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.

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.

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.

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.