTA was added to the pre-equilibrated Eu bentonite systems at 0.01 M, a concentration that was sufficient to suppress sorption in a system where EDTA was present prior to the contact of Eu(III) with bentonite. A fraction of the Eu was released instantaneously (30–50%), but a significant amount remained bound. With time, the amount of Eu(III) retained by the bentonite reduced, with a slow fraction dissociation rate constant of approximately 4.3 × 10–8 s–1 (values in the range 2.2 × 10–8 – 1.0 × 10–7 s–1) for pre-equilibration times ≥7 days. Eventually, the amount of Eu(III) remaining bound to the bentonite was within error of that when EDTA was present prior to contact (4.5% ± 0.6), although in systems with pre-equilibration times >100 days, full release took up to 500 days. Europium interactions with colloidal bentonite were also studied, and the dissociation rate constant measured by a resin competition method. For the colloids, more Eu was found in the slowly dissociating fraction (60–70%), but the first-order dissociation rate constant was faster, with an average rate constant of 8.8 × 10–7 s–1 and a range of 7.7 × 10–7 –9.5 × 10–7 s–1. For both bulk and colloidal bentonite, although slow dissociation was observed for Eu(III), there was no convincing evidence for 'irreversible' binding.

Previously, it has been suggested that metal ions complexed to humic acid in the environment might show slower dissociation than those added to humic substances in the laboratory, which has serious implications for the transport of radionuclides in the environment. The dissociation of lanthanide and anthropogenic actinide ions from humic substance complexes has been studied as a function of humic concentration and metal ion:humic concentration ratio. The results suggest that the apparently slower kinetics observed for metal ions complexed in the environment are probably due to the large humic concentrations that are used in those studies. Further, there is no evidence that the dissociation rate constant varies at very low metal ion concentrations. Although humic samples size-fractionated by ultrafiltration showed that more metal may be bound non-exchangeably, there was no evidence for different rate constants. Ultrafiltration of Eu(III)/humic acid mixtures did show a shift in Eu from smaller to larger fractions over a period of two days. Therefore, the results suggest that dissociation rate constants determined in the laboratory at metal ion concentrations higher than those expected in the environment may be used in predicting radionuclide mobility, provided that the humic acid concentration is in the range expected at the site.