Eudialyte-related compounds have been synthesised hydrothermally at T = 600°C and P = 2 kbar from a stoichiometric mixture of Na2CO3, CaO, Fe2O3, ZrOCl2 and SiO2 using the Na:Ca:Fe:Zr:Si ratios corresponding to the eudialyte end-member Na15Ca6Fe3Zr3Si(Si25O73)(OH)Cl2⋅H2O, in the presence of 1 M aqueous solutions of NaCl and NaF. The synthesis was carried out in platinum ampoules over 10 days. Natural raslakite (a Ca-deficient member of the eudialyte group) was used as a seed and added in amounts corresponding to 2 wt.% of the whole charge. The products were characterised by powder X-ray diffraction, IR and Raman spectroscopy, morphological features, and electron probe microanalyses. In experiments with NaCl, almost pure eudialyte-type compounds were obtained. Synthesis in the presence of a NaF solution resulted in the formation of a F-dominant eudialyte-type compound related to raslakite as the main product and aegirine, vlasovite and lalondeite as by-products. All synthesised eudialyte-type compounds are Zr-rich and Fe-deficient, similar to eudialyte-group minerals from hyperagpaitic rocks related to foyaites. The increased NaCl contents in the reaction system results in increased Ca content in the synthesised eudialyte-related compounds. The crystal-chemical formulae of the synthesised eudialyte-type compounds are derived based on general regularities established earlier for eudialyte-group minerals.

Poikilitic eudialyte outcrops in a strongly peralkaline phonolithic cumulo-dome in Jabal Al Hasawinah, Libya. Textural relationships reveal that the eudialyte has formed at a very late stage of the rock petrogenesis. Electron microprobe analyses confirm its volatile (hydrous) nature and low REE content.

Accessory rare earth element (REE) minerals occur in small quantities in agpaitic and miaskitic nepheline syenite gneisses of the Sushina Hill Complex, India. The REE-rich minerals restricted mainly to the agpaitic rocks are rinkite, cerianite-(Ce), and cerian thorite. Rinkite, formed at the ortho-magmatic stage predates other REE-rich phases and is the most Nd-F-rich rinkite (6.62–7.45 wt.% Nd2O3; 8.75–9.74 wt.% F) with very high Nd/Ce (>2.46) ratios reported to date. Hydrothermal cerianite-(Ce), formed by the decomposition of eudialyte in the agpaitic rocks, occurs as small rounded crystals rich in Ce (∼63–74 wt.% CeO2) and Y (6.03–11.69 wt.% Y2O3). The presence of cerianite-(Ce) indicates formation in an evolving hydrothermal fluid in an oxidizing milieu. Hingganite-(Ce) is present in the miaskitic unit and is considered to represent the superposition of an agpaitic mineral on an initial miaskitic assemblage. Hingganite-(Ce) is characterized by elevated contents of Ce (18.03–21.94 wt.% Ce2O3), and Nd (13.90–15.40 wt.% Nd2O3). Experimental data, coupled with the observed assemblage, suggest that the hingganite-(Ce) precipitated from the hydrothermal fluid between 400 and 300°C followed by cerianite-(Ce) (<∼300°C). This conclusion implies that eudialyte decomposition was probably initiated above 400°C.

The tectonic position of the intraplate, alkaline volcanic province of N. Tanzania in a broad rift-controlled area astride the boundary between the Tanzania Craton and the circum-cratonic Mozambique Fold Belt, strongly resembles that of the Gardar province of S. Greenland. Earlier-identified petrological analogies between Gardar magmatism and that in the Kenya sector of the East African Rift Valley can be extended to volcanism in N. Tanzania, and analogies specifically with the Gardar agpaitic suite are strengthened by the occurrence of eudialyte and aenigmatite in some Tanzanian peralkaline, silicic volcanics.

Weakly peralkaline syenite ejecta within the plinian fall deposits of Agua de Pau volcano (São Miguel, Azores Islands) are divisible into (1) silica-undersaturated and (2) silica-saturated/oversaturated groups. The first group occurs in the pre-Fogo-A pyroclastic falls (15.2 ka) whereas the second occurs in the Fogo-A pumices (5 ka). The petrography indicates that the syenites of both groups crystallized at shallow depths and whole-rock geochemistry shows that they have compositions reflecting those of the Agua de Pau trachyte magmas. The syenites are inferred to be derived from solidification zones around the margins of the parental magma chamber. Mineral parageneses in both syenite groups permit distinction of three magmatic stages of crystallization: (1) an early crystallization stage; (2) a main crystallization stage during which most of the feldspar growth occurred; and (3) a late interstitial stage. Crystallization of the trachytic magmas yielded peralkaline residuals, highly enriched in volatiles, alkalis, HFSE and REE. In the silica-undersaturated syenites, the complex Zr-Ti silicate minerals, eudialyte and a låvenite-like mineral, crystallized interstitially from the residual magmas. In contrast, the zircono-silicate dalyite, and REE-rich minerals (chevkinite-(Ce), britholite-(Ce) and pyrochlore), together with thorite, were late-stage interstitial products of the silica-saturated/oversaturated syenites.

It is now generally agreed that the term ‘agpaitic’ should be restricted to peralkaline nepheline syenites (and phonolites) containing minerals such as eudialyte and rinkite, that is complex silicates of Zr, Ti, the rare earth elements (REE), and F and other volatiles. There are, however, cases of transition into more common types of nepheline syenites containing zircon, titanite, ilmenite, etc.

The agpaitic rocks are characterized by extremely high contents of rare elements such as Li, Be, Nb, Ta, REE, Zr, Th, etc. and of volatiles, first of all F and Cl. This gives rise to a wealth of mineral species, more than 500 in the Lovozero and Khibina complexes of the Kola peninsula, about 250 in Mont Saint-Hilaire, Quebec, Canada, and about 200 in the type locality, the Ilímaussaq complex, South Greenland.

These rocks have very long melting intervals and solidus temperatures as low as 500 to 400°C. They are accompanied by a gas phase rich in methane and other hydrocarbons and most probably also by sodium-rich fluids as indicated by the presence of minerals such as ussingite (NaAlSi3O8·NaOH) and villiaumite (NaF) and of pegmatites and hydrothermal veins rich in sodium and rare and volatile elements.

Agpaitic nepheline syenites are considered to have been formed by consolidation of melts oversaturated in alkalis, especially sodium, under conditions preventing the volatiles from escaping. These melts have been derived by extreme fractionation processes in alkali basaltic or nephelinitic magmas. The main stage of crystallization of the melts is characterized by minerals such as nepheline (sometimes also sodalite), alkali feldspars, arfvedsonite, aegirine and eudialyte, but the most highly developed, hyperagpaitic lujavrites of the Ilímaussaq complex have been formed from melts with extreme concentrations of sodium and volatiles resulting in the formation of naujakasite instead of nepheline, ussingite instead of sodalite and alkali feldspars, and steenstrupine instead of eudialyte. During the late stages of crystallization, sodium-rich fluids are the cause of late- and postmagmatic alteration and of the formation of hydrothermal mineralizations. The late stages are characterized by water-soluble sodium-rich minerals of which more than 80 have been found in the Khibina and Lovozero complexes.

The mineralogy of the highly peralkaline Junguni nepheline syenite intrusion of the Chilwa alkaline province has been investigated. The rocks comprise alkali feldspar, very abundant nepheline, locally exceptionally abundant sodalite, sodic pyroxenes, scarce biotite, rare amphibole, and an extensive range of accessory minerals. Electron microprobe analyses indicate that the pyroxenes define an evolutionary trend from salite through aegirine-augite to aegirine, which is unusual in its broadness and ill-definition. This is explained by a series of overlapping trends produced by fluctuating Fe3+/Fe2+ ratios caused by variations in alkali content of the magma, probably produced by periodic alkali loss by surface de-gassing. Much of the sodalite occurs as a primary liquidus phase, but the paragenesis of certain ramifying sodalite veins is more problematical. It is possible that such ramifying masses are the product of coupled migration of alkalis and volatiles by diffusion in a gravitation field under pressure gradients generated by eruptive events, or by the formation of immiscible Na- and Cl-rich liquids. Both early calcic and late mangan-fluor eckermannitic/arfvedsonitic amphiboles occur. The micas vary from biotites with Mg: Fe ratios < 0·5 to almost pure annites; they are fluor-micas and characterized by high Mn contents. Analyses of niobian rutile, mangan ilmenite, ferroan pyrophanite, manganese-rich eucolite, låvenite, mangan-titan låtvenite, rosenbuschite, wöhlerite, pyrochlore, eudialyte and what is believed to be only the second occurrence of kupletskite are given. Many of these minerals are rich in Zr, Nb, Na and Mn and thus typical of the assemblages found in extreme agpaitic complexes such as Ilimaussaq and Lovozero.

The North Qôroq centre comprises a series of nested nepheline syenite intrusions and forms part of the mid-late Proterozoic Gardar province of South Greenland. Within the centre fractionation has produced varied rock types ranging from augite-syenite to lujavrite, a eudialyte microsyenite. Samples of eudialyte from the lujavrites of unit SN1B of the centre show evidence for two-stage alteration. This alteration ranges from slight modification along crystal margins to complete breakdown and replacement by new pseudomorphing phases. Modification to crystal margins is accompanied by increasing Nb and Zr contents and is related to metasomatism produced by the intrusion of younger syenite units of the North Qôroq centre. More extensive alteration is as a result of metasomatism followed by lower-temperature supergene alteration. Simplified reactions for this breakdown include eudialyte + metasomatic fluid = allanite + nepheline; eudialyte + metasomatic fluid = titanite + aegirine + møsandrite + wöhlerite; eudialyte + fluid = zirfesite + fluid. Mass balance calculations for altered compared with unaltered samples of lujavrite show that alteration took place at approximately constant volume with an overall increase in Fe (+2.41 g/100g), Si and K (+0.65 and +0.61 g/100g), whilst Na (−2.67 g/100g) and all trace elements, particularly La, Y, Nb and Zr (−5.6 to −166 g/10000g) are lost from the system.

The layered agpaitic nepheline syenites (kakortokites) of the Ilímaussaq complex, South Greenland, host voluminous accumulations of eudialyte-group minerals (EGM). These complex Na-Ca-zirconosilicates contain economically attractive levels of Zr, Nb and rare-earth elements (REE), but have commonly undergone extensive autometasomatic/hydrothermal alteration to a variety of secondary mineral assemblages. Three EGM alteration assemblages are recognized, characterized by the secondary zirconosilicates catapleiite, zircon and gittinsite. Theoretical petrogenetic grid models are constructed to assess mineral stabilities in terms of component activities in the late-stage melts and fluids. Widespread alteration of EGM to catapleiite records an overall increase in water activity, and reflects interaction of EGM with late-magmatic Na-, Cl- and F-rich aqueous fluids at the final stages of kakortokite crystallization. Localized alteration of EGM and catapleiite to the rare Ca-Zr silicate gittinsite, previously unidentified at Ilímaussaq, requires an increase in CaO activity and suggests post-magmatic interaction with Ca-Sr bearing aqueous fluids. The pseudomorphic replacement of EGM in the kakortokites was not found to be associated with significant remobilization of the primary Zr, Nb and REE mineralization, regardless of the high concentrations of potential transporting ligands such as F and Cl. We infer that the immobile behaviour essentially reflects the neutral to basic character of the late-magmatic fluids, in which REE-F compounds are insoluble and remobilization of REE as Cl complexes is inhibited by precipitation of nacareniobsite-(Ce) and various Ca-REE silicates. A subsequent decrease in F– activity would furthermore restrict the mobility of Zr as hydroxyl-fluoride complexes, and promote precipitation of the secondary zirconosilicates within the confines of the replaced EGM domains.

The Proterozoic Sushina Hill Complex is the only agpaitic complex, reported from India and is characterized by a eudialyte-rinkite-bearing nepheline syenite. The complex is considered a ‘metamorphosed agpaitic complex'. This study describes the mineral assemblages formed during successive stages of evolution from magmatic to hydrothermal stages and low-temperature subsolidus re-equilibration assemblage. The primary-late magmatic assemblage is characterized by albite, orthoclase, unaltered nepheline, zoned diopside-hedenbergite, rinkite, late magmatic eudialyte and magnesio-arfvedsonite formed at ∼700°C with maximum aSiO2 of 0.60. In contrast, a deuteric assemblage (400-348°C) is represented by aegirine-jadeite-rich clinopyroxene, post-magmatic eudialyte, sodalite, analcime and the decomposition assemblages formed after eudialyte with decreasing aSiO2 (0.52-0.48). A further low-temperature subsolidus assemblage (≤250°C) represented by late-forming natrolite could be either related to regressive stages of metamorphism or a continuum of the subsolidus processes. Considering the P/T range of the greenschist - lower-amphibolite facies of metamorphism it is evident that the incorporation of a jadeite component within pyroxene is related to a subsolidus process between ∼400°C and 348°C in a silica deficient environment. We emphasize that the deuteric fluid itself acted as an agent of metamorphism and the decomposition assemblage formed after eudialyte is retained even after metamorphism due to the convergence of subsolidus and metamorphic domains. The formation of jadeite-rich aegirine is not considered to result from metamorphism. Overall it is near-impossible to discern any bona fide metamorphic textures or mineral assemblages in these syenites which appear to preserve a relict mineralogy regardless of their occurrence in country rocks which have experienced greenschist - amphibolite facies metamorphism. The Sushina complex is very similar in this respect to the Norra Kärr complex (Sweden).

Accurate quantification of the chemical composition of eudialyte group minerals (EGM) with the electron probe microanalyzer is complicated by both mineralogical and X-ray-specific challenges. These include structural and chemical variability, mutual interferences of X-ray lines, in particular of the rare earth elements, diffusive volatility of light anions and cations, and instability of EGM under the electron beam. A novel analytical approach has been developed to overcome these analytical challenges. The effect of diffusive volatility and beam damage is shown to be minimal when a square of 20×20 µm is scanned with a beam diameter of 6 µm at the fastest possible speed, while measuring elements critical to electron beam exposure early in the measurement sequence. Appropriate reference materials are selected for calibration considering their volatile content and composition, and supplementary offline overlap correction is performed using individual calibration factors. Preliminary results indicate good agreement with data from laser ablation inductively coupled plasma mass spectrometry demonstrating that a quantitative mineral chemical analysis of EGM by electron probe microanalysis is possible once all the parameters mentioned above are accounted for.