Daqingshanite in the Kamthai REE deposit (India) occurs as two paragenetic types: primary granular coarse grained crystals coexisting with primary carbocernaite, baryte and bastnäsite; and as aligned micro-ovoid globules within clasts of Sr-bearing calcite. Carbocernaite forming trellis-type lamellae in some of these calcite clasts do not represent exsolution and are considered as replacement textures as they formed subsequent to daqingshanite. The origins of the textural relations of the microglobules of daqingshanite to their host Sr-calcite cannot be unambiguously determined, although an exsolution origin is not considered feasible. The textures are similar to those of ‘chalcopyrite disease’ and as such could be interpreted as replacement features formed in a low temperature carbothermal environment which should facilitate replacement. Given that daqingshanite is an early crystallising phase it is also possible that cotectic crystallisation with Sr-calcite occurred, followed by subsolidus re-equilibration with recrystallisation along specific crystallographic planes in the calcite. The Kamthai REE deposit is best described as a low temperature carbothermalite microbreccia consisting of a wide variety of clasts resulting from the autobrecciation of rocks formed during, and after, the magmatic to carbothermal transition of an undetermined parental calcite carbonatite-forming magma. Many clasts have been replaced by late stage La-enriched carbothermal fluids mixed with exogenous water during the final low-temperature stage of evolution of the deposit.

Liquid immiscibility has become the preferred mode of genesis for the carbonatite rocks, which commonly, but not exclusively, accompany silicate rocks in alkaline-rock complexes. This concept has been universally based on the presumption that nephelinitic and phonolitic magmas can evolve to a stage where two conjugate immiscible liquids separate. It is assumed that these two liquids separate quickly, or even instantaneously, into discrete bodies of magma capable of being intruded or extruded with subsequent independent crystallization. Supporting evidence generally given is: alleged consanguinity as discrete occurrence of the two rock types; similarity of radiogenic isotope ratios; trace element contents similar to those predicted from experimentally derived partition coefficients. We do not accept that a general case for liquid immiscibility has been demonstrated; although we do accept that silicate and carbonate liquids are inherently immiscible, we maintain that they are not conjugate in a petrogenetic context. We have reviewed and critically examined the experimental data purporting to establish liquid immiscibility and find that when applied to natural rocks, they are based on inappropriate experimental designs, which are not relevant to the genesis of calcite or dolomite carbonatites, although they might have some relevance to Oldoinyo Lengai nyerereite–gregoryite lavas. The design of these experiments guarantees immiscibility and ensures that the carbonate liquids formed will be calcitic or sodium-rich. We dispute the validity of comparing the trace element contents of natural rocks, which in many instances do not represent liquid compositions, to experimentally determine partition coefficients. We consider that experimental design inadequacies, principally assuming but not proving, that the liquids involved are conjugate, indicate that these coefficients are merely an expression of the preference of certain elements for particular liquids, regardless of how the liquids formed. Proof of consanguinity in alkaline complexes requires more accurate age determinations on the relevant rock types than has generally been the case, and in most complexes, consanguinity can be discounted. We dispute the contention that melt inclusions represent parental melts, although they might elucidate the character of magmas undergoing fractional crystallization from magmatic to carbothermal stages. Radiogenic isotope data are shown to be too widely variable to support a case for liquid immiscibility. We address the contention that calcite cannot crystallize from a dolomitic liquid formed by direct mantle melting, and must therefore have crystallized from a calcite carbonate liquid generated by liquid immiscibility, and demonstrate that it is an unsupported hypothesis as calcite can readily crystallize from dolomitic liquids. We observe that, because immiscible dolomite liquids have never been produced experimentally, the liquid immiscibility proposition could at best be applied only to calcite carbonatites, thus leaving unexplained the large number of dolomite carbonatites and those of either type, which are not accompanied by alkaline silicate rocks. The assumed bimodality of alkaline-rock carbonatite complexes is considered to be fallacious and no actual geological or petrographic evidence for immiscibility processes is evident in these complexes. Several examples of alkaline rock carbonatite complexes for which immiscibility has been proposed are evaluated critically and shown to fail in attempts to establish them as exemplifying immiscibility. We conclude that no actual geological or experimental data exist to establish liquid immiscibility being involved in the genesis of calcite or dolomite carbonatite-forming magmas.

This work describes the mineralogy of dolomite carbonatite occurring at the Newania carbonatite complex, Rajasthan, north-western India. The mineralogy records the textural and compositional features of magmatic and post-magmatic stages of carbonatite evolution. Ferroan dolomite is the principal constituent and displays variable degrees of deformation, ranging from brittle-to-ductile deformation regimes. Apatite exhibits textural and compositional evolutionary trends from early-to-late stages of carbonatite evolution. Two varieties of amphibole are reported for the first time from this complex, ferri-winchite and cummingtonite; the former is magmatic and the latter is metamorphic in origin. The columbite–tantalite-series minerals are columbite-(Fe), and their paragenesis evolves from composite grains with pyrochlore to individual crystals. Pyrochlore is magmatic with U–Ta–Ti-rich compositions and shows evolution from calciopyrochlore to kenopyrochlore, followed by alteration during late-stages of carbonatite evolution. Monazite and baryte constitute the post-magmatic mineral assemblage; the former is hydrothermal and crystallised after precursor apatite, whereas the latter is associated exclusively with columbite–pyrochlore composites. On the basis of the mineralogy of the carbonatite, it is concluded that the parent magma was generated by low-degree partial melting of magnesite–phlogopite-bearing peridotite.

The Twyfelskupje carbonatite complex, Southern Namibia, exhibits the typical igneous emplacement structures of carbonatites, including plugs, cone sheets and dyke stockworks. The excellent exposure allows for detailed studies of the high-level geochemical and structural evolution of the carbonatite, and the nature of the concomitant rare earth element mineralization. Radiogenic isotope analyses (Sr, Nd, Pb) reveal that, in common with many other carbonatites, the Twyfelskupje carbonatite complex appears to be predominantly derived from mixing between HIMU and EM1 mantle end-members. Following partial melting of these mantle sources, the geochemical and structural evolution of the Twyfelskupje carbonatite complex proceeded by a staged process involving separate magma pulses, a series of emplacement structures, sub-solidus crystallization, fractionation and low-temperature hydrothermal alteration. The dominant rare earth element minerals in the Twyfelskupje carbonatite complex are fluorcarbonates and monazite, and are characterized by variable Ca, high F and light rare earth elements in the order Ce>La>Nd. Comparison between the rare earth element concentrations of the whole rocks, dominant rare earth element minerals and carbonates suggests that ∼95 % of the total rare earth element abundance of the Twyfelskupje carbonatite complex is contained within fluorcarbonates and monazite. Overall, the early calcio-carbonatite plugs are rare earth element enriched (mean 4.47 wt % rare earth oxides) relative to the magnesio-carbonatite cone sheets (mean 2.51 wt % rare earth oxides).

Carbonatites are igneous carbonate rocks. They are the main source of the rare earth elements (REE) that are essential in low carbon and high technology applications. Exploration targeting and mine planning would both benefit from a better understanding of the processes that create the almost ubiquitous alkaline and REE-bearing metasomatic aureoles in the surrounding country rocks.

Using scanning electron microscopy and whole-rock geochemistry, we investigated the composition and mineralogy of the fenite aureoles developed around the REE-poor Chilwa Island carbonatite and the REE-rich Kangankunde carbonatite, which intrude similar country rocks in the Chilwa Alkaline Province of Southern Malawi. Although common characteristics and trends in their mineralogy and composition may be typical of fenites in general, there are significant differences in their petrography and petrogenesis. For example, the mineralogically diverse breccia at Kangankunde contrasts with the intensely altered potassic breccia of Chilwa Island. This might be caused by differing sequences of fluids expelled from the carbonatites into the aureoles. The main REE-bearing mineral in fenite is different at each complex, and reflects the characteristic REE-bearing mineral of the main carbonatite: fluorapatite at Chilwa Island; and monazite at Kangankunde. Each fenite has distinctive mineral assemblages, in which the relative abundance of the REE-bearing minerals appears to be determined by the mineralogy of their respective host carbonatites.

At both localities, the REE minerals in fenite are less enriched in lanthanum and cerium than their equivalents in carbonatite, a characteristic that we attribute to REE fractionation within fluids in the aureole.

Identifying the mineral assemblages present in fenite and understanding the sequence of alkaline and mineralising fluid events could therefore be useful in predicting whether a fenite is associated with a REE-rich carbonatite. Detailed studies of other aureoles would be required to assess the reliability of these characteristics.

The Mount Mather Creek sodalite-bearing carbohydrothermal breccia dyke is located ~35 km northwest of Golden, British Columbia, Canada, within the Foreland Belt on the eastern side of the Mississippian-to-Devonian British Columbia Alkaline Province. The dyke occurs in situ on the western side of the Mount Mather Creek gully, cropping out over a distance of ~80 m with a thickness of up to 10 m, intruding a syncline of Middle and Upper Cambrian Chancellor Group carbonate rocks. To date, no parental alkaline complex has been found adjacent or proximal to the dyke. The breccia dyke is flow-banded and matrix-supported and consists of host rock clasts, medium- to coarse-grained, anhedral-to-poikilitic carbonate-rich syenite segregations that occur as veins and pods, and fine-grained banded sodalite plus carbonate fragments in a carbonate-rich matrix. The sodalite-carbonate segregations consist dominantly of sodalite, ferroan dolomite, calcite and microcline, with an extensive suite of trace minerals enriched in rare earth elements (REE), Na, Ba and Sr, including albite, analcime, ancylite-(Ce), chabazite-Na, fluorapatite, baryte, barytocalcite, cancrinite, galena, goethite, gonnardite, harmotome, edingtonite, a potentially new Mg-bearing edingtonite-like mineral, natrolite, nordstrandite, pyrite, quintinite and sphalerite. Alteration of the primary silicate–carbonate assemblage has resulted in a secondary assemblage of hydrothermal or carbohydrothermal REE–Ba–Sr–Na phases including albite, analcime, cancrinite, gonnardite and nordstrandite after sodalite, together with complex intergrowths of ancylite-(Ce), barytocalcite, edingtonite, and a potentially-new Mg-bearing edingtonite-like mineral. Remobilisation of Ba and Sr from barytocalcite resulted in crystallisation of late-stage baryte and Sr-rich calcite. Mount Mather Creek is only the fifth Canadian occurrence of the Ba-zeolite, edingtonite, and the second Canadian occurrence of the rare layered double hydroxide quintinite. The Mount Mather Creek breccia is a carbohydrothermal deposit, the product of a low temperature (<450°C), highly evolved, alkaline, SiO2-undersaturated, Na–Ba–REE–Cl-rich, residual carbonated silicate melt whose parental origins remain unknown.

Enrichment of the heavy rare earth elements (HREE) in carbonatites is rare as carbonatite petrogenesis favours the light (L)REE. We describe HREE enrichment in fenitized phonolite breccia, focusing on small satellite occurrences 1–2 km from the Songwe Hill carbonatite, Malawi. Within the breccia groundmass, a HREE-bearing mineral assemblage comprises xenotime, zircon, anatase/rutile and minor huttonite/thorite, as well as fluorite and apatite.

A genetic link between HREE mineralization and carbonatite emplacement is indicated by the presence of Sr-bearing carbonate veins, carbonatite xenoliths and extensive fenitization. We propose that the HREE are retained in hydrothermal fluids which are residually derived from a carbonatite after precipitation of LREE minerals. Brecciation provides a focusing conduit for such fluids, enabling HREE transport and xenotime precipitation in the fenite. Continued fluid–rock interaction leads to dissolution of HREE-bearing minerals and further precipitation of xenotime and huttonite/thorite.

At a maximum Y content of 3100 µg g−1, HREE concentrations in the presented example are not sufficient to constitute ore, but the similar composition and texture of these rocks to other cases of carbonatite-related HREE enrichment suggests that all form via a common mechanism linked to fenitization. Precipitation of HREE minerals only occurs where a pre-existing structure provides a focusing conduit for fenitizing fluids, reducing fluid – country-rock interaction. Enrichment of HREE and Th in fenite breccia serves as an indicator of fluid expulsion from a carbonatite, and may indicate the presence of LREE mineralization within the source carbonatite body at depth.

Pyrochlore-group minerals are common accessory rare-metal bearing minerals in the calcite and ankerite carbonatites of the Amba Dongar complex (India). Pyrochlore from the Amba Dongar carbonatites differs from that in other Indian complexes in Ta, Zr, Ti, rare earth element (REE) and Pb contents, but is similar with respect to Ca, Ba and Sr abundances. The evolution of pyrochlore composition was studied to understand the alteration processes and the formation of late-stage pyrochlores enriched in REE and Pb. The early magmatic pyrochlore are calcio- and niobium-dominant types and were replaced by secondary cation-deficient varieties as a consequence of the action of hydrothermal fluids and supergene weathering. These processes produce changes mainly at the A site, rarely at the B site, and the original F is replaced by OH– groups. Calcium and Na can be extracted from the structure at the alteration stage and charge balance is achieved by the introduction of REE, Th, U, Ba or Sr. At the latest supergene stages, marginal and fractured zones of pyrochlore grains are altered to Pb-rich, Si-rich and cation-deficient hydrated varieties. The magmatic pyrochlore was crystallised in a highly alkaline environment at a high activity of Ca and at temperatures near 600°C, the alteration of pyrochlore began in a hydrothermal environment at temperatures below 350°C. The major compositional changes that are associated with the alteration are summarised by the following reactions: Ca2+ + Nb5+→ REE3+ + Ti4+; Nb5+ + Fe3+ → Ti4+ + Zr4+; and 2Nb5+ + Ca2+ → Ti4+ + Si4+ + U4+.

The Quaternary carbonatite–nephelinite Kerimasi volcano is located within the Gregory rift in northern Tanzania. It is composed of nephelinitic and carbonatitic pyroclastic rocks, tuffs, tuff breccias and pyroclastic breccias, which contain blocks of different plutonic (predominantly ijolite) and volcanic (predominantly nephelinite) rocks including carbonatites. The plutonic and volcanic carbonatites both contain calcite as the major mineral with variable amounts of magnetite or magnesioferrite, apatite and forsterite. Carbonatites also contain accessory baddeleyite, kerimasite, pyrochlore and calzirtite. Zr and Nb minerals are rarely observed in rock samples, though they are abundant in eluvial deposits of carbonatite tuff/pyroclastic breccias in the Loluni and Kisete craters. Pyrochlore, ideally (CaNa)Nb2O6F, occurs as octahedral and cubo-octahedral crystals up to 300 μm in size. Compositionally, pyrochlore from Loluni and Kisete differs. The former is enriched in U (up to 19.4 wt.% UO2), light rare earth elements (up to 8.3 wt.% LREE2O3) and Zr (up to 14.4 wt.% ZrO2), and the latter contains elevated Ti (up to 7.3 wt.% TiO2). All the crystals investigated were crystalline, including those with high U content (a = 10.4152(1) Å for Loluni and a = 10.3763(1) Å for Kisete crystals). They have little or no subsolidus alteration nor low-temperature cation exchange (A-site vacancy up to 1.5% of the site), and are suitable for single-crystal X-ray diffraction analysis (R1 = 0.0206 and 0.0290; for all independent reflections for Loluni and Kisete crystals, respectively). Observed variations in the pyrochlore composition, particularly Zr content, from the Loluni and Kisete craters suggest crystallisation from compositionally different carbonatitic melts. The majority of pyrochlore crystals studied exhibit exceptionally well-preserved oscillatory- and sometimes sector-type zoning. The preferential incorporation of smaller and higher charged elements into more geometrically constrained sites on the growing surfaces explains the formation of the sector zoning. The oscillatory zoning can be rationalised by considering convectional instabilities of carbonatite magmas during their emplacement.

A major debris flow, the Trig Point Hill flow, originating from Kerimasi volcano (Tanzania) contains numerous blocks of extrusive/pyroclastic carbonatites similar to those exposed at the rim of the currently inactive crater. The blocks of calcite carbonatite consist of: (1) large clasts of corroded and altered coarse grained calcite; (2) primary prismatic inclusion bearing phenocrystal calcite; and (3) a matrix consisting primarily of fine-grained prismatic calcite. The large clasts are inclusion free and exhibit a ‘corduroy-like’ texture resulting from solution along cleavage planes. The resulting voids are filled by brown Fe–Mn hydroxides/oxides and secondary calcite. The prismatic or lath-shaped phenocrystal calcite is not altered and contains melt inclusions consisting principally of primary Na–Ca carbonates which contain earlier-formed crystals of monticellite, periclase, apatite, Mn–Mg-magnetite, Mn–Fe-sphalerite and Nb-perovskite. Individual Na–Ca carbonate inclusions are of uniform composition, and the overall range of all inclusions analysed (wt.%) is from 28.7 to 35.9 CaO; 16.7–23.6 Na2O; 0.5–2.8 K2O, with minor SO3 (1.1–2.2) and SrO (0.34–1.0). The Na–Ca carbonate compositions are similar to that of shortite, although this phase is not present. The Na–Ca carbonates are considered to be primary deuteric phases and not secondary minerals formed after nyerereite. Monticellite shows limited compositional variation and contains 2–4 wt.% MnO and 12 wt.% FeO and is Mn-poor relative to monticellite in Oldoinyo Lengai natrocarbonatite. Periclase is Fe-bearing with up to 13 wt.% FeO. Spinels are Cr-free, Mn-poor and belong to the magnetite–magnesioferrite series in contrast to Mn-rich spinels of the magnetite–jacobsite series occurring in Oldoinyo Lengai natrocarbonatite. The matrix in which the ‘corduroy’ clasts and phenocrystal calcite are set consists of closely packed small prisms of calcite lacking melt inclusions, with interstitial fine-grained apatite, baryte, strontianite and minor fluorite. Pore spaces are filled with secondary Mn–Fe hydroxides/oxides, anhydrite and gypsum. The hypothesis that flow-aligned calcite in volcanic calciocarbonatites from Kerimasi, Tinderet, Homa and Catanda is altered nyerereite is discussed and it is considered that these calcite are either primary phases or altered melilite. The nyerereite alteration hypothesis is discussed with respect to the volumetric and compositional aspects of pseudomorphism by dissolution–precipitation replacement mechanisms. This study concludes that none of the volcanic calciocarbonatites containing flow-aligned calcite phenocrysts are altered natrocarbonatite.

Carbonatite melts derived from the mantle are enriched in CO2- and H2O-bearing fluids. This melt can metasomatize the peridotitic lithosphere and liberate a considerable amount of CO2. Experimental studies have also shown that a CO2–H2O-rich fluid can form Fe- and Mg-rich carbonate by reacting with olivine. The Sung Valley carbonatite of NE India is related to the Kerguelen plume and is characterized by rare occurrences of olivine. Our study shows that this olivine is resorbed forsterite of xenocrystic nature. This olivine bears inclusions of Fe-rich magnesite. Accessory apatite in the host carbonatite contains CO2–H2O fluid inclusions. Carbon and oxygen isotopic analyses indicate that the carbonatites are primary igneous carbonatites and are devoid of any alteration or fractionation. We envisage that the forsterite is a part of the lithospheric mantle that was reprecipitated in a carbonatite reservoir through dissolution–precipitation. Carbonation of this forsterite, during interaction between the lithospheric mantle and carbonatite melt, formed Fe-rich magnesite. CO2–H2O-rich fluid derived from the carbonatite magma and detected within accessory apatite caused this carbonation. Our study suggests that a significant amount of CO2 degassed from the mantle by carbonatitic magma can become entrapped in the lithosphere by forming Fe- and Mg-rich carbonates.

The Huanglongpu carbonatites are located in the north-western part of the Qinling orogenic belt in central China. Calcite carbonatite dykes at the Dashigou open pit are unusual due to their enrichment in heavy rare earth elements (HREE) relative to light rare earth elements (LREE), leading to a flat REE pattern, and in that the majority of dykes have a quartz core. They also host economic concentrations of molybdenite. The calcite carbonatite dykes show two styles of mineralogy according to the degree of hydrothermal reworking, and these are reflected in REE distribution and concentration. The REE in the little-altered calcite carbonatite occur mostly in magmatic REE minerals, mainly monazite-(Ce), and typically have ΣLREE/(HREE+Y) ratios from 9.9 to 17. In hydrothermally altered calcite carbonatites, magmatic monazite-(Ce) is partially replaced to fully replaced by HREE-enriched secondary phases and the rocks have ΣLREE/(HREE+Y) ratios from 1.1 to 3.8. The fluid responsible for hydrothermal REE redistribution is preserved in fluid inclusions in the quartz lenses. The bulk of the quartz lacks fluid inclusions but is cut by two later hydrothermal quartz generations, both containing sulfate-rich fluid inclusions with sulfate typically present as multiple trapped solids, as well as in solution. The estimated total sulfate content of fluid inclusions ranges from 6 to >33 wt.% K2SO4 equivalent. We interpret these heterogeneous fluid inclusions to be the result of reaction of sulfate-rich fluids with the calcite carbonatite dykes. The final HREE enrichment is due to a combination of factors: (1) the progressive HREE enrichment of later magmatic calcite created a HREE-enriched source; (2) REE–SO42– complexing allowed the REE to be redistributed without fractionation; and (3) secondary REE mineralisation was dominated by minerals such as HREE-enriched fluorocarbonates, xenotime-(Y) and churchite-(Y) whose crystal structures tends to favour HREE.

Sulfur-bearing monazite-(Ce) occurs in silicified carbonatite at Eureka, Namibia, forming rims up to ~0.5 mm thick on earlier-formed monazite-(Ce) megacrysts. We present X-ray photoelectron spectroscopy data demonstrating that sulfur is accommodated predominantly in monazite-(Ce) as sulfate, via a clino-anhydrite-type coupled substitution mechanism. Minor sulfide and sulfite peaks in the X-ray photoelectron spectra, however, also indicate that more complex substitution mechanisms incorporating S2– and S4+ are possible. Incorporation of S6+ through clino-anhydrite-type substitution results in an excess of M2+ cations, which previous workers have suggested is accommodated by auxiliary substitution of OH– for O2–. However, Raman data show no indication of OH–, and instead we suggest charge imbalance is accommodated through F– substituting for O2–. The accommodation of S in the monazite-(Ce) results in considerable structural distortion that may account for relatively high contents of ions with radii beyond those normally found in monazite-(Ce), such as the heavy rare earth elements, Mo, Zr and V. In contrast to S-bearing monazite-(Ce) in other carbonatites, S-bearing monazite-(Ce) at Eureka formed via a dissolution–precipitation mechanism during prolonged weathering, with S derived from an aeolian source. While large S-bearing monazite-(Ce) grains are likely to be rare in the geological record, formation of secondary S-bearing monazite-(Ce) in these conditions may be a feasible mineral for dating palaeo-weathering horizons.

The Good Hope carbonatite is located adjacent to the Prairie Lake alkaline rock and carbonatite complex in northwestern Ontario. The occurrence is a heterolithic breccia consisting of diverse calcite, dolomite and ferrodolomite carbonatites containing clasts of magnesio-arfvedsonite + potassium feldspar, phlogopite + potassium feldspar together with pyrochlore-bearing apatitite clasts. The apatitite occurs as angular, boudinaged and schlieren clasts up to 5 cm in maximum dimensions. In these pyrochlore occurs principally as euhedral single crystals (0.1–1.5 cm) and can comprise up to 25 vol.% of the clasts. Individual clasts contain compositionally- and texturally-distinct suites of pyrochlore. The pyrochlores are hosted by small prismatic crystals of apatite (~100–500 μm × 10–25 μm) that are commonly flow-aligned and in some instances occur as folds. Allotriogranular cumulate textures are not evident in the apatitites. The fluorapatite does not exhibit compositional zonation under back-scattered electron spectroscopy, although ultraviolet and cathodoluminescence imagery shows distinct cores with thin (<50 μm) overgrowths. Apatite lacks fluid or solid inclusions of other minerals. The apatite is rich in Sr (7030–13,000 ppm) and rare earth elements and exhibits depletions in La, Ce, Pr and Nd (La/NdCN ratios (0.73–1.14) relative to apatite in cumulate apatitites (La/NdCN > 1.5) in the adjacent Prairie Lake complex. The pyrochlore are primarily Na–Ca pyrochlore of relatively uniform composition and minor Sr contents (<2 wt.% SrO). Irregular resorbed cores of some pyrochlores are A-site deficient (>50%) and enriched in Sr (6–10 wt.% SrO), BaO (0.5–3.5 wt.%), Ta2O5 (1–2 wt.%) and UO2 (0.5–2 wt.%). Many of the pyrochlores exhibit oscillatory zoning. Experimental data on the phase relationships of haplocarbonatite melts predicts the formation of apatite and pyrochlore as the initial liquidus phases in such systems. However, the texture of the clasts indicates that pyrochlore and apatite did not crystallise together and it is concluded that pyrochlores formed in one magma have been mechanically mixed with a different apatite-rich magma. Segregation of the apatite–pyrochlore assemblage followed by lithification resulted in the apatitites, which were disrupted and fragmented by subsequent batches of diverse carbonatites. The genesis of the pyrochlore apatitites is considered to be a process of magma mixing and not simple in situ crystallisation.

The Cretaceous Okorusu carbonatite, Namibia, includes diopside-bearing and pegmatitic calcite carbonatites, both exhibiting hydrothermally altered mineral assemblages. In unaltered carbonatite, Sr, Ba and rare earth elements (REE) are hosted principally by calcite and fluorapatite. However, in hydrothermally altered carbonatites, small (<50 µm) parisite-(Ce) grains are the dominant REE host, while Ba and Sr are hosted in baryte, celestine, strontianite and witherite. Hydrothermal calcite has a much lower trace-element content than the original, magmatic calcite. Regardless of the low REE contents of the hydrothermal calcite, the REE patterns are similar to those of parisite-(Ce), magmatic minerals and mafic rocks associated with the carbonatites. These similarities suggest that hydrothermal alteration remobilised REE from magmatic minerals, predominantly calcite, without significant fractionation or addition from an external source. Barium and Sr released during alteration were mainly reprecipitated as sulfates. The breakdown of magmatic pyrite into iron hydroxide is inferred to be the main source of sulfate. The behaviour of sulfur suggests that the hydrothermal fluid was somewhat oxidising and it may have been part of a geothermal circulation system. Late hydrothermal massive fluorite replaced the calcite carbonatites at Okorusu and resulted in extensive chemical change, suggesting continued magmatic contributions to the fluid system.

Natrocarbonatite lavas erupted from hornitos T37B and T49B at Oldoinyo Lengai (Tanzania) during 23–30 July, 2000 are unusual in containing sylvite and fluorite microcrysts together with fluorite-nyerereite intergrowths. The latter are relatively coarse grained and exhibit granular textures indicative of slow crystallization rates relative to those of their host subaerial lavas. Fluorite microcrysts are considered to be derived by the fragmentation of the fluorite-nyerereite clasts. Sylvite microcrysts contain inclusions of ferroan alabandite [(Mn0.67-0.71Fe0.33-0.29)S] and are poor in Na (1.9–7.7 wt.% Na; 6.1–23.4 mol.% NaCl). Intergrowth and microcrystal fluorite contains 1–3.5 wt.% Sr. Intergrowth nyerereite has a composition similar to that occurring as bona fide phenocrysts. The groundmass of lava erupted from hornito T37B contains nyerereite microphenocrysts (4–8 wt.% BaO) that are epitaxially mantled by barian nyerereite (12–20 wt.% BaO). The latter are compositionally and texturally distinct from the groundmass phase X, which is considered to be a burbankite-group mineral. The fluorite-nyerereite clasts are considered to be derived from the magma chamber underlying hornitos T37B and T49B, and thus representative of some of the products of crystallization of natrocarbonatite magma under hypabyssal conditions. The origins of the sylvite microcrysts cannot, as yet, be determined.

The formation of crystalline rare earth element (REE) (e.g. La, Ce, Pr, Nd) carbonates from aqueous solutions was examined at ambient temperature using UV-Vis spectrophotometry, combined with X-ray diffraction, high-resolution microscopy and infrared spectroscopy. In all experiments REE-lanthanites (REE2(CO3)3·8H2O) formed via a highly hydrated, nanoparticulate and poorlyordered REE-carbonate precursor. The lifetime of this precursor as well as the kinetics of crystallization of the various REE-lanthanites were dependent on the specific REE3+ ion involved in the reaction. The induction time and the time needed to fully form the crystalline REE-lanthanite end products increase linearly with the ionic potential. The authors show here that the differences in ion size and ionic potential as well as differences in dehydration energy of the REE3+ ions control the lifetime of the poorly ordered precursor and thus also the crystallization kinetics of the REE-lanthanites; furthermore, they also affect the structural characteristics (e.g. unit-cell dimensions and idiomorphism) of the final crystalline lanthanites.