The new REE-rich, monoclinic, epidote-supergroup minerals ferriakasakaite-(La) and ferriandrosite-(La), found in tephroite calcite veinlets cutting the stratiform ferromanganese deposit from the Shobu area, Ise City, Mie Prefecture, Japan, were studied using electron microprobe analysis and single-crystal X-ray diffraction methods. Ferriakasakaite-(La), ideally A1CaA2LaM1Fe3+M2AlM3Mn2+(SiO4)(Si2O7)O(OH) (Z = 2, space group P21/m), has a new combination of dominant cations at A1(Ca) and M3(Mn2+), which are the key sites to determine a root name for epidote-supergroup minerals. The unit-cell parameters are a = 8.8733(2), b = 5.7415(1), c = 10.0805(3) Å, β = 113.845(2)° and V = 469.73(2) Å3. According to the structural refinement (R1 = 3.13%), the determined structural formula is A1(Ca0.54Mn2+0.46)A2[(La0.48Ce0.20Pr0.07Nd0.18Gd0.02)Σ0.95Ca0.05]M1(Fe0.423+V0.343+Al0.18Ti0.064+)M2(Al0.96Fe0.043+)M3(Mn0.502+Fe0.432+Mg0.07)(SiO4)(Si2O7)O(OH). Ferriandrosite-(La), ideally A1Mn2+A2LaM1Fe3+M2AlM3Mn2+(SiO4)(Si2O7)O(OH) (Z = 2, space group P21/m), is the M1Fe3+ analogue of androsite. The unit-cell parameters are a = 8.8779(1), b = 5.73995(1), c = 10.0875(2) Å, β = 113.899(1)° and V = 469.97(2) Å3, and the structural formula is A1(Mn0.562+Ca0.44)A2[(La0.49Ce0.20Pr0.08Nd0.19Gd0.02)Σ0.97Ca0.03]M1(Fe0.403+V0.283+Al0.20Fe0.052+Ti0.074+)M2(Al0.97Fe0.033+)M3(Mn0.502+Fe0.402+Mg0.10)(SiO4)(Si2O7)O(OH) (R1 = 2.93%). The two new minerals, which are compositionally very similar overall, are distinguished by occupancy of A1, Ca vs. Mn2+. The structural properties of these minerals depend not only on the REE content at A2, but also on the Mn content at A1.

Moraskoite, a new natural phosphate of composition Na2Mg(PO4)F, has been found in the Morasko IAB-MG iron meteorite. The new phosphate occurs in a graphite-troilite inclusion enclosed in a kamacite-taenite matrix. Associated minerals in the inclusions are chlorapatite, buchwaldite, brianite, merrillite, a new phosphate phase of composition Na4MgCa3(PO4)4, chromite, enstatite (bronzite), kosmochlor, kosmochlor–augite, olivine, albite, orthoclase, quartz, cohenite, schreibersite, nickelphosphide, altaite, pyrrhotite, sphalerite, daubreelite, djerfischerite, whitlockite and native Cu. The inclusions are rimmed by a schreibersite-cohenite halo. Moraskoite forms aggregates up to 1.5 mm in size, with individual grains 20–300 μm across. It is colourless and transparent, with a white streak and vitreous lustre; fluorescence is weak blue in ultraviolet radiation (254 and 360 nm); hardness is 4–5; it has irregular, conchoidal fracture and cleavage is rarely observed. Calculated density (using the empirical formula) is 2.925 g cm–3. The moraskoite structure (Pbcn, a = 5.2117(10), b = 13.711(3), c = 11.665(2) Å, V = 833.6(3) Å3 and Z = 8) is similar to that of its synthetic analogue. The strongest diffraction lines of the moraskoite powder diffraction pattern are as follows (dhkl, I): 3.909(75), 3.382(52), 2.955(90), 2.606(100), 2.571(96), 2.545(68), 1.691 (67). In the Raman spectrum, the following characteristic bands are distinguished (cm–1, strong bands bold): 1114, 1027, 962, 589, 438, 336, 308, 279, 262, 244, 193, 184, 147 and 131. The Raman data prove the absence of H2O and CO2. Moraskoite is interpreted as being a primary phosphate, which crystallized together with graphite, troilite and other accessories inside the nodule.

Anzaite-(Ce), ideally Ce43+Fe2+Ti6O18(OH)2, is a new, structurally complex mineral occurring as scarce minute crystals in hydrothermally altered silicocarbonatites in the Afrikanda alkali-ultramafic complex of the Kola Peninsula, Russia. The mineral is a late hydrothermal phase associated with titanite, hibschite, clinochlore and calcite replacing the primary magmatic paragenesis. The rare-earth elements (REE) (dominated by Ce), Ti and Fe incorporated in anzaite-(Ce) were derived from primary Ti oxides abundant in the host rock. Anzaite-(Ce) is brittle and lacks cleavage; the density calculated on the basis of structural data is 5.054(6) g cm–3. The mineral is opaque and grey with a bluish hue in reflected light; its reflectance values range from 15–16% at 440 nm to 13–14% at 700 nm. Its infrared spectrum shows a prominent absorption band at 3475 cm–1 indicative of OH– groups. The average chemical composition of anzaite-(Ce) gives the following empirical formula calculated on the basis of 18 oxygen atoms and two OH– groups: (Ce2.18Nd0.85La0.41Pr0.26Sm0.08Ca0.36Th0.01)Σ4.15Fe0.97(Ti5.68Nb0.22Si0.04)Σ5.94O18(OH)2. The mineral is monoclinic, space group C2/m, a = 5.290(2), b = 14.575(6), c = 5.234(2) Å, β = 97.233(7)°, V = 400.4(5) Å3, Z = 1. The ten strongest lines in the X-ray micro-diffraction pattern are [dobs in Å (I)hkl]: 2.596 (100) 002; 1.935 (18) 170; 1.506 (14) 133; 1.286 (13) 1.11.0; 2.046 (12) 241; 1.730 (12) 003; 1.272 (12) 0.10.2; 3.814 (11) 111; 2.206 (9) 061; 1.518 (9) 172. The structure of anzaite-(Ce), refined by single-crystal techniques to R1 = 2.1%, consists of alternating layers of type 1, populated by REE (+ minor Ca) in a square antiprismatic coordination and octahedrally coordinated Fe2+, and type 2, built of five-coordinate and octahedral Ti, stacked parallel to (001). This atomic arrangement is complicated by significant disorder affecting the Fe2+, five-coordinate Ti and two of the four anion sites. The order-disorder pattern is such that only one half of these positions in total occupy any given (010) plane, and the disordered (010) planes are separated by ordered domains comprising REE, octahedral Ti and two anion sites occupied by O2–. Structural and stoichiometric relations between anzaite-(Ce) and other REE-Ti (±Nb, Ta) oxides are discussed. The name anzaite-(Ce) is in honour of Anatoly N. Zaitsev of St Petersburg State University (Russia) and The Natural History Museum (UK), in recognition of his contribution to the study of carbonatites and REE minerals. The modifier reflects the prevalence of Ce over other REE in the composition of the new mineral.

The new mineral geschieberite (IMA2014-006), K2(UO2)(SO4)2(H2O)2, was found in the Svornost mine, Jáchymov, Czech Republic, where it occurs as a secondary alteration phase after uraninite in association with adolfpateraite and gypsum. Geschieberite forms crystalline aggregates of bright green colour (when thick) composed of multiply intergrown prismatic crystals elongated on [001] typically reaching 0.1–0.2 mm across; observable forms are {010} and {001}. Crystals are translucent to transparent with a vitreous lustre. The mineral is brittle, with perfect cleavage on {100} and an uneven fracture. It has a greenish-white streak and a probable Mohs hardness of ∼2. The mineral is slightly soluble in cold H2O. The calculated density is 3.259 g cm–3. The mineral exhibits strong yellowish-green fluorescence under both shortwave and longwave UV radiation. Optically, geschieberite is biaxial (–), with β = 1.596(2) and γ = 1.634(4) (measured at 590 nm), with X = a. Electron-microprobe analyses provided Na2O 0.23, K2O 14.29, MgO 2.05, CaO 0.06, UO3 49.51, SO3 27.74, H2O 6.36 (structure), total 100.24 wt.%, yielding the empirical formula (K1.72Mg0.29Na0.04Ca0.01)Σ2.06(U0.98O2)(S0.98O4)2(H2O)2 based on 12 O atoms per formula unit. The Raman spectrum is dominated by the symmetric stretching vibrations of UO22+, SO42– and weaker O–H stretching vibrations. Geschieberite is orthorhombic, Pna21, with a = 13.7778(3), b = 7.2709(4), c = 11.5488(2) Å, V = 1156.92(7) Å3, Z = 4. The eight strongest powder X-ray diffraction lines are [dobs in Å (hkl) Irel]: 6.882 (200) 100, 5.622 (111) 53, 4.589 (211) 12, 4.428 (202) 16, 3.681 (311) 18, 3.403 (013) 12, 3.304 (401,1̄13) 15 and 3.006 (122) 17. The structure, refined to R = 0.028 for 1882 I > 3σ(I) reflections, contains [(UO2)(SO4)2(H2O)]2– sheets that are based on the protasite anion topology. Sheets are stacked perpendicular to a. Potassium atoms and one H2O molecule are located between these sheets, providing an interlayer linkage. The remaining H2O molecule is localized within the structural unit, at the free vertex of the uranyl pentagonal bipyramid; this vertex does not link to sulfate tetrahedra. The mineral is named for one of the most important ore veins in Jáchymov – the Geschieber vein.

Cement in radioactive waste repositories will produce leachates of pH > 10 which may alter the host rock, affecting its ability to act as a barrier to radionuclide migration. To complement the many laboratory and modelling studies of rock alteration in cement leachates, analogue sites have been investigated to understand reactions at time scales relevant to geodisposal. However, analogue site histories may be poorly constrained and these systems may be influenced by site specific factors. Therefore increasing the number of sites studied is important to minimize uncertainty in the applicability of results. Herbert's Quarry has been characterized and assessed as a potential anthropogenic analogue. Streamwater sampling at the site identified Ca-rich fluids, ≤ pH 12, analogous to cement leachates. However, rock and sediment samples exhibited extensive CaCO3 precipitation in these fluids and no reaction of silicate rock. The streamwaters were also found to be oxidizing, unlike the reducing conditions expected at a repository, and temperatures were 15–25°C below those predicted for repositories. Therefore, Herbert's Quarry is believed to have limited applicability as an analogue in this context.

We report the first crystal-structure determinations of chromites from an acapulcoite and from ordinary chondrites. Cell edges range from 8.3212 (3) to 8.3501 (1) Å, while the oxygen positional parameters are in the range 0.2624 (3) to 0.26298 (9). Their compositions show they are very close to the chromite end-member FeCr2O4 with limited Al and Mg content. Titanium oxide content exceeds 1 wt.%, whereas the amount of Fe3+ is negligible. Extraterrestrial chromite is distinguished readily from terrestrial analogues on the basis of the cell edge and oxygen positional parameter. These distinctions will facilitate ongoing attempts to reconstruct the palaeoflux of meteorites to Earth from resistant extraterrestrial spinel grains recovered from ancient sediments.

Carbonated strontium fluor-, hydroxyl- and chlorapatites (carbonated Sr10(PO4)6X2 = CSrApX, where X= OH, Cl and F) were synthesized in aqueous solution. The substitution mode of carbonate was determined from infrared (IR) stretching frequencies for carbonate and from the variation in unit-cell axial lengths as a function of carbonate content. The a-axis lengths of CSrApF and CSrApCl decrease, whereas the a-axis length of CSrApOH increases slightly with increasing carbonate substitution. The carbonate IR stretching region from ∼1390 to 1590 cm–1 contains two doublets for both CSrApOH and CSrApCl, indicating the presence of both A- and B-type carbonate. The carbonate spectral region for CSrApF is reminiscent of that for CCaApF, which contains one doublet for B-type carbonate with a small shoulder attributable to A-type carbonate. Activity-based Ksp values (assuming B-type substitution) were determined for all three series of carbonated Sr apatites and show that the solubilities of CSrApOH and CSrApCl increase at higher carbonate values, whereas those of CSrApF stay constant. The Ksp values for uncarbonated SrApOH, SrApCl and SrApF were determined by extrapolation to zero percent carbonate (10–120, 10–112 and 10–113 for SrApOH, SrApCl and SrApF, respectively).

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.

Imayoshiite, Ca3Al(CO3)[B(OH)4](OH)6·12H2O, occurs in cavities in the altered gabbro xenolith in the sepentinized dunite exposed at Suisho-dani, Ise City, Mie Prefecture, Japan. Imayoshiite is colourless and transparent with a vitreous lustre and its aggregates are white with a silky lustre. Imayoshiite has a white streak. Its Mohs hardness is 2–3. It is brittle, the cleavage is distinct on {100} and the fracture is uneven. The mineral is uniaxial (–) with the indices of refraction ω = 1.497(2) and ε = 1.470(2) in white light. Imayoshiite is hexagonal, P63, a = 11.0264(11), c = 10.6052(16) Å by powder diffraction and a = 11.04592(2), c = 10.61502(19) Å by single-crystal diffraction. The structural refinement converged to R1 = 2.35%. Imayoshiite is the first member of the ettringite group with both CO3 and B(OH)4 anions.

Waimirite-(Y) (IMA 2013-108), orthorhombic YF3, occurs associated with halloysite, in hydrothermal veins (up to 30 mm thick) cross-cutting the albite-enriched facies of the A-type Madeira granite (∼1820 Ma), at the Pitinga mine, Presidente Figueiredo Co., Amazonas State, Brazil. Minerals in the granite are 'K-feldspar', albite, quartz, riebeckite, 'biotite', muscovite, cryolite, zircon, polylithionite, cassiterite, pyrochlore-group minerals, 'columbite', thorite, native lead, hematite, galena, fluorite, xenotime-(Y), gagarinite-(Y), fluocerite-(Ce), genthelvite–helvite, topaz, 'illite', kaolinite and 'chlorite'. The mineral occurs as massive aggregates of platy crystals up to ∼1 μm in size. Forms are not determined, but synthetic YF3 displays pinacoids, prisms and bipyramids. Colour: pale pink. Streak: white. Lustre: non-metallic. Transparent to translucent. Density (calc.) = 5.586 g/cm3 using the empirical formula. Waimirite-(Y) is biaxial, mean n = 1.54–1.56. The chemical composition is (average of 24 wavelength dispersive spectroscopy mode electron microprobe analyses, O calculated for charge balance): F 29.27, Ca 0.83, Y 37.25, La 0.19, Ce 0.30, Pr 0.15, Nd 0.65, Sm 0.74, Gd 1.86, Tb 0.78, Dy 8.06, Ho 1.85, Er 6.38, Tm 1.00, Yb 5.52, Lu 0.65, O (2.05), total (97.53) wt.%. The empirical formula (based on 1 cation) is (Y0.69Dy0.08Er0.06Yb0.05Ca0.03Gd0.02Ho0.02Nd0.01Sm0.01Tb0.01Tm0.01Lu0.01)Σ1.00[F2.54〈0.25O0.21]Σ3.00. Orthorhombic, Pnma, a = 6.386(1), b = 6.877(1), c = 4.401(1) Å, V = 193.28(7) Å3, Z = 4 (powder data). Powder X-ray diffraction (XRD) data [d in Å (I) (hkl)]: 3.707 (26) (011), 3.623 (78) (101), 3.438 (99) (020), 3.205 (100) (111), 2.894 (59) (210), 1.937 (33) (131), 1.916 (24) (301), 1.862 (27) (230). The name is for the Waimiri-Atroari Indian people of Roraima and Amazonas. A second occurrence of waimirite-(Y) is described from the hydrothermally altered quartz-rich microgranite at Jabal Tawlah, Saudi Arabia. Electron microprobe analyses gave the empirical formula (Y0.79Dy0.08Er0.05Gd0.03Ho0.02Tb0.01Tm0.01Yb0.01)Σ1.00[F2.85O0.08〈0.07]Σ3.00. The crystal structure was determined with a single crystal from Saudi Arabia. Unit-cell parameters refined from single-crystal XRD data are a = 6.38270(12), b = 6.86727(12), c = 4.39168(8) Å, V = 192.495(6) Å3, Z = 4. The refinement converged to R1 = 0.0173 and wR2 = 0.0388 for 193 independent reflections. Waimirite-(Y) is isomorphous with synthetic SmF3, HoF3 and YbF3. The Y atom forms a 9-coordinated YF9 tricapped trigonal prism in the crystal structure. The substitution of Y for Dy, as well as for other lanthanoids, causes no notable deviations in the crystallographic values, such as unit-cell parameters and interatomic distances, from those of pure YF3.

The crystal structure of the spinel-related, Sb mineral tegengrenite from the Filipstad district, Värmland, Sweden, has been solved in the space group R3 [a = 16.0285(9), c = 14.8144(8) Å, V = 3296.1(3) Å3, Z = 42] and refined up to R = 0.0484 for 3589 reflections with Fo > 4σ(Fo). Tegengrenite exhibits a rhombohedrally distorted spinel-type structure with cations occupying 1/8 of the tetrahedral (T) and 1/2 of the octahedral (M) interstices of a nearly regular cubic close-packing of oxygen atoms. Due to the cation ordering, which leads to a complex superstructure with a unit-cell volume of 21/4 that of a common spinel, the M and T sites of the spinel-type structure split into ten and six independent sites, respectively. Chemical composition determined by electron microprobe led to the empirical formula Mg1.26Mn0.852+Zn0.04Mn0.193+Al0.01Si0.12Ti0.03Sb0.505+O4, on the assumption that no vacancies occur in the mineral (Σcat = 3.00 and Σcharge = 8.00 per formula unit). Crystal-chemical considerations indicate that octahedra are occupied mainly by Mg, Mn3+ and Sb5+ (+Al, + Ti), whereas tetrahedra are filled mainly by Mn2+ and Mg (+Zn) with Si ordered in a specific site. However, the structure refinement shows a low site-scattering factor for one octahedral site, implying substantial vacancies and a larger overall mean Mn valence than stated above. Long mean distances also suggest some Mn2+ on octahedral sites. Together, these observations necessitate the presence of substantial Mn3+ on tetrahedral sites.

The removal of dissolved trace metals during neutralization of acid mine drainage has usually been described and modelled as a progressive, pH-dependent sorption onto standard ferric or aluminous adsorbent. In the absence of adsorbent mineral surfaces, trace metals tend to form amorphous to low-crystallinity compounds which are often difficult to characterize. Here, we study the behaviour of the more soluble metals (Cu2+, Zn2+, Mn2+, Co2+, Ni2+, Cd2+) in the absence of ferric and aluminous adsorbent by neutralization experiments with waters from two acidic pit lakes. The objectives of our study were to identify the mineral products formed by trace-metal precipitation and the pH ranges at which these metals are removed from the solutions. Both geochemical modelling and detailed mineralogical and chemical analyses (XRD, SEM, TEM, XRF, ICP-AES) were undertaken to characterize the products. The schwertmannite and hydrobasaluminite colloids formed in the initial neutralization stages were removed from the waters at pH 3.5 and 5.1, respectively. These two minerals had previously adsorbed the Cr3+ and Pb2+ initially present in the solutions. The Cu precipitates were amorphous to X-rays, though chemical and modelling data suggest that Cu probably precipitated as a precursor of brochantite (Cu4(SO4)(OH)6·2H2O) at pH >6.0, together with minor quantities of other Cu hydroxysulfates (langite, antlerite) and Cu(OH)2. At higher pH, other divalent metals (Zn2+, Mn2+) precipitated as silicates, carbonates and/or (possibly) minor oxides and (oxy)hydroxides. The high concentration of aqueous SiO2 in the solutions allowed Zn to precipitate as willemite (Zn2SiO4) at pH >7.0. Similarly, the presence of inorganic carbon (originally as CO2 (aq.)) greatly influenced the nature of the corresponding precipitate of Mn. This metal was initially present as Mn2+ and experienced a partly oxidative precipitation forming, in combination with Mg2+, the hydroxyl carbonate desautelsite (Mg6Mn2(CO3)(OH)16·4H2O) at pH 9.0–10.0. The formation of Mn3+/Mn4+ oxides and hydroxides (hausmannite, manganite, birnessite) could not be demonstrated, although geochemical calculations support their subordinate formation. Other metallic cations such as Co2+, Ni2+ and Cd2+ did not form discrete mineral phases but were totally removed by sorption onto and/or incorporation into the cited Zn and Mn compounds. The discrepancies between theoretical and demonstrated mineralogy and the significance of these minerals for future pit-lake remediation initiatives are discussed.

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.

Calcium silicate hydrate (C-S-H) alteration was studied with flow-through experiments at 25°C and pH 9.2. Three materials with apparent Ca/Si ratios (C/S ratios) of 1.47, 1.38 and 0.86 were investigated. Physical (thermogravimetric analyses/differential thermal analysis), mineralogical (X-ray diffraction) and chemical (electron probe microanalysis, transmission electron microscopy/energy dispersive X-ray spectrometry) analyses were performed to characterize the reacting minerals. Initial stoichiometric C/S ratios were 1.22, 1.22 and 0.85, respectively. The excess of Ca is attributed mainly to the presence of calcium hydroxide intimately mixed in with C-S-H particles.

The C-S-H chemical compositions were monitored during flow-through experiments in order to determine the mineral stoichiometry needed for reaction kinetics. Under our experimental conditions the stoichiometric C/S ratios decreased continuously with time. A close to stoichiometric dissolution was observed after 2 days of experiments. Using an integrated approach, the kinetics was found to be a function of the C/S.

A decrease in layer-to-layer distance in the early stage of the alteration process is interpreted as interlayer Ca/Na exchange (Na being part of the pH buffering solution). A second dissolution step, marked by a close to stoichiometric release of Ca and Si, undoubtedly results from layer dissolution. The structural similarity of C-S-H and tobermorite was confirmed.

It is UK Government policy to dispose of higher activity radioactive waste through geological disposal into an engineered deep underground geological disposal facility (GDF; DECC, 2014). Those wastes include low-level (LLW) and intermediate-level (ILW) radioactive wastes that are very heterogeneous, containing a range of inorganic and organic materials, the latter including cellulosic items. After closure of the GDF, eventual resaturation with groundwater is expected, resulting in the development of a hyperalkaline environment due to the proposed use of a cementitious backfill. Under these high-pH conditions, cellulose is unstable and will be degraded chemically, forming a range of water-soluble, low molecular weight compounds, of which the most abundant is isosaccharinic acid (ISA). As ISA is known to form stable soluble complexes with a range of radionuclides, thereby increasing the chance of radionuclide transport, the impact of microbial metabolism on this organic substrate was investigated to help determine the role of microorganisms in moderating the transport of radionuclides from a cementitious GDF. Anaerobic biodegradation of ISA has been studied recently in high-pH cementitious ILW systems, but less work has been done under anaerobic conditions at circumneutral conditions, more representative of the geosphere surrounding a GDF. Here we report the fate of ISA in circumneutral microcosms poised under aerobic and anaerobic conditions; the latter with nitrate, Fe(III) or sulfate added as electron acceptors. Data are presented confirming the metabolism of ISA under these conditions, including the direct oxidation of ISA under aerobic and nitrate-reducing conditions and the fermentation of ISA to acetate, propionate and butyrate prior to utilization of these acids during Fe(III) and sulfate reduction. The microbial communities associated with these processes were characterized using 16S rRNA gene pyrosequencing. Methane production was also quantified in these experiments, and the added electron acceptors were shown to play a significant role in minimizing methanogenesis from ISA and its breakdown products.

New results (compositional data and reflectance values) are reported for some rare sulfides enriched in K, Tl and Pb, which are related to djerfisherite, thalfenisite, bartonite, a “Cl-bearing bartonite”, or chlorbartonite, and also for shadlunite, from the Noril'sk and Salmagorsky complexes, Russia. Our observations and comparisons with relevant data in the literature imply that: (1) bartonite is probably a S-dominant (or Cl-free) analogue of djerfisherite; and a “Cl-bearing bartonite” and chlorbartonite are probably compositional variants of the djerfisherite–bartonite series. (2) The most probable formulae of bartonite and djerfisherite are (K,Me2+)6(Fe,Cu,Ni)25–xS26(S,Cl) and (K,Me2+)6(Fe,Cu,Ni)25–xS26(Cl,S), where 0 ≤ x ≤ 5, respectively. (3) Two independent substitution mechanisms probably operate in the natural series. A coupled substitution [Me2+ + S2– ↔ K+ + Cl–] is reflected by an observed deficit in K, accompanied by the incorporation of Me2+(Pb, Fe, or Ni) in the K site. Another mechanism is inferred to be [2Fe3+ + 〈 ↔ 3Fe2+], which assumes the existence of vacancy-type defects at the Me site. Thus, the second mechanism could possibly control the existing variations of Σ(Fe, Cu, Ni) in the range of ∼21 to 25 a.p.f.u., documented in djerfisherite- and bartonite-type minerals. The minerals analysed from Noril'sk, which are free of Cl and related to bartonite and to a Tl-dominant analogue of bartonite (unnamed species), probably crystallized from microvolumes of late fluid rich in K and Tl, under conditions of relatively low oxygen fugacity in the environment. Uniform contentss of Fe and Cu, observed in coexisting phases of normal (Cl-bearing) djerfisherite and bartonite (or Cl-free analogue of djerfisherite) at Salmagorsky imply that they reached equilibrium with regard to the distribution of these elements during crystallization. These phases probably formed as a result of fluctuations in the ratios of sulfur and chlorine fugacity in a fluid at a postmagmatic hydrothermal stage.

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.