ALBERT

Description: 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.

Description: 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.

Description: 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.

Description: Magnetite is present in most carbonatites, and in the most abundant and best-known form of carbonatite, coarse-grained intrusions, it typically falls in a narrow composition range close to Fe3O4. A fine-grained carbonatite from Zambia contains magnetites with an extraordinary array of compositions (from 18–1% TiO2, 10–2% Al2O3, and 16–4% MgO) outranging previously-reported examples. Zoning trends are from high TiO2 to high Al2O3 and MgO. No signs of exsolution are seen. Checks on similar rocks from Germany, Uganda and Tanzania reveal magnetites with comparable compositions, ranges, and zoning. Magnetites from alkaline and alkaline ultramafic silicate volcanic rocks cover only parts of this array. Magnetite analyses from some other fine-grained carbonatites, reported in the literature, fall in the same composition field, suggesting that this form of carbonatite may be distinctive. The chemistry and zoning would be consonant with rapid high-temperature crystallization in the carbonatite melts, with the lack of exsolution pointing to fast quenching: this contrasts with coarse-grained intrusive carbonatites, in which the magnetite compositions are attributed to slow cooling, with final equilibration at low temperature. In some complexes, both forms of carbonatite, with their different magnetite compositions, are represented.

Description: The Rockeskyll complex in the north, central part of the Quaternary West Eifel volcanic field encapsulates an association of carbonatite, nephelinite and phonolite. The volcanic complex is dominated by three eruptive centres, which are distinct in their magma chemistry and their mode of emplacement. The Auf Dickel diatreme forms one centre and has erupted the only known carbonatite in the West Eifel, along with a broad range of alkaline rock types. Extrusive carbonatitic volcanism is represented by spheroidal autoliths, which preserve an equilibrium assemblage. The diatreme has also erupted xenoliths of calcite-bearing feldspathoidal syenite, phonolite and sanidine and clinopyroxene megacrysts, which are interpreted as fragments of a sub-volcanic complex. The carbonate phase of volcanism has several manifestations; extrusive lapilli, recrystallized ashes and calcite-bearing syenites, fragmented during diatreme emplacement.A petrogenetic link between carbonatites and alkali mafic magmas is confirmed from Sr and Nd isotope systematics, and an upper mantle origin for the felsic rocks is suggested. The chemistry and mineralogy of mantle xenoliths erupted throughout the West Eifel indicate enrichment in those elements incompatible in the mantle. In addition, the evidence from trace element signatures and melts trapped as glasses support interaction between depleted mantle and small volume carbonate and felsic melts. This close association between carbonate and felsic melts in the mantle is mirrored in the surface eruptives of Auf Dickel and at numerous alkaline-carbonatite provinces worldwide.

Description: 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.

Description: Extensive use of cement and concrete is envisaged in the construction of geological disposal facilities for radioactive wastes. The hyperalkaline porefluids typical of groundwaters that have reacted with these materials have the potential to react chemically with other engineered barrier components such as bentonite, potentially degrading their performance. Analcime, NaAlSi2O6.H2O, has been identified from previous modelling and experimental studies as a potential alteration product of bentonite.Laboratory experiments to investigate the stability of analcime under hyperalkaline porefluid conditions have been performed. Experiments used both batch and fluidized bed equipment at 25, 50, 70 and 90°C in K-based pH buffer solutions, both under- and over-saturated with respect to analcime. Results from dissolution experiments demonstrate that release of Na was greatly enhanced (by up to a factor of thirty) over that for Si and Al, particularly at pH 10 and 11. However, enhanced release of both Na and Al occurred in the batch experiments at pH 12–13. Near stoichiometric dissolution was observed in fluidized bed experiments under steady-state conditions at 70°C. Sodium was removed from the analcime structure by ion exchange for K, without involving dissolution and re-precipitation of the analcime framework. Scanning electron microscopy of reacted analcime grains showed that some grains had pronounced cracks parallel to original cleavage traces. These cracks were a result of volume decrease due to the substitution of K for Na ions and water molecules in the analcime structure to form leucite, KAlSi2O6.Synthesis of the dissolution data shows that the rate of dissolution increased with increasing temperature in the range 25–70°C and with pH at each temperature. Absolute rates of dissolution ranged from 10−10 mol m−2 s−1 at pH 9.5 at 25°C to 10−7 mol m−2 s−1 a pH 12 at 70 and 90°C. The rate of dissolution at any temperature was pH-dependent, such that the rate could be described by k (aH+)n, where k is the rate constant and n is −0.3 at 25°C, −0.4 at 50°C, −0.6 at 70°C and −0.7 at 90°C. Attempts to measure the growth rate of analcime in supersaturated solutions at 70 and 90°C were unsuccessful, although a limiting rate at 70°C, pH 10 was calculated to be 4 × 10−11 mol m−2 s−1, roughly 100× less than the rate of dissolution under the same conditions.These results imply that any trace amounts of analcime in bentonite will be converted to leucite by reaction with cement fluids with a high K/Na ratio. In some instances, leucite may thus incorporate K+ in preference to other phases (e.g. illite, K-feldspar) during alteration of bentonite by cement porefluids.

Description: Italian carbonatites form part of a suite with melilitites, normally an association characteristic of continental interiors; the perfect analogue of the Italian suite being the kamafugites (from the type area in SW Uganda, where the western branch of the East African Rift Zone cuts across the craton). The latter are commonly attributed to plume generation, whereas the Italian carbonatites, strung along the Appennine front, are usually linked to subduction. Evidently these two mechanisms are not essential, since neither can apply in both provinces. This conclusion is re-inforced by the related magmatism registered in both provinces in the Cretaceous. Phlogopite is ubiquitous in the mantle debris, and compositions from the two provinces overlap. Xenolithic phlogopites are distinct from cognate micas in the lavas, and from the carrier melt compositions, with similar distribution patterns in both suites. Kamafugitic magmas must be products of exceptional conditions, and added to the many near-identical magmatic features, the Italian and Ugandan volcanoes have sampled similar mantle conditions. Although the large scale geodynamic regimes are in total contrast, as are the deep mantle tomographic structures, the crucial common factor at the igneous province level is extensional tectonics. Extension, promoting release of volatiles (esp. CO2), is the vital trigger for this small volume, primary magmatism.

Description: SummaryFluorine, chlorine, zinc, niobium, zirconium, yttrium, and rubidium have been deter-mined on fifteen obsidians from Eburru volcano (Kenya Rift Valley), spanning the range from pantel-leritic trachyte to pantellerite. All pairs of elements show positive correlation coefficients, ranging between 0·769 and 0·998, but with most values better than 0·900. In spite of some very high correlations, only two of the twenty-one best-fit lines pass near the origin of the Cartesian coordinates. Linear distributions are found within two separate groups of elements: F, Zr, Rb; and Cl, Nb, Yt. Zn behaves in general as a member of the second group but seems to be subject to an additional variation. When an element from the fluorine group is plotted against one from the chlorine group the resulting pattern is non-linear. Therefore, although the elements in both groups would generally be considered ‘residual’ (partition coefficients between crystals and liquid approaching zero) there are clearly detectable differences in their variation, and hence their behaviour.Major-element variations in the obsidians are such that a vapour (fluid) phase would be needed to account for any magma evolution. The trace-element patterns are also impossible by closed-system crystal fractionation and suggest that this fluid may have been rich in halogens, with the metallic elements forming preferred ‘complexes’ with either F or Cl. The F-Zr-Rb ‘complex’ also varies quite independently of the important major oxides (e.g. A12O3) in the rocks. In the case of Rb this is but one aspect of a more significant anomaly, in which there is no sign of any influence of alkali feldspar (which partitions Rb) in the variation. This is remarkable because trachytes and rhyolites have normative ab+or 〉 50 %, and any evolutionary process controlled by crystal ⇋ liquid interactions must be dominated by the melting or crystallization of alkali feldspar. The results on the Eburru obsidians show that if they are an evolutionary series then either, the process was not crystal ⇋ liquid controlled, or that any such process has been overriden (or buffered) by other processes that have superimposed the observed trace-element patterns. In the latter event, the buffering phase may have been a halogen-bearing vapour.The same considerations must apply to other pantellerite provinces where Rb appears to have behaved as a ‘residual’ element.