The Older Giant Dyke Complex is a differentiated alkaline intrusion of Proterozoic age (1154±16 Ma) and is the earliest of the late Gardar intrusions in the Tugtutôq-Ilímaussaq region. The dyke is approximately 20 km long by 0·5 km broad and comprises (i) marginal ‘border group’ rocks of alkali olivine gabbro, grading inwards to ferro-syenogabbro and (ii) an axial ‘central group’ of salic rocks ranging from augite syenite in the WSW to sodalite foyaite in the ENE.

Chilled margins contain plagioclase (An53), olivine (Fo53), magnetite, ilmenite, and apatite as liquidus phases and later-crystallized augite (Di69Hd27Ac4) and biotite (Annite32). The coexisting Fe-Ti oxides indicate fO2 and T values just below the synthetic QFM buffer curve. In the border group, plagioclase cores zone into anorthoclase and soda-sanidine rims, olivines reach Fo16, pyroxenes Di32Hd59Ac9, and biotites Annite86. Interstitial pargasitic amphibole appears close to the innermost margins. In the central group, feldspars are all perthitic alkali feldspars and nepheline becomes a major, early crystallizing phase. Olivines range from Fo10-Fo4, in the augite-syenites where they coexist with ferro-salites Di50Hd47Ac3, but olivine is absent from foyaitic assemblages in which the pyroxenes range through aegirine-augite to pure aegirine. Interstitial amphiboles range from ferro-pargasite or hastingsite to katophorite and thence towards arfvedsonite, but are absent from the most differentiated rocks, whereas biotite occurs throughout the entire group in the range Annite71-Annite100.

The parental magma, represented by the chilled margins, was a relatively anhydrous alkali olivine-basalt with an initial 87Sr/86Sr ratio of 0.70326. Its high Ti, P, Ba, and F contents are inferred to be features inherited from a primary magma, derived from the mantle as a small partial melt fraction which involved significant amounts of fluor-apatite and phlogopite. While all lithologies are considered as differentiates from this parental magma, there is both a well-defined field junction and a compositional hiatus between the border group and the central group rocks. Mineralogical considerations and REE patterns suggest that the later, more salic (?benmoreitic) magma from which the central group crystallized, related to the parental magma by ol-fsp-ap-FeTi oxide fractionation. Congelation in both border group and central group occurred by side-wall crystallization, but the salic magma became compositionally stratified, with upward concentration of alkalis and volatiles to produce a phonolitic upper facies which is preserved at the ENE end of the intrusion owing to subsequent axial tilting.

Mafic lamprophyre dykes in northern England were emplaced soon after the final closure of the Iapetus Ocean at the end of the Caledonian orogeny. High Mg/(Mg+Fe) ratios and Cr and Ni contents are consistent with equilibrium with mantle peridotite. Incompatible trace element abundances suggest that the mantle sources were metasomatized prior to the melting events. Three components are recognized in the lamprophyre chemistry: (i) a depleted mantle source, taken to be that overlying the subducting lithosphere; (ii) a H2O-rich subduction zone component, related to the dehydration of the subducting oceanic crust; and (iii) a CO2-rich phase thought to result from the degassing of the mantle after ocean closure. This multi-component origin may be applicable to other lamprophyres of calc-alkaline affinity.

The Carnmenellis pluton is a post-orogenic granite of Hercynian age, comprised largely of porphyritic biotite granites which possess LREE enriched patterns with slight negative Eu anomalies. Electron microprobe and ICP spectrometry data are presented for monazite, which occurs as an accessory mineral in all granite types, and it is demonstrated that this mineral is the principal host for LREE in the biotite granites. HREE are strongly partitioned into the accessory minerals xenotime, apatite, and zircon; only Eu substitutes significantly into the essential minerals. The behaviour of the REE during granite differentiation is controlled by the behaviour of the radioactive accessory minerals, which limits the usefulness of these elements in the petrogenetic modelling of granitic rocks.

The geochemical evolution of tin-tungsten deposits and their associated sulphides can be discussed in terms of four sequential processes: acquisition of the ore-forming elements (OFEs) by the granitic magma, emplacement of these elements in minerals and residual melt of the crystallizing granite, release of the OFEs to the circulating hydrothermal fluids and transport to the depositional sites, and finally, deposition of ore minerals through interaction of these fluids with the wall rock. Based on their crystallographic behaviour, it is useful to distinguish three principal classes of OFEs, here identified as BOC, LHC, and ALC elements. BOC (bivalent octahedral cation) elements are similar to ferrous iron and here are represented mainly by Zn, Mn, and perhaps Cu. Li also belongs to this class, although it is monovalent. LHC (large highly charged cations) elements encompass As, Nb, Mo, Sn, Sb, Ta, and W and they are similar to ferric iron or titanium in their crystallographic role. ALC (alkali-like cations) are capable of occupying alkali positions and are represented mainly by Pb, Ag, and Hg.

LHCs are rejected from the polymerized silicate liquid network and become enriched in the roof of the acid magma chamber, where more non-bridging oxygens are available. Transport to the roof may be enhanced by the formation of hydrous complexes, as is the pronounced enrichment of Na and Li. BOCs, along with Cl, F, and B, fractionate strongly into the vapour phase during vesiculation. HCl in the ore fluid is crucial for the alteration process and can be produced during boiling by a hydrolysis reaction of the NaCl dissolved or immiscibly present in the silicate magma.

Considerable laboratory information is available concerning release mechanisms of the OFEs to hydrothermal fluids. We can distinguish congruent and incongruent dissolution, both in response to acid buildup, as well as congruent and incongruent exchange not involving HCl. Melt-fluid fractionation is also thought to be important, though the physical mechanisms are not well understood. Any of these release mechanisms may be coupled with reduction or oxidation reactions. LHC, BOC, and ALC elements respond differently to each of these mechanisms, and these differences may in part be responsible for the observed separation of ore minerals in space and time. It is suggested that LHC elements are released preferentially during acid, non-oxidizing conditions typical of early stages, while BOC elements respond more readily to later acid-oxidizing environments, as well as exchange reactions with or without oxidation.

Depositional reactions have been formulated with respect to two contrasting types of country rocks: carbonates and schists. Differences are related to the process of neutralization of the HCl produced by ore deposition: carbonate dissolution on one hand and feldspar-muscovite or biotite-muscovite conversion on the other. In carbonate rocks, evaporite-related sulphates may provide the H2S necessary for sulphide precipitation, while in schists disseminated sulphides and organic matter may be important sulphur reservoirs in addition to the sulphur liberated from the granite. A variety of situations can be envisaged with respect to the sources of the OFEs and the sulphur species required for ore deposition, including granite and wall rocks. Chloride is recognized as the crucial anion for OFE release, transport, and deposition, although F and B play a role yet to be evaluated. Final HCl neutralization is an essential step in the reactions responsible for the deposition of ore minerals.

The ultimate sources of the OFEs must be related to the continental material involved in the process of melt production by partial melting. Oxidized sediments provide sources for LHC and ALC elements in the form of heavy minerals and clastic feldspars and micas. Organic-rich reduced sediments are hosts to BOC and LHC elements as sulphides and ALC elements in organic matter. Remelting of igneous and metamorphic rocks can enrich LHC, BOC, and ALC elements in the melt by extraction from opaques, Fe-Mg silicates, feldspars, and micas.

Pelitic rocks in North Wales, ranging in age from late Precambrian to Silurian were sampled. XRD analysis was used to determine the mineralogy and white mica crystallinity of separated < 2 µm fractions. Results show that three stages of metapelite recrystallization can be distinguished. Stage I metapelites are uncleaved or feebly cleaved with crystallinities > 0.43Δ°2θ; the 1Md polytype dominates < 2 µm fractions, occurring as K-and Na-micas. Stage II metapelites show variable cleavage development and crystallinities in the range 0.26-0.43Δ°2θ; 1Md and 2M1 polytypes occur and K- and Na-micas are commonly regularly interstratified. Stage III metapelites are strongly cleaved with crystallinities < 0.26Δ°2θ; the 2M1 polytype is dominant, occurring as K-mica and paragonite. Pelites bearing pyrophyllite, rectorite, and corrensite are found close to plug-like intrusions and were contact altered prior to regional metamorphism. 1M mica is common in deeply buried but relatively undeformed volcaniclastic rocks of the Arfon Group.

Contours of equal crystallinity (isocrysts) are plotted with metabasite zones on a metamorphic map. This shows that stage I metapelites are equivalent to the subpumpellyite zone (≡?laumontite zone). Stage II metapelites are equivalent to the prehnite-pumpellyite facies and stage III metapelites to the clinozoisite and biotite zones of the greenschist facies.

Data for U, Th, and K, determined by epithermal neutron activation methods, are reported for Lower and Middle Dalradian lithologies from Co. Donegal, Ireland. Abundances are identical to rocks with stratigraphical correlation in the Scottish Dalradian and appear not to have been affected by regional metamorphism to biotite and possibly even garnet grade during the Grampian orogenic phase, or later contact metamorphism in the aureole of the Main Donegal pluton. Uraniferous Dalradian lithologies have not been encountered in Donegal. Incorporation of Dalradian rocks, either by assimilation or as extensive raft trains within the Main Donegal granite, is therefore unlikely to have contributed to the development of known pegmatite-hosted U mineralization associated with this late Caledonian pluton.

The system Na2O-CaO-MgO Al2O3-SiO2-H2O is proposed to model phase equilibria and mineral parageneses for low-temperature metamorphism of basaltic rocks. Univariant reactions marking the transitions between various sub-greenschist facies are identified and some have been experimentally determined. The introduction of Fe2O3 into the model system at fixed FeO/MgO ratio creates continuous reactions for facies boundaries and discontinuous reactions for invariant points of the model system. Both qualitative and quantitative effects on P-T displacement and phase compositions are discussed. The XFe3+ isopleths for epidote were plotted to exemplify the transition from the zeolite through prehnite-pumpellyite to prehnite-actinolite facies. T-XFe3+ relations were established for continuous and discontinuous reactions relating such facies transitions. Because of the common occurrence of two or three Ca-Al hydrosilicates in low-grade metabasites, an isobaric Al-Ca-Fe3+ projection from chlorite may be used to illustrate mineral assemblages and compositions of the coexisting Ca-Al silicates in the presence of quartz, albite, and chlorite. Reported occurrences in several classic burial metamorphic terrains and ocean-floor metabasites in ophiolites are described. Only the composition of a mineral from a buffered assemblage can constrain the intensive properties for metamorphism; previously reported compositional trends for pumpellyite and epidote with increasing metamorphic grade are oversimplified.

Högbomite occurs in two contrasting mineral assemblages within the Currywongaun-Dough-ruagh intrusion of north Connemara: a cordierite-rich pelitic xenolith and an orthopyroxenite. In the latter, högbomite and green spinel form blebs within magnetite-ilmenite grains. The högbomite displays significant compositional variation from grain to grain: TiO2 (3.0–6.3%), FeO (21.6–21.3%), MgO (10.0–7.5%), ZnO (3.6–2.4%). This chemical heterogeneity appears to represent variable degrees of partial substitution of Mg and Zn by Ti, in the replacement of spinel by högbomite. By contrast, in the cordierite-hornfels, the högbomite compositions are more notably enriched in iron: TiO2 (4.7–7.0%), FeO (29.6–24.3%), MgO (4.2–6.2%), ZnO (2.7–2.1%). This iron-rich högbomite appears to have formed primarily by interaction between opaque ore and adjacent cordierite, rather than by replacement of spinel.

Two high-grade metamorphic episodes appear to be necessary for högbomite growth, one determining chemical composition and the other appropriate physical parameters. In the Connemara occurrences thermal metamorphism and partial melting, coupled with contamination of the surrounding magma, controlled the formation of mineral assemblages rich in Fe, Mg, Al, Ti, and Zn. Emplacement of the intrusion was accompanied by amphibolite facies regional metamorphism and it is to this metamorphic event that the growth of högbomite may be attributed.

In the aureole of the late Caledonian Omey granite corundum develops in the Dalradian country rocks in a zone up to 250 m from the granite contact. The distribution of andalusite and K-feldspar in pelites and calcite+wollastonite+grossularite in marbles is consistent with inner-aureole metamorphic conditions of 615±25°C at 2.5±0.25 kbar, and ⋍ 0.85. Corundum develops from the reaction muscovite → corundum + K-feldspar+H2O and first appears over 100 m further from the granite than the assemblage wollastonite + grossularite + anorthite. Experimentally determined equilibria can be satisfied only if for the corundum-producing reaction was less than 0.6 and perhaps as low as 0.4. Corundum always grows within large muscovite crystals;fH2O within the crystal lattice is unrelated to that in the grain-boundary fluid of the surrounding rock.

Although whole-rock oxidation ratios are irregularly distributed within the aureole they are uniformly low in corundum-bearing rocks. Reducing conditions probably resulted from localized flow of H2O-rich fluid away from the granite in a diffuse channelway that contains most of the corundum localities and also a distinctive skarn. Although corundum growth within muscovite is sealed off from the external water vapour conditions, it is suggested that movement of H2O down a thermal gradient (and hence down an fH2O gradient at constant pressure) promotes the escape of (OH)− from the muscovite lattice and so allows the corundum reaction to proceed.

Short-range order in the oxygen co-ordination shell of the Ca ion in a glass of composition Ca3Mg4Al2Si7O24 is investigated by analysis of the extended X-ray absorption fine structure. The estimate of disorder in the short-range oxygen co-ordination is no greater than that for crystalline samples of diopside and bytownite. An estimate of the oxygen environment of calcium in the particular glass is included.

Partially melted basalts enclosing amygdales which have been completely melted formed at Scawt Hill adjacent to a Tertiary dolerite plug. Melting of the basalts commenced in a clay-rich mesostasis to produce a feldspathic liquid which then crystallized to an assemblage of dendritic olivine, skeletal hypersthene, opaque oxide and Mg-hercynite in a microcrystalline plagioclase matrix. An original mineral assemblage of zeolite, calcite, and saponite-nontronite in the amygdales melted and quenched to a brown glass now containing complexly zoned pyroxenes with plagioclase and opaque oxide. Melting commenced between 700–800°C, reaching a maximum temperature of 1168°C, and was followed by rapid cooling. The assimilation of remelted basalt may alter the course of crystallization of contaminated magmas.

Previous studies of low-grade metamorphism in the Southern Uplands accretionary terrain indicated prehnite-pumpellyite facies/anchizone conditions developed throughout the area, except for local preservation of trench-slope sediments and an accreted seamount at zeolite facies/advanced diagenetic grade. New graptolite reflectance data are presented that show a general northward increase in temperature in the Southern Uplands. The results from two cross-strike traverses in the southern and central belts in contemporaneous sequences, using illite crystallinity, illite lateral spacing (bo) , and graptolite reflectance, indicate the development of systematic accretion-related low-grade metamorphism. Well-developed and constant anchizone conditions occur throughout the NE (Langholm) traverse, associated with common, F1 accretion-related folding and a regionally penetrative S1 cleavage. In the SW (Kirkcudbright) traverse, however, the youngest, last accreted packets are preserved at a transitional diagenetic stage and lack a penetrative S1 cleavage. Illite crystallinity, graptolite reflectance, and bo increase systematically northward through earlier accreted packets, reaching values of the NE traverse only at the northern end. The concomitant increase of bo with illite crystallinity suggests the relatively high P-low T trajectory characteristic of subduction zones. Integration of metamorphic and structural data relates increasing intensity of aceretion-related F1 folding, developmertt of S1 fabric, and onset of later fold phases to grade of metamorphism and structural level within the accretionary pile.

Most countries intend to dispose of their high-level radioactive wastes by converting them into a solidified wasteform which is to be buried within the earth. SYNROC is a titanate ceramic wasteform which has been designed for this purpose on the basis of geochemical principles. It comprises essentially rutile TiO2, ‘hollandite’ Ba(Al,Ti)Ti6O16, zirconolite CaZrTi2O7, and perovskite CaTiO3. The latter three phases have the capacity to accept the great majority of radioactive elements occurring in high-level wastes into their crystal lattice sites. These minerals (or their close relatives) also occur in nature, where they have demonstrated their capacity to survive for many millions of years in a wide range of geological environments. The properties of SYNROC and the crystal chemistry of its constituent minerals are reviewed in some detail and current formulations of SYNROC are summarized. A notable property of SYNROC it its extremely high resistance to leaching by groundwaters, particularly above 100°C. In addition, it can be shown that the capacity of SYNROC minerals to immobilize high-level waste elements is not markedly impaired by high levels of radiation damage. Current investigations are focused on developing a satisfactory production technology for SYNROC and progress towards this objective is described. The high leach resistance of SYNROC at elevated temperatures increases the range of geological environments in which the waste may be finally interred; in particular, SYNROC is well adapted for disposal in deep drill-holes, both in continental and marine environments. The fact that SYNROC is comprised of minerals which have demonstrated long-term geological stability is significant in establishing public confidence in the ability of the nuclear industry to immobilize high-level wastes for the very long periods required.

Three ion exchange equilibrium isotherms between muscovite-paragonite solid solution and 2-molal KCl-NaCl aqueous solutions have been studied at (1) 420°C 1 kbar, (2) 420°C, 2 kbar, and (3) 550°C, 2 kbar. The ΔG°(Joules) ± 2σ of the ion exchange reaction are: ΔG° (1) = −17 259±686, ΔG° (2) = −18 268 ± 560, ΔG° (3) = −16018 ± 336. The excess mixing parameters (‘subregular solution’) of the solid solution (at 1 bar) have been calculated:

The corresponding binodal compositions are (muscovite mol fraction): 12–56% at 420 °C, 1 bar and 15–51% at 550 °C 1 bar. The compositions of micas in equilibrium with perthites (high structural state) at 400, 500, 600 °C and 2 kbar are respectively: Xmus = 91, 86, and 82%.

The mixing properties of the solution were estimated using the speciation of two molal chloride solutions calculated from the dissociation constants of NaCl and KCl in aqueous solution. Although NaCl appears to be substantially more dissociated than KCl, the resulting excess free energy of mixing of the hydrothermal (Na,K)Cl solution was found less than 500 J at temperatures above 400 °C and pressures up to 2 kbar.

The difference in Gibbs free energy of formation (from the elements at 25 °C, 1 bar) between NaCl and KCl in two molal aqueous solutions is proposed:

Two specimens of tremolite and one of richterite, all with nephrite jade texture, have been examined by transmission electron microscopy using ion-thinning for specimen preparation. The specimens contain clusters of very small lath-like crystallites with z-axes approximately parallel but in a range of azimuthal orientations. It is suggested that these clusters which are themselves in varied orientations are the result of post-tectonic recrystallization of strained amphibole crystals, the new crystals inheriting the z-axis orientations of the old. The extreme toughness of nephrite jade is attributed to a number of the sub-microscopic features observed, including the sizes, habits, and orientations of its crystallites, and the nature of its grain boundaries.