Carbonatites have always been controversial (Mitchell, 2005). Their magmatic origin was disputed in the early days of the last century, regardless of the fact that experiments clearly demonstrated the crystallization of magmatic calcite (Wyllie and Tuttle, 1960). The observation of the eruption of natrocarbonatite lava in Oldoinyo Lengai (Dawson 1962) finally convinced petrologists that they were dealing with the products of magmatic carbonate liquids. Since that time, further controversies have emerged, especially regarding the ultimate origin of carbonatite magmas, for which there are two ‘endmember’ hypotheses. The generally accepted hypothesis is based on isotopic evidence and suggests that carbonatites are from deep asthenospheric sources, such as mantle plumes (Bell, 2001; Bell et al., 2004). This fails to explain why carbonatites are essentially confined to the continental lithosphere and are extremely rare in the ocean basins (Woolley and Kjarsgaard, 2008; Woolley and Bailey, this issue), and leads to the alternative hypothesis of lithosphere-generated carbonatitic magmatism. It may be that this is simply because we have not yet understood how to identify carbonatites in oceanic regions (Bailey and Kearns, this volume), or there may be some more profound reason why carbonatites cannot form within or erupt through oceanic lithosphere.

The residual melts that remained after the consolidation of the Jálama batholith crystallized to form a group of intra-granitic pegmatite dykes, which are hosted by its outermost facies (the External Unit), and the most evolved residual melts migrated through fractures to form the Cruz del Rayo field of pegmatite dykes, which are hosted by pre-Ordovician low-grade metasedimentary rocks. The increasing activity of phosphorus as magmatic differentiation took place led to the crystallization of primary phosphates, including members of the triplite–zwieselite and the amblygonite–montebrasite series. A strong albitization of the granitic and pegmatite rocks led to the replacement of the primary assemblage by other phosphates such as alluaudite. The influx of post-magmatic hydrothermal fluids, produced quartz veins, gave rise to the crystallizationof ore minerals and triplite, and altered the granites, aplites and pegmatites, replacing some of the phosphate minerals and feldspars and depositing goyazite, montebrasite and childrenite–eosphorite. The interaction of the residual hydrothermal fluids with those from the surrounding metamorphic rocks during later alteration events resulted in the influx of large quantities of Ca and Mg, and produced phosphate assemblages enriched in those elements. Finally, late goyazite, hydroxylapatite and an unidentified Fe-rich phosphate were formed as a result of supergene alterationby percolating meteoric waters, which added Ca, Sr and other elements into the system, and increased fO2.

Two crystals of the uranyl carbonate mineral grimselite, ideally K3Na[(UO2)(CO3)3](H2O), from Jáchymov in the Czech Republic were studied by single-crystal X-ray diffraction and electron-probe microanalysis. One crystal has considerably more Na than the ideal chemical composition due to substitution of Na into KO8 polyhedra; the composition of the other crystal is nearer to ideal, and similar to synthetic grimselite. The presence of Na atoms in KO8 polyhedra, which are located in channels in the crystal structure, reduces their volume, and as a result the unit-cell volume also decreases. Structure refinement shows that the formula for the sample with the anomalously high Na content is (K2.43Na0.57)Σ3.00Na[(UO2)(CO3)3](H2O). The unit-cell parameters, refined in space group P2c, are a = 9.2507(1), c = 8.1788(1) Å, V = 606.14(3) Å3 and Z = 2. The crystal structure was refined to R1 = 0.0082 and wR1 = 0.0185 with a GOF = 1.33, based on 626 observed diffraction peaks [Iobs>3σ(I)].

Aspects of the bond topology and chemical composition of a mineral may be incorporated into a general formula by writing the local topological details of each cation and anion, along with their chemical identity, as a general expression called a structure-generating function. Here, this procedure is described for polysomatic T–O–T and H–O–H structures. We may write tetrahedrally coordinated cations and their associated anions as {T2nΘm}. For {T2nΘm} to be a chain or ribbon, 5n < m ≤ 6n, and we may write m as 5n + N, where N is an integer. Within the {T2nΘ(5n+N)} unit, we may recognize three types of anion vertices: (1) bridging anions, Θbr, that are bonded to two T cations; (2) apical anions, Θap, that are involved in linkage to other cations out of the plane of the bridging anions; and (3) linking anions, Θl, that link to non-T cations in the plane of the bridging anions. We may incorporate the connectivity of the cations in our algebraic representation of the chain as follows: {T2nΘbraΘapbΘlc} where a + b + c = 5n + N. The apical anions of the T- or H-sheets provide some anions of the layer of octahedra. We may use the handshaking di-lemma of graph theory to examine the interaction between the two types of layers, and write a Structure-Generating Function, S(N;n), that gives both the stoichiometry and aspects of the bond topology of the structures.

Where N = 1, the T-sheet consists of ribbons of the form {T2nΘ(5n+1)} = {T2nΘbr(3n–1)Θap2nΘl2}. Each T–Θbr–T linkage spans an octahedron, and hence there are (3n – 1) octahedrally coordinated cations between opposing {T2nΘbr(3n–1)Θap2nΘl2} ribbons. There are an additional (n–1) vertices, Ψ, required to complete the coordination of the M cations on one side of the O-sheet, and we may write the structure-generating function for biopyriboles as follows: S(1;n) = Xi[M(3n–1)Ψ2(n–1){T2nΘbr(3n–1)Θap2nΘl2}2] = [M(3n–1)Ψ2(n–1){T2nΘ(5n+1)}2]. Where N = 2, the general form of the T-ribbon is {T2nΘ(5n+2)}, a component of the H-sheet in the polysomatic H–O–H minerals in which the T-ribbons are linked laterally by [5]- or [6]-coordinated high-valence cations, D, which have the coordination (Dφ41φapφt), where ft may or may not be present depending on the coordination number, [6] or [5], of the D cation. The general formula for an H-sheet is [Dφap{T2nΘbr(3n–2)Θap2nΘl4}φt0–1], where φt (written after the T-sheet) occurs on the outside of the H-sheet and may be involved in linkage between adjacent H–O–H blocks. The H-sheet links via its apical anions to the O-sheet, giving the general formula of an H–O–H block as [M(3n+1)(DφapΨn{T2nΘ(5n+2)}φt0–1)2]. These H–O–H blocks may link directly or indirectly through the φt anions of the (DΘl4φapφt) octahedra, giving S(2;n) = Xi[M(3n+1)Ψ2n(D2φap2{T2nΘbr(3n–2)Θap2nΘl4}2)φt0–2]. Combining the expressions for the structure-generating functions gives a single function for T–O–T and H–O–H structures:

S(N;n) = Xi[M(3n+2N–3)?2(n+N–2)(D2(N–1)f2ap(N–1){T2nT(3n–N)brT2napT2N1}2)f0–2(N–1)t]

This expression also generates mixed-ribbon polysomatic structures. Thus S(1;2+3) gives the chemical composition and structure of the mixed-chain pyribole chesterite, and S(2;1+4) gives the chemical composition and structure of the mixed-chain H–O–H mineral, veblenite.

A recent database and world distribution map of carbonatites supports previous observations of the spatial and temporal aspects of these rocks, and provides new observations that are important for understanding their petrogenesis. These data reveal that there is an overwhelming concentration of carbonatites in Precambrian cratonic areas, most of which are elevated topographically. Thus, although approximately two-thirds of carbonatites are Phanerozoic in age, at least 88% of all dated carbonatites are located in the cratons, demonstrating a remarkable tendency for a Precambrian host. This observation suggests a link with kimberlites as diamond-bearing kimberlites are confined to the Archaean areas of cratons. The age data show that in many carbonatite-bearing provinces there has been repetition of carbonatite emplacement, with up to five episodes separated by hundreds of millions of years. In at least three provinces such activity extends from the late Archaean to relatively recent times and, because of the drift of the plates, this would seem to preclude any direct role for mantle plumes in carbonatite genesis. Magmatism is activated when lithosphere lesions are reopened in response to major changes in global plate movement patterns.

Iron oxides and oxyhydroxides are commonly of considerable importance in the sorption of ions onto rocks, soils and sediments. They can be the controlling sorptive phases even if they are present in relatively small quantities. In common with other oxides and clay minerals, the sorption pH-edge of metals is directly linked to their hydrolysis: the higher the residual charge on the metal ion, the lower the pH-edge. Modelling of this process has been successfully carried out using different microscopic or macroscopic definitions of the interface (e.g. surface complexation or ion exchange models that may or may not include mineralogical descriptions). The influence of organic material on the sorption of many metals is of significant. This organic material includes simple organic molecules and more complex exopolymeric substances (e.g. humic substances) produced by the decay of natural organic matter. Sorption of this organic material to mineral surfaces has been the subject of a large body of work. The various types of organic substances do not share the same affinities for mineral surfaces in general, and for iron oxides and oxyhydroxides in particular. In those cases in which successful models of the component binary systems (i.e. metal–surface, metal–organic, organic–surface) have been developed, the formation of mixed surface complexes, the evolution of the surface itself, the addition order in laboratory systems, and the evolution of natural organic matter fractions during sorption, have often precluded a satisfactory description of metal–surface–organic ternary systems over a sufficiently wide range of parameter values (i.e. pH, ionic strength, concentration of humic substances). This manuscript describes the reasons for some successes and failures in the modelling of the ternary systems. Promising recent advances and possible methods of providing more complete descriptions of these intricate systems are also discussed.

Schäferite, NaCa2Mg2(V5+O4)3; palenzonaite, NaCa2Mn22+(V5+O4)3; berzeliite, NaCa2Mg2(As5+O4)3; and manganberzeliite, NaCa2Mn2+2(As5+O4)3, are cubic minerals with garnet structures (space group Iad) in which tetrahedrally coordinated V5+ and/or As5+ at the Z site are charge balanced by disordered Na+ and Ca2+ at the X site, and divalent Mg2+ and Mn2+ cations at the octahedrally coordinated Y site. The crystal chemistry of palenzonaite (from the Molinello and Gambatesa mines, Italy, and the Fianel mine, Switzerland), berzeliite (from Långban, Sweden, and Montaldo, Italy), and manganberzeliite (from Varenche, Italy, and the Gozaisho mine, Japan) were studied by electron microprobe analysis and single-crystal X-ray diffraction methods. Structure refinements converged to R1 values of 1.36–2.42%. The tetrahedral site in these garnet structures is mainly occupied by pentavalent As5+ or V5+ (only up to about 20% randomly distributed Si4+ is present). Charge balance is maintained by variations in the Ca/Na ratio at the X site. Heterovalent substitution (Na+ ↔ Ca2+) at the distorted square antiprism X site in vanadate- and arsenate-bearing garnets allows full occupancy of the octahedral Y site by divalent cations (primarily Mg2+ and Mn2+). There is a positive correlation between the <Z–O> and <Y–O> bond lengths and the mean ionic radii of the substituent elements, but there is no correlation between the <X–O> bond length and the variable Na/Ca site occupancy. The ionic radii of octahedrally coordinated Mg2+ and Mn2+ are such that the shared octahedral–dodecahedral edges are similar in length to the unshared octahedral edges, which is a measure of lattice distortion in garnet structures.

Magnesium hydroxyfluoride, Mg(OH)F, has been synthesized by a subcritical hydrothermal route from a 1:1 molar mixture of brucite, Mg(OH)2, and sellaite, MgF2 with a rutile type structure, in excess water. Using a combination of synchrotron X-ray and time-of-flight neutron powder diffraction, the structure of Mg(OH)F has been solved in the diaspore space group Pnma with a = 10.116(3), b = 4.6888(10) and c = 3.0794(7) Å at ambient conditions. The most intense diffraction lines are [dobs (hkl) Iobs]: 2.291 (211) 10, 4.253 (101) 7, 1.747 (212) 7, 2.229 (401) 6 and 1.480 (610) (4) Å, with the largest d-spacing at 5.058 Å. Sharp infrared stretching bands are located at 3679 and 3645 cm–1, with a broader band at 3535 cm–1. The topology of the structure is intermediate between that of the OH and F endmembers, being derived through notional shearing nearly normal to the sheets of octahedra of the CdI2/Mg(OH)2-type structure. Further similar shearing at an interval 1/2a would lead to a Cd(OH)F-type structure, which is also related to the rutile structure type. The observations and model presented here indicate a close correlation between the structural properties of the endmembers and Mg(OH)F.

Tazzoliite, ideally Ba2CaSr0.5Na0.5Ti2Nb3SiO17[PO2(OH)2]0.5, is a new mineral (IMA 2011-018) from Monte delle Basse, Euganei Hills, Galzignano Terme, Padova, Italy. It occurs as lamellar pale orange crystals, which are typically a few m m thick and up to 0.4 mm long, closely associated with a diopsidic pyroxene and titanite. Tazzoliite is transparent. It has a white streak, a pearly lustre, is not fluorescent and has a hardness of 6 (Mohs' scale). The tenacity is brittle and the crystals have a perfect cleavage along {010}. The calculated density is 4.517 g cm–3. Tazzoliite is biaxial (–) with 2Vmeas of ~50º, it is not pleochroic and the average refractive index is 2.04. No twinning was observed. Electronmicroprobe analyses gave the following chemical formula: (Ba1.93Ca1.20Sr0.52Na0.25Fe0.102+)Σ4 (Nb2.88Ti2.05Ta0.07Zr0.01V0.015+)Σ5.02SiO17[(P0.13Si0.12S0.07)Σ0.32O0.66(OH)0.66][F0.09(OH)0.23]Σ0.32.

Tazzoliite is orthorhombic, space group Fmmm, with unit-cell parameters a = 7.4116(3), b = 20.0632(8), c = 21.4402(8) Å, V = 3188.2(2) Å3 and Z = 8. The crystal structure, obtained from single-crystal X-ray diffraction data, was refined to R1(F2) = 0.063. It consists of a framework of Nb(Ti) octahedra and BaO7 polyhedra sharing apexes or edges, and Si tetrahedra sharing apexes with Nb(Ti) octahedra and BaO7 polyhedra. The structure, which is related to the pyrochlore structure, contains three Nb(Ti) octahedra: two are Nb dominant and one is Ti dominant. Chains of A2O8 polyhedra [A2 being occupied by Sr(Ca, Fe)] extend along [100] and are surrounded by Nb octahedra. Channels formed by six Nb(Ti) octahedra and two tetrahedra, or four A1O8(OH) polyhedra (A1 being occupied by Ba), alternate along [100]. The channels are partially occupied by [PO2(OH)2] in two possible mutually exclusive positions, alternating with fully occupied A3O7 polyhedral pairs [A3 being occupied by Ca(Na)]. The seven strongest X-ray powder diffraction lines [d in Å (I/I0) (hkl)] are: 3.66 (60) (044), 3.16 (30) (153), 3.05 (100) (204), 2.98 (25) (240), 2.84 (50) (064), 1.85 (25) (400) and 1.82 (25) (268). Raman spectra of tazzoliite were collected in the range 150–3700 cm–1 and confirm the presence of OH groups. Tazzoliite is named in honour of Vittorio Tazzoli in recognition of his contributions to the fields of mineralogy and crystallography.

The safe implementation of geological disposal must be underpinned by sound science. This paper describes the approaches taken by the Nuclear Decommissioning Authority Radioactive Waste Management Directorate, the implementing body for geological disposal in the UK, to build an evidence base of scientific data and understanding which is robust to scrutiny and so provides confidence in the safety of geological disposal.

The crystal structure of the rare skarn mineral trabzonite, Ca4[Si3O9(OH)]OH, from the type locality near Ikizdere, Turkey and from the Upper Chegem caldera, Northern Caucasus, Kabardino-Balkaria, Russia has been solved and refined using single-crystal X-ray data. This shows that the chemical formula should be modified from Ca4(Si3O10)˙2H2O, reported in the original trabzonite description, to an OH-bearing composition. The crystal structure, which contains Si3O10 trimers embedded in a framework of CaO6–8 polyhedra, has orthorhombic symmetry, space group Ama2, a = 20.6, b = 9.1, c = 10.3 Å. The orthorhombic A-centred cell is easily obtained by transformation from the original monoclinic cell of P21/m symmetry. The revised formula means that trabzonite and foshagite are polymorphs; foshagite has wollastonite-like silicate chains and in contrast to trabzonite it does not contain silanol groups. The structure and composition of killalaite from both localities was also studied. Single-crystal X-ray structure refinement of killalaite from the Northern Caucasus confirmed it to be non-stoichiometric with a composition between Ca6[Si2O6(OH)]2(OH)2 and Ca7[Si2O7]2(OH)2(Z = 2). Trabzonite, killalaite and dellaite form a series of modular structures which differ mainly in the degree of condensation of the SiO4 units.

In the UK, radioactive wastes currently planned for disposal in a geological disposal facility (GDF) include intermediate level waste, some low level waste and high level waste. Disposal of other materials, including spent fuel, uranium and plutonium is also being evaluated to inform the safety case for a GDF, if such materials were to be classified as wastes in the future. This paper describes the generic safety functions through which waste packages can contribute to the safety case of a GDF in the UK. It describes the engineering approach used or envisaged, in the UK and internationally, to ensure that waste packages retain their safety functions for the required periods of time and summarizes the scientific basis underpinning the current understanding of relevant evolution processes. Where gaps in the knowledge exist, the Nuclear Decommissioning Authority Radioactive Waste Management Directorate has identified specific research activities needed to close out such gaps to a level of maturity sufficient for this stage of the disposal programme (generic). This paper describes the latest results from their R&D programme and presents a summary of the research activities planned to meet the current needs of the disposal programme with specific reference to the topics of package evolution and criticality safety.

Kazanskyite, Ba & TiNbNa3Ti(Si2O7)2O2(OH)2(H2O)4, is a Group-III TS-block mineral from the Kirovskii mine, Mount Kukisvumchorr, Khibiny alkaline massif, Kola Peninsula, Russia. The mineral occurs as flexible and commonly bent flakes 2–15 μm thick and up to 330 μm across. It is colourless to pale tan, with a white streak and a vitreous lustre. The mineral formed in a pegmatite as a result of hydrothermal activity. Associated minerals are natrolite, barytolamprophyllite, nechelyustovite, hydroxylapatite, belovite-(La), belovite-(Ce), gaidonnayite, nenadkevichite, epididymite, apophyllite-(KF) and sphalerite. Kazanskyite has perfect cleavage on {001}, splintery fracture and a Mohs hardness of 3. Its calculated density is 2.930 g cm–3. Kazanskyite is biaxial positive with α 1.695, β 1.703, γ 1.733 (λ590 nm), 2Vmeas = 64.8(7)°, 2Vcalc = 55.4°, with no discernible dispersion. It is not pleochroic. Kazanskyite is triclinic, space group P, a 5.4260(9), b 7.135(1), c 25.514(4) Å, α 90.172(4), β 90.916(4), γ 89.964(3)°, V 977.61(3) Å3. The strongest lines in the X-ray powder-diffraction pattern [d(Å)(I)(hkl)] are: 2.813(100)(12,1), 2.149(82)(22,20,207,220,22), 3.938(70)(13,112), 4.288(44)(11,10,110,11), 2.128(44)(22,2,14,221,14,221,23), 3.127(39)(16,115), 3.690(36)(14), 2.895(33)(13,121) and 2.955(32)(10,120,12). Chemical analysis by electron microprobe gave Nb2O59.70, TiO219.41, SiO228.21, Al2O30.13, FeO 0.28, MnO 4.65, BaO 12.50, SrO 3.41, CaO 0.89, K2O 1.12, Na2O 9.15, H2O 9.87, F 1.29, O = F –0.54, sum 100.07 wt.%; H2O was determined from structure refinement. The empirical formula is (Na2.55Mn0.31Ca0.11Fe2+0.03)Σ3(Ba0.70Sr0.28K0.21Ca0.03)Σ1.22(Ti2.09Nb0.63Mn0.26Al0.02)Σ3Si4.05O21.42H9.45F0.59, calculated on 22 (O + F) a.p.f.u., Z = 2. The structural formula of the form AP2MH2MO4(Si2O7)2XO4XPMXPA(H2O)n is (Ba0.56Sr0.22K0.15Ca0.03☐0.04)Σ1(☐0.74Ba0.14Sr0.06K0.06)Σ1(Ti0.98Al0.0 2)Σ1(Nb0.63Ti0.37)Σ1(Na2.55Mn0.31Ca0.11Fe2+0.03)Σ3(Ti0.74Mn0.26)Σ1(Si2O7)2O2(OH1.41F0.59)Σ2(H2O)(☐0.74H2O0.26)Σ1(H2O)2.74. Simplified and ideal formulae are as follows: Ba(☐,Ba)Ti(Nb,Ti)(Na,Mn)3(Ti,Mn)(Si2O7)2O2(OH,F)2(H2O)4 and Ba☐TiNbNa3Ti(Si2O7)2O2(OH)2(H2O)4. The Raman spectrum of the mineral contains the following bands: 3462 cm–1 (broad) and 3545 and 3628 cm–1 (sharp). The crystal structure was solved by direct methods and refined to an R1 index of 8.09%. The crystal structure of kazanskyite is a combination of a TS (titanium silicate) block and an I (intermediate) block. The TS block consists of HOH sheets (H is heteropolyhedral and O is octahedral). The TS block exhibits linkage and stereochemistry typical for Group-III (Ti = 3 a.p.f.u.) Ti-disilicate minerals. The TS block has two different H sheets where (Si2O7) groups link to [5]-coordinated Ti and [6]-coordinated Nb polyhedra, respectively. There are two peripheral sites, AP(1,2), occupied mainly by Ba (less Sr and K) at 96% and 26%. There are two I blocks: the I1 block is a layer of Ba atoms; the I2 block consists of H2O groups and AP(2) atoms. The TS and I blocks are topologically identical to those in the nechelyustovite structure. The mineral is named in honour of Professor Vadim Ivanovich Kazansky, a prominent Russian ore geologist and an expert in Precambrian metallogeny.

In the Calatrava province of central Spain, numerous Quaternary pyroclastic vents have erupted carbonatite magmas carrying silicate melt fragments, mantle debris and megacrysts. Lava flows are rare. Maar and scoria deposits have carbonate matrices and pass into tuff sheets with carbonate contents >50%, which are spread widely away from the eruptive centres and constitute the most abundant form of effusive carbonate. Immense quantities of mantle debris are present in the erupted material. The tuffs have a distinctive fabric, which consists of a pale matrix carrying black silicate glass clasts that contain globules of immiscible carbonate and carbonate phenocrysts. There is evidence of similar volcanism in the Limagne province of central France and in other intra-continental provinces in Europe and Africa. About 500 vents have been identified in France and Spain: all the vents examined to date have erupted carbonatite magma. Such eruptions are not generally recognized in classical volcanology. As pyroclastic carbonatite was not previously recognized in Spain and France, a detailed examination of other mafic and ultramafic alkaline provinces, where research has traditionally concentrated on lava flows, is vital. For any search to be successful, evidence from the pyroclastic rocks will be required.

The rocks of the Jasra intrusive complex (Shillong Plateau, northeastern India) include phlogopite clinopyroxenites (with olivine or perovskite relics), alkali gabbros/monzodiorites, syenites and nepheline syenites. They have a potassic affinity (Na2O/K2O ∼1), and their mineralogy is dominated by clinopyroxene with which phlogopite, olivine, amphibole, feldspars, feldspathoids, oxides, orthopyroxenes, perovskite, titanite and other accessory phases are variably associated. The Jasra intrusive rocks are cumulates derived from at least two distinct magmatic liquids. The potassic affinity of the Jasra rocks differs from the nearby Sung Valley ijolitic-carbonatitic complex and from the ultrapotassic lamproitic rocks of the Damodar Valley, which are of approximately the same age. This suggests major variability in the mantle sources of small-volume alkaline volcanism in the Early Cretaceous of northeastern India.