Subduction-related Late Cretaceous high-K volcanism in the Central Pontides orogenic belt: constraints on geodynamic implications

Mineral chemistry, major and trace elements, ⁴⁰Ar/³⁹Ar age and Sr–Nd–Pb isotopic data are presented for the Late Cretaceous Hamsilos volcanic rocks in the Central Pontides, Turkey. The Hamsilos volcanic rocks mainly consist of basalt, andesite and associated pyroclastics (volcanic breccia, vitric tuff and crystal tuff). They display shoshonitic and high-K calc-alkaline affinities. The shoshonitic rocks contain plagioclase, clinopyroxene, alkali feldspar, phlogopite, analcime, sanidine, olivine, apatite and titanomagnetite, whereas the high-K calc-alkaline rocks contain plagioclase, clinopyroxene, orthopyroxene, magnetite / titanomagnetite in microgranular porphyritic, hyalo-microlitic porphyritic and glomeroporphyritic matrix. Mineral chemistry data reveal that the pressure condition of the clinopyroxene crystallisation for the shoshonitic rocks are between 1.4 and 6.3 kbar corresponds to 6–18-km depth and the high-K calc-alkaline rocks are between 5 and 12 km. ⁴⁰Ar/³⁹Ar age data changing between 72 ± .5 Ma and 79.0 ± .3 Ma (Campanian) were determined for the Late Cretaceous Hamsilos volcanic rocks, contemporaneous with the subduction of the Neo-Tethyan Ocean beneath the Pontides. The studied volcanic rocks were enriched in the large-ion lithophile and light rare earth element contents, with pronounced depletion in the contents of high-field-strength elements. Chondrite-normalised rare earth element patterns (La_N/Lu_N = 6–17) show low to medium enrichment, indicating similar sources of the rock suite. Initial ⁸⁷Sr/⁸⁶Sr values vary between .70615 and .70796, whereas initial ¹⁴³Nd/¹⁴⁴Nd values change between .51228 and .51249. Initial ²⁰⁶Pb/²⁰⁴Pb values vary between 18.001 and 18.349, ²⁰⁷Pb/²⁰⁴Pb values between 15.611 and 15.629 and ²⁰⁸Pb/²⁰⁴Pb values between 37.839 and 38.427. The main solidification processes involved in the evolution of the volcanic rocks consist of fractional crystallisation, with minor amounts of crustal contamination ± magma mixing. According to geochemical evidence, the shoshonitic melts in the Hamsilos volcanic rocks were possibly derived from the low degree of partial melting of a subcontinental lithospheric mantle (SCLM), while the high-K calc-alkaline melts were derived from relatively high degree of partial melting of SCLM that was enriched by fluids and/or sediments from a subduction of oceanic crust.     

Granulite-facies metabasite ejecta in the Laacher See area,Eifel, West Germany

Near the village of Engeln, Laacher See area, garnet-bearing pyriclasite and pyribolite ejecta were recognized as constituents of alkaline basaltic tuffs; they are interpreted as fragments of the lowermost crust. During the first main stage of granulite facies metamorphism, assemblages with garnet (Alm₄₇Pyr₃₄Spess₂Gross + Andr₁₇), clinopyroxene (Wo₃₇En₃₅Fs₁₅Ts_8.5Jd_4.5), orthopyroxene I (En₃₄Fs₃₈Ts₄Jd₂), and plagioclase I (An₄₀-An₆₀) were formed in a temperature range of 730–850°C and rock pressures somewhere between 6.5 and 12 kb, $\text{P}{}_{\mathrm{tot}}\text{>}\text{P}{}_{\mathrm{<mtext>H</mtext>}}{}_2\text{O}\text{> 0}$. The rare sulfate-rich meionite, and at least a part of the ubiquitous brown hornblende were presumably also formed during this stage. A retrograde metamorphic event under slightly lower pressures and temperatures led to the breakdown of the assemblage garnet + clinopyroxene thereby forming coronas of plagioclase II $\text{(}\text{An}{}_{75}\text{) +}\text{orthopyroxene}\text{II +}\text{Ti-magnetite}\text{±}\text{brown hornblende}$.     

Pyroxene geothermometry and geobarometry: experimental and thermodynamic evaluation of some subsolidus phase relations involving pyroxenes in the system CaO-MgO-Al2O3-SiO2

One petrogenetic grid for plagioclase-, spinel- and garnet-lherzolite analogues in the system CaO-MgO-Al₂O₃-SiO₂ is presented from 1 bar to 30 kbar and 400 to 1500°C. Another grid for olivine-gabbro, spinel-gabbro and garnet-pyroxenite analogues in the same system is presented from 1 bar to 25 kbar and 500 to 1500°C. Both grids show the distribution of the mineral assemblages and the variations in the composition of clinopyroxene with temperature and pressure. They were developed by applying simple thermodynamic mixing models of clinopyroxene to experimentally determined clino-pyroxene compositions.Calcium tschermak's pyroxene (CaAl₂SiO₆) in complex CaMgSi₂O₆-CaAl₂SiO₆-Mg₂Si₂O₆ clinopyroxenes is best represented by a local charge balance mixing model where Enthalpy and entropy changes of subsolidus reactions involving variations in the CaAl₂SiO₆ and Mg₂Si₂O₆ content of clinopyroxene are interdependent due to nonideal mixing of these two end-members. CaAl₂SiO₆ can strongly reduce the mutual solubility of clinopyroxene and orthopyroxene at moderate pressures and high temperatures. Failure to take this into account can result in temperature underestimates (up to 150°C) of spinel-lherzolites, garnet-pyroxenites, low pressure garnet-lherzolites, spinel-gabbros, and high pressure plagioclase-lherzolites and olivine-gabbros. However, at temperatures and pressures where the Al₂O₃ content of clinopyroxene is low (e.g. garnet-lherzolite nodules in kimberlite), the mutual solubility is adequantely represented by experimental results in the system CaO-MgO-SiO₂.     

Volatiles in submarine volcanic rocks from the Mariana Island arc and trough

High temperature mass spectrometric analyses of glasses from quenched pillow rims of andesites dredged from 1170 m water depth in the northern portion of the Mariana Island arc indicate substantially less H₂O (~ 1 wt.%) and more CO₂ (~ 0.24 wt.%) than previously reported for volcanic arc rocks. Glass-vapor inclusions within plagioclase phenocrysts from quenched rims have $\text{CO}{}_2\text{H}{}_2\text{O}$ ratios of 1:1. These results are similar to analyses of basaltic samples from the Mariana Trough (a back-arc basin). Generally, F and Cl contents are higher and S lower in the arc rocks compared to the samples from the back-arc basin. These results favor models for the production of island arc magmas which involve melting of the subducted slab, rather than just melting of the overlying mantle wedge because of the high volatile content needed to produce island arc magmas from peridotite (10–15 wt.%). The trough samples, although similar in non-volatile composition to mid-ocean ridge rocks, have much higher H₂O. somewhat higher CO₂ and lower S contents. Either near surface addition of voiatiles has enriched the magmas or H₂O must be a more important component in the generation and evolution of back-arc basin lavas than in the genesis of mid-ocean ridge basalts.     

Geochemistry and petrogenesis of lamproites,late cretaceous age,Woodson County,Kansas, U.S.A.

Lamproite sills and their associated sedimentary and contact metamorphic rocks from Woodson County, Kansas have been analyzed for major elements, selected trace elements, and strontium isotopic composition. These lamproites, like lamproites elsewhere, are alkalic (molecular $\text{K}{}_2\text{O + Na}{}_2\text{O}\text{Al}{}_2\text{O}{}_3\text{= 1.6–2.6}$), are ultrapotassic $\text{(}\text{K}{}_2\text{O}\text{Na}{}_2\text{O}\text{= 9.6–150)}$, are enriched in incompatible elements (LREE or light rare-earth elements, Ba, Th, Hf, Ta, Sr, Rb), and have moderate to high initial strontium isotopic compositions (0.7042 and 0.7102). The silica-saturated magma (olivine-hypersthene normative) of the Silver City lamproite could have formed by about 2 percent melting of a phlogopite-garnet lherzolite under high $\text{H}{}_2\text{O}\text{CO}{}_2$ ratios in which the Iherzolite was enriched before melting in the incompatible elements by metasomatism. The Rose Dome lamproite probably formed in a similar fashion although the extreme alteration due to addition of carbonate presumably from the underlying limestone makes its origin less certain. Significant fractional crystallization of phases that occur as phenocrysts (diopside, olivine, K-richterite, and phlogopite) in the Silver City magma and that concentrate Co, Cr, and Sc are precluded as the magma moved from the source toward the surface due to the high abundances of Co, Cr, and Sc in the magma similar to that predicted by direct melting of the metasomatized Iherzolite.Ba and, to a lesser extent, K and Rb and have been transported from the intrusions at shallow depth into the surrounding contact metamorphic zone. The Silver City lamproite has vertical fractionation of some elements due either to volatile transport or to variations in the abundance of phenocrysts relative to groundmass most probably due to flow differentiation although multiple injection or fractional crystallization cannot be conclusively rejected.     

The role of CO2 in the chemical modification of deep continental crust

Compositional differences between granulite facies rocks and equivalent amphibolite facies rocks and the observation of CO₂-rich fluid inclusions in granulites, have led to the suggestion that CO₂ must play a role in modifying the composition of deep continental crust. How CO₂ effects this change has remained unclear. Using the thermodynamic properties of aqueous ions in a fluid of evolving $\text{CO}{}_2\text{H}{}_2\text{O}$ ratio, it is possible to model the incongruent dissolution of feldspars under conditions appropriate for granulite facies metamorphism. The results demonstrate that dissolution will be strongly enhanced at high $\text{CO}{}_2\text{H}{}_2\text{O}$ ratios, with ion solubilities being Na⁺ >K⁺ ? Ca⁺⁺. This enhancement is compatible with the reported compositional contrasts between granulite and amphibolite facies rock, but requires large fluid volumes.To test the dissolution model, a detailed field and petrologic study was conducted in a well exposed granulite facies terrane in West Greenland. Strong correlation between fluid composition and bulk rock chemistry can be documented; CO₂-rich regions contain rocks which consistently have low ratios, while H₂O-rich regions consistently have high ratios. Magnetite rims on sulfide grains are ubiquitous in high regions and are absent in high regions, and they provide evidence that CO₂ was introduced into the region. These correlations and observations are predictable from the properties of the dissolution process. These considerations, along with observations regarding graphite petrogenesis, provide strong arguments that the total fluid volume interacting with the rock during metamorphism was very large, in some cases equaling or exceeding total rock volume. Such large fluid volumes can lead to significant compositional modification of the crust, and will mask the original protolith chemistry. Such processes should lead to Ca- and Al-enriched, Na-, K-, S- and Si-depleted residues in the deep crust.     

The petrology and tectonic setting of Quaternary—Recent volcanic centres of Lombok and Sumbawa,Sunda arc

In the Sunda arc, only the Bali—Lombok—Sumbawa sector is apparently flanked both north and south by oceanic crust. South of Lombok Island the oceanic crust is probably of Early Cretaceous or Late Jurassic age, whereas the oldest rocks known from Lombok and Sumbawa islands are the Lower Miocene to Pliocene sediments and volcanics of the basement beneath the Quaternary—Recent volcanic centres.Three large active volcanoes form the northern parts of Lombok and Sumbawa. The volcanic rocks of Rindjani on Lombok belong to a basalt—andesite—dacite association, rich in plagioclase and hy- and Q-normative. East of Lombok, the volcanic rocks of Tambora and Sangeang Api on Sumbawa belong to a potassic ne—trachybasalt—trachy-andesite association. All three volcanoes occur only 150–190 km above the active north-dipping Benioff zone.Extinct Quaternary centres occur south of the active volcanoes on Sumbawa. Two of these centres, Soromundi and Sangenges, erupted markedly ne- and lc-normative leucitites together with andesites, dacites and trachybasalts.The volcanic composition—space—time relations in the Lombok—Sumbawa sector of the Sunda arc are not in accordance with the generalized island-arc schemata. Conventionally, potassic ne-mnormative island-arc associations are supposed to occur over the deep part of the Benioff zones, far from the trenches of mature island arcs. The SiO₂|K₂O relations of the Rindjani association are reasonably appropriate for a volcano overlying intermediate Benioff-zone depths, but both the Tambora and the Sangeang Api associations are far more potassic than would be predicted by generalized schemata, and also occur in a relatively young arc sector that apparently has developed only since Miocene time.Basalts, trachybasalts and leucitites from the Lombok—Sumbawa sector have been compared: at similar MgO contents and Mg/(Mg+Fe), the progression from hy- and Q-normative to ne- and lc-normative magmas is not marked by significant enrichment in TiO₂, Na₂O, Zr, Nb and P, but is accompanied by a substantial increase in K₂O, Rb, Sr and LREE, by increasing $\text{K}{}_2\text{O}\text{Na}{}_2\text{O}$ and by decreasing K/Rb.${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios from Rindjani (0.70386–0.70402) and Tambora (0.70385–0.70389) are very similar and among the lowest for the Sunda arc, but from Sangeang Api (0.70460–0.70500) are significantly higher and more variable in spite of the similar tectonic setting and petrological affinities. ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios of leucities tend to be higher (0.70488–0.70529).The petrogenesis of the volcanic associations of Lombok and Sumbawa cannot be readily explained. Although even the leucitites display the poverty in TiO₂ that generally characterizes volcanics from simple island-arc tectonic settings, there is very obvious uncoupling within the “incompatible elements”: enrichment in the LIL group (K, Rb, Sr but not Na) is not accompanied by similar behaviour in the group of small highly-charged ions (Ti, Zr, Nb, P). It has proved impossible to model this behaviour without invoking inhomogeneities in the source regions, both in mineralogy and in chemical composition. Similar uncoupling within the incompatible elements has also been reported from basalt groups from the Mid-Atlantic Ridge, may also occur in the Birunga province, and might not arise from processes unique to the island-arc environment.We suggest that a LIL-rich component is being progressively added to the source regions. This component could be incorporated by the crystallization of additional phases such as phlogopite or paragasite. If this component occurs deep within the mantle, it might gain passage to shallower regions either by percolating up the downgoing slab to yield the familiar arc magma zonation, or up substantial cross-arc fractures.     

Concentrations,sources, and losses of H2O,CO2, and S in Kilauean basalt

Basaltic glasses included in olivine phenocrysts from Kilauea volcano contain concentrations of H₂O, CO₂, and S similar to glassy Kilauean basalt dredged from the deep sea floor and greater than vesicular, subaerial Kilauean basalt. Our result contrasts with earlier reports that inclusions of basaltic glass in phenocrysts have little or no H₂O and large ratios of $\text{CO}{}_2\text{H}{}_2\text{O}$. Our analysed inclusions of glass are larger than 100 micrometers thick and similar in chemical composition to the host glass surrounding the olivine crystals indicating that the trapped melts are representative of the bulk liquid from which the crystals grew. Crystallization of about 2–8% of olivine from the melts after they were trapped is indicated by slight departures from the experimentally established equilibrium distribution of Mg and Fe between olivine and liquid. The measured concentrations of CO₂ correspond to phenocryst crystallization pressures of about 1.3 kbar for a subaerial basalt and about 5 kbar for a submarine basalt, consistent with geophysical models of Kilauea volcano. The compositions of volcanic gas predicted from our analyses are consistent with restored compositions of actual Kilauean gases. The rate of sulfur emission predicted from our analyses is greater than the sulfur dioxide emission rate observed during repose, but probably consistent with total degassing including eruptive episodes. The concentrations of H₂O, K₂O, Cl, and P in parental Kilauean basalt can be derived from upper mantle phlogopitic mica, pargasitic amphibole and apatite with compositions close to those of natural primary minerals in ultramafic xenoliths from continental kimberlites, or solely from apatite and phlogopitic mica with $\text{H}{}_2\text{O}\text{K}{}_2\text{O}$ near 0.47 ± 0.03, slightly higher than the range of values reported. The amounts of phlogopitic mica and pargasitic amphibole contributing volatiles to Kilauean tholeiite is about 10 percent by mass of the parental liquid, or about 5% if the source does not include amphibole. In view of an estimated 20% of partial melting of mantle source rock to produce Kilauean tholeiites, there may be about 2 weight percent of mica plus amphibole in part of the mantle beneath Kilauea, or about 1 weight percent of phlogopitic mica if amphibole is absent.     

Serpentinization of cumulate ultramafic rocks from the North Arm Mountain massif of the Bay of Islands ophiolite

Partially serpentinized dunites and wehrlites comprise the bulk of the cumulate ultramafic unit at the North Arm Mountain massif of the Bay of Islands ophiolite complex, Newfoundland. In a suite of 59 dunites and werhlites from the base of the unit, the serpentinized portions consist of lizardite + chrysotile + brucite + (accessory) magnetite. The ratio of $\text{(}\text{lizardite}\text{+}\text{chrysotile}\text{)}\text{to brucite}\text{= ~8:2 (}\text{weight percent}\text{)}$. Petrographic observations show that most serpentinization occurred at the expense of olivine; only limited amounts of clinopyroxene were serpentized. An estimated volume increase of 32% accompanied serpentinization of the peridotites. Reconstructions of the primary modal proportions of wehrlites (made taking this volume increase into account) contain an average of 6% more clinopyroxene and 6% less olivine than do modal reconstructions that ignore the volume increase. Mass balance calculations provide no clear evidence for appreciable metasomatism of Al₂O₃, CaO, FeO, MgO, or SiO₂ during Serpentinization. The presence of brucite, the evidence that most serpentinization occurred at the expense of olivine, and the lack of appreciable metasomatism, suggest that the primary reaction that controlled serpentinization of the peridotites is: $\text{2Mg}{}_2\text{SiO}{}_2\text{+ 3H}{}_2\text{O ? Mg}{}_3\text{Si}{}_2\text{O}{}_5\text{(OH)}{}_4\text{+ Mg(OH)}{}_2$. olivine added serpentine brucite     

Kiglapait Geochemistry III: Potassium and Rubidium

The regular geometry and completeness of the Kiglapait intrusion permit its bulk composition to be obtained by summation, and the composition of successive liquids to be obtained by subtraction. The summations for K and Rb give 1806 and 1.08 ppm, yielding Rfrsol|K/Rb= 1670 for the intrusion, taken as equal to the parent magma. R increases slightly from this initial value to 2000 at the end of crystallization where MgO approaches zero in the rocks. K and Rb are therefore closely coherent and their distribution coefficients can differ only by a small amount in the Kiglapait system.Apparent feldspar/liquid distribution coefficients (D^F/L) can be estimated from detailed plots of feldspar and liquid compositions against F_L. The Kiglapait data imply that these coefficients are linear 1:1 functions of plagioclase composition within experimental error, having values given by D_KF/L = 1.42? X_AnD_RbF/L = 1.13? X_An with minimum values of 0.75 and 0.49, respectively. The ratio $\text{R}{}^{\mathrm{F}}\text{R}{}^{\mathrm{L}}$ lies in the range of 1.53± 0.03 for the plagioclase composition range X_An= 0.34 to 0.67 showing that high-R rocks such as anorthosite crystallized from high-R liquids.The apparent feldspar distribution coefficients are much closer to 1.0 than common literature values. They can be reduced by assuming that the cumulate pile was continuously recharged by the circulating magma until an advanced stage of differentiation was reached, and assuming that alkalies were exchanged to the feldspars from the magma. When such an ‘aquifer recharge’ model is calibrated using olivine-liquid equilibria as a time marker for the liquid, the inferred minimum equilibrium values of the distribution coefficients are $\text{D}{}_{\mathrm{K}}\text{F}\text{L}$= 0.42, $\text{D}{}_{\mathrm{Rb}}\text{F}\text{L}$ = 0.25 at the base of the intrusion. Their variation is given by $\text{D}{}_{\mathrm{K}}\text{F}\text{L}\text{= 1.66?1.88X}{}_{\mathrm{An}}$, $\text{D}{}_{\mathrm{Rb}}\text{F}\text{L}\text{= 1.17?1.41X}{}_{\mathrm{An}}$, The equilibrium values are considered to be appropriate for deducing liquid compositions in plutonic bodies where alkali exchange can be shown or inferred to have been inhibited, such as in small intrusions. The apparent values are considered to be appropriate, even though they may be artificial, for large intrusions similar to the Kiglapait.The bulk K and Rb concentrations in the Kiglapait intrusion are consistent with a plagioclase-rich abyssal tholeiite magma. Clinopyroxene and olivine fractionation in the mantle may contribute to the production of such high-Rmagmas.     

The Archaean Marda igneous complex,Western Australia

The Marda complex is a sequence of andesitic to dacitic to rhyolitic volcanic rocks filling a synformal structure in submarine basalt, banded iron-formation and siliceous sediments in the Archaean Yilgarn Block of Western Australia. The Marda volcanic rocks are in part subaerial and exhibit calc-alkaline chemistry. Their Rb/Sr age is 2635 ± 80 m.y. with an initial $\text{Sr}{}^{87}\text{Sr}{}^{86}$ ratio of 0.7029 ± 0.0015. The Marda lavas represent products of a differentiated late to syn-tectonic, anatectic magma derived from the base of the Archaean crust. Calc-alkaline volcanic complexes are uncommon in the Yilgarn Block.     

Characteristics and tectonic setting of the shoshonite rock association

A review of the major occurrences of shoshonitic rocks suggests there is a group that is near-silica saturated, K-rich and has low iron enrichment that cannot be unambigously classified as part of calc-alkaline or alkali-basalt associations. This group is here referred to as the shoshonite rock association. The shoshonite rock association is characterised by: hypersthene-olivine normative basalts, low iron enrichment, high Na₂O + K₂O, high content of light ion lithophile elements, high but variable Al₂O₃, high Fe₂O₃/FeO and low TiO₂. Mineralogical characteristics include: coexisting plagioclase and sanidine in the groundmass, K-feldspar rims on plagioclase phenocrysts, plagioclase An_50?85 Ab_40?15 Or_10?0 and low TiO₂ content and lack of iron enrichment in clinopyroxene. Shoshonitic rocks on continental margins are younger, stratigraphically higher and more distant from the oceanic trench than the high-K calc-alkaline or calc-alkaline suites, but there is a complete gradation between the suites. A similar zonation occurs in some island arcs. In other island arcs there is no spatial zonation of the suites but successively more K-rich lavas are produced above an ever steepening subduction zone. Steepening leads to ‘failure’ or flipping of the subduction zone and uplift and block faulting within the arc. Shoshonitic rocks are most commonly associated with this phase of island are development.     

M and Mg values in igneous rocks: proposed usage and a comment on currently employed Fe2O3 corrections

It is proposed that the ‘M value’ of an igneous rock should be 100Mg/(Mg + ΣFe) and that the ‘Mg value’ should be 100Mg/(Mg + Fe²⁺). A plea is made to standardize any necessary corrections for Fe₂O₃ so that $\text{Fe}{}_2\text{O}{}_3\text{(Fe}{}_2\text{O}{}_3\text{+ FeO)}\text{= 02}$ for basic rocks.     

Geochemical modelling of basalts from DSDP Leg 65, East Pacific Rise,Gulf of California

Major and rare earth element (REE) data for basalts from Holes 483, 483B, and 485A of DSDP Leg 65, East Pacific Rise, mouth of the Gulf of California, support a simple fractional crystallization model for the genesis of rocks from this suite. The petrography and mineral chemistry (presented in detail elsewhere) provide no evidence for magma mixing, but rather a simple multistage cooling process. Based on its lowest TiO₂ content (0.88%), $\text{FeO}{}^1\text{MgO}$ ratio (0.95 with total Fe as FeO), and Mg# (100 $\text{Mg}\text{Mg + Fe}\text{″ = 70}$), sample 483-17-2-(78–83) has been selected as the most primitive primary magma of the samples analyzed. This is supported by the REE data which show this sample has the lowest total REE content, a $\text{La}\text{Sm}{}_{\mathrm{cn}}$ (chondrite-normalized) = 0.36, and $\text{Eu}\text{Sm}{}_{\mathrm{cn}}$ = 1.05. Because other samples analyzed have higher SiO₂, lower Mg#, and a negative Eu anomaly ($\text{Eu}\text{Sm}{}_{\mathrm{cn}}$ as low as 0.89), they are most likely derivative magmas. Wright-Doherty and trace element modelling support fractional crystallization of 14.1% plagioclase (An₈₈), 6.7% olivine (Fo₈₆), and 4.7% clinopyroxene (Wo₄₁En₄₉Fs₁₀) from 483-17-2-(78–83) to form the least differentiated sample with Mg# = 63. The $\text{La}\text{Sm}{}_{\mathrm{cn}}$ of this derivative magma is almost identical to the parent magma (0.35 to 0.36), but the other samples have higher $\text{La}\text{Sm}{}_{\mathrm{cn}}$ (0.45 to 0.51), more total REE, and lower Mg# (60 to 56). Both Wright-Doherty and trace element modelling indicate that the primary magma chosen cannot produce these more evolved samples. For the major elements, the TiO₂ and P₂O₅ are too low in the calculated versus the observed (1.38 to 1.90; 0.11 to 0.17, respectively, for example). Rayleigh fractionation calculates a lower $\text{La}\text{Sm}{}_{\mathrm{cn}}$ and requires about 60% crystal removal versus 40% for the Wright-Doherty. These more evolved samples must be derived from a parent magma different from the one selected here and, unfortunately, not sampled in this study. A magma formed by a smaller degree of partial melting with slightly more residual clinopyroxene left in the mantle than for sample 483-17-2-(78–83) is required.     

Distribution coefficients of Eu and Sr for plagioclase-liquid and clinopyroxene-liquid equilibria in oceanic ridge basalt: an experimental study

The distribution coefficients of Eu and Sr for plagioclase-liquid and clinopyroxene-liquid pairs as a function of temperature and oxygen fugacity were experimentally investigated using an oceanic ridge basalt enriched with Eu and Sr as the starting material. Experiments were conducted between 1190° and 1140°C over a range of oxygen fugacities between 10^?8 and 10^?14 atm.The molar distribution coefficients are given by the equations: log^PL_Sr = 7320/T ? 4.62logK^CPX_Sr = 18020/T ? 13.10. Similarly, the weight fraction distribution coefficients are given by the equations: logD^PL_Sr = 6570/T ? 4.30logD^CPX_Sr = 18434/T ? 13.62.Although the mole fraction distribution coefficients have a smaller dependence on bulk composition than do the weight fraction distribution coefficients, they are not independent of bulk composition, thereby restricting the application of these experimental results to rocks similar to oceanic ridge basalts in bulk composition.Because the Sr distribution coefficients are independent of oxygen fugacity, they may be used as geothermometers. If the temperature can be determined independently — for example, with the Sr distribution coefficients, the Eu distribution coefficients may be used as oxygen geobarometers. Throughout the range of oxygen fugacities ascribed to terrestrial and lunar basalts, plagioclase concentrates Eu but clinopyroxene rejects Eu.     

Rutile solubility and titanium coordination in silicate melts

The solubility of rutile has been determined in a series of compositions in the K₂O-Al₂O₃-SiO₂ system ($\text{K}{}^1\text{=}\text{K}{}_2\text{O}\text{(K}{}_2\text{O}$ + Al₂O₃) = 0.38–0.90), and the CaO-Al₂O₃-SiO₂ system ($\text{C}{}^1\text{=}\text{CaO}\text{(CaO + Al}{}_2\text{O}{}_3\text{)}\text{= 0.47–0.59}$). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the $\text{K}{}^1$ ratio. For example, at 1475°C the amount of TiO₂ required for rutile saturation varies from 9.5 wt% ($\text{K}{}^1\text{= 0.38}$) to 11.5 wt% ($\text{K}{}^1\text{= 0.48}$) to 41.2 wt% ($\text{K}{}^1\text{= 0.90}$). In the CAS system at 1475°C, rutile solubility is not a strong function of $\text{C}{}^1$. The amount of TiO₂ required for saturation varies from 14 wt% ($\text{C}{}^1\text{= 0.48}$) to 16.2 wt% ($\text{C}{}^1\text{= 0.59}$).The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K⁺ in excess of that needed to charge balance Al³⁺. The suggested stoichiometry of this complex is K₂Ti₂O₅ or K₂Ti₃O₇. In CAS melts, the data suggest that Ca²⁺ in excess of A1³⁺ is not as effective at complexing with Ti as is K⁺. The greater solubility of rutile in CAS melts when $\text{C}{}^1$ is less than 0.54 compared to KAS melts of equal $\text{K}{}^1$ ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K).TiK_β x-ray emission spectra of KAS glasses ($\text{K}{}^1\text{= 0.43–0.60}$) with 7 mole% added TiO₂, rutile, and Ba₂TiO₄, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba₂TiO₄, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules.     

Geochemistry of Archean metasedimentary rocks from West Greenland

Archean metasedimentary rocks occur as components of the Isua supracrustals, Akilia association and Malene supracrustals of southern West Greenland. Primary structures in these rocks have been destroyed by metamorphism and deformation. Their chemistry and mineralogy is consistent with a sedimentary origin, but other possible parents (e.g. acid volcanics, altered pyroclastic rocks) cannot be excluded for some of them. There is little difference in the composition of metasedimentary rocks from the early Archean Isua supracrustals and probable correlative Akilia association. Both have a wide range in rare earth element (REE) patterns with $\text{La}{}_{\mathrm{<mtext>N</mtext>}}\text{Yb}{}_{\mathrm{<mtext>N</mtext>}}$ ranging from 0.61?5.8. The REE pattern of one Akilia sample, with low $\text{La}{}_{\mathrm{<mtext>N</mtext>}}\text{Yb}{}_{\mathrm{<mtext>N</mtext>}}$, compares favourably with that of associated tholeiites and it is likely that such samples were derived almost exclusively from basaltic sources. Other samples with very steep REE patterns are similar to felsic volcanic boulders found in a conglomeratic unit in the Isua supracrustals. Samples with intermediate REE patterns are best explained by mixing of basaltic and felsic end members. Metasedimentary rocks from the Malene supracrustals can be divided into low silica (≤55% SiO₂) and high silica (>77% SiO₂) varieties. These rocks also show much variation in $\text{La}{}_{\mathrm{<mtext>N</mtext>}}\text{Yb}{}_{\mathrm{<mtext>N</mtext>}}$ (0.46?14.0) and their origin is explained by derivation from a mixture of mafic volcanics and felsic igneous rocks. The wide range in trace element characteristics of these metasedimentary rocks argues for inefficient mixing of the various source lithologies during sedimentation. Accordingly, these data do not rigorously test models of early Archean crustal composition and evolution. The systematic variability in trace element geochemistry provides evidence for the bimodal nature of the early Archean crust.     

An unusual basalt fragment in Luna 20 sample L2010

A Luna 20 basaltic fragment contains 70 per cent pyroxene, 25 per cent plagioclase (An₈₀) and 5 per cent ilmenite. There are two varieties of augite which differ markedly in their alumina content. The composition of this fragment, calculated from the analyses of the minerals, shows that the $\text{Al}{}_2\text{O}{}_3\text{FeO}$ ratio is different from that of other lunar basalts.