The high-temperature (HT) behaviour of a sample of natural alunite was investigated by means of in situ HT single-crystal X-ray diffraction from room temperature up to the dehydroxylation temperature and consequent collapse of the crystal structure. In the temperature range 25–500°C, alunite expands anisotropically, with most of the contribution to volume dilatation being produced by expansion in the c direction. The thermal expansion coefficients determined over the temperature range investigated are: αa = 0.61(2) × 10–5 K–1 (R2 = 0.988), αc = 4.20(7) × 10–5 K–1 (R2 = 0.996), αc/αa = 6.89, αV = 5.45(7) × 10–5 K–1 (R2 = 0.998). At ∼275–300°C, a minor discontinuity in the variation of unit-cell parameters with temperature is observed and interpreted on the basis of loss of H3O+ that partially substitutes for K+ at the monovalent A site in the alunite structure. Increasing temperature causes the Al(O,OH)6 sheets, which remain almost unaltered along the basal plane, to move further apart, and this results in an expansion of the coordination polyhedron around the intercalated potassium cation. Sulfate tetrahedra act as nearly rigid units, they contract a little in the lower temperature range to accommodate the elongation of the Al octahedra.

Calciodelrioite, ideally Ca(VO3)2(H2O)4, is a new mineral (IMA 2012-031) from the uraniumvanadium deposits of the eastern Colorado Plateau in the USA. The type locality is the West Sunday mine, Slick Rock district, San Miguel County, Colorado.The new mineral occurs on fracture surfaces in corvusite- and montroseite-impregnated sandstone and forms as a result of the oxidative alteration of these phases. At the West Sunday mine, calciodelrioite is associated with celestine, gypsum, huemulite, metarossite, pascoite and rossite. Themineral occurs as transparent colourless needles, bundles of tan to brown needles and star bursts of nearly black broad blades composed of tightly intergrown needles. Crystals are elongate and striated parallel to [100], exhibiting the prismatic forms {001} and {011} and having terminationspossibly composed of the forms {100} and {61}. The mineral is transparent and has a white streak, subadamantine lustre, Mohs hardness of about 2½, brittle tenacity, irregular to splintery fracture, one perfect cleavage on {001} and possibly one or more additional cleavages parallel to [100].Calciodelrioite is soluble in water. The calculated density is 2.451 g cm– 3. It is optically biaxial (+) with α = 1.733(3), β = 1.775(3), γ = 1.825(3) (white light), 2Vmeas = 87.3(9)° and 2Vcalc = 87°. The optical orientationis X = b; Z ≈ a. No pleochroism was observed. Electronmicroprobe analyses of two calciodelrioite samples and type delrioite provided the empirical formulae (Ca0.88Sr0.07Na0.04K0.01)Σ1.00(V1.00O3)2(H2.01O)4,(Ca0.76Sr0.21Na0.01)Σ0.98(V1.00O3)2(H2.01O)4 and (Sr0.67Ca0.32)Σ0.99(V1.00O3)2(H2.00O)4, respectively.Calciodelrioite is monoclinic, I2/a, with unit-cell parameters a = 14.6389(10), b = 6.9591(4), c = 17.052(2) Å, β = 102.568(9)°, V = 1695.5(3) Å3 and Z = 8. The seven strongest lines in the X-ray powder diffractionpattern [listed as dobs Å (I)(hkl)] are as follows: 6.450(100)(011); 4.350(16)(013); 3.489(18)(020); 3.215(17)(022); 3.027(50)(multiple); 2.560(28)(15,413); 1.786(18)(028). In the structure of calciodelrioite (refined to R1 = 3.14% for1216 Fo > 4σF), V5+O5 polyhedra link by sharing edges to form a zigzag divanadate [VO3] chain along a, similar to that in the structure of rossite. The chains are linked via bonds to Ca atoms, which also bond to H2Ogroups, yielding CaO3(H2O)6 polyhedra. The Ca polyhedra form a chain along b. Each of the two symmetrically independent VO5 polyhedra has two short vanadyl bonds and three long equatorial bonds. Calciodelrioite and delrioite are isostructuraland are the endmembers of the series Ca(VO3)2(H2O)4–Sr(VO3)2(H2O)4. Calciodelrioite is dimorphous with rossite, which has a similar structure; however, the smaller 8-coordinate Ca site in rossitedoes not accommodate Sr.

The partitioning of Sr, Ba and Rb between alkali feldspar and melt has been determined at 0.1 GPa water vapour pressure, mainly on one Na-rich series and one K-rich series within the system nepheline-kalsilite-quartz. Experiments were also carried out with small amounts of the anorthite molecule or peralkaline components (Na, K metasilicates). The compositions of the alkali feldspars and coexisting quenched glasses were determined by electron microprobe analysis. Except for some peralkaline compositions, the crystal/liquid partition coefficients for Sr and Ba are always >1; the crystal/liquid partition coefficient for Rb is always <1. For sodic alkali feldspars DSr > DBa and for potassic feldspars DSr < DBa. Partition coefficients for Sr and Ba increase: (1) with decreasing temperature; (2) with increasing Or content of feldspar; (3) with increasing silica-undersaturation of the melt; (4) with decreasing peralkalinity. The variation in the value of DRb is less clear, but it is higher for K-rich feldspars. Multiple linear regression equations are fitted to correlate ln(D) with independent compositional and physical variables. Where rock/groundmass major-element data are available for felsic natural rocks, equations are recommended for obtaining reliable alkali feldspar partition coefficients for modelling fractional crystallization processes. The structural properties of silicate melts and crystal chemical relations are used to rationalize trends in partition coefficients.

The effect of pressure on the naturally occurring hydroxide-perovskite stottite, FeGe(OH)6, has been studied in situ by micro-Raman spectroscopy to 21 GPa at 300 K. The ambient spectrum contains six OH-stretching bands in the range 3064 3352 cm–1. The presence of six non-equivalent OH groups is inconsistent with space group P42/n. In view of this inconsistency a new ambient structure determination of stottite from Tsumeb was carried out, but this did not allow the clear rejection of P42/n symmetry. However, a successful refinement was also carried out in space group P2/n, a subgroup of P42/n, which allows for six non-equivalent O atoms. The two refinements are of comparable quality and do not allow a choice to be made based purely on the X-ray data. However, taken with the ambient and 150 K Raman spectra, a good case can be made for stottite having P2/n symmetry at ambient conditions. On this basis, the pressure induced spectroscopic changes are interpreted in terms of a reversible phase transition P2/n ↔ P42/n.

Geological repository designs employ a multi-barrier approach. The materials, which include wasteforms, backfill and host rock, are typically porous quasi-brittle. Mechanical damage (e.g. nucleation and growth of microcracks) can result in significant changes in permeability. A knowledge of how the permeability is affected is critical to accurate modelling of radionuclide transport. This work proposes a novel 3D lattice-type model for the damage evolution in such materials, referred to as the site-bond model. Its advantages over previous models are that the shape of the lattice cell is physically realistic and that any macroscopic elastic response can be represented, including those of cementitious and geological materials. Damage accumulates as bonds fail upon reaching prescribed failure strengths. These are dictated by a predefined pore size distribution. Concrete is used as a study material. It is demonstrated that the model can predict the macroscopic stress–strain response under unconfined tension and compression with emergent non-linearity due to damage evolution. Ongoing work on the prediction of permeability changes with damage is discussed. This is based on the interaction between the model proposed here and a lattice model of the pore space.

Sodalites and sulfatic sodalites in holocrystalline K-feldspar-rich ejecta from the Somma Vesuvius volcanic complex, Italy, have been characterized by combined chemical, structural and spectroscopic analyses. Sodalite has a relatively homogeneous chemical composition, with the ubiquitous presence of CO32– and H2O/OH–. The sulfatic sodalites are isomorphous and have cage structures which can contain a wide variety of anions, molecular species and cations. Molecular CO2 and H2O/OH– are present in sulfatic sodalites, instead of the CO32– anions that are present in sodalite sensu stricto. The cell dimensions of the all of the studied sodalite samples are very similar, the sulfatic sodalite cell dimensions are more variable. Structure refinement of a distinctly green sample confirms the P3n space group. Metasomatic magma-derived fluids that are rich in H2O, CO2, Cl and S are believed to be responsible for the genesis of the relatively late-stage phases which form the ejecta containing the sodalite-group minerals.

The Nuclear Decommissioning Authority (NDA) is developing a safety case for the long-term management of higher activity wastes. This includes safety assessments of transport to and operations at the repository. One of the main faults and hazards to be considered is waste package response to impact accidents.

The criteria of impact performance for waste packages are based upon activity release of particulates generated from the break up of the waste form during impact. The NDA approach to impact performance is based upon waste package response from finite element modelling in combination with break-up tests.

Previous break up research commissioned by the NDA has concentrated on commercial graphite and glass samples. These extended studies, undertaken by the National Nuclear Laboratory in collaboration with the Department of Aerosol Technology of the Fraunhofer Institute of Toxicology and Experimental Medicine, provide break-up data specific to nuclear facilities and waste materials. These include archived unirrradiated graphite used to construct Magnox reactor cores and reflectors, simulant high level waste glass, selected grout formulations and selected metal-in-grout formulations.

Ambient temperature X-ray diffraction data were collected at different pressures from two crystals of β-As4S4, which were made by heating realgar under vacuum at 295ºC for 24 h. These data were used to calculate the unit-cell parameters at pressures up to 6.86 GPa. Above 2.86 GPa, it was only possible to make an approximate measurement of the unit-cell parameters. As expected for a crystal structure that contains molecular units held together by weak van der Waals interactions, β-As4S4 has an exceptionally high compressibility. The compressibility data were fitted to a third-order Birch–Murnaghan equation of state with a resulting volume V0 = 808.2(2) Å3, bulk modulus K0 = 10.9(2) GPa and K' = 8.9(3). These values are extremely close to those reported for the low-temperature polymorph of As4S4, realgar, which contains the same As4S4 cage-molecule. Structural analysis showed that the unit-cell contraction is due mainly to the reduction in intermolecular distances, which causes a substantial reduction in the unit-cell volume (∼21% at 6.86 GPa). The cage-like As4S4 molecules are only slightly affected. No phase transitions occur in the pressure range investigated.

Micro-Raman spectra, collected across the entire pressure range, show that the peaks associated with As–As stretching have the greatest pressure dependence; the S–As–S bending frequency and the As–S stretching have a much weaker dependence or no variation at all as the pressure increases; this is in excellent agreement with the structural data.

Krásnoite is a new mineral (IMA2011-040) from the Huber open pit, Krásno ore district, Czech Republic and the Silver Coin mine, Nevada, USA. Krásnoite is the fluorophosphate analogue of perhamite. Krásnoite occurs as compact to finely crystalline aggregates, balls and rosette-like clusters up to 1 mm across. Individual crystals are platy, show a hexagonal outline and can reach 0.1 mm on edge at Krásno and 0.4 mm at Silver Coin. At both localities, krásnoite occurs very late in phosphaterich paragenetic sequences. Krásnoite crystals are partly transparent with a typically pearly lustre, but can also appear greasy (Krásno) or dull (Silver Coin). The streak is white and the hardness is 5 on the Mohs scale. Crystals are brittle, have an irregular fracture, one imperfect cleavage on {001} and are not fluorescent under SW and LW ultraviolet light. Penetration twinning ⊥ {001} is common. The density for both Krásno and Silver Coin material is 2.48(4) g cm–3, measured by the sink–float method in an aqueous solution of sodium polytungstate. The calculated density is 2.476 g cm–3 (Krásno). Krásnoite crystals are uniaxial (+), with ω = 1.548(2) and ε = 1.549(2) (Krásno) and ω = 1.541(1) and ε = 1.543(1) (Silver Coin). The simplified formula of krásnoite is: Ca3Al7.7Si3P4O23.5(OH)12.1F2·8H2O. Krásnoite is trigonal, space group Pm1, with a = 6.9956(4), c = 20.200(2) Å, V = 856.09(9) Å3 and Z = 3. Raman and infrared spectroscopy, coupled with magic-angle spinning nuclear magnetic resonance (MAS–NMR) spectrometry, confirmed the presence of PO3F, PO4, SiO4, H2O and OH in the crystal structure of krásnoite.

The crystal structure of kraisslite, orthorhombic (pseudo-hexagonal), a = 8.1821(1), b = 14.1946(3), c = 43.9103(8) Å, V = 5099.8(2) Å3, Z = 4 and d calc = 4.083 g cm–3, has been solved bydirect methods and refined in the space group C2221 to an R 1 index of 1.68% for 7432 observed (|F o| > 4σ|F|) reflections. Electron-microprobe analysis gave the following chemical composition: As2O510.86,As2O36.18, SiO213.39, Al2O30.25, Fe2O32.06, MnO 51.14, ZnO 7.39, MgO 2.13, CaO 0.05, H2Ocalc = 4.50, sum 97.95 wt.%; and empirical formula: Zn2.91(Mn23.07Mg1.69Ca0.03)Σ=24.79(Fe0.83 3+Al0.16)Σ=0.99(As3+O3)2[(Si0.71As0.30 5+)O4]10(OH)16 calculated on the basis of 62 anions with (OH) = 16 and As3+/(As3++ As5+) taken from the refined crystal structure. The general formula, [4]Zn3(Mn,Mg)25(Fe3+,Al)(As3+O3)2[(Si,As5+)O4]10(OH)16, differs from those given previously.

There is one As3+ site with a <As–O> distance of 1.780 Å and a stereochemistry typical of a stereoactive lone-pair of electrons. There are five tetrahedrally coordinated T sites with <T–O> distances from 1.635 to 1.692 Å; the T(1)site is fully occupied by As5+, and the T(2)–T(5) sites are occupied by both Si and As5+. There are two tetrahedrally coordinated Zn sites with <T–O> distances of ∼1.996 Å, both of which are occupied by dominantZn and minor Mn2+. There are thirteen octahedrally coordinated M sites, twelve of which are occupied by dominant Mn2+ with lesser Mg and minor Zn; <M–O> distances are in the range 2.197–2.284 Å. The <M(13)–O> distanceis 2.083 Å and its lower site scattering indicates occupancy by Fe3+, Mn2+, Mg and Al. The structure consists of five crystallographically distinct layers of polyhedra, labelled m = 0 – 4. Layer m = 0 consists of corner-sharing Zn and (Si, As5+)tetrahedra, and layers m = 1–4 each consist of trimers of Mn2+ octahedra linked by (Si, As5+) tetrahedra and intrasheet hydrogen bonds (m = 1, 3) or (Si, As5+) tetrahedra and (Fe3+,Al) octahedra (m = 2) or (As5+)tetrahedra and (As3+O3) triangular pyramids and intrasheet hydrogen bonds (m = 4). The layers stack along [001] with reversals of the sequence m = 1, 2, 3, 4 at z = 0, ¼, ½ and ¾. Kraisslite is a member of the mcgovernite family.

Layered double hydroxide (LDH) compounds are characterized by structures in which layers with a brucite-like structure carry a net positive charge, usually due to the partial substitution of trivalent octahedrally coordinated cations for divalent cations, giving a general layer formula [(M1–x2+M3+x)(OH)2]x+. This positive charge is balanced by anions which are intercalated between the layers. Intercalated molecular water typically provides hydrogen bonding between the brucite layers. In addition to synthetic compounds, some of which have significant industrial applications, more than 40 mineral species conform to this description. Hydrotalcite, Mg6Al2(OH)16[CO3]·4H2O, as the longest-known example, is the archetype of this supergroup of minerals. We review the history, chemistry, crystal structure, polytypic variation and status of all hydrotalcite-supergroup species reported to date. The dominant divalent cations, M2+, that have been reported in hydrotalcite supergroup minerals are Mg, Ca, Mn, Fe, Ni, Cu and Zn; the dominant trivalent cations, M3+, are Al, Mn, Fe, Co and Ni. The most common intercalated anions are (CO3)2–, (SO4)2– and Cl–; and OH–, S2– and [Sb(OH)6]– have also been reported. Some species contain intercalated cationic or neutral complexes such as [Na(H2O)6]+ or [MgSO4]0. We define eight groups within the supergroup on the basis of a combination of criteria. These are (1) the hydrotalcite group, with M2+:M3+ = 3:1 (layer spacing ∼7.8 Å); (2) the quintinite group, with M2+:M3+ = 2:1 (layer spacing ∼7.8 Å); (3) the fougèrite group, with M2+ = Fe2+, M3+ = Fe3+ in a range of ratios, and with O2– replacing OH– in the brucite module to maintain charge balance (layer spacing ∼7.8 Å); (4) the woodwardite group, with variable M2+:M3+ and interlayer [SO4]2 –, leading to an expanded layer spacing of ∼8.9 Å; (5) the cualstibite group, with interlayer [Sb(OH)6]– and a layer spacing of ∼9.7 Å; (6) the glaucocerinite group, with interlayer [SO4]2– as in the woodwardite group, and with additional interlayer H2O molecules that further expand the layer spacing to ∼11 Å; (7) the wermlandite group, with a layer spacing of ∼11 Å, in which cationic complexes occur with anions between the brucite-like layers; and (8) the hydrocalumite group, with M2+ = Ca2+ and M3+ = Al, which contains brucite-like layers in which the Ca:Al ratio is 2:1 and the large cation, Ca2+, is coordinated to a seventh ligand of 'interlayer' water.

The principal mineral status changes are as follows. (1) The names manasseite, sjögrenite and barbertonite are discredited; these minerals are the 2H polytypes of hydrotalcite, pyroaurite and stichtite, respectively. Cyanophyllite is discredited as it is the 1M polytype of cualstibite. (2) The mineral formerly described as fougèrite has been found to be an intimate intergrowth of two phases with distinct Fe2+:Fe3+ ratios. The phase with Fe2+:Fe3+ = 2:1 retains the name fougèrite; that with Fe2+:Fe3+ = 1:2 is defined as the new species trébeurdenite. (3) The new minerals omsite (IMA2012-025), Ni2Fe3+(OH)6[Sb(OH)6], and mössbauerite (IMA2012-049), Fe3+6O4(OH)8[CO3]·3H2O, which are both in the hydrotalcite supergroup are included in the discussion. (4) Jamborite, carrboydite, zincaluminite, motukoreaite, natroglaucocerinite, brugnatellite and muskoxite are identified as questionable species which need further investigation in order to verify their structure and composition. (5) The ranges of compositions currently ascribed to motukoreaite and muskoxite may each represent more than one species. The same applies to the approved species hydrowoodwardite and hydrocalumite. (6) Several unnamed minerals have been reported which are likely to represent additional species within the supergroup.

This report has been approved by the Commission on New Minerals, Nomenclature and Classification (CNMNC) of the International Mineralogical Association, voting proposal 12-B.

We also propose a compact notation for identifying synthetic LDH phases, for use by chemists as a preferred alternative to the current widespread misuse of mineral names.

Arsenoflorencite-(La), ideally LaAl3(AsO4)2(OH)6, was studied at high pressure by single-crystal X-ray diffractometry. The unit cell was determined at nine pressures up to 7.471(8) GPa; no evidence of a phase transformation was found in this range. The pressure volume data (refined simultaneously) were fitted to a third-order Birch Murnaghan equation of state which gave V0 = 710.71(8) Å3, KT0 = 106(2) GPa and K' = 9.2(9). These values were confirmed independently from an FE–fE plot. The crystal structure was refined at 1.596, 3.622, 5.749 and 7.471 GPa, the first time this has been done for a member the alunite supergroup. The compressibility of arsenoflorencite-(La) is strongly anisotropic, with βc > βa. The main compression mechanism was found to be governed by the internal angle O3 La O2 of the La polyhedron, where the O2 and O3 atoms move toward the c axis during compression.

The crystal structure of deliensite, Fe[(UO2)2(SO4)2(OH)2](H2O)7, was solved by direct methods and refined to R 1 = 6.24% for 5211 unique observed reflections [I obs > 3σ(I)],on a crystal that was found to consist of rotational and inversion (merohedral) twins, from Jeroným mine, Abertamy in the Czech Republic. The presence of four twin domains was taken into account in the refinement. The structure is orthorhombic, space group Pnn2, with unit-cellparameters a = 15.8514(9), b = 16.2478(7), c = 6.8943(3) Å, V = 1775.6(1) Å3 and Z = 4. The crystal structure of deliensite contains uranyl-sulfate sheets with a phosphuranylite topology, consisting of dimers of edge-sharing uranylpentagonal bipyramids linked by corner-sharing with sulfate tetrahedra. The sheets lie in the (100) plane and are decorated by [Fe2+O(H2O)5] octahedra; two weakly bonded H2O molecules are present in the interlayer. The [Fe2+O(H2O)5]octahedron is linked directly to the sheet via the uranyl oxygen atom. Adjacent sheets are linked by hydrogen bonds only. The sheet topology and geometrical isomerism is discussed and a comparison of the composition obtained from electron-probe microanalysis, powder-diffraction data, Ramanand infrared spectra of deliensite samples from Mas d'Alary, Lodève, France; L'Ecarpière mine, Gétigné, France; and several localities at Jáchymov, Western Bohemia, Czech Republic is made.

Strontium-rich epidote, including epidote-(Sr) and epidote with major amounts of Sr (i.e. epidote containing up to 17.3 wt.% SrO), was found in pumpellyite schist and epidote blueschist in a tectonic block in the serpentinite mélange of the Kurosegawa Zone, central Kyushu, Japan. The tectonic block is 20 m wide and made primarily of lawsonite blueschist, with subordinate amounts of pumpellyite schist and epidote blueschist. The pumpellyite schist typically occurs at the edge of the block and is composed mainly of pumpellyite with subordinate amounts of strontium-poor epidote, albite and chlorite, and thin veins of fine-grained calcite and clinopyroxene. Epidote-(Sr) forms rims around strontium-poor epidote, fills fractures in strontium-poor epidote and also occurs interstitially between pumpellyite aggregates and along the boundaries between pumpellyite and calcite-clinopyroxene veins. The epidote blueschist is found between the pumpellyite schist and lawsonite blueschist, and consists mainly of sodic amphibole, epidote and titanite, with albite veining. Strontium-rich epidote occurs as rims, replacing Sr-poor epidote near the albite vein. The bulk strontium contents of the rocks are as follows: lawsonite blueschist (200 ppm), epidote blueschist (2800 ppm) and pumpellyite schist (~10,700 ppm). The chemical and petrological characteristics of the Sr-rich epidote-bearing metabasites suggest that the infiltration of a metamorphic fluid promoted extensive Sr metasomatism during the later stages of high-pressure metamorphism.

The current route in the UK for the conditioning and immobilization of most intermediate level waste for interim storage and geological disposal is to encapsulate in a cementitious matrix. However, certain waste materials, such as those containing reactive metals (e.g. uranium and aluminium), can corrode in the presence of the highly alkaline water in a cementitious environment. In their initial, undegraded form, polymeric materials can provide the appropriate, unreactive environment needed for the encapsulation of chemically active metals.

This study examines the effects of gamma radiation on the stability of six candidate polymeric encapsulants, including a vinyl ester styrene resin (VES) and five epoxy resin formulations. The polymeric encapsulants were exposed to radiation doses up to 10 MGy using AMEC's cobalt-60 gamma irradiation facility and their radiation and chemical stability characterized by the use of a number of analytical techniques. These included flexural and compressive testing, Fourier transform infrared spectroscopy (FTIR), gel fraction, leach testing and gas evolution. The results show that the most stable resin in terms of radiation resistance and chemical stability was VES. Most of the epoxy resin materials also showed good generic stability, but the FTIR analysis showed the potential for dose-rate effects in one formulation.

Preliminary geological work on samples from Davdar in China indicate that emerald occurs in quartz veins hosted within upper greenschist grade Permian metasedimentary rocks including quartzite, marble, phyllite and schist. Fluid inclusion studies indicate highly saline fluids ranging from approximately 34 to 41 wt.% NaCl equivalent, with minimal amounts of CO2 estimated at a mole fraction of 0.003. Fluid inclusion, stable isotope and petrographic studies indicate the Davdar emeralds crystallized from highly saline brines in greenschist facies conditions at a temperature of ∼350°C and a pressure of up to 160 MPa. The highly saline fluid inclusions in the emeralds, the trace-element chemistry and stable isotope signatures indicate that the Davdar emeralds have some similarities to the Khaltaro and Swat Valley emerald deposits in Pakistan, but they show the greatest similarity to neighbouring deposits at Panjshir in Afghanistan.

A detailed electron microprobe (EMP) and laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) study of zircon from six types of miaskitic and agpaitic alkaline pegmatite from the Larvik Plutonic Complex, Oslo rift valley, Norway, was undertaken to shed light on the pegmatite petrogenesis. Detailed rare earth element (REE) analyses indicate important differences between the zircon from each type of pegmatite. Primary zircon from miaskitic Stavern-, Tvedalen- and Stålaker-type pegmatites has a mean ΣREE = 704 ppm, is depleted in LREE and has a significant positive Ce anomaly (Ce/Ce* = 44–67) and negative Eu anomaly (Eu/Eu* = 0.15–0.18). Secondary Tvedalen-type zircon is REE-enriched (ΣREE = 5035 ppm), with a flatter REE pattern, Ce/Ce* = 0.97 and a Eu anomaly similar to primary Tvedalen-type zircon (Eu/Eu* = 0.21). Secondary zircon from agpaitic Langesundsfjord-type pegmatites display a distinctive flat REE pattern characterized by overall REE enrichment (ΣREE = 967), Ce/Ce* = 1.92, and a minor negative Eu anomaly (Eu/Eu* = 0.37). Zircon from agpaitic Bratthagen-type pegmatites occurs as both altered primary and secondary phases and is strongly enriched in REE relative to other zircon (ΣREE = 4178 and 8388, respectively). Primary Bratthagen-type zircon has a similar REE pattern to miaskitic zircon, with a steeper HREE profile and smaller Ce and Eu anomalies (Eu/Eu* = 0.73; Ce/Ce* = 6.22). Secondary Bratthagen-type zircon is strongly enriched in LREE compared to primary zircon, does not display a positive Ce anomaly and has Eu/Eu* = 0.56. The altered primary and secondary Bratthagen-type zircons have elevated Th/UN ratios, suggesting a different melt source for Bratthagen-type agpaitic pegmatites. Zircon from external pegmatites has trace-element signatures similar to Stavern-, Tvedalen- and Staålaker-type primary zircon with Ce/Ce* = 214 and Nb/Ta and Th/U ratios that are similar to those of secondary Langesundsfjord- and Bratthagen-type zircon. It is suggested that the parental melt of the external pegmatites is the same as the miaskitic pegmatites, but that it has undergone alteration by hydrothermal fluids derived from the host basalt, or by post-magmatic F-rich fluids which mobilize Nb and Th. On the basis of texture, morphology and geochemistry, two populations of zircon can be recognized: (1) primary zircon from miaskitic pegmatites; and (2) secondary zircon from post-magmatic, hydrothermal assemblages. The U–Th–Pb isotope analyses indicate that the secondary and altered zircon are depleted in 238U, and enriched in LREE. Interaction of a post-magmatic hydrothermal fluid with an externally derived meteoric fluid is suggested to have influenced the REE signatures, and in particular the Eu and Ce anomalies of the late-stage zircons.

Atomic force microscopy (AFM) enables in situ observations of mineral fluid reactions to be made at a nanoscale. During the past 20 years, the direct observation of mineral surfaces at molecular resolution during dissolution and growth has made significant contributions toward improvements in our understanding of the dynamics of mineral fluid reactions at the atomic scale. Observations and kinetic measurements of dissolution and growth from AFM experiments give valuable evidence for crystal dissolution and growth mechanisms, either confirming existing models or revealing their limitations. Modifications to theories can be made in the light of experimental evidence generated by AFM. Significant changes in the kinetics and mechanisms of crystallization and dissolution processes occur when the chemical and physical parameters of solutions, including the presence of impurity molecules or background electrolytes, are altered. Calcite has received considerable attention in AFM studies due to its central role in geochemical and biomineralization processes. This review summarizes the extensive literature on the dissolution and growth of calcite that has been generated by AFM studies, including the influence of fluid characteristics such as supersaturation, solution stoichiometry, pH, temperature and the presence of impurities.