Partition of trace elements in co-existing biotite,muscovite and potassium feldspar of granitic rocks,northern Portugal

Chemical analyses are given for Na, K, and trace elements of muscovite and potassium feldspar of granitic rocks. The distribution of trace elements in co-existing minerals suggests that equilibrium was attained and that muscovite is a primary mineral. These observations and the comparison of the trace-element chemistry of megacrysts and groundmass potassium feldspars of porphyritic rock types lead to the conclusion that the megacrysts are in face phenocrysts which crystallized in equilibrium with the other minerals of the rock.The ranges of values of the distribution coefficients K_D(Rb/K) and K_D(Cs/K) in mineral pairs confirm other observations on the equilibrium among various minerals. However, application of experimental data on the temperature effect on K_D leads to results conflicting with the petrologic observations. The possible influence of other factors on K_D is analyzed and among these factors the composition of the feldspar and the solidus-liquidus temperature interval may play a dominant role.     

Effet de la température sur les distributions de Na,Rb et Cs entre la sanidine,la muscovite,la phlogopite et une solution hydrothermale sous une pression de 1 kbar

The distribution of trace amounts of Na, Rb and Cs, between muscovite, phlogopite, sanidine and hydrothermal solution have been studied by ion exchange in a temperature range from 400 to 800°C.These distributions have been expressed with a partition ratio P^aq?m_x = $\text{(}\text{X}\text{K}\text{)}{}^{\mathrm{aq}}\text{(}\text{X}\text{K}\text{)}{}^{\mathrm{m}}$ (where X is Na, Rb or Cs).In the case of Na and Cs in muscovite, even for the dilute solutions, the ratio P^aq?m_x is not the equilibrium constant k_x of exchange reactions. In other cases, P^aq?m_x does not depend on the trace alkali ion concentration in silicates (X) and is equal to k_x. Variations of P_x or k_x with T are greater for Na and Cs than for Rb. Generally, k_x decreases with increase in T. The function log $\text{P}{}_{\mathrm{x}}\text{= f(}\text{1}\text{T}\text{)}$ is not linear for Na or Cs, but in the case of Rb, $\text{f(}\text{1}\text{T}\text{)}$ is linear and the standard enthalpy and entropy of exchange reactions have been estimated by applying the Arrhenius relation.The distribution relations obtained between silicate and vapour phase permit the determination of distributions of Na, Rb and Cs between two minerals mI and mII, relative to K. These have been expressed with the partition ratio Q_x =$\text{(}\text{X}\text{K}\text{)}{}^{\mathrm{mI}}\text{(}\text{X}\text{K}\text{)}{}^{\mathrm{mII}}$. Variations of Q_x with T are not remarkable, and even for Rb between phlogopite and feldspar are negligible. Nevertheless, one may use the distributions of Rb and Cs between muscovite and feldspar for geothermometry. Experimental results have been applied to some rocks by effecting corrections from the major element composition of the natural minerals. Estimated temperatures are near to 400°C in the granites and pegmatite studied here.     

Experimentally determined partitioning of Rb between richterites and aqueous (Na, K)-chloride solutions

The distribution of Rb-Na and Rb-K between richterite and a 2-molal aqueous (Na, K, Rb)-chloride solution has been investigated with hydrothermal experiments at 800^∘C and 200 MPa. Experiments were performed as syntheses in which amphiboles grew in the presence of an excess fluid containing the exchangeable cations Na⁺-Rb⁺ or Na⁺-K⁺-Rb⁺. The obtained amphiboles were large enough (up to 20 m in width) for reliable EMP analysis. They were chemically homogeneous and HRTEM investigations showed that they were structurally well ordered. The Rb, Na, K, Ca and Mg concentrations in coexisting fluids were measured by ICP-AES. According to the possible incorporation of Na, K and Rb on the A-site, solid solutions in the ternary Na(NaCa) Mg₅[Si₈O₂₂/(OH)₂] (richterite)-K(NaCa)Mg₅[Si₈O₂₂/(OH)₂] (K-richterite)-Rb(NaCa)Mg₅[Si₈O₂₂/(OH)₂] (Rb-richterite) were expected. However, Rb-rich richterites always had significant amounts of A-site vacancy concentrations (X _□ ^amph=□ ^A /(Rb^A+K^A +Na^A+□^A) of up to 0.42 in the K-free (Na,Rb)-richterites and of up to 0.67 in the (Na, K, Rb)-richterites which corresponds to the same content of tremolite+cummingtonite-component. Amphiboles containing practically only Rb besides vacancies and no Na and/or K on the A-site were also synthesized, however. The Rb-Na and Rb-K exchange coefficients between fluid and richterites are similar. Rubidium always fractionated strongly into the fluid phase. For low Rb-concentrations in richterite (X _Rb ^amph<0.1) a linear correlation between X _Rb ^fluid and X _Rb ^amph exists. In this concentration range, the derived exchange coefficients K _D(Rb−K) ^amph−fluid and K _D(Rb−Na) ^amph−fluid were 0.08 ± 0.04 and 0.04 ± 0.02, respectively. These low exchange coefficients show that significant amounts of Rb in amphiboles require a Rb-rich fluid phase. The results indicate that K-Rb fractionation between alkali amphiboles and fluids is significantly different from K-Rb fractionation between alkali feldspar/ phlogopite and fluid, with K_Ds of about 0.5 and 1.2, respectively. Formation of richterites will drastically alter the K/Rb-ratios of fluids or melts. These results may have important implications for the genetical interpretation of various geological settings, e.g., MARID-type rocks. Received: 6 October 1997 / Accepted: 7 July 1998     

Ar and K partitioning between clinopyroxene and silicate melt to 8 GPa

The relative incompatibility of Ar and K are fundamental parameters in understanding the degassing history of the mantle. Clinopyroxene is the main host for K in most of the upper mantle, playing an important role in controlling the K/Ar ratio of residual mantle and the subsequent time-integrated evolution of ⁴⁰Ar/³⁶Ar ratios. Clinopyroxene also contributes to the bulk Ar partition coefficient that controls the Ar degassing rate during mantle melting. The partitioning of Ar and K between clinopyroxene and quenched silicate melt has been experimentally determined from 1 to 8 GPa for the bulk compositions Ab₈₀Di₂₀ (80 mol% albite-20 mol% diopside) and Ab₂₀Di₈₀ with an ultraviolet laser ablation microprobe (UVLAMP) technique for Ar analysis and the ion microprobe for K. Data for Kr (UVLAMP) and Rb (ion probe) have also been determined to evaluate the role of crystal lattice sites in controlling partitioning. By excluding crystal analyses that show evidence of glass contamination, we find relatively constant Ar partition coefficients (D_Ar) of 2.6 × 10⁻⁴ to 3.9 × 10⁻⁴ for the Ab₈₀Di₂₀ system at pressures from 2 to 8 GPa. In the Ab₂₀Di₈₀ system, D_Ar shows similar low values of 7.0 × 10⁻⁵ and 3.0 × 10⁻⁴ at 1 to 3 GPa. All these values are several orders of magnitude lower than previous measurements on separated crystal-glass pairs.D_K is 10 to 50 times greater than D_Rb for all experiments, and both elements follow parallel trends with increasing pressure, although these trends are significantly different in each system studied. The D_K values for clinopyroxene are at least an order of magnitude greater than D_Ar under all conditions investigated here, but D_Ar appears to show more consistent behavior between the two systems than K or Rb. The partitioning behavior of K and Rb can be explained in terms of combined pressure, temperature, and crystal chemistry effects that result in changes for the size of the clinopyroxene M2 site. In the Ab₂₀Di₈₀ system, where clinopyroxene is diopside rich at all pressures, D_K and D_Rb increase with pressure (and temperature) in an analogous fashion to the well-documented behavior of Na. For the Ab₈₀Di₂₀ system, the jadeite content of the clinopyroxene increases from 22 to 75 mol% with pressure resulting in a contraction of the M2 site. This has the effect of discriminating against the large K⁺ and Rb⁺ ions, thereby countering the effect of increasing pressure. As a consequence D_K and D_Rb do not increase with pressure in this system.In contrast to the alkalis (Na, K, and Rb), D_Kr values are similar to D_Ar despite a large difference in atomic radius. This lack of discrimination (and the constant D_Ar over a range of crystal compositions) is also consistent with incorporation of these heavier noble gases at crystal lattice sites and a predicted consequence of their neutrality or “zero charge.” Combined with published D_Ar values for olivine, our results confirm that magma generation is an efficient mechanism for the removal of Ar from the uppermost 200 km of the mantle, and that K/Ar ratios in the residuum are controlled by the amount of clinopyroxene. Generally, Ar is more compatible than K during mantle melting because D_Ar for olivine is similar to D_K for clinopyroxene. As a result, residual mantle that has experienced variable amounts of melt extraction may show considerable variability in time-integrated ³⁶Ar/⁴⁰Ar.     

Melting of hydrous pyroxenites with alkali amphiboles in the continental mantle: 2. Trace element compositions of melts and minerals

The trace element compositions of melts and minerals from high-pressure experiments on hydrous pyroxenites containing K-richterite are presented. The experiments used mixtures of a third each of the natural minerals clinopyroxene, phlogopite and K-richterite, some with the addition of 5% of an accessory phase ilmenite, rutile or apatite. Although the major element compositions of melts resemble natural lamproites, the trace element contents of most trace elements from the three-mineral mixture are much lower than in lamproites. Apatite is required in the source to provide high abundances of the rare earth elements, and either rutile and/or ilmenite is required to provide the high field strength elements Ti, Nb, Ta, Zr and Hf. Phlogopite controls the high levels of Rb, Cs and Ba.Since abundances of trace elements in the various starting mixtures vary strongly because of the use of natural minerals, we calculated mineral/melt partition coefficients (D_Min/melt) using mineral modes and melting reactions and present trace element patterns for different degrees of partial melting of hydrous pyroxenites. Rb, Cs and Ba are compatible in phlogopite and the partition coefficient ratio phlogopite/K-richterite is high for Ba (1 3 6) and Rb (12). All melts have low contents of most of the first row transition elements, particularly Ni and Cu ((0.1–0.01) × primitive mantle). Nickel has high D_Min/melt for all the major minerals (12 for K-richterite, 9.2 for phlogopite and 5.6 for Cpx) and so behaves at least as compatibly as in melting of peridotites. Fluorine/chlorine ratios in melts are high and D_Min/melt for fluorine decreases in the order apatite (2.2) > phlogopite (1.5) > K-richterite (0.87). The requirement for apatite and at least one Ti-oxide in the source of natural lamproites holds for mica pyroxenites that lack K-richterite. The results are used to model isotopic ageing in hydrous pyroxenite source rocks: phlogopite controls Sr isotopes, so that lamproites with relatively low ⁸⁷Sr/⁸⁶Sr must come from phlogopite-poor source rocks, probably dominated by Cpx and K-richterite. At high pressures (>4 GPa), peritectic Cpx holds back Na, explaining the high K₂O/Na₂O of lamproites.     

An absarokite from a phlogopite lherzolite source

An absarokite (SiO₂ 47.72 wt %, K₂O 3.41 wt %) occurs in the Katamata volcano, SW Japan. The rock carries phenocrysts of olivine, phlogopite, clinopyroxene, and hornblende. Chemical compositions of bulk rock (FeO^*/ MgO 0.73) and minerals (Mg-rich olivine and phlogopite, Cr-rich chromite) suggest that the absarokite is not differentiated. Melting experiments at high pressures on the Katamata absarokite have been conducted. The completely anhydrous absarokite melt coexists with olivine, orthopyroxene, and clinopyroxene at 1310° C and 1.0 GPa. The melt with 3.29 wt % of H₂O also coexists with the above three phases at 1230° C and 1.4 GPa; phlogopite appears at temperatures more than 80° C below the liquidus. On the other hand, the melt is not saturated with lherzolite minerals in the presence of 5.13 wt % of H₂O and crystallizes olivine and phlogopite as liquidus phases; the stability limit of phlogopite is little affected at least by the present variation of H₂O content in the absarokite melt. It is suggested that the absarokite magma was segregated from the upper mantle at 1170° C and 1.7 GPa leaving a phlogopite lherzolite as a residual material on the basis of the above experimental results and the petrographical observation that olivine and phlogopite crystallize at an earlier stage of crystallization sequence than clinopyroxene. The contribution of phlogopite at the stage of melting processes is also suggested by the geochemical characteristics that the absarokite is more enriched in Rb, K, and Ba and depleted in Ca and Na than a typical alkali olivine basalt from the same volcanic field.     

Mineralogy, Petrology, and Geochemistry of an Ultrapotassic Basaltic Suite, Central Sierra Nevada, California, U.S.A.

Ultrapotassic basaltic lavas erupted 3.4–3.6 m.y. ago(K/Ar) in the central Sierra Nevada and originated by partialmelting of a phlogopite-enriched, garnet-bearing upper mantlesource. Ultrapotassic basanites (K₂O: 5–9 per cent), whichare spatially related to contemporaneous potassic olivine basalts(K₂O: 3–5 per cent) and alkali olivine basalts (K₂O: 1–3per cent), contain the K₂O-bearing minerals phlogopite, sanidine,and leucite as well as olivine, diopside, apatite, magnetite,and pseudobrookite. The presence and modal abundance of theK₂O-bearing minerals closely reflects the east to west increasein K₂O throughout the basaltic suite. Many lines of evidence support the derivation of the ultrapotassicbasanites and the related basalts from an upper mantle source:TiO₂ in phlogopite phenocrysts and groundmass crystals, 2–3and 7–9 per cent respectively, support phlogopite phenocrystcrystallization at high pressure, whole rock Mg values (100Mg/Mg + 0.85 Fe) range from 66–78, phlogopite-rich pyroxeniticand periodotitic nodules are included in some flows, and geobarometriccalculations indicate depths of generation at 100–125km. Also, model calculations show that the major, rare earth,and trace elements, except for Ba, Rb, and Sr, can be accuratelygenerated by 1.0–2.5 per cent melting of a phiogopite-and garnet-bearing clinopyroxene-rich upper mantle source. Partialmelting occurred after a general upper mantle enrichment beneaththe Sierra Nevada, the phlogopite- and clinopyroxene-rich sourceof the ultrapotassic lavas being the extreme result of the enrichmentprocess. Clinopyroxene enrichment of the upper mantle probablyoccurred by introduction of a partial melting fraction intothe upper mantle source areas. Enrichment of the upper mantlein the alkali and alkali-earth elements was not accomplishedby a partial melt, but resulted from influx of a fluid phaserich in Ba, K, Rb, Sr, and, probably, H₂O The continuous rangein K₂O of the erupted lavas implies that the upper mantle enrichmentis a cumulative process. The inverse relationship in the SierraNevada between uplift and the K₂O content of the erupted basaltsimplies that a critical relationship may exist between upliftand upper mantle enrichment.     

Unique accessory Ti-Ba-P mineralization in the Kvalöya ultrapotassic dike,Northern Norway

Unusual ultrapotassic dikes were recently found on the Kvalöya Island in Northern Norway. The dikes crosscutting granites 1.8 Ga in age are 0.1–1.0 m thick and consist of phlogopite phenocrysts in a fine-grained groundmass of K-magnesioarfvedsonite, orthoclase, apatite, and secondary chlorite. According to the composition of the rock-forming minerals (4.5–6.0 wt % K₂O and 0.7–3.5 wt % TiO₂ in magnesioarfved-sonite, 1.6–3.6 wt % FeO in orthoclase, 9.2–10.7 wt % Al₂O₃ and 2.1–2.6 wt % TiO₂ in phlogopite) and its bulk chemical composition (K/Na = 2.3–2.9, K/Al = 1.0–1.2, (Na + K)/Al = 1.4–1.7, Mg# V = 65–73, (La/Yb) _n = 100–140, 3.2–4.0 wt % TiO₂, 0.55–1.47 wt % BaO, 2.5–3.0 wt % P₂O₅, 2650–3000 ppm Zr, 900–1260 ppm REE total, 2300–2500 ppm Sr), the rock corresponds to lamproite of the transitional type. The unique chemical composition of the rock resulted in uncommon Ti-Ba-P accessory mineralization, including baotite Ba₄(Ti,Nb)₈Si₄O₂₈Cl (up to 5 vol %), Sr-apatite (5–7 vol %), and previously unknown Na-Mg-Ba phosphate. Baotite forms anhedral elongated and isometric grains 10–500 μm in size. It is characterized by low Nb (0.03–0.05 f.c.); admixtures of K (0.04–0.12 f.c.) and Sr (0.04–0.07) replacing Ba and Fe (0.01–0.03 f.c.); and Al (0.03–0.04 f.c.) substituting Ti. Euhedral elongated zonal apatite crystals are extremely enriched in SrO (8–12 wt %) and REE₂O₃ + Y₂O₃ (6–9 wt %) in the marginal zone. Na-Mg-Ba phosphate occurs as prismatic grains 10–100 μm in size. The atomic ratio of its major cations Na: Mg: Ba: P ～ 2: 1: 1: 2 corresponds to the conventional formula Na₂MgBa(PO4)2; the mineral contains Sr, Mn, Fe, Ca, Si, and Al admixtures.     

Rubidium,strontium content and strontium isotopic composition of strongly alkalic basaltic rocks from the Cape Verde islands

The Cape Verde islands are characterized by the presence of very strongly alkalic lavas. Cenozoic volcanics—covering the broadest compositional range present in the archipelago—and ranging from alkali-basalts to phonolites, associated with plutonic essexites and nepheline syenites, were analyzed for Sr isotopic compositions and concentrations in K, Rb and Sr. The close values of the Sr⁸⁷/Sr⁸⁶ ratios (ranging from 0.7029 to 0.7033) indicate a comagmatic origin for the different rock types; no correlation appears between the Sr isotopic composition and the K-content of the lavas, thus indicating that the lavas with high K₂O/K₂O + Na₂O ratio are generated from a primary magma by differentiation at shallow depths. The values of the Sr isotopic composition are distinctly lower than most values obtained for lavas of other oceanic islands. The origin of the magma type is discussed on the basis of these isotopic compositions and the K/Rb and Rb/Sr ratios: it is suggested that the primary magma has a nephelinitic composition and was formed by partial melting of a small fraction of undepleted mantle peridotite, containing phlogopite; the deeper part of the mantle where this nephelinitic magma generates would have a strontium isotopic ratio of about 0.703 and a Rb/Sr ratio lower than that of the upper part.     

X-ray diffraction study of Fe2+-Mg order-disorder in orthopyroxene. Some kinetic results

Kinetic rates of Fe²⁺-Mg disordering in three orthopyroxenes (mean value of X_Fe = Fe²⁺/(Fe²⁺+Mg) = 0.175,0.482,0.770 respectively) have been determined employing heating experiments and single crystal X-ray structural refinements. Disordering rate constants \((\vec K)\) (550800° C) for two pyroxenes are given by: ln \((\vec K)\) = 27.107(±5.177)?32062(±783)T^?1(X_Fe = 0.175) ln \((\vec K)\) = 16.142(±0.057)?18227(±423)T^?1(X_Fe = 0.770) The distribution coefficients K_D (representing a steady state of disordering Fe_M2 + Mg_M1 ? Fe_M1 + Mg_M2) are given by: ln K_D = 5.016(±0.223)-7033(±1473) T^?1(X_Fe = 0.175) ln K_D = 1.988(±0.122)-3809(±913)T^?1(X_Fe = 0.770) These distribution coefficients provide the constraint of the disordering reaction on the value of the equilibrium constant for Fe²⁺-Mg order-disorder. Until the low temperature dependence of K_D is well constrained, the calculation of cooling rates of pyroxenes and host rocks cannot be done reliably.     

Conditions of diamond growth: a proton microprobe study of inclusions in West Australian diamonds

Crystalline primary inclusions in diamonds from the Argyle and Ellendale lamproites have been analyzed for Mn, Ni, Cu, Zn, Ga, Pb, Rb, Sr, Y, Zr, Nb, Ta, Ba and Mo by proton microprobe. Eclogite-suite inclusions dominate at Argyle and occur in equal proportions with peridotite-suite inclusions at Ellendale. Eclogitic phases present include garnet, omphacitic clinopyroxene, coesite, rutile, kyanite and sulfide. Eclogitic clinopyroxenes are commonly rich in K and contain 300–1060 ppm Sr and 3–70 ppm Zr: K/Rb increases with K content up to 1400 at 0.7–1.1% K. Rutiles have high Zr and Nb contents with Zr/Nb=1.5–4 and Nb/Ta 16. Of the peridotite-suite inclusions, olivine commonly contains > 10 ppm Sr and Mo; Cr-pyropes are depleted in Sr, Y and Zr, and enriched in Ni, relative to eclogitic garnets.Eclogite-suite diamonds grew in host rocks that were depleted in Mn, Ni and Cr, and enriched in Sr, Zn, Cu, Ga and Ti, relative to Type I eclogite xenoliths from the Roberts Victor Mine. Crystallization temperatures of the eclogite-suite diamonds, as determined by coexisting garnet and clinopyroxene from single diamonds, range from 1085 to 1575° C. Log K _D (C _i ^cpx /C _i ^gnt ) varies linearly with 1/T for Zr, Sr and Ga in most of the same samples. This supports the validity of the temperature estimates; Argyle eclogite-suite diamonds have grown over a T range 400° C. Comparison with data from eclogite xenoliths in kimberlites suggests that K _D ^Sr and K _D ^Zr are mainly T-dependent, while K _D ^Ga may be both temperature-and pressuredependent. K _D ^Ni , K _D ^Cu and K _D ^Zn show no T dependence in these samples.In several cases, significant major-and/or trace-element disequilibrium is observed between different grains of the same mineral, or between pyroxene and garnet, within single diamonds. This implies that these diamonds grew in an open system; inclusions trapped at different stages of growth record changes in major and trace-element composition occurring in the host rock. Diamond growth may have been controlled by a fluid flux which introduced or liberated carbon and modified the composition of the rock. The wide range of equilibration temperatures and the range of composition recorded in the inclusions of single diamonds suggest that a significant time interval was involved in diamond growth.     

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).     

Geochemistry of micas from the Finero spinel-lherzolite,Italian Alps

The Finero lherzolite is distinct amongst the tectonically emplaced slices of mantle in the Ivrea Zone (Italian Alps) for its abundant coarse phlogopite. An average composition (SiO₂ 39.9, TiO₂ 0.97, Al₂O₃ 16.0, Cr₂O₃ 1.16, FeO 2.73, MgO 24.5, NiO 0.16, BaO 0.31, Na₂O 0.58, K₂O 8.7, Rb₂O 0.056, Cl 0.03, F 0.10 wt.%) is similar in Fe, Cr, Ni, Ba and F/Cl to primary-textured micas from coarse garnet-lherzolite xenoliths from S. Africa, but is higher in Ti, Na, Rb, and Al, and lower in halogens. The distinct values of Ti and Fe for five specimens of Finero peridotites demonstrate local spatial variation. The overall ranges of TiO₂ (0.5–1.7) and FeO (2.3–3.6) fall within the range for secondary-textured micas in peridotite xenoliths from S. Africa. The Finero micas are lower in both K/Rb and K/Ba than the primary and secondary micas from S. Africa, and their mean values of K/Rb (110–220) and K/Ba (15–39) are lower than for almost all bulk rocks, but fit well with the ranges of 109–180 and 12–49 for the high-K lavas of the Roman region.Although all evidence is indicative rather than conclusive, the chemical properties of the Finero micas are consistent with introduction of an alkaline phase into peridotite during or before emplacement of the Finero complex from the upper mantle into the crust, and the coarse, partly-deformed textures can be explained by incomplete metamorphic equilibration during prolonged deformation. The alkaline phase is tentatively attributed to the uppermost mantle.     

Thallium-rich murunskite from the Lovozero pluton,Kola Peninsula,and partitioning of alkali metals and thallium between sulfide minerals

A new thallium-rich variety of murunskite has been found in the Palitra peralkaline pegmatite at Mount Kedykverpakhk, the Lovozero alkaline pluton, Kola Peninsula, Russia. This mineral occurs as a flattened dark bronze segregation (0.3 × 0.8 × 0.8 mm) overgrowing ussingite in a cavity. The chemical composition is as follows, wt %: 8.35 K, 24.31 Tl, 29.01 Cu, 14.58 Fe, 23.26 S, total is 99.51. The empirical formula is (K_1.18Tl_0.66)_1.84(Cu_2.53Fe_1.45)_3.98S_4.02. According to X-ray powder diffraction data, the dimensions of the tetragonal unit cell are: a = 3.869 (1), c = 13.206 (6) Å, V = 197.7 (2) ų. This variety is the closest to the intermediate member of the murunskite-thalcusite series. The youngest mineral complex of the Palitra Pegmatite includes four sulfides belonging to three different structure types. These sulfides also may be regarded as three topological types distinguished by the arrangement of alkali metal atoms in their structures: (1) bartonite and chlorbartonite belonging to the zero-dimensional topological type with K atoms in isolated cells, (2) pautovite pertaining to the one-dimensional type with Cs (+Rb, K, Tl) atoms making up chains in ample tunnels, and (3) murunskite belonging to the two-dimensional type with K (+Tl) atoms forming sheets. There is pronounced partitioning of K (Cs + Rb) and Tl between these sulfides: bartonite and chlorbartonite contain 9.5–9.7 wt % K and 0.2 wt % Tl; pautovite, 36.1 wt % Cs, 1.3 wt % Rb, 0.5 wt % Tl, and 0.2 wt % K; and murunskite, 8.35 wt % K and 24.31 wt % Tl.     

Diffusion of Na,K, Rb and Cs in glasses of albite and orthoclase composition

The measurement of diffusion coefficients for Na, K, Rb and Cs has been realized by the technique of active salt deposits on glasses of albite and orthoclase composition, at normal pressure and in the temperature range 300–1000°C. The values of D are between 10^?6 and 10^?12 cm² s^?1 and, for every type of run, they vary with temperature according to Arrhenius laws, with activation energies ranging from 13 to 68 kcal mole^?1. These important variations are related to the size of the diffusing element (at 700°C in albite glass D_Na/D_K/D_RbD_Cs ～- 10⁷/10⁵/10³/1) and to the size of the major alkali element (for rubidium at 800°C D_or·gl/D_ab·gl ～- 20). By comparison with available data on diffusion in feldspars, we emphasize the influence of the defect density on the diffusion process.     

Strontium and hydrogen isotope geochemistry of fresh and metabasalt dredged from the Mid-Atlantic Ridge

Fresh basalt and metabasalt dredged from the Mid-Atlantic Ridge were studied for Na, K, Rb, Sr, and H₂O(+) contents, and strontium and hydrogen isotope ratios. Na, K, Rb, and Sr contents of these samples are within the range of those of oceanic tholeiite. H₂O(+) content, strontium, and hydrogen isotope ratios vary widely. The variation in water content of metabasalt is apparently related to the chlorite content. The metamorphic temperature was about 550 °C based on the estimated δD value of chlorite. There is positive linear relationship between water content and strontium isotope ratio. Based on this relationship, the variation of strontium isotope ratio of the metabasalt was interpreted as follows: complete exchange occurred between strontium in the chlorite portion of the metabasalt and strontium in sea water (⁸⁷Sr/⁸⁶Sr ratio=0.7090), while the original strontium (⁸⁷Sr/⁸⁶Sr∼0.7023) was retained in the non-altered portion of the basalts.     

Petrology of Lamproites from Smoky Butte, Montana

Hyalo-armalcolite-phlogopite lamproites and sanidine-phlogopitelamproites occurring at Smoky Butte, Montana are rocks formedfrom rapidly quenched, high temperature, uncontaminated lamproiticmagma. Petrographic variations are attributable to differentcooling histories of several batches of compositionally identicalmagma. Compared with other occurrences of lamproite, the rocksare unusually rich in TiO₂ and are characterized by the presenceof abundant armalcolite and the most TiO₂-rich phlogopites yetfound in this paragenesis. Compositional data are given fortitanian phlogopite, olivine, diopside, titanian potassian richterite,armalcolite, sanidine, analcite, and glass. The mafic mineralsare Al-deficient and exhibit very little compositional variation.Original leucite has been pseudomorphed by sanidine or analcite.The latter mineral was probably formed at the same time thatthe glass lost K, and gained Na, during alteration by groundwater.All of the lamproites are strongly enriched in Ta, Hf, and thelight REE (La /Yb = 162–280), and have high MgO and Crcontents. Mineralogical, geochemical, and previously publishedisotopic data are combined in developing a petrogenetic modelwhich suggests that these lamproites were derived from an ancient(2.5 Ga) doubly metasomatized harzburgitic source, and thatthey represent relatively primitive lamproites which were intrudedat near-liquidus temperatures.     

Geochemistry and petrogenesis of acid volcano-plutonic rocks of the Siner area, Siwana Ring Complex, Northwestern Peninsular India

Petrochemical studies on acid plutonic (granite, microgranite) and volcanic (rhyolite, trachyte) rocks occurring in the Siner area of the Siwana Ring Complex, Malani Igneous Suite have been carried out. These rocks are characterized by high concentrations of SiO₂, Na₂O, K₂O, Zr, Nb, Y and REE (except Eu) but low in MgO, Fe₂O₃(t), CaO, Cr, Ni, Sr; indicating their A-type affinity. Field studies in conjunction with the geochemical characteristic indicate that the magmatism in the Siner area is generally represented by peralkaline suite of rocks which are formed due to rift tectonics. It is also suggested that these acidic rocks could have been derived by low degree partial melting of crustal material. Characteristics of certain pathfinder elements such as Rb, Ba, Sr, K, Zr, Nb, REE and the ratios of K/Rb, Zr/Rb, Ba/Rb along with the multi elemental primitive mantle normalized spidergrams suggest that the Siner peralkaline granites and microgranites have the potential for rare metal and rare earth mineralizations.     

First Evidence of Lamprophyric Magmatism from the Konya Region,Turkey: a Genetic Link to High-K Volcanism

In the vicinity of Konya （Turkey）,mafic,micro-porphyritic sub-volcanic rocks intrude into the Mesozoic units,which represents the only example of such a rock type in the region.40Ar/39Ar dating of two whole rock samples from the sub-volcanics gave ages of 13.72±0.13 and 12.40±0.11 Ma,suggesting temporal association to the Late Miocene-Pliocene high-K calc-alkaline volcanism in the region.The mineral chemistry and geochemical data permit us to classify the rocks as ＂minette＂ lamprophyres.They include diopside and phlogopite phenocrysts in a microcrystalline groundmass composed of sanidine,phlogopite,diopside and titano-magnetite.Segregation and ocelli-like globular structures occur commonly in the samples.In terms of major elements,the lamprophyres are calcalkaline,and potassic to ultrapotassic rocks.All the lamprophyres display strong enrichments in LILE （Rb,Ba,K,Sr）,radiogenic elements （Th,U） and LREE （La,Ce） and prominent negative Nb,Ta,and Ti anomalies on primordial mantle-normalized trace element diagrams.Geochemical data suggest that the lamprophyres and high-K calc-alkaline rocks in the region derived from a subduction-modified lithospheric mantle source affected by different metasomatic events.Lamprophyric magmatism sourced phlogopite-bearing veins generated by sediment-related metasomatism via subduction,but high-K calc-alkaline magmas are possibly derived from a mantle source affected by fluid-rich metasomatism.