Geochemical and geo-electrical study of mud pools at the Mutnovsky volcano (South Kamchatka,Russia): Behavior of elements,structures of feeding channels and a model of origin

This study presents data on the geochemical composition of boiling mud pools at the Mutnovsky volcano. The physicochemical characteristics of the pools and the concentrations of major, minor and trace elements in pool solutions vary widely. A comparison of the geochemical compositions of host rocks and solutions indicates that leaching from rocks is not the only source of chemicals in thermal solutions. Geophysical studies reveal the inner structure of thermal fields, which reflect the shapes of the underground reservoirs and feed channels. Using geophysical methods (electrical resistivity tomography and frequency domain investigations), it was shown that the vertical structure and complex geochemical zonation of the feed channels leads to a high contrast in the compositions of the mud solutions. These findings answer questions about the origin and composition of surface manifestations. To elucidate the mechanisms of solution formation, an attempt was made to describe the magmatic fluid evolution and the resulting mixing of waters by physical and mathematical models. The model illustrates fluid migration from a magma chamber to the surface. It is shown that the formation of brines corresponding to the mud pool composition is possible during secondary boiling.     

Drastic shift in lava geochemistry in the volcanic-front to rear-arc region of the Southern Kamchatkan subduction zone: Evidence for the transition from slab surface dehydration to sediment melting

The shift of lava geochemistry between volcanic front to rear-arc volcanoes in active subduction zones is a widespread phenomenon. It is somehow linked to an increase of the slab surface depth of the subducting oceanic lithosphere and increasing thickness of the mantle wedge and new constraints for its causes may improve our understanding of magma generation and element recycling in subduction zones in general. As a case study, this paper focuses on the geochemical composition of lavas from two adjacent volcanic centres from the volcanic front (VF) to rear-arc (RA) transition of the Southern Kamchatkan subduction zone, with the aim to examine whether the shift in lava geochemistry is associated with processes in the mantle wedge or in the subducted oceanic lithosphere or both. The trace element and O-Sr-Nd-Hf-Pb (double-spike)-isotopic composition of the mafic Mutnovsky (VF) and Gorely (RA) lavas in conjunction with geochemical modelling provides constraints for the degree of partial melting in the mantle wedge and the nature of their slab components. Degrees of partial melting are inferred to be significantly higher beneath Mutnovsky (∼18%) than Gorely (∼10%). The Mutnovsky (VF) slab component is dominated by hydrous fluids, derived from subducted sediments and altered oceanic crust, eventually containing minor but variable amounts of sediment melts. The composition of the Gorely slab component strongly points to a hydrous silicate melt, most likely mainly stemming from subducted sediments, although additional fluid-contribution from the underlying altered oceanic crust (AOC) is likely. Moreover, the Hf-Nd-isotope data combined with geochemical modelling suggest progressive break-down of accessory zircon in the melting metasediments. Therefore, the drastic VF to RA shift in basalt chemistry mainly arises from the transition of the nature of the slab component (from hydrous fluid to melt) in conjunction with decreasing degrees of partial melting within ∼15 km across-arc. Finally, systematic variations of key inter-element with high-precision Pb-isotope ratios provide geochemical evidence for a pollution of the Mutnovsky mantle source with Gorely melt components but not vice versa, most likely resulting from trench-ward mantle wedge corner flow. We also present a geodynamic model integrating the location of the Mutnovsky and Gorely volcanic centres and their lava geochemistry with the recently proposed thermal structure of the southern Kamchatkan arc and constraints about phase equilibria in subducted sediments and AOC. Herein, the slab surface hosting the subducted sediments suffers a transition from dehydration to melting above a continuously dehydrating layer of AOC. Wider implications of this study are that an onset of (flush-) sediment melting may ultimately be the main trigger for the VF to RA transition of lava geochemistry in subduction zones.     

Mud volcano gas hydrates in the Gulf of Cadiz

ABSTRACT This paper presents new geochemical data on gas-hydrate-bearing mud volcanoes discovered for the first time in the Gulf of Cadiz during cruises TTR9 and TTR10 of the R/V Professor Logachev in 1999–2000. The estimated gas hydrate content is 3–16% of sediment volume and 5–31% of pore space volume. Estimated values of the water isotopic composition for the Ginsburg mud volcano are very heavy for δ¹⁸O (up to +53‰) and light for δD (up to − 210‰). Gas released from the hydrates contains 81% of C₁ and 19% of C₂₊. The inferred source of the gas in the hydrates is enriched in C₂–C₆ (≤ 5%), indicating that the gas has a thermogenic origin. Gas hydrate of cubic structure II should be formed from a gas of such composition. It is interpreted that the composition of the mud volcano fluid corresponds to deep oil basins below the Gulf of Cadiz.     

Geochemical Constraints on Possible Subduction Components in Lavas of Mayon and Taal Volcanoes, Southern Luzon, Philippines

Mayon is the most active volcano along the east margin of southernLuzon, Philippines. Petrographic and major element data indicatethat Mayon has produced a basaltic to andesitic lava seriesby fractional crystallization and magma mixing. Trace elementdata indicate that the parental basalts came from a heterogeneousmantle source. The unmodified composition of the mantle wedgeis similar to that beneath the Indian Ocean. To this mantlewas added a subduction component consisting of melt from subductedpelagic sediment and aqueous fluid dehydrated from the subductedbasaltic crust. Lavas from the highly active Taal Volcano onthe west margin of southern Luzon are compositionally more variablethan Mayon lavas. Taal lavas also originated from a mantle wedgemetasomatized by aqueous fluid dehydrated from the subductedbasaltic crust and melt plus fluid derived from the subductedterrigenous sediment. More sediment is involved in the generationof Taal lavas. Lead isotopes argue against crustal contamination.Some heterogeneity of the unmodified mantle wedge and differencesin whether the sediment signature is transferred into the lavasource through an aqueous fluid or melt phase are needed toexplain the regional compositional variation of Philippine arclavas. KEY WORDS: Mayon Volcano; Philippines; sediment melt; subduction component; Taal Volcano     

An estimate of gas emissions and magmatic gas content from Kilauea volcano

Emission rates of CO₂ have been measured at Kilauea volcano, Hawaii, in the east-rift eruptive plume and CO₂ and SO₂ have been measured in the plume from the noneruptive fumaroles in the summit caldera. These data yield an estimate of the loading of Kilauean eruptive gases to the atmosphere and suggest that such estimates may be inferred directly from measured lava volumes. These data, combined with other chemical and geologic data, suggest that magma arrives at the shallow summit reservoir containing (wt.%) 0.32% H₂O, 0.32% CO₂ and 0.09% S. Magma is rapidly degassed of most of its CO₂ in the shallow reservoir before transport to the eruption site. Because this summit degassing yields a magma saturated and in equilibrium with volatile species and because transport of the magma to the eruption site occurs in a zone no shallower than the summit reservoir, we suggest that eruptive gases from Kilauea characteristically should be one of two types: a ‘primary’ gas from fresh magma derived directly from the mantle and a carbon-depleted gas from magma stored in the summit reservoir.     

Preliminary estimate of CO2 output from Pantelleria Island volcano (Sicily,Italy): evidence of active mantle degassing

Total CO₂ output from fumaroles, bubbling and water dissolved gases and soil gases was investigated at Pantelleria Island volcano, Italy. The preliminary results indicate an overall output of 0.39 Mt a⁻¹ of CO₂ from the island. The main contribution to the total output was from diffuse soil degassing (about 0.32 Mt a⁻¹), followed by dissolved CO₂ (0.034 Mt a⁻¹), focussed soil degassing (0.028 Mt a⁻¹) and bubbling CO₂ (0.013 Mt a⁻¹). The contribution of CO₂ from fumarole gases was found to be negligible (1.4×10⁻⁶ Mt a⁻¹). Carbon-13 values for CO₂ coupled with those for associated He in gases from fumaroles and sites of focussed soil degassing clearly rule out any significant organic CO₂ component and suggest a common mantle origin for these gas species. The inferred mantle source beneath Pantelleria would seem to have peculiar geochemical characteristics, quite distinct from those of mantle producing MORB but compatible with those of magmatic sources of central Mediterranean and central European volcanoes. These findings indicate that the Pantelleria volcanic complex is a site of active mantle degassing that is worthy of attention for future geochemical surveillance of the island.     

Vector analysis of chemical variation in the lavas of Parícutin volcano,Mexico

Compositional variations in the lavas of Parícutin volcano, Mexico, have been examined by an extended method of Q-mode factor analysis. Each sample composition is treated as a vector projected from an original eight-dimensional space into a vector system of three dimensions. The compositions represented by the vectors after projection are closely similar to the original compositions except for Na₂Oand Fe₂O₃.The vectors in the three-dimensional system cluster about three different planes that represent three stages of compositional change in the Parícutin lavas. Because chemical data on the compositions of the minerals in the lavas are presently lacking, interpretations of the mineral phases that may have been involved in fractional crystallization are based on CIPW norm calculations. Changes during the first stage are attributed largely to the fractional crystallization of plagioclase and olivine. Changes during the second stage can be explained by the separation of plagioclase and pyroxene. Changes during the final stage may have resulted mostly from the assimilation of a granitic material, as previously proposed by R. E. Wilcox.     

High pressure phase relations of primitive high-alumina basalts from Medicine Lake volcano,northern California

Anhydrous phase relations were determined at 1 atm and 10 to 15 kbar for primitive high-alumina basalts (79–35g and 82–72f) from Giant Crater at Medicine Lake volcano. These compositions are multiply saturated with olivine+augite+plagioclase+spinel+/-orthopyroxene near the liquidus at about 11 kbar. Experiments on mixtures of sample 79–35g with orthopyroxene and olivine determined the location of the multiple saturation boundaries where liquid coexists with the assemblage olivine+augite+orthopyroxene+plagioclase at 10 kbar and olivine+augite+orthopyroxene+spinel at 15 kbar. The mix experiments showed that primitive Medicine Lake high alumina basalts (HABs) are close in composition to liquids in equilibrium with a mantle lherzolite source containing olivine+augite+ orthopyroxene+spinel+plagioclase at 11 kbar. Orthopyroxene observed as a near liquidus phase in an 11 kbar experiment on sample 82–72f supports this conclusion. The most primitive HABs from Medicine Lake are low in K₂O (0.07 wt.%), high in MgO (>10 wt.%) and Ni (231 ppm), and have light-rare earth element depletions and large ion lithophile element enrichments. A model for the origin of these near-primary high-alumina basalts is that they are partial melts of a MORB-like mantle lherzolite source that has been enriched by a fluid component derived from the subducted slab. The HAB magma segregated from its mantle residue just below the base of the crust near the crust-mantle boundary.     

P-wave tomography and origin of the Changbai intraplate volcano in Northeast Asia

We present the first seismic image of the upper mantle beneath the active intraplate Changbai volcano in Northeast Asia determined by teleseismic travel time tomography. The data are measured at a new seismic network consisting of 19 portable stations and 3 permanent stations. Our results show a columnar low-velocity anomaly extending to 400-km depth with a P-wave velocity reduction of up to 3%. High velocity anomalies are visible in the mantle transition zone, and deep-focus earthquakes occur at depths of 500–600 km under the region, suggesting that the subducting Pacific slab is stagnant in the transition zone, as imaged clearly by global tomography. These results suggest that the intraplate Changbai volcano is not a hotspot like Hawaii but a kind of back-arc volcano related to the deep subduction and stagnancy of the Pacific slab under Northeast Asia.     

Magmatic inclusions in phenocrystals from andesitic lavas,Krakatau volcano,Indonesia

There is a great number of magmatic inclusions in different types of phenocrystals in andesitic lavas from the Krakatau volcano, Indonesia. Sequence of crystallization (from early to late) has been established for the phenocrystals on the basis of homogenization temperatures and chemical compositions of the magmatic inclusions: the cantral phase of plagioclase phenocrystals (An 83.2–72.6), olivine→ the intermediate phase of plagioclase phenocrystals (An 61.3), clinopyroxene, titanomagnetite→ the peripheral phase of plagioclase phenocrystals (An 54.4–42.6). The crystallization of the central phase of plagioclase phenocrystals takes place in the depth of magma chamber at about 5 Kbar. High pressures and high titanium contents favor the silicate-liquid immiscibility in the magmatic inclusions of early plagioclase phenocrystals. This is typical of many andesitic lavas generated in subduction regions.     

The emergence of a Galápagos shield volcano, Roca Redonda

Roca Redonda volcano is a mostly submarine shield volcano that rises nearly 3 km from the adjacent seafloor. Over twenty lava flows and palagonite tuff are exposed in a 60 meter high oblong outcrop above sea level, and several other flows are exposed in the shallow water surrounding the islet. Thick, slightly alkaline picritic flows form the base of the section. Thinner picrites interbedded with sparsely porphyritic alkali-olivine basaltic pahoehoe toes characterize the upper section. The subaerial section probably records the filling of a palagonite tuff cone with younger lavas. Numerous fumaroles that may have a magmatic component are present in the shallow (<30 m) submarine zone and indicate that the volcano is probably still active. Three lava types are exposed: the basal picrites with 19% > MgO > 14%, high-Mg basalts with MgO of about 9%, and low-Mg basalts with MgO of about 6%. The Sr and Nd isotopic ratios of the three lava types are within analytical uncertainty. Olivine compositions indicate that the picrites are basaltic liquids that have accumulated olivine whose composition is in equilibrium with the host basaltic liquid. Apparently, basaltic magmas percolated through dunite and troctolite that had crystallized from slightly older Roca Redonda basaltic magma. Lavas from Roca Redonda have enriched trace element contents and isotopic ratios relative to nearby Wolf volcano, but they are quite similar to lavas from Cerro Azul and Ecuador volcanoes. The common characteristic of these volcanoes is that they lie on the periphery of the archipelago and are in a stage of subaerial growth. This suggests that Galápagos volcanoes may go through a juvenile alkaline stage before a mature tholeiitic stage, analogous to the Loihi stage of Hawaiian volcanism. A low ³He/⁴He ratio in olivine from one of the picrites indicates a small contribution by the Galápagos mantle plume. Received: 15 December 1997 / Accepted: 6 May 1998     

Petrogenesis of a voluminous Quaternary adakitic volcano: the case of Baru volcano

The origin of adakite magmas remains controversial because initially the term adakite had petrogenetic significance implying an origin by direct melting of the eclogitized subducting oceanic crust. Many models have been produced for their origin, and until now there has not been a straightforward method to discriminate between these models in a given adakite suite. Here, we use detailed chronological and geochemical studies of selected adakitic edifices that allows for the determination of the magmatic output rate parameter (Qe), which has been correlated with the rates of magma generation deep within subduction zones. By providing temporal and eruption rate estimates, we provide constraints on the possible petrogenetic processes involved in the generation of adakite-like signatures. Adakite magmas derived from the melting of the subducting slab should be volumetrically insignificant when compared to the adakite-like magmas produced by typical arc magma generation processes. In this study, we use this observation and the extraordinary stratigraphic exposure from Miocene to present in an adakitic volcano in Panama and to study the temporal and chemical variation in erupted magmas to estimate rates of magma generation. Detailed chemical and geochronological analyses of Baru volcano indicate that the volcanic edifice was constructed in its entirety during the Quaternary and magmas display adakite-like features such as steep rare earth elements patterns, pronounced depletions in the heavy rare earth elements, low Y, high Sr, and high Sr/Y. The magmatic output rates (Qe) that we have calculated show that compared to other typical adakitic volcanoes, most of the volcanic edifice of Baru volcano was constructed extremely rapidly (<~213 k.a.) and in time frames that are similar to typical arc volcanoes. The observed chemical and mineralogical variation, coupled with the high magma production rates, indicate that Baru volcano is more representative of a typical arc volcano than a small-volume melt of the subducting oceanic crust. The technique we outline may have broader application in determining the petrogenetic conditions of other adakite suites.     

The origin and evolution of the parental magmas of frontal volcanoes in Kamchatka: Evidence from magmatic inclusions in olivine from Zhupanovsky volcano

The paper presents data on naturally quenched melt inclusions in olivine (Fo 69–84) from Late Pleistocene pyroclastic rocks of Zhupanovsky volcano in the frontal zone of the Eastern Volcanic Belt of Kamchatka. The composition of the melt inclusions provides insight into the latest crystallization stages (∼70% crystallization) of the parental melt (∼46.4 wt % SiO₂, ∼2.5 wt % H₂O, ∼0.3 wt % S), which proceeded at decompression and started at a depth of approximately 10 km from the surface. The crystallization temperature was estimated at 1100 ± 20°C at an oxygen fugacity of ΔFMQ = 0.9–1.7. The melts evolved due to the simultaneous crystallization of olivine, plagioclase, pyroxene, chromite, and magnetite (Ol: Pl: Cpx: (Crt-Mt) ∼ 13: 54: 24: 4) along the tholeiite evolutionary trend and became progressively enriched in FeO, SiO₂, Na₂O, and K₂O and depleted in MgO, CaO, and Al₂O₃. Melt crystallization was associated with the segregation of fluid rich in S-bearing compounds and, to a lesser extent, in H₂O and Cl. The primary melt of Zhupanovsky volcano (whose composition was estimated from data on the most primitive melt inclusions) had a composition of low-Si (∼45 wt % SiO₂) picrobasalt (∼14 wt % MgO), as is typical of parental melts in Kamchatka and other island arcs, and was different from MORB. This primary melt could be derived by ∼8% melting of mantle peridotite of composition close to the MORB source, under pressures of 1.5 ± 0.2 GPa and temperatures 20–30°C lower than the solidus temperature of “dry” peridotite (1230–1240°C). Melting was induced by the interaction of the hot peridotite with a hydrous component that was brought to the mantle from the subducted slab and was also responsible for the enrichment of the Zhupanovsky magmas in LREE, LILE, B, Cl, Th, U, and Pb. The hydrous component in the magma source of Zhupanovsky volcano was produced by the partial slab melting under water-saturated conditions at temperatures of 760–810°C and pressures of ∼3.5 GPa. As the depth of the subducted slab beneath Kamchatkan volcanoes varies from 100 to 125 km, the composition of the hydrous component drastically changes from relatively low-temperature H₂O-rich fluid to higher temperature H₂O-bearing melt. The geothermal gradient at the surface of the slab within the depth range of 100–125 km beneath Kamchatka was estimated at 4°C/km.     

Constraints on the source of Cu in a submarine magmatic-hydrothermal system,Brothers volcano,Kermadec island arc

Most magmatic-hydrothermal Cu deposits are genetically linked to arc magmas. However, most continental or oceanic arc magmas are barren, and hence new methods have to be developed to distinguish between barren and mineralised arc systems. Source composition, melting conditions, the timing of S saturation and an initial chalcophile element-enrichment represent important parameters that control the potential of a subduction setting to host an economically valuable deposit. Brothers volcano in the Kermadec island arc is one of the best-studied examples of arc-related submarine magmatic-hydrothermal activity. This study, for the first time, compares the chemical and mineralogical composition of the Brothers seafloor massive sulphides and the associated dacitic to rhyolitic lavas that host the hydrothermal system. Incompatible trace element ratios, such as La/Sm and Ce/Pb, indicate that the basaltic melts from L’Esperance volcano may represent a parental analogue to the more evolved Brothers lavas. Copper-rich magmatic sulphides (Cu?>?2 wt%) identified in fresh volcanic glass and phenocryst phases, such as clinopyroxene, plagioclase and Fe–Ti oxide suggest that the surrounding lavas that host the Brothers hydrothermal system represent a potential Cu source for the sulphide ores at the seafloor. Thermodynamic calculations reveal that the Brothers melts reached volatile saturation during their evolution. Melt inclusion data and the occurrence of sulphides along vesicle margins indicate that an exsolving volatile phase extracted Cu from the silicate melt and probably contributed it to the overlying hydrothermal system. Hence, the formation of the Cu-rich seafloor massive sulphides (up to 35.6 wt%) is probably due to the contribution of Cu from a bimodal source including wall rock leaching and magmatic degassing, in a mineralisation style that is hybrid between Cyprus-type volcanic-hosted massive sulphide and subaerial epithermal–porphyry deposits.     

Silica and volatile-element metasomatism of Archean mantle: a xenolith-scale example from the Kaapvaal Craton

Textural evidence in a composite garnet harzburgite mantle xenolith from Kimberley, South Africa, suggests metasomatism of a severely melt-depleted substrate by a siliceous, volatile-rich fluid. The fluid reacted with olivine-rich garnet harzburgite, converting olivine to orthopyroxene, forming additional garnet and introducing phlogopite, and small quantities of sulfide and probable carbonate. Extensive reaction (>50%) forming orthopyroxenite resulted from channelized flow in a vein, with orthopyroxene growth in the surrounding matrix from a pervasive grain-boundary fluid. The mineralogy of the reaction assemblage and the bulk composition of the added component dominated by Si and Al, with lesser quantities of K, Na, H, C and S, are consistent with experimental studies of hybridization of siliceous melts or fluids with peridotite. However, low Na, Fe and Ca compared with melts of eclogite suggest a fluid phase that previously evolved by reaction with peridotitic mantle. Garnet and phlogopite trace element compositions indicate a fluid rich in large-ion lithophile (LIL) elements, but poor in high field-strength elements (HFSE), qualitatively consistent with subduction zone melts and fluids. An Os isotope (T_RD) model age of 2.97 ± 0.04 Ga and lack of compositional zonation in the xenolith indicate an ancient origin, consistent with proposed 2.9 Ga subduction and continental collision in the Kimberley region. The veined sample reflects the silicic end of a spectrum of compositions generated in the Kimberley mantle lithosphere by the metasomatizing effects of fluids derived from oceanic lithosphere. These results provide petrographic and chemical evidence for fluid-mediated Si-, volatile- and trace-element metasomatism of Archean mantle, and support models advocating large-scale modification of regions of Archean subcontinental mantle by subduction processes that occurred in the Archean.     

A petrological and geochemical study on time-series samples from Klyuchevskoy volcano,Kamchatka arc

To understand the generation and evolution of mafic magmas from Klyuchevskoy volcano in the Kamchatka arc, which is one of the most active arc volcanoes on Earth, a petrological and geochemical study was carried out on time-series samples from the volcano. The eruptive products show significant variations in their whole-rock compositions (52.0–55.5 wt.% SiO₂), and they have been divided into high-Mg basalts and high-Al andesites. In the high-Mg basalts, lower-K and higher-K primitive samples (>9 wt.% MgO) are present, and their petrological features indicate that they may represent primary or near-primary magmas. Slab-derived fluids that induced generation of the lower-K basaltic magmas were less enriched in melt component than those associated with the higher-K basaltic magmas, and the fluids are likely to have been released from the subducting slab at shallower levels for the lower-K basaltic magmas than for higher-K basaltic magmas. Analyses using multicomponent thermodynamics indicates that the lower-K primary magma was generated by ~13% melting of a source mantle with ~0.7 wt.% H₂O at 1245–1260?°C and ~1.9 GPa. During most of the evolution of the volcano, the lower-K basaltic magmas were dominant; the higher-K primitive magma first appeared in AD 1932. In AD 1937–1938, both the lower-K and higher-K primitive magmas erupted, which implies that the two types of primary magmas were present simultaneously and independently beneath the volcano. The higher-K basaltic magmas evolved progressively into high-Al andesite magmas in a magma chamber in the middle crust from AD 1932 to ~AD 1960. Since then, relatively primitive magma has been injected continuously into the magma chamber, which has resulted in the systematic increase of the MgO contents of erupted materials with ages from ~AD 1960 to present.     

Carbon and helium isotopic ratios at Kusatsu-Shirane Volcano,Japan

We have measured the chemical compositions, He/Ne ratios, He and C isotopes of 14 gas samples collected from the crater lake, fumaroles and hot springs associated with Kusatsu-Shirane Volcano, Japan. The³He/⁴He ratio decreases with increasing distance from the central crater of the volcano to the sampling site whereas the δ¹³C value of CO₂ increases with the distance. This tendency suggests that high³He/⁴He-low δ¹³C magmatic gas is mixed with and/or diluted by low³He/⁴He-high δ¹³C crustal gas with increasing distance from the crater. Alternatively, the variation of δ¹³C values may be the result of isotope fractionation during migration since the isotope shift is relatively small. Based on the apparent mixing trend in a³He/⁴He-δ¹³C diagram, the magmatic He and CO₂ in the volcano may have a³He/⁴He ratio of 8 R_atm and a δ¹³C value of −3.2%, respectively. The CO₂/³He ratios show a positive correlation with temperature of fumaroles or hot springs, which may be caused by a difference of temperature dependencies of the solubilities between CO₂ and He.     

Multi-stage mixing in subduction zones: Application to Merapi volcano (Java island, Sunda arc)

Many studies have argued for the contribution of at least three components, namely the mantle wedge, the subducted oceanic crust, and its sediment cover, to describe the geochemistry of island arc volcanics. However, isotope correlations reflecting a simple binary mixing can be observed at the scale of a single arc island or volcano. Here we investigate the possibility that these trends reflect pseudo-binary mixing relationships in a three-component system. We present a simplified, two-stage model for the systematic isotope modelling of a cogenetic suite of arc lavas. This includes metasomatism of portions of the mantle wedge by hydrous phases released from the down-going oceanic crust, and sediments, followed by progressive mixing and melting. A consequence of this model is that it leads to a two end-member mixing process from the mantle wedge, oceanic crust, and sediment components. To solve the model we reduce it to a step-by-step procedure combined with a Monte-Carlo simulation. The procedure consists of: (i) producing a large number of random values on each variable of the model; (ii) using the computed values to calculate the isotopic compositions of lavas; and (iii) comparing the obtained isotopic compositions with measured data. Applied to a new set of Sr, Nd, and Pb isotope data for volcanics (basalts, basaltic andesites, trachybasalts, and basaltic trachyandesites) from Merapi volcano (Java island, Sunda arc), the model successfully reproduces the binary mixing relationships previously documented for the medium-K and high-K lava series from this volcano, thus giving further support to the hypothesis that this distinction is inherited from the primary magmas and primarily reflects a property of the mantle source. The results allow identification of a set of numerical values for bulk partition coefficients (solid/hydrous fluid, and solid/H₂O-rich melt) and variables (e.g., the mass ratio between the metasomatizing phase and the mantle wedge), which can be used for quantitative arc-lava petrogenetic calculations. They also require a direct relationship between dehydration of the slab and melting of the metasomatized mantle wedge. Finally, our evaluation shows that for isotope modelling of the Merapi lavas, the two-stage procedure is controlled more by the considered source components (mantle wedge, oceanic crust, sediments, and their derivatives) than by the various processes involved (dehydration, melting, and mixing).     

Sources of unique rhenium enrichment in fumaroles and sulphides at Kudryavy volcano

Rhenium (Re) is one of the least abundant elements in Earth, averaging 0.28 ppb in the primitive mantle. The unique occurrence of rheniite ReS₂ (74.5 wt% of Re) in Kudryavy volcano precipitates raises questions about recycling of Re-rich reservoirs within the Kurile-Kamchatka volcanic Island arc setting. The sources of this unique Re enrichment have been inferred from studies of Re-Os isotope systematic and trace elements in volcanic gases, sulphide precipitates and host volcanic rocks. The fumarolic gas condensates are enriched in hydrophile trace elements relative to fluid-immobile elements and exhibit high Ba/Nb (133-204), Rb/Y (16-406) and Th/Zr (0.01-0.25) ratios. They are characterised by high Re (7-210 ppb) and Os abundances (0.4-0.9 ppb), with ¹⁸⁷Os/¹⁸⁸Os ratios in a range 0.122-0.152. This Os isotopic compositional range is similar to that of the peridotite xenoliths from the metasomatised mantle wedge above the subducted Pacific plate, the radiogenic isotopic signature of which is probably due to radiogenic addition from a slab-derived fluid.Re- and Os-rich sulphide and oxide minerals precipitate from volcanic gases within fumarolic fields. Molybdenite (MoS₂), powellite (CaMoO₄) and cannizzarite (Pb₄Bi₆S₁₃) contain 1.5-1.7 wt%, 10 ppm, and 65-252 ppb of Re, respectively. Both molybdenite and rheniite contain normal Os concentrations, with total Os abundances in a range from 0.6 to 3.1 ppm for molybdenite, and 2.3-24.3 ppb for the rheniite samples. Repeated analyses of osmium isotope ratios for two rheniite samples form a best-fit line with an initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.32 ± 0.15 and an age of 79 ± 11 yr, which is the youngest age ever measured in natural samples. The high Re contents in molybdenite and rheniite led to high radiogenic ¹⁸⁷Os values, even in the limited period of time, with ¹⁸⁷Os/¹⁸⁸Os ratios up to 3.3 for molybdenite and up to 4.4 for rheniite.The Os isotopic compositions of andesite-basaltic rocks from the Kudryavy volcano (¹⁸⁷Os/¹⁸⁸Os up to 0.326) are more radiogenic than those of residual peridotites and fumarolic gas condensates that are mainly constituted from magmatic vapor. Such radiogenic values can be attributed either to the addition of a radiogenic Os-rich subduction component to the depleted mantle, or to the assimilation of older dacitic caldera walls (¹⁸⁷Os/¹⁸⁸Os = 0.6) during arc magma ascent and emplacement. The latter hypothesis is supported by the correlation between ¹⁸⁷Os/¹⁸⁸Os ratio and indicators of fractionation such as MgO or Ni, and by low contents of potentially hydrophile trace elements such as Ba, Rb and Th relative to fluid-immobile elements such as Nb, Zr and Y. The high Re flux in the Kudryavy volcano (estimated at ∼46 kg/yr) can be explained by remobilisation of Re by Cl-rich water from an underplated mantle wedge and subducted organic-rich sediments of the Pacific plate.     

Geochemical constraints on magma processes in a peralkaline system: The Paisano volcano,west Texas

Major and trace element data for a sequence of peralkaline silicic lavas and pyroclastic flows, exposed in the caldera wall of the Paisano volcano, west Texas, document systematic fractional crystallization during magmatic evolution and an open system, magma mixing event in the upper parts of the sequence. Stratigraphically lowest flows are comendite and comenditic quartz trachyte lavas and ash flow tufts. Overlying these units is a trachyte with compositional, textural and mineralogical features indicating that it is the product of magma-mixing; similar flows occur in other parts of the volcano at the same stratigraphic level. This composite trachyte is considered to be a mixture of mugearitic or mafic trachytic magma, derived from a similar source region which yielded the earlier caldera wall flows. Trace element concentrations of the post-trachyte comenditic quartz trachyte lavas suggest they were erupted from a chamber whose magma was diluted by an influx of mugearitic or mafic trachytic magma during a magma mixing event.Rayleigh fractionation calculations show that the comendites and comenditic quartz trachytes can be derived from a parental mugearite magma by 88% to 93% fractionation of dominantly plagioclase and alkali feldspar, with lesser amounts of clinopyroxene, magnetite and apatite. Zircon was not a significant fractionating phase. The composition, mineralogy and depth of the source region(s) which generated these magmas cannot be constrained from the present data set.