The mineralogy of Ba- and Zr-rich alkaline pegmatites from Gordon Butte,Crazy Mountains (Montana,USA): comparisons between potassic and sodic agpaitic pegmatites

At Gordon Butte (Crazy Mountains, Montana), agpaitic nepheline-syenite pegmatites intrude potassic alkaline rocks (principally, malignites and nepheline microsyenites). All pegmatite veins are composed predominantly of potassium feldspar, nepheline, prismatic aegirine, barytolamprophyllite, wadeite, eudialyte, loparite-(Ce) and altered rinkite ("vudyavrite") embedded in spherulitic and fibrous aegirine. Well-differentiated veins contain "pockets" filled with calcite, fluorapatite, mangan-neptunite, Mn-Ti-enriched prismatic aegirine, calcium catapleiite, and an unidentified Ca-Ti silicate. The potassium feldspar corresponds to Ba-rich sanidine with relatively low Na contents. The nepheline contains low levels of SiO₂ and elevated Fe contents. The compositions of nepheline cluster in the lower portion of the Morozewicz-Buerger convergence field, indicating low-temperature crystallization and/or chemical re-equilibration of this mineral. The association of sanidine with nearly stoichiometric nepheline is unusual for agpaitic rocks and probably reflects inhibition of Al/Si ordering in the feldspar by Ba. At least four types of clinopyroxene can be distinguished on the basis of their morphology and composition. All these types correspond to Al- and Ca-poor aegirine (typically <0.6 and 2.6 wt% Al₂O₃ and CaO, respectively). The overall evolutionary trend of clinopyroxene in the Gordon Butte rocks is from Fe-poor diopside to aegirine-augite in the malignites and nepheline microsyenites, and culminates with the pegmatitic aegirine. This trend is characteristic for potassic alkaline complexes and results from preferential partitioning of Fe²⁺ into biotite during the magmatic crystallization. Barytolamprophyllite in the pegmatites is primary (as opposed to deuteric); only a few crystals contain a core composed of lamprophyllite. The evolutionary history of the Gordon Butte pegmatites can be subdivided into primary, agpaitic, and deuteric stages. The earliest paragenesis to crystallize included accessory zircon and thorite. Sr-rich loparite also precipitated relatively early serving as a major repository for Sr, REE, and Nb. During the agpaitic stage, diverse titano- and zircono-silicates (barytolamprophyllite, eudialyte, wadeite, and rinkite, among others) consumed most of the Ba, Sr, Ti, Zr, and Nb still remaining in the melt. The final stage in the evolution of the pegmatites involved interaction of the earlier-formed mineral assemblages with deuteric fluids. In common with the Rocky Boy pegmatites, Sr-REE-Na-rich fluorapatite, Ba-Fe titanates and REE-bearing carbonates (ancylite, calcio-ancylite, and bastnäsite-parisite series) are chief products of the deuteric stage. The alteration of the primary mineral assemblages by deuteric fluids also produced muscovite-zeolite pseudomorphs after nepheline, replacement of wadeite and eudialyte by catapleiite-group minerals, re-deposition of Ba in the form of hyalophane, baotite, and benitoite, and cation leaching from rinkite, eudialyte, and loparite. The mineralogy of the pegmatites from Gordon Butte, other potassic complexes, and sodic agpaitic occurrences is compared in detail.     

Nephelines from the Somma-Vesuvius volcanic complex (Southern Italy): crystal-chemical,structural and genetic investigations

Sixteen nephelines from different geological occurrences were sampled at the type-locality, the Somma-Vesuvius volcanic complex (southern Italy), and investigated for their chemistry and crystal structure obtained by both single-crystal and powder X-ray diffraction. Nepheline-bearing samples are metamorphic or from magmatic ejecta and pumice deposits. The lower K contents characterize the pumice- and some metamorphic-derived nephelines, whereas the higher ones are found in some samples from magmatic nodules. The amount of the anorthite molecule, quite low on average, can be more variable in the metamorphic nephelines. The crystal-structure investigations on Somma-Vesuvius samples compare well with previous studies of natural nephelines. All 16 nepheline samples adopt space group P6₃. The observed lattice parameters vary between 9.9768–9.9946 Å (for a) and 8.3614–8.3777 Å (for c), respectively. Furthermore, chemical analysis revealed that all specimens exhibit an excess of Si relative the ideal Si:Al ratio of 1:1. The analysis of the T-O distances in our samples clearly indicates a distinct ordering process of aluminium and silicon on the tetrahedral sites which is an agreement with Loewenstein’s rule. A linear correlation between the distance of symmetry equivalent split atoms O(1)-O(1)’ and the T(1)-O(1)-T(2) tilt angle was observed. The average <B-O> (B = Na) distances of all crystals are very similar which is consistent with the outcome of the site population refinement indicating full occupancy with sodium. Oriented precession-type sections of reciprocal space indicated the presence of at least the most intense family of satellite peaks, demonstrating that this group of satellite reflections can occur not only in nephelines from pegmatites and ijolites but also in rocks from completely different petrological settings.     

Ion exchange between tectosilicates with the nepheline-kalsilite framework and molten MNO3 or MO (M = Li,Na, K,Ag)

Natural nepheline, a synthetic Na-rich nepheline, and synthetic kalsilite were ion exchanged in molten MNO₃ or MCl (M = Li, Na, K, Ag) at 220–800° C. Crystalline products were characterized by wet chemical and electron microprobe analysis, single crystal and powder X-ray diffraction, and transmission electron microscopy and diffraction. Two new compounds were obtained: Li-exchanged nepheline with a formula near (Li,K_0.3,□)Li₃[Al₃(Al,Si)Si₄O₁₆] and a monoclinic unit cell with a = 951.0(6) b = 976.1(6) c = 822.9(5)pm γ = 119.15°, and Ag-exchanged nepheline with a formula near (K,Na,□)Ag₃[Al₃(Al,Si)Si₄O₁₆] and a hexagonal unit cell with a = 1007.4(8) c = 838.2(1.0) pm. Both compounds apparently retain the framework topology of the starting material. Ion exchange isotherms and structural data show that immiscibility between the end members is a general feature in the systems Na-Li, Na-Ag, and Na-K. For the system Na-K, a stepwise exchange is observed with (K,D)Na₃[Al₃(Al,Si)Si₄O₁₆] as an intermediate composition which has the nepheline structure and is miscible with the sodian end member (Na,□)Na₃[Al₃(Al,Si)Si₄O₁₆], but not with the potassian end member (K,□)₄[Al₃(Al,Si)Si₄O₁₆] which shows the kalsilite structure; there was no indication for the formation of trior tetrakalsilite (K/(K + Na)≈0.7) at the temperatures studied (350 and 800° C). The exact amount of vacancies □ on the alkali site depends upon the starting material and was found to be conserved during exchange, with ca 0–0.2 and 0.3–0.4 vacancies per 16 oxygen atoms for the synthetic and natural precursors, respectively. Thermodynamic interpretation of the Na-K exchange isotherms shows, as one important result, that the sodian end member is unstable with respect to the intermediate at K/(K+Na)≈0.25 by an amount of ca 45 kJ/mol Na in the large cavity at 800° C (52 kJ/mol at 350° C).     

Defects and short-range order in nepheline group minerals: a silicon-29 nuclear magnetic resonance study

²⁹Si magic-angle spinning nuclear magnetic resonance (NMR) spectra are presented for seven crystalline phases of the nepheline group: natural nephelines from a plutonic environment (Bancroft, Ontario) and a volcanic deposit (Mt. Somma, Italy), kalsilite, synthetic pure Na nepheline, carnegieite, and two samples of orthorhombic KAlSiO₄. In all phases, nearly all of the Si sites have four Al neighbors, indicating nearly complete Al-Si ordering. Excess Si over the 1:1 stoichiometric Si/Al ratio appears to substitute randomly for Al on an ordered lattice, adding Si sites with 3 and 0 Al neighbors in a 3:1 ratio. Various types of structural disorder, including Al-Si disorder, that are reported from some x-ray diffraction studies are probably long range in nature and are due to the presence of ordered domains. In naturally occurring nepheline, the relative abundance of T sites with three-fold local symmetry is maintained at the ideal stoichiometric value of 1/4, even when the K/(K+Na) ratio is substantially lower. This is in agreement with conclusions reached about the average structure from x-ray data. The distinction between the two sites, at least in terms of the local structure that is reflected in ²⁹Si NMR chemical shifts, is lost in a pure Na nepheline sample.     

Some Crystallo-chemical Relations of Nephelines and Feldspars on Stjerny, North Norway

Chemical, X-ray, and optical data are given for coexisting nephelinesand potassium feldspars separated from a nepheline syenite,and of nepheline and albite from pegmatites. Li, Rb, Cs (detectedonly in one nepheline), Ba, and Sr were determined, in additionto the major elements. (Pb and Tl were not detected by the spectrographicmethod used.) Some peculiarities of the mineral structures which are consideredto be important for the partition of elements between the coexistingphases are discussed. The importance of vacancies in nephelines,and their probable restriction to the large cavities in thestructure, is emphasized. It is pointed out that since low concentrations of Rb, Cs, Pb,and Tl are found in both nepheline and feldspar, they cannotbe caused by an unfavourable nepheline structure. They are eithera property of the parent magma or are the result of the physicalconditions of crystallization (i.e. escaping gas phase). Thelow concentrations of Sr, and especially of Ba, in nephelinesare in contrast to the high contents of these elements in thecoexisting feldspars. This is explained by considering the nephelinestructure. The unit cell contains eight structural sites forthe large cations (Na, K, Ca), and there are eight valenciesto satisfy. Six of the sites are smaller than the other two,and preferentially incorporate Na (and Ca) ions. The two largersites will tend to remain as vacant sites. Those which haveto be filled in order to satisfy the charge balance, will preferentiallyincorporate the large univalent ions (K and H₃O). The higher-chargedions (Ba² and Sr²) will pull the anions closer together andreduce the size of the site. They are, therefore, rejected fromthese positions. When nephelines coexist with feldspar, theywill incorporate the maximum amount of Si possible at the temperatureof formation. The substitution of Al for Si simultaneously withthe entry of a divalent cation (as in feldpspar) is, therefore,not possible except in non-feldspathic, extremely desilicifiedrocks. Thus, the entry of a divalent cation will not effectivelyclose the vacant sites. The somewhat higher contents of Sr relativeto Ba in the nephelines is because Sr is more easily incorporatedin the small sites (with Na and Ca).     

Geochemistry of granitic aplite-pegmatite dykes and sills and their minerals from the Gravanho-Gouveia area in Central Portugal

Two distinct series of Variscan granitic rocks have been distinguished in the Gravanho-Gouveia area of Portugal, based on field work, variation diagrams for major and trace elements, rare earth patterns and δ¹⁸O versus total FeO diagram of rocks, anorthite content of plagioclase, BaO and P₂O₅ contents of feldspars and Al^VI versus Fe²⁺ diagram for magmatic muscovite. One series consists of a late-orogenic porphyritic biotite > muscovite granite (G1), less evolved beryl-columbite pegmatites and more evolved beryl-columbite pegmatites showing gradational contacts. The other series consists of post-orogenic porphyritic muscovite > biotite granodiorite to granite (G2), slightly porphyritic muscovite > biotite granite (G3) and lepidolite pegmatites. In each series, pegmatites are derived from the parent granite magma by fractional crystallization of quartz, plagioclase, K-feldspar, biotite and ilmenite. Some metasomatic effects occur like muscovite replacing feldspars, chlorite in pegmatites of the first series and a late muscovite in pegmatites of the second series, probably due to hydrothermal fluids. The lepidolite pegmatites contain cassiterite and two generations of rutile. The first magmatic generation consists of homogeneous crystals and the second generation occurs as heterogeneous zoned crystals derived from hydrothermal fluids. The beryl-columbite pegmatites and lepidolite pegmatites also contain the first magmatic generation and the late hydrothermal generation of zoned columbite-group minerals. More evolved beryl-columbite pegmatites were converted into episyenite by intense hydrothermal alteration and regional circulation of fluids in the granitic rocks.     

Early Cretaceous Sung Valley ultramafic-alkaline-carbonatite complex, Shillong Plateau, Northeastern India: petrological and genetic significance

Summary The Shillong Plateau of northeastern India hosts four Early Cretaceous (105–107Ma) ultramafic-alkaline-carbonatite complexes (UACC), which have been associated with the Kerguelen plume igneous activity. Petrological and geochemical characteristics of one of these UACC, the Sung Valley, are presented. The Sung Valley UACC was emplaced in to the Proterozoic Shillong Group of rocks and consists of ultramafics (serpentinized peridotite, pyroxenite, and melilitolite), alkaline rocks (ijolite and nepheline syenite), and carbonatites. Serpentinized peridotite, pyroxenite, and ijolitic rocks form the major part of the complex, the others constitute less than 5% of the total volume. Ijolite and melilitolite intrude peridotite and pyroxenite, while nepheline syenite and carbonatite intrude the ultramafic rocks as well as ijolite. Mineralogically, the carbonatites are classified as calcite carbonatite with minor apatite, phlogopite, pyrochlore and ilmenite. The serpentinized peridotites are wehrlitic. Chemical compositions of the silicate rocks do not show a distinct co-genetic relationship amongst them, nor do they show any geochemical relationships with the carbonatites. No noticeable fractionation trend is observed on the chemical variation diagrams of these rocks. It is difficult to establish the genetic evolution of the Sung Valley UACC through fractional crystallization of nephelinitic magma or through immiscible liquids. On the basis of petrological and geochemical data and previously published isotopic results from these rocks, it is suggested that they have been derived from a primary carbonate magma generated by the low-degree melting of a metasomatized mantle peridotite.     

Emplacement age and isotope geochemistry of Sung Valley alkaline–carbonatite complex, Shillong Plateau, northeastern India: implications for primary carbonate melt and genesis of the associated silicate rocks

The early Cretaceous (Albian–Aptian) Sung Valley ultramafic–alkaline–carbonatite complex is one of several alkaline intrusions that occur in the Shillong Plateau, India. This complex comprises calcite carbonatite and closely associated ultramafic (serpentinized peridotite, pyroxenite and melilitolite) and alkaline rocks (ijolite and nepheline syenite). Field relationship and geochemical characteristics of these rocks do not support a genetic link between carbonatite and associated silicate rocks. There is geochemical evidence that pyroxenite, melilitolite and ijolite of the complex are genetically related. Stable (C and O) and radiogenic (Nd and Sr) isotope data clearly indicate a mantle origin for the carbonatite samples. The carbonatite Nd (+0.7 to +1.8) and Sr (+4.7 to +7.0) compositions overlap the field for Kerguelen ocean island basalts. One sample of ijolite has Nd and Sr isotopic compositions that also plot within the field for Kerguelen ocean island basalts, whereas the other silicate–carbonatite samples indicate involvement with an enriched component. These geochemical and isotopic data indicate that the rocks of the Sung Valley complex were derived from and interacted with an isotopically heterogeneous subcontinental mantle and is consistent with interaction of a mantle plume (e.g. Kerguelen plume) with lithosphere. A U–Pb perovskite age of 115.1±5.1 Ma obtained for a sample of Sung Valley ijolite also supports a temporal link to the Kerguelen plume. The observed geochemical characteristics of the carbonatite rocks indicate derivation by low-degree partial melting (0.1%) of carbonated mantle peridotite. This melt, containing a substantial amount of alkali elements, interacted with peridotite to form metasomatic clinopyroxene and olivine. This process could progressively metasomatize lherzolite to form alkaline wehrlite.     

Zirconology of pegmatites of the Ilmeny Mountains

Zircons extracted from the nepheline and feldspar crystals of miaskitic and feldspar pegmatites, respectively, are analyzed with the SHRIMP method for the first time. The early (Silurian) zircons coincide in age (432 Ma), composition, and mineralogical peculiarities with early zircons from miaskites. It is concluded that the pegmatite melt is a derivative of the miaskite melt. Permian (240–260 Ma) metamorphic zircons are widespread in pegmatites and miaskites. Zircons from these rocks are characterized by genetic commonality.     

ALKALIC PEGMATITES OF THE AFRIKANDA MASSIF

Paragenetic sequences observed in ore-bearing and barren pegmatites associated with alkalic ultramafic rocks are described. The Afrikanda massif is located in the western part of the Kola peninsula and is represented by nepheline pyroxenite. In its central part are ore-bearing pegmatites containing concentrations of titanomagnetite, knopite, schorlomite garnet, nepheline, pyroxene, and phlogopite. Processes of replacement are described and a comparison is made of geochemical features of these pegmatites as compared to granitic pegmatites, nepheline syenite pegmatites, and gabbroic pegmatites. --M. Russell.     

The mineralogy of primary inclusions in apatite crystals extracted from Alnö ijolite

Apatite crystals extracted from altered Alnö ijolite pegmatites contain primary aqueous saline inclusions and solid inclusions. The solid inclusions consists mainly of calcite, but the aqueous saline inclusions contain a variety of daughter minerals which include nahcolite (NaHCO₃), alkali halides and sulphates. These inclusions represent samples of a concentrated, highly alkaline aqueous solution and were originally trapped as homogeneous liquids during the growth of apatite. In the samples studied these fluids are late-stage and are thought to be responsible for the alteration seen in the host ijolite.     

On the occurrence of analcime in the northeastern Azerbaijan volcanics (northwestern Iran)

Euhedral, phenocryst-like crystals of analcime, as well as microlites, are rather common in phonolitic and tephritic lavas and in some anaicitic dikes and lenses of the Upper Cretaceous and Lower Tertiary volcanics of eastern Azerbaijan (Iran). The mineralogy and petrology of these extrusive rocks are described with the aim of establishing the origin of the big analcime crystals. While the mineralogical data (e.g. true symmetry, Al/Si disorder and Na atom distribution, structural refinements) are not conclusive, the paragenesis and microprobe analyses of analcime and associated phases, mainly feldspars, lead us to believe they are of a secondary, metasomatic origin. It is suggested that during late or post-magmatic stages analcime may have originated either from ion-exchanged leucite or by alteration or interaction between pre-existing Na-rich phases such as nepheline, feldspars and glass at subsolidus temperatures.     

Thermodynamics of plagioclases I: Theory of the I\bar 1 - P\bar 1 phase transition in anorthite and Ca-rich plagioclases

Landau theory of the \(P\bar 1 - I\bar 1\) phase transition in Ca-rich plagioclases reveals the sensitivity of the phase transition behaviour to a) Al, Si disorder, b) structural replacement of Ca by Na, and c) inhomogeneities of lattice strains. The following effects are predicted:

1. A tricritical phase transition exists in fully ordered anorthite. Al, Si disorder and Na, Ca exchange lead to second order phase transitions.
2. The transition temperatures depend sensitively on the degree of Al, Si disorder and the chemical composition of the Ca-rich plagioclases. Increasing Na-content decreases the transition temperatures.
3. The thermal evolution of c and d reflections depends on the homogeneity of the crystal and do not necessarily reflect the temperature evolution of the macroscopic lattice strain. A simple quadratic dependence of the X-ray scattering intensity on the order parameter exists only for fully ordered, homogeneous anorthite.

The role of inhomogeneous Al, Si distributions and lattice relaxations are discussed including possible structural modulations.     

Na and K distribution in agpaitic pegmatites

Composition and zoning of amphibole in agpaitic pegmatites of the 1.16 Ga Ilímaussaq complex, South Greenland record the chemical evolution of the final stages of an already extremely fractionated melt. Our results show that the general differentiation trends found in the earlier rocks of the complex are continued in the pegmatites, albeit with some significant modifications: the dominating exchange mechanism of Na + Si Ca + Al in the amphiboles of the magmatic stage changes to K + Si Ca + Al and K Na in some pegmatitic samples. Na/K ratios in amphiboles, which generally increase in the course of the Ilímaussaq fractionation, partly display a reversal during the crystallization of the most differentiated amphiboles.

The alkali trends are probably related to the buffering of Na⁺and K⁺activity by the co-crystallization of albite and microcline. This buffering favors Na⁺in cooling fluids. This mechanism is lost when analcime replaces feldspar as a stable phase in the late stages of crystallization, e.g. due to locally elevated H₂O activity. Analcime does not incorporate significant amounts of K and accordingly, amphibole incorporates more K in analcime-bearing assemblages. The Na–K variation in amphiboles in the Ilímaussaq pegmatites allow a detailed view into the late-stage evolutionary trends of a textbook agpaitic complex. The transition from silicate melt to aqueous fluid is recorded by the change of the dominant alkali ion in the pegmatitic amphiboles from Na to K.

Only in the very latest stage, virtually K-free mineral assemblages in analcime–aegirine veins support the existence of a Na-dominated aqueous fluid.     

New data on REE and rare-metal mineralization in pegmatites of the Slyudyanogorsk muscovite deposit in the Southern Urals

The Slyudyangorsk muscovite deposit in the southern Urals was explored and mined in 1926–1957. By the mid-1950s, 104 veins of quartz–feldspar pegmatites including 21 muscovite-bearing veins have been found. Pegmatites with giant black Y-bearing epidote crystals are crosscut by veins with giant muscovite crystals, which, in turn, are intersected by veins of two-mica–quartz–two-feldspar pegmatites with rare-metal and REE mineralization. Microprobe data on compositions of complex Ti–Ta–Nb oxides [fergusonite-(Y), samarskite-(Y), euxenite-(Y), polycrase-(Y), columbite-(Fe), pyrochlore supergroup] are characterized, as well as of uraninite, ilmenorutile, scheelite, Y-bearing epidote, certain sulfides and rock-forming minerals from the Slyudyanogorsk deposit. The morphology and interrelation of minerals indicate that they are the result of crystal growth in cavities rather than of metasomatic replacement of gneisses, as has been suggested earlier. Thus, it is more promising for rare-metal and REE minerals in the Slyudorudnik area to be found in igneous rocks (granitic muscovite–quartz–feldspar pegmatites with the Nb–Ta–Ti–Y–U–W–Mo mineralization) than in metasomatic rocks.     

Geochemistry of boron in the Ilímaussaq alkaline complex, South Greenland

The distribution of boron has been studied in rocks and minerals of the Ilímaussaq complex, South Greenland, using optical emission spectrometry. In the silica-undersaturated rocks of intrusive phases 1 and 3, average B contents increased from 5.6 ppm in augite syenite to a maximum of 8.9 ppm in sodalite-rich agpaitic nepheline syenite (naujaite roof cumulate) and then decreased to 5.4 ppm in the final lujavrites. Boron only behaved as an incompatible element during certain stages of the fractionation history. Starting at the naujaite stage, sodalite crystals (60–45 ppm B) were fractionated by flotation and were also trapped among the heavy cumulus phases of the bottom cumulates. This prevented the significant build-up of B in late derivatives as seen in other nepheline syenites. Nevertheless, in late pegmatites and veins associated with the agpaitic rocks, B was locally concentrated in certain Be minerals and metamict/reworked minerals. In the silica-oversaturated rocks of intrusive phase 2, average B contents increased from 8.6 ppm in quartz syenite to 13 ppm in alkali granite.     

Partition of major and minor elements and equilibration in coexisting pyroxenes

The partition of Si, Al, Ti, Fe³⁺, Mg, Fe²⁺, Mn, Ca and Na between coexisting Ca-rich and Ca-poor pyroxenes from a wide variety of igneous and metamorphic rocks have been investigated systematically. Many of the distributions, and especially those for the partition of Ti, Mg, Fe²⁺, Mn and Na, indicate characteristic trends for pyroxenes from the various petrologic groups identified. The partition of Mg, Fe²⁺ and Mn correlate with inferred cooling rates, the partition co-efficients of pyroxenes from extruded and other quickly cooled rocks most nearly approaching unity. In contrast, the partition of Si and Ti and the absolute amounts of Al may be related to the physicochemical conditions prevailing during original crystallisation; Ti being particularly relatively enriched in Ca-rich pyroxenes of ultramafic associations. The trends of the compositions of the Ca-rich pyroxenes plotted in the pyroxene quadrilateral also correlate with cooling rates and comparison with the limited data available on the phase relations of coexisting pyroxenes suggests that sub-solidus chemical readjustments have occurred in both phases.     

Composition and structure of minerals from Paleoproterozoic sedimentary rocks in the section of the Kola Superdeep Borehole and their homologs in outcrops

Geochemical and structural features of microcline, quartz, and carbonates from the sedimentary Luchlompolo Formation (III SF) of the Pechenga volcano sedimentary complex were compared in outcrops at a depth of 20–400 m in the section of satellite Borehole IX and of 4.8 km in the Kola Superdeep Borehole (SD-3). The rocks occupying an identical position in the section of this formation are homologous and characterized by similar composition and spectroscopic properties of rock-forming minerals. A certain variance in defect structure is revealed in minerals from shallow and deep levels. The crystal structure of microcline and dolomite from deep levels of the Kola Superdeep is distinguished by a larger amount of defects. The isomorphic replacement of Ca with Mn ions in dolomite increases with depth, probably owing to more intense metamorphism and further long-term standing at elevated pressure and temperature. The concentration of Al admixture in quartz decreases with depth, and isomorphic substitution of Al for Si shifts toward compensation with the alkali element in response to the same factors. The decrease in the number of natural paramagnetic Al centers in quartz and decrease in oxygen vacancies with depth is regarded as an effect of the current PT conditions.     

Peralkaline nephelinites. I. Comparative petrology of Shombole and Oldoinyo L'engai,East Africa

Shombole, a nephelinite-carbonatite volcano in south Kenya, erupted silicate lavas, carbonatite dikes and tuffs, and pyroclastic rocks similar to those at other East African alkaline centres. Shombole lavas containing cpx + nepheline + accessory minerals range from perovskite-bearing nephelinites (43% SiO₂, volatile-free) to sphene-bearing and phonolitic nephelinites (46–49% SiO₂) and phonolites (49–56% SiO₂) and have low peralkalinity ([Na+K]/Al 1.15) which does not correlate with SiO₂. Early fractionation of olivine and clinopyroxene strongly depleted Ni and Cr concentrations (10 ppm); fractionation of perovskite, melanite, sphene, and apatite produced negative correlations of all REE with SiO₂. Many lavas contain cognate intrusive xenoliths and xenocrysts and oscillatory zoning is a common feature of clinopyroxene, nepheline, and melanite crystals, indicating recycling of intrusive material. Irregular calcite-rich bodies in many samples are interpreted as quenched immiscible Ca-carbonatite liquid, and [Ca-carbonate]-silicate liquid immiscibility is observed in experiments with one nephelinite. Chemical variation in the Shombole suite can be modeled as a combination of crystal fractionation (clinopyroxene and heavy minor phases) and retention of neutral density nepheline derived from disaggregated xenoliths entrained during emplacement of dike swarms. Six newly analyzed lavas from Oldoinyo L'engai, northern Tanzania, are geochemically similar to Shombole nephelinites except that they have relatively high Na₂O+K₂O (average 18% vs 12%) and Zr (average 680 ppm vs 400 ppm). They are extremely peralkaline and are not typical of nephelinites from other centres. Three with [Na+K]/Al1.5 contain euhedral wollastonite phenocrysts; three with [Na+K]/Al2.0 contain combeite (Na₂Ca₂Si₃O₉) phenocrysts and pseudomorphs after wollastonite. Both types contain abundant sodalite phenocrysts (+nepheline+clinopyroxene+melanite+sphene). Seven other wollastonite nephelinite samples from L'engai have been described, but it is a lava type rarely seen in other centres. Combeite has been described from only two other locations (Mt. Shaheru, Zaire; Mayener Feld, Eifel). The hyperalkaline L'engai nephelinites have compositions similar to those of experimental silicate liquids immiscible with natrocarbonatite. Textural evidence for both carbonate-silicate (as carbonate globules) and silicate-silicate (as two optically discrete glasses with distinct compositions) liquid immiscibility is observed in the samples.     

Geochemistry of water-rock interaction in the area of the Khibiny alkaline massif

The interaction of natural and industrial waters with the rocks and apatite ores of the Khibiny alkaline massif was studied to estimate the extent of anthropogenic influence on natural processes. The abundance of the major rock-forming elements of the nepheline syenites and foidolites in the natural waters indicates that dissolution of nepheline and feldspathoids in natural water plays a significant role under the conditions of slow weathering in the Far North. Experiments showed that fine nepheline particles are transformed into amorphous phases at a fixed water volume at 18–20°C and pH 7.5–8.1. This process became observable already within the first day and continued for months. It is possible in stagnant reservoirs of natural waters and clearly expressed in industrial settling tanks. This is supported by the high content of amorphous phases enriched in Na, K, Al, and Si in the top layer of lacustrine sediments at the zone affected by the sewage of a concentrating mill.