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.

Lapilli formed by a Strombolian eruption are associated with the formation of a large lava flow of natrocarbonatite on or about 21–22 July, 2000 at Oldoinyo Lengai volcano, Tanzania. Fresh lapilli consist of vesicular natrocarbonatite similar to that occurring in rapidly quenched lavas. The lapilli were altered at low temperature (<50°C) by degassing to aggregates of sodian sylvite, potassian halite, trona, thermonatrite and a novel F-bearing sodium phosphate-carbonate. The latter is considered to be a new mineral as it has a composition (Na5–4.5PO4(CO3,F,Cl) that is not similar to that of nahpoite (Na2HPO4), dorfmanite [Na2(PO3OH).2H2O] or natrophosphate [Na7(PO4)2F.19H2O]. However, in common with these minerals, it is ephemeral and undergoes rapid decomposition under normal atmospheric conditions. The sodium phosphate-carbonate and associated halide-sodium carbonate assemblages are considered to be a part of a previously unrecognized hyperagpaitic assemblage forming as sublimates at Oldoinyo Lengai.

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.

A unique hybrid natrocarbonatite, collected from the new ash cone of the volcano Oldoinyo Lengai. Tanzania in July 2008, consists of phenocrysts of nyerereite and gregoryite together with xenocrysts of clinopyroxene, nepheline and Ti-andradite set in a groundmass of cuspidine, sodalite, ferroan manganoan monticellite, K-Fe sulphide and manganoan titanian magnetite and gregoryite. The xenocrysts were not in equilibrium with the melt which formed their current host, as clinopyroxenes and Ti-andradite are mantled by cuspidine, and nepheline by sodalite and phlogopite—potassian kinoshitalite solid solutions. A microxenolith of ijolite exhibits similar reaction phenomena. The minerals of the xenocryst suite have similar compositions to plutonic ijolites found at Oldoinyo Lengai, and are thus considered to be derived by the fragmentation of such material in a previously contaminated natrocarbonatite melt. The latter, which has cuspidine, sodalite and monticellite as primary liquidus phases, is considered to have been formed by the complete assimilation of ijolitic material in a natrocarbonatite magma at depth in the volcano conduit. The occurrence of trace amounts of cuspidine, Fe-Mn-monticellite, K-Fe sulphide and Mn-Ti-spinel in recently erupted natrocarbonatites is ascribed to similar, but less extensive, assimilation of silicate material prior to their eruption.

A peralkaline nephelinite lava ([Na+K]/Al 2.15) from the active carbonatite volcano Oldoinyo Lengai, contains combeite, Ba lamprophyllite, a phase with affinities to delhayelite, CeSrNb perovskite, a CaNa phosphate high in Sr, Ba and K, and peralkaline glass; in addition to Fe-rich nepheline, aegirine-rich clinopyroxene and FeK-rich sodalite. The high alkali concentrations relative to alumina in the bulk rock could not have been achieved by fractionational crystallisation of the known Al-rich phenocryst phases (nepheline and sodalite) and some other process must be invoked.

Several K-Fe sulphide minerals have been described from natrocarbonatite lavas erupted from the Tanzanian volcano Oldoinyo Lengai but uncertainty remains about their exact identity. They do not appear to be any of the established K-Fe sulphides according to Dawson et al. (1995) and Mitchell (1997). Here, we describe yet another variant which is a Mn- and F-bearing variety of rasvumite. It appears to have formed by reaction of Fe alabandite grains with natrocarbonatite magma and occurs as minute rims on the alabandite. Its formula is: (K0.94Na0.06)(Fe1.91Mn0.13Ca0.01Sr0.01)(S2.06F0.24Cl0.04).

Lapilli and spatter of natrocarbonatite extruded from the T56B cone of Oldoinyo Lengai (Tanzania) in August 2003 are unusually rich in apatite, silicate, oxide and sulphide minerals. These minerals occur primarily within inclusions of quenched natrocarbonatite in gregoryite and fractures in nyerereite-gregoryite intergrowths. Silicates include members of the sodian cuspidine–niobian cuspidine–niocalite solid-solution series and manganoan monticellite. Oxides are represented by members of the magnesioferrite–jacobsite–magnetite solid-solution series. Sulphides occurring in decreasing order of abundance include: ferroan alabandite, manganoan ferroan sphalerite, galena and pyrrhotite. Petrographic and compositional data for these minerals are interpreted to indicate that all are high-temperature (<900–650°C), early-crystallizing phases from relatively-unevolved natrocarbonatite magma, with the sulphides forming prior to the silicates, and the latter before gregoryite. Sulphur fugacityand oxygen fugacity of natrocarbonatite magma are considered to decrease and increase, respectively, during the formation of the sulphide-oxide assemblage. Crystallization of cuspidine-niocalite, monticellite and Si-bearing apatite rapidly depletes natrocarbonatite magma of its initial low silica content, preventing crystallization of late-stage groundmass silicates.

A calcite-rich block in nephelinitic agglomerate at Oldoinyo Lengai comprises Sr-calcite, apatite, fluorite, a Ba-Mn oxide akin to romanrchite, and a distinctive Mn-Fe spinel. Formerly reported as sövite, on textural, mineralogical and stable isotope grounds it is now re-interpreted as a highly-altered natrocarbonatite lava. An implication of this study is that natrocarbonatite is not just a modern phenomenon, but has been extruded from Oldoinyo Lengai for at least around 1250 years.

The Tinderet volcano (19.9 to 5.5 Ma), located within the Kavirondo rift in Kenya, contains blocks of carbonatite lavas with calcite, minor apatite, fluorite, spinel-group minerals, accessory perovskite and 'plumbopyrochlore'; nyerereite is present as inclusions in the perovskite. At least four types of calcite are present in the carbonatite lavas; they differ in morphology, composition and origin. The dominant variety is secondary type-II calcite, which is enriched in sodium (up to 1.1 wt.% Na2O) and strontium (up to 1.3 wt.% SrO). The spinel-group minerals are manganese-bearing and include Mn-rich magnetite, magnesioferrite and jacobsite. Oxygen isotope data for bulk carbonatite samples (δ18O = +16.2 % to +22.6 % VSMOW) support a low crystallization temperature for the secondary calcite. Petrographic, mineralogical and isotopic data indicate that the Tinderet carbonatites are similar to natrocarbonatites from the Oldoinyo Lengai and Kerimasi volcanoes that have altered and recrystallized to form calcite carbonatites. These data support the hypothesis that some of the Tinderet carbonatites were originally alkali-rich rocks which contained primary nyerereite.

Lapilli from the August 1966 eruption of the carbonatite volcano Oldoinyo Lengai consist of carbonate-cemented aggregates of (i) mono- and poly-mineralic fragments of ijolitic rocks, (ii) single grains and clusters of euhedral nepheline, Ti-andradite, and Ti-magnetite, and (iii) corroded pyroxene and wollastonite grains surrounded by coronas containing combeite, melilite, Ca-silicates (possibly larnite and rankinite), and rounded bodies of submicrometre intergrowths with complex bulk compositions dominated by Na,K,Ca-phosphate-carbonate and alkali-iron-sulphide-carbonate. The (ii,iii) materials, together with abundant Na-carbonate, sylvite and fluorite occurring as cement and shells in the lapilli, are attributed to mixing and incomplete reaction of ijolite and carbonatite magmas during the explosive eruption. The rounded submicrometre intergrowths are interpreted as the quench products of two types of immiscible liquids whose properties should be studied by controlled synthesis.

The September 2007 ash eruption at Oldoinyo Lengai terminated a period of >30 y of relatively quiet extrusion of natrocarbonatite lavas. Ash erupted on the 24th September comprised nuclei of ijolitic phases, surrounded by finer peralkaline, silica-undersaturated material. The mantling material, as well as that forming nucleus-free particles, is dominated by nepheline, Ti-andradite, Na-melilite, combeite and a Na-Ca-phosphate-carbonate with minor amounts of K-Fe-sulphide and Mn-magnetite in a sparse matrix of alkali carbonate. The absence of clinopyroxene precludes this material from being termed either nephelinite or melilitite. We propose that the material represented by the mantles is an extremely undersaturated, peralkaline hybrid magma resulting from interaction between natrocarbonatite and nephelinite.

Alumoåkermanite, (Ca,Na)2(Al,Mg,Fe2+)(Si2O7), is a new mineral member of the melilite group from the active carbonatite-nephelinite-phonolite volcano Oldoinyo Lengai, Tanzania. The mineral occurs as tabular phenocrysts and microphenocrysts in melilite-nephelinitic ashes and lapilli-tuffs. Alumoåkermanite is light brown in colour; it is transparent, with a vitreous lustre and the streak is white. Cleavages or partings are not observed. The mineral is brittle with an uneven fracture. The measured density is 2.96(2) g/cm3. The Mohs hardness is ~4.5–6. Alumoåkermanite is uniaxial (–) with ω = 1.635(1) and ε = 1.624–1.626(1). In a 30 mm thin section (+N), the mineral has a yellow to orange interference colour, straight extinction and positive elongation, and is nonpleochroic. The average chemical formula of the mineral derived from electron microprobe analyses is: (Ca1.48Na0.50Sr0.02 K0.01)(Si1.99Al0.01O7). Alumoåkermanite is tetragonal, space group P421m with a = 7.7661(4) Å, c = 5.0297(4) Å, V = 303.4(1) Å3 and Z = 2. The five strongest powder-diffraction lines [d in Å, (I/Io), hkl] are: 3.712, (13), (111); 3.075, (25), (201); 2.859, (100), (211); 2.456, (32), (311); 1.757, (19), (312). Single-crystal structure refinement (R1 = 0.018) revealed structure topology typical of the melilite-group minerals, i.e. tetrahedral [(Al,Mg)(Si2O7)] sheets interleaved with layers of (CaNa) cations. The name reflects the chemical composition of the mineral.

Natrocarbonatite magma, erupted as lava flows in the Tanzanian volcano Oldoinyo Lengai in June and November of 1988, has evolved chemically since its formation. The June and November flows of 1988 display increasing Cl, F, Ba, K, Mg and Mn, concomitantly with Na, Ca and P depletion. Furthermore, the June magma, at the time of eruption, had higher Cl, F, Ba and K contents and lower Ca than the November magma and evolved to higher levels of Cl, F, Ba and K content and lower Ca, Na and P. The mineralogy of the lavas reflects these trends. Crystallization of fluorite and halite–sylvite solid solution, usually as a symplectic intergrowth, occurs when Cl and F concentrations reach the critical value necessary to stabilize both minerals and explains why neither occurs as a phenocryst phase. Natrocarbonatite magma has undergone considerable and rapid magmatic evolution, probably in small and separate magma chambers. Two minerals, nyerereite and gregoryite, have dominated the crystallization history of natrocarbonatite magma, and many lavas are phenocryst-rich. However, because most of the lavas are composed principally of these two minerals, crystal accumulation has not greatly changed their composition and, consequently, we suggest that the bulk composition of the lavas closely approximates that of the parental magma.

Stalactites formed by the chemical weathering of natrocarbonatite lava decorate the roofs of hollow inactive hornitos at Oldoinyo Lengai, Tanzania. The stalactites are composed principally of trona with lesser and very variable amounts of nahcolite, (NaHCO3), thermonatrite (Na2CO3.H2O), aphthitalite [(K,Na)3Na(SO4)2], kogarkoite [Na3(SO4)F], schairerite [Na21 (SO4)7F6Cl], halite and sylvite. Stalactites are considered to form by the evaporation of Ca-free highly alkaline brines seeping from the altered lavas which form the roofs of the hornitos. The principal subaerial weathering products of natrocarbonatite, i.e. pirsonnite, gaylussite, shortite and calcite are not found in the stalactites and are retained in the altered lavas of the homito roof. Fluorine required for the formation of kogarkoite and schairerite is derived from the decomposition of fluorite at high pH (>10). Sulphur is derived from the decomposition of gregoryite.

In 1962 Dawson described a calcite carbonatite (specimen BD83) from the Tanzanian volcano Oldoinyo Lengai as a sövite, thus implying that at an earlier stage in its evolution this volcano had crystallized magmatic calciocarbonatites as well as the highly alkalic natrocarbonatite lava that has been erupted in more recent times. This proposition is difficult to reconcile with the currently fashionable hypothesis whereby the natrocarbonatite lava separated immiscibly from a type of nephelinite magma, most recently thought to be a wollastonite nephelinite. In 1993 Dawson sought to discredit the magmatic origin of this sövite specimen by arguing that it was derived from natrocarbonatite lava through extreme alteration (calcitization) in which process the original nyerereite was replaced by calcite in near-perfect pseudomorphs. We suggest that the arguments advanced in support of this concept are unconvincing and that the specimen is exactly what it was originally described as, namely a magmatic sövite in which the calcite crystallized from a magma rather than having replaced nyerereite. We do not seek to discredit the liquid immiscibility hypothesis but do believe that whatever process is responsible for the Oldoinyo Lengai natrocarbonatites and silicate rocks must also allow for the crystallization of calciocarbonatite.

Porphyritic natrocarbonatite lavas erupted from the Oldoinyo Lengai volcano (Tanzania) on 17 October 1995 and 15–19 December 1995 differ from previously studied lavas in that they preserve textures indicative of groundmass carbonate-carbonate immiscibility. The immiscible fractions are considered to involve: a Na-K-Ca-CO2-Cl-rich, F-bearing fluid crystallizing gregoryite, sodian sylvite, potassium neighborite as well as a complex Ba-rich carbonate; and a Na-rich, Cl-poor carbonate liquid approximating to a nyerereite-gregoryite cotectic composition. Compositional data are given for potassium neighborite, this mineral being the first recognized occurrence of a fluorine-based perovskite group mineral in a magmatic environment. New compositional data are also given for a previously recognized potassium iron sulphide which indicate that this phase is probably a solid solution between the ternary sulphides, KFe3S4, K2Fe3S4, and KFe2S3. Textural and paragenetic data are interpreted to suggest that these recent lavas are more evolved than previously investigated Oldoinyo Lengai lavas and that natrocarbonatite is a highly evolved rather than a primitive magma.