Sixty thousand years of magmatic volatile history before the caldera-forming eruption of Mount Mazama, Crater Lake, Oregon

The well-documented eruptive history of Mount Mazama, Oregon, provides an excellent opportunity to use pre-eruptive volatile concentrations to study the growth of an explosive silicic magmatic system. Melt inclusions (MI) hosted in pyroxene and plagioclase crystals from eight dacitic–rhyodacitic eruptive deposits (71–7.7?ka) were analyzed to determine variations in volatile-element concentrations and changes in magma storage conditions leading up to and including the climactic eruption of Crater Lake caldera. Temperatures (Fe–Ti oxides) increased through the series of dacites, then decreased, and increased again through the rhyodacites (918–968 to ~950 to 845–895?°C). Oxygen fugacity began at nickel–nickel-oxide buffer (NNO) +0.8 (71?ka), dropped slightly to NNO +0.3, and then climbed to its highest value with the climactic eruption (7.7?ka) at NNO +1.1 log units. In parallel with oxidation state, maximum MI sulfur concentrations were high early in the eruptive sequence (~500?ppm), decreased (to ~200?ppm), and then increased again with the climactic eruption (~500?ppm). Maximum MI sulfur correlates with the Sr content (as a proxy for LREE, Ba, Rb, P₂O₅) of recharge magmas, represented by basaltic andesitic to andesitic enclaves and similar-aged lavas. These results suggest that oxidized Sr-rich recharge magmas dominated early and late in the development of the pre-climactic dacite–rhyodacite system. Dissolved H₂O concentrations in MI do not, however, correlate with these changes in dominant recharge magma, instead recording vapor solubility relations in the developing shallow magma storage and conduit region. Dissolved H₂O concentrations form two populations through time: the first at 3–4.6 wt% (with a few extreme values up to 6.1 wt%) and the second at ≤2.4 wt%. CO₂ concentrations measured in a subset of these inclusions reach up to 240?ppm in early-erupted deposits (71?ka) and are below detection in climactic deposits (7.7?ka). Combined H₂O and CO₂ concentrations and solubility models indicate a dominant storage region at 4–7?km (up to 12?km), with drier inclusions that diffusively re-equilibrated and/or were trapped at shallower depths. Boron and Cl (except in the climactic deposit) largely remained in the melt, suggesting vapor–melt partition coefficients and gas fractions were low. Modeled Li, F, and S vapor–melt partition coefficients are higher than those of B and Cl. The decrease in maximum MI CO₂ concentration following the earliest dacitic eruptions is interpreted to result from a broadening of the shallow storage region to greater than the diameter of subjacent feeders, so that greater proportions of reservoir magma were to the side of CO₂-bearing vapor bubbles ascending vertically from the locus of recharge magma injection, thereby escaping recarbonation by streaming vapor bubbles. The Mazama melt inclusions provide a picture of a growing magma storage region, where chemical variations in melt and magma occur due to changes in the nature and supply rate of magma recharge, the timing of degassing, and the possible degree of equilibration with gases from below.     

Contribution of mafic melt to porphyry copper mineralization: evidence from Mount Pinatubo, Philippines, and Bingham Canyon, Utah, USA

Mount Pinatubo in the Philippines, known for its cataclysmic eruption in 1991, hosts several porphyry copper deposits and active geothermal systems. An underlying mafic melt supplied much of the sulphur for the dacitic magma and its injection into the dacitic magma chamber triggered the eruption. The eruption caused purging of the sulphur-rich fluid from the dacite to the atmosphere and extensive fracturing. Similar events took place at Bingham Canyon, Utah, site of the largest copper and gold deposit in North America at 38 Ma. The Bingham Canyon mineralization took place beneath an active stratovolcano and pyroclastic flows contemporaneous with the mineralization show evidence for magma mingling. Ascent of mafic melt supplied sulphur and chalcophile elements to the felsic magma, which consolidated to form the Bingham stock and its underlying magma chamber. Injections of the mafic melt caused periodic eruptions of felsic magma to form the stratovolcano and deposition of sulphide minerals in highly fractured rocks in and around the stock.     

Geochemical constraints on the origin of mafic and silicic magmas at Cordón El Guadal, Tatara-San Pedro Complex, central Chile

The aim of this study is to quantify the crustal differentiation processes and sources responsible for the origin of basaltic to dacitic volcanic rocks present on Cordón El Guadal in the Tatara-San Pedro Complex (TSPC). This suite is important for understanding the origin of evolved magmas in the southern Andes because it exhibits the widest compositional range of any unconformity-bound sequence of lavas in the TSPC. Major element, trace element, and Sr-isotopic data for the Guadal volcanic rocks provide evidence for complex crustal magmatic histories involving up to six differentiation mechanisms. The petrogenetic processes for andesitic and dacitic lavas containing undercooled inclusions of basaltic andesitic and andesitic magma include: (1) assimilation of garnet-bearing, possibly mafic lower continental crust by primary mantle-derived basaltic magmas; (2) fractionation of olivine + clinopyroxene + Ca-rich plagioclase + Fe-oxides in present non-modal proportions from basaltic magmas at ∼4–8 kbar to produce high-Al basalt and basaltic andesitic magmas; (3) vapor-undersaturated (i.e., P _H2O<P _TOTAL) partial melting of gabbroic crustal rocks at ∼3–7 kbar to produce dacitic magmas; (4) crystallization of plagioclase-rich phenocryst assemblages from dacitic magmas in shallow reservoirs; (5) intrusion of basaltic andesitic magmas into shallow reservoirs containing crystal-rich dacitic magmas and subsequent mixing to produce hybrid basaltic andesitic and andesitic magmas; and (6)␣formation and disaggregation of undercooled basaltic andesitic and andesitic inclusions during eruption from shallow chambers to form commingled, mafic inclusion-bearing andesitic and dacitic lavas flows. Collectively, the geochemical and petrographic features of the Guadal volcanic rocks are interpreted to reflect the development of shallow silicic reservoirs within a region characterized by high crustal temperatures due to focused basaltic activity and high magma supply rates. On the periphery of the silicic system where magma supply rates and crustal temperatures were lower, cooling and crystallization were more important than bulk crustal melting or assimilation. Received: 2 July 1997 / Accepted: 25 November 1997     

Pre-eruptive Conditions of the Huerto Andesite (Fish Canyon System, San Juan Volcanic Field, Colorado): Influence of Volatiles (C-O-H-S) on Phase Equilibria and Mineral Composition

Crystallization experiments at 400 MPa, oxidized condition (logfO₂= NNO + 1, where NNO is nickel–nickel oxide buffer) andover a range of temperatures (850–950°C) and fluidcomposition (XH₂O_in = 0·3–1) have been carriedout to constrain the storage conditions of the sulphur-richmagma of the Huerto Andesite (an anhydrite, pyrrhotite, andS-rich apatite-bearing, post-Fish Canyon Tuff mafic lava). Theresults are used to evaluate the role of fluids released fromthe crystallization of magmas such as the Huerto Andesite onthe remobilization of the largely crystallized dacitic FishCanyon magma body. Experiments were performed using the naturalandesitic bulk composition with and without added sulphur. Thepresence of sulphur slightly affects the phase equilibria bychanging the phase proportions, stability fields of plagioclase,pyroxenes and ilmenite, and also affects the plagioclase composition.Phase equilibria and mineral composition data indicate thatthe magma may have contained 4·5 wt % water in the meltand that the pre-eruptive temperature was 875 ± 25°C.Assuming that the magma was in equilibrium with a fluid phase,the CO₂ concentration of the melt is estimated to be in therange 2000–4000 ppm (at 400 MPa). Before eruption, theandesite had an oxidation state very close to, or slightly within,the co-stability field of anhydrite–pyrrhotite at NNO+ 1·1. At these conditions, the sulphur content in themelt is 500 ppm. Assuming open-system degassing resulting fromcontinuing crystallization at depth, most of the CO₂ dissolvedin the andesitic melt should be released after the crystallizationof <10 vol. % of the magma, corresponding to a cooling from875 to 825–850°C. Thus, the fluids released owingto crystallization processes should be mainly composed of waterat temperatures below 825°C. KEY WORDS: experimental study; andesite; volatile; Fish Canyon Tuff; Huerto Andesite     

Ar/Ar age and geochemistry of the post-collisional Miocene Yamadağ volcanics in the Arapkir area (Malatya Province), eastern Anatolia, Turkey

The Neogene Yamadağ volcanics occupy a vast area between Sivas and Malatya in eastern Anatolia, Turkey. These volcanic rocks are characterized by pyroclastics comprising agglomerates, tuffs and some small outcrops of basaltic–andesitic–dacitic rocks, overlain upward by basaltic and dacitic rocks, and finally by basaltic lava flows in the Arapkir area, northern Malatya Province. The basaltic lava flows in the Arapkir area yield a ⁴⁰Ar/³⁹Ar age of 15.8 ± 0.2 Ma, whereas the dacitic lava flows give ⁴⁰Ar/³⁹Ar ages ranging from 17.6 through 14.7 ± 0.1 to 12.2 ± 0.2 Ma, corresponding to the Middle Miocene. These volcanic rocks have subalkaline basaltic, basaltic andesitic; alkaline basaltic trachyandesitic and dacitic chemical compositions. Some special textures, such as spongy-cellular, sieve and embayed textures; oscillatory zoning and glass inclusions in plagioclase phenocrysts; ghost amphiboles and fresh biotite flakes are attributable to disequilibrium crystallization related to magma mixing between coeval magmas. The main solidification processes consist of fractional crystallization and magma mixing which were operative during the soldification of these volcanic rocks. The dacitic rocks are enriched in LILE, LREE and Th, U type HFSE relative to the basaltic rocks. The basaltic rocks also show some marked differences in terms of trace-element and REE geochemistry; namely, the alkaline basaltic trachyandesites have pronounced higher HFSE, MREE and HREE contents relative to the subalkaline basalts. Trace and REE geochemical data reveal the existence of three distinct magma sources – one subalkaline basaltic trachyandesitic, one alkaline basaltic and one dacitic – in the genesis of the Yamadağ volcanics in the Arapkir region. The subalkaline basaltic and alkaline basaltic trachyandesitic magmas were derived from an E-MORB type enriched mantle source with a relatively high- and low-degree partial melting, respectively. The magmatic melt of dacitic rocks seem to be derived from an OIB-type enriched lithospheric mantle with a low proportion of partial melting. The enriched lithospheric mantle source reflect the metasomatism induced by earlier subduction-derived fluids. All these coeval magmas were generated in a post-collisional extensional geodynamic setting in Eastern Anatolia, Turkey.     

Magma evolution and the formation of porphyry Cu–Au ore fluids: evidence from silicate and sulfide melt inclusions

Silicate and sulfide melt inclusions from the andesitic Farallón Negro Volcanic Complex in NW Argentina were analyzed by laser ablation ICPMS to track the behavior of Cu and Au during magma evolution, and to identify the processes in the source of fluids responsible for porphyry-Cu-Au mineralization at the 600 Mt Bajo de la Alumbrera deposit. The combination of silicate and sulfide melt inclusion data with previously published geological and geochemical information indicates that the source of ore metals and water was a mantle-derived mafic magma that contained approximately 6 wt.% H₂O and 200 ppm Cu. This magma and a rhyodacitic magma mixed in an upper-crustal magma chamber, feeding the volcanic systems and associated subvolcanic intrusions over 2.6 million years. Generation of the ore fluid from this magma occurred towards the end of this protracted evolution and probably involved six important steps: (1) Generation of a sulfide melt upon magma mixing in some parts of the magma chamber. (2) Partitioning of Cu and Au into the sulfide melt (enrichment factor of 10,000 for Cu) leading to Cu and Au concentrations of several wt.% or ppm, respectively. (3) A change in the tectonic regime from local extension to compression at the end of protracted volcanism. (4) Intrusion of a dacitic magma stock from the upper part of the layered magma chamber. (5) Volatile exsolution and resorption of the sulfide melt from the lower and more mafic parts of the magma chamber, generating a fluid with a Cu/Au ratio equal to that of the precursor sulfide. (6) Focused fluid transport and precipitation of the two metals in the porphyry, yielding an ore body containing Au and Cu in the proportions dictated by the magmatic fluid source. The Cu/S ratio in the sulfide melt inclusions requires that approximately 4,000 ppm sulfur is extracted from the andesitic magma upon mixing. This exceeds the solubility of sulfide or sulfate in either of the silicate melts and implies an additional source for S. The extra sulfur could be added in the form of anhydrite phenocrysts present in the rhyodacitic magma. It appears, thus, that unusually sulfur-rich, not Cu-rich magmas are the key to the formation of porphyry-type ore deposits. Our observations imply that dacitic intrusions hosting the porphyry–Cu–Au mineralization are not representative of the magma from which the ore-fluid exsolved. The source of the ore fluid is the underlying more mafic magma, and unaltered andesitic dikes emplaced immediately after ore formation are more likely to represent the magma from which the fluids were generated. At Alumbrera, these andesitic dikes carry relicts of the sulfide melt as inclusions in amphibole. Sulfide inclusions in similar dykes of other, less explored magmatic complexes may be used to predict the Au/Cu ratio of potential ore-forming fluids and the expected metal ratio in any undiscovered porphyry deposit.Editorial handling: B. Lehmann     

Compositional and Dynamic Controls on Mafic--Silicic Magma Interactions at Continental Arc Volcanoes: Evidence from Cordn El Guadal, Tatara-San Pedro Complex, Chile

Heterogeneous andesitic and dacitic lavas on Cordn El Guadalbear on the general problem of how magmas of differing compositionsand physical properties interact in shallow reservoirs beneathcontinental arc volcanoes. Some of the lavas contain an exceptionallylarge proportion (<40%) of undercooled basaltic andesiticmagma in various states of disaggregation. Under-cooled maficmagma occurs in the silicic lavas as large (<40 cm) basalticandesitic magmatic inclusions, as millimeter-sized crystal-clotsof Mg-rich olivine phenocrysts plus adhering Carich plagioclasemicrophenocrysts (An_50–70), and as uniformly distributed,isolated phenocrysts and microphenocrysts. Compositions andtextures of plagioclase phenocrysts indicate that inclusion-formingmagmas are hybrids formed by mixing basaltic and dacitic melts,whereas textural features and compositions of groundmass phasesindicate that the andesitic and dacitic lavas are largely mechanicalmixtures of dacitic magma and crystallized basaltic andesiticmagma. This latter observation is significant because it indicatesthat mechanical blending of undercooled mafic magma and partiallycrystallized silicic magma is a possible mechanism for producingthe common porphyritic texture of many calc-alkaline volcanicrocks. The style of mafic-silicic magma interaction at CordonEl Guadal was strongly dependent upon the relative proportionsof the endmembers. Equally important in the Guadal system, however,was the manner in which the contrasting magmas were juxtaposed.Textural evidence preserved in the plagioclase phenocrysts indicatesthat the transition from liquid-liquid to solid-liquid mixingwas not continuous, but was partitioned into periods of magmachamber recharge and eruption, respectively. Evidently, duringperiods of recharge, basaltic magmas rapidly entrained smallamounts of dacitic magma along the margins of a turbulent injectionfountain. Conversely, during periods of eruption, dacitic magmagradually incorporated small parcels of basaltic andesitic magma.Thus, the coupled physical-chemical transition from mixed inclusionsto commingled lavas is presumably not coincidental. More likely,it probably provides a partial record of the dynamic processesoccurring in shallow magma chambers beneath continental arevolcanoes. KEY WORDS: Chile; commingling; magma mixing; magmatic inclusions ^*Present address: Department of Earth Sciences, Montana State University, Bozeman, MT 59717, USA     

Amphibole perspective to unravel pre-eruptive processes and conditions in volcanic plumbing systems beneath intermediate arc volcanoes: a case study from Ciomadul volcano (SE Carpathians)

Ciomadul is the youngest volcano in the Carpathian–Pannonian region produced crystal-rich high-K dacites that contain abundant amphibole phenocrysts. The amphiboles in the studied dacites are characterized by large variety of zoning patterns, textures, and a wide range of compositions (e.g., 6.4–15 wt% Al₂O₃, 79–821 ppm Sr) often in thin-section scale and even in single crystals. Two amphibole populations were observed in the dacite: low-Al hornblendes represent a cold (<800 °C) silicic crystal mush, whereas the high-Al pargasites crystallized in a hot (>900 °C) mafic magma. Amphibole thermobarometry suggests that the silicic crystal mush was stored in an upper crustal storage (~8–12 km). This was also the place where the erupted dacitic magma was formed during the remobilization of upper crustal silicic crystal mush body by hot mafic magma indicated by simple-zoned and composite amphiboles. This includes reheating (by ~200 °C) and partial remelting of different parts of the crystal mush followed by intensive crystallization of the second mineral population (including pargasites). Breakdown textures of amphiboles imply that they were formed by reheating in case of hornblendes, suggesting that pre-eruptive heating and mixing could take place within days or weeks before the eruption. The decompression rim of pargasites suggests around 12 days of magma ascent in the conduit. Several arc volcanoes produce mixed intermediate magmas with similar bimodal amphibole cargo as the Ciomadul, but in our dacite the two amphibole population can be found even in a single crystal (composite amphiboles). Our study indicates that high-Al pargasites form as a second generation in these magmas after the mafic replenishment into a silicic capture zone; thus, they cannot unambiguously indicate a deeper mafic storage zone beneath these volcanoes. The simple-zoned and composite amphiboles provide direct evidence that significant compositional variations of amphiboles do not necessarily mean variation in the pressure of crystallization even if the Al-tschermak substitution can be recognized, suggesting that amphibole barometers that consider only amphibole composition may often yield unrealistic pressure variation.     

Sulfur isotope fractionation during the May 2003 eruption of Anatahan volcano, Mariana Islands: Implications for sulfur sources and plume processes

Sulfur isotope compositions of pumice and adsorbed volatiles on ash from the first historical eruption of Anatahan volcano (Mariana arc) are presented in order to constrain the sources of sulfur erupted during the period 10-21 May, 2003. The isotopic composition of S extracted from erupted pumice has a narrow range, from δ³⁴S_V-CDT +2.6‰ to +3.2‰, while the composition of sulfur adsorbed onto ash has a larger range (+2.8‰ to +5.3‰). Fractionation modeling for closed and open system scenarios suggests that degassing of SO₂ raised the δ³⁴S_V-CDT value of S dissolved in the melt from an initial composition of between +1.6‰ and +2.6‰ for closed-system degassing, or between −0.5‰ and +1.5‰ for open-system degassing, however closed-system degassing is the preferred model. The calculated values for the initial composition of the magma represent a MORB-like (δ³⁴S_V-CDT ∼ 0‰) mantle source with limited contamination by subducted seawater sulfate (δ³⁴S_V-CDT +21‰). Modeling also suggests that the δ³⁴S_V-CDT value of SO₂ gas in closed-system equilibrium with the degassed magma was between +0.9‰ and +2.5‰. The δ³⁴S_V-CDT value of sulfate adsorbed onto ash in the eruption plume (+2.8‰ to +5.1‰) is consistent with sulfate formation by oxidation of magmatic SO₂ in the eruption column. The sulfur isotope composition of sulfate adsorbed to ash changes from lower δ³⁴S values for ash erupted early in the eruption to higher δ³⁴S values for ash erupted later in the eruption. We interpret the temporal/stratigraphic change in sulfate isotopic composition to primarily reflect a change in the isotopic composition of magmatic SO₂ released from the progressively degassing magma and is attributed to the expulsion of an accumulated gas phase at the beginning of the eruption. More efficient oxidation of magmatic SO₂ gas to sulfate in the early water-rich eruption plume probably contributed to the change in S isotope compositions observed in the ash leachates.     

Sulfur partition coefficient between apatite and rhyolite: the role of bulk S content

Experimental studies have been performed to constrain sulfur behavior during apatite crystallization and to determine sulfur partition coefficient between apatite and melt (Kd_S^apatite/melt) at oxidizing conditions. Crystallization experiments have been conducted with a hydrous rhyolitic melt and different bulk sulfur contents (0.15 to 2 wt.% S) at 900 and 1,000°C, 200 MPa and Δlog =NNO+3.6. The sulfur content in the glass increases with increasing amount of added S. Anhydrite crystallizes for S added = 0.75 wt.% (0.10 and 0.13 wt.% SO₃ in glass at 900 and 1,000°C, respectively). The amount of anhydrite increases and the amount of apatite decreases with increasing amount of added sulfur. The sulfur exchange reaction in apatite is influenced by the bulk composition of the melt (e.g., P content). However, changing melt composition has only little effect on Kd_S^apatite/melt for the investigated rhyolitic composition. The Kd_S^apatite/melt does not depend directly on temperature, decreases from 14.2 to 2.7 with increasing S content in glass from SO₃=0.03 to 0.19 wt.%, respectively, and can be predicted from the following equation: ln Kd = −0.0025×S in melt (in ppm)+2.9178. The combination of experimental data obtained for rhyolitic and andesitic melts reveals that the sulfur partition coefficient tends toward a value of 2 for high-sulfur content in the glass (>0.2 wt.% SO₃). Using S in apatite as proxy for determining S content in melt is promising but additional experimental data are needed to clarify the individual effects of T, , and P and Ca content in the melt on S partitioning.     

Mineral chemistry of high-Mg diorites and skarn in the Han-Xing Iron deposits of South Taihang Mountains,China: Constraints on mineralization process

The Han-Xing region is located in the south Taihang Mountains (TM) in the central part of the North China Craton, and is an important iron producing area. The iron deposits in this region are of skarn type, related to an Early Cretaceous high-Mg diorite complex, including gabbro diorite, hornblende diorite, diorite, diorite porphyrite, and monzonite. In this study we report the detailed mineral chemistry of the high-Mg diorites and skarn rocks. The olivine in the gabbro diorite shows chemical composition similar to that in mantle peridotite xenoliths. Clinopyroxene in the gabbro diorite is dominantly augite, with only minor diopside, whereas the clinopyroxenes in the diorite and monzonite are diopside. Amphiboles in the high-Mg diorites show compositional range from magnesiohornblende to magnesiohastingsite, with minor pargasite and tschermakite. Most plagioclase in the high-Mg diorite is andesine and oligoclase. The magnesio-biotite in gabbro diorites shows chemical characteristics of re-equilibrated primary biotites and those in calc-alkaline rocks. In the diorite and diorite porphyrite, plagioclase shows complex chemical zoning. Clinopyroxene and garnet in skarn rocks show varying FeO contents, the former containing low FeO (< 9 wt.%) and occurring as the major skarn mineral in large-scale iron deposits, and the latter within small-scale iron deposits with high FeO (mostly > 25 wt.%) content. We computed the pressure, temperature, oxygen fugacity and water contents based on the mineral chemistry of amphibole and biotite. Based on the results, the magma crystallization can be divided into two stages, one within the deep magma chamber, forming clinopyroxene, amphibole and plagioclase phenocrysts; the other after emplacement, forming the rim of phenocrysts and matrix minerals. The magma during the early stage shows high temperature (~ 900 °C–950 °C), pressure (~ 300 MPa–500 MPa), relatively high logfO₂ (NNO–NNO + 2), and H₂O content in melt (4%–8%). During the late stage, the magma temperature dropped to about 750 °C, and pressure came down to less than 100 MPa, with the logfO₂ rising to NNO + 1–NNO + 2.The zoning of amphibole and plagioclase records the process of magma mixing and crystallization, with injection of mafic magma into the felsic magma chamber. The relatively high logfO₂ and H₂O content inhibited partitioning of iron into mafic minerals and favored concentration of Fe in the melt. Iron ore precipitation occurred when the magma was emplaced at shallow level, and was principally controlled by the chemical composition of carbonate wall rocks. The high logfO₂, Fe^3 + rich ore-forming fluid generated andradite and clinopyroxene when it reacted with limestone and dolomitic limestone respectively.     

Formation of extremely F-rich hydrous melt fractions and hydrothermal fluids during differentiation of highly evolved tin-granite magmas: a melt/fluid-inclusion study

Quartz crystals from topaz–zinnwaldite–albite granites from Zinnwald (Erzgebirge, Germany) contain, in addition to primary and secondary fluid inclusions (FIs), abundant crystalline silicate-melt inclusions (MIs) with diameters up to 200 m. These MIs represent various stages of evolution of a highly evolved melt system that finally gave rise to granite-related Sn–W mineralization. The combination of special experimental techniques with confocal laser Raman-microprobe spectroscopy and EMPA permits precise measurement of elevated contents of H₂O, F, and B in re-homogenized MIs. The contents of H₂O and F were observed to increase from 3 to 30 and 1.9 to 6.4 wt%, respectively, during magma differentiation. However, there is a second MI group, very rich in H₂O, with values up to 55 wt% H₂O and an F concentration of approximately 3 wt%. Ongoing enrichment of volatiles H₂O, F, B, and Cl and of Cs and Rb can be explained in terms of magma differentiation triggered by fractional crystallization and thus, is suggested to reflect elemental abundances in natural magmas, and not boundary-layer melts. Partitioning between melt and cogenetic fluids has further modified the magmatic concentrations of some elements, particularly Sn. The coexistence of two types of MIs with primary FIs indicates fluid saturation early in the history of magma crystallization, connected with a continuous sequestration of Sn, F, and B. The results of this study provide additional evidence for the extraordinary importance of the interplay of H₂O, F, and B in the enrichment of Sn during magma differentiation by decreasing the viscosity of and increasing the diffusivity in the melts as well as by the formation of various stable fluoride complexes in the melt and coexisting fluid.

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S-rich apatite-hosted glass inclusions in xenoliths from La Palma: constraints on the volatile partitioning in evolved alkaline magmas

The composition of S-rich apatite, of volatile-rich glass inclusions in apatite, and of interstitial glasses in alkaline xenoliths from the 1949 basanite eruption in La Palma has been investigated to constrain the partitioning of volatiles between apatite and alkali-rich melts. The xenoliths are interpreted as cumulates from alkaline La Palma magmas. Apatite contains up to 0.89 wt% SO₃ (3560 ppm S), 0.31 wt% Cl, and 0.66 wt% Ce₂O₃. Sulfur is incorporated in apatite via several independent exchange reactions involving (P⁵⁺, Ca²⁺) vs. (S⁶⁺, Si⁴⁺, Na⁺, and Ce³⁺). The concentration of halogens in phonolitic to trachytic glasses ranges from 0.15 to 0.44 wt% for Cl and from <0.07 to 0.65 wt% for F. The sulfur concentration in the glasses ranges from 0.06 to 0.23 wt% SO₃ (sulfate-saturated systems). The chlorine partition coefficients (D_Cl^{apatite/glass}) range from 0.4 to 1.3 (average D_Cl^{apatite/glass} = 0.8), in good agreement with the results of experimental data in mafic and rhyolitic system with low Cl concentrations. With increasing F in glass inclusions D_F^{apatite/glass} decreases from 35 to 3. However, most of our data display a high partition coefficient (~30) close to D_F^{apatite/glass} determined experimentally in felsic rock. D_S^{apatite/glass} decreases from 9.1 to 2.9 with increasing SO₃ in glass inclusions. The combination of natural and experimental data reveals that the S partition coefficient tends toward a value of 2 for high S content in the glass (>0.2 wt% SO₃). D_S^{apatite/glass} is only slightly dependent on the melt composition and can be expressed as: SO_{3 apatite} (wt%) = 0.157 * ln SO_{3 glass} (wt%) + 0.9834. The phonolitic compositions of glass inclusions in amphibole and haüyne are very similar to evolved melts erupted on La Palma. The lower sulfur content and the higher Cl content in the phonolitic melt compared to basaltic magmas erupted in La Palma suggest that during magma evolution the crystallization of haüyne and pyrrhotite probably buffered the sulfur content of the melt, whereas the evolution of Cl concentration reflects an incompatible behavior. Trachytic compositions similar to those of the (water-rich) glass inclusions analyzed in apatite and clinopyroxene are not found as erupted products. These compositions are interpreted to be formed by the reaction between water-rich phonolitic melt and peridotite wall-rock.     

Phase relations in silicic systems at one-atmosphere pressure

An important control on magma rheology is the extent to which the magma crystallizes during ascent as a result of the effective undercooling created by volatile exsolution. To assess this undercooling, we need to know the final (anhydrous) one-atmosphere phase relations of silicic magmas. For this reason, we have performed one-atmosphere controlled-fO₂ crystallization experiments on dacitic to rhyolitic melt compositions (67–78 wt% SiO₂) and determined equilibrium phase assemblages, melt fractions, and some phase compositions over a range of temperatures. Experiments were run at oxygen fugacities between NNO+1 and NNO+2 and temperatures of 1,000 to 1,250°C. Constant phase compositions and sample crystallinities in runs longer than 3.5 days suggest that these runs closely approached compositional equilibrium. Additionally, melting experiments with similar compositions yielded results closely resembling those obtained in crystallization experiments. All samples have liquidus temperatures between 1,250 and 1,200 °C, with plagioclase the liquidus phase for the two most mafic samples and quartz for the most silicic sample. When associated glass compositions are projected into the Qz-Ab-Or system they define a revised one-atmosphere quartz-feldspar cotectic 5–10% less quartz normative than previously estimated. Glass compositions from each sample plot along this cotectic between 1,100 and 1,000 °C, consistent with the plagioclase-quartz co-crystallization textures found in runs at these temperatures. This cotectic constrains glass compositions to a maximum silica content of 76±1 wt% SiO₂. Reported glass compositions in excess of 77 wt% SiO₂ in volcanic samples suggest non-equilibrium crystallization, perhaps a consequence of large melt undercoolings.Editorial responsibility: I. Carmichael     

Fluid history of UHP metamorphism in Dabie Shan, China: a fluid inclusion and oxygen isotope study on the coesite-bearing eclogite from Bixiling

This paper characterizes late Holocene basalts and basaltic andesites at Medicine Lake volcano that contain high pre-eruptive H₂O contents inherited from a subduction related hydrous component in the mantle. The basaltic andesite of Paint Pot Crater and the compositionally zoned basaltic to andesitic lavas of the Callahan flow erupted approximately 1000 ¹⁴C years Before Present (¹⁴C years b.p.). Petrologic, geochemical and isotopic evidence indicates that this late Holocene mafic magmatism was characterized by H₂O contents of 3 to 6 wt% H₂O and elevated abundances of large ion lithophile elements (LILE). These hydrous mafic inputs contrast with the preceding episodes of mafic magmatism (from 10,600 to ∼3000 ¹⁴C years b.p.) that was characterized by the eruption of primitive high alumina olivine tholeiite (HAOT) with low H₂O (<0.2 wt%), lower LILE abundance and different isotopic characteristics. Thus, the mantle-derived inputs into the Medicine Lake system have not always been low H₂O, primitive HAOT, but have alternated between HAOT and hydrous subduction related, calc-alkaline basalt. This influx of hydrous mafic magma coincides temporally and spatially with rhyolite eruption at Glass Mountain and Little Glass Mountain. The rhyolites contain quenched magmatic inclusions similar in character to the mafic lavas at Callahan and Paint Pot Crater. The influence of H₂O on fractional crystallization of hydrous mafic magma and melting of pre-existing granite crust beneath the volcano combined to produce the rhyolite. Fractionation under hydrous conditions at upper crustal pressures leads to the early crystallization of Fe-Mg silicates and the suppression of plagioclase as an early crystallizing phase. In addition, H₂O lowers the saturation temperature of Fe and Mg silicates, and brings the temperature of oxide crystallization closer to the liquidus. These combined effects generate SiO₂-enrichment that leads to rhyodacitic differentiated lavas. In contrast, low H₂O HAOT magmas at Medicine Lake differentiate to iron-rich basaltic liquids. When these Fe-enriched basalts mix with melted granitic crust, the result is an andesitic magma. Since mid-Holocene time, mafic volcanism has been dominated primarily by hydrous basaltic andesite and andesite at Medicine Lake Volcano. However, during the late Holocene, H₂O-poor mafic magmas continued to be erupted along with hydrous mafic magmas, although in significantly smaller volumes. Received: 4 January 1999 / Accepted: 30 August 1999     

Evolution of a Porphyry-Cu Mineralized Magma System at Santa Rita, New Mexico (USA)

The magmatic processes leading to porphyry-Cu mineralizationat Santa Rita are reconstructed on the basis of petrographicstudies, thermobarometry, and laser-ablation inductively-coupled-plasmamass-spectrometry analyses of silicate melt and sulfide inclusionsfrom dikes ranging from basaltic andesite to rhyodacite. Combinedresults suggest that magma evolution at Santa Rita is similarto that of sulfur-rich volcanoes situated above subduction zones,being characterized by repeated injection of hot, mafic magmainto an anhydrite-bearing magma chamber of rhyodacitic composition.The most mafic end-member identified at Santa Rita is a shoshoniticbasaltic andesite that crystallized at 1000–1050°C,1–3 kbar and log f_O2 = NNO + 0·7 to NNO + 1·0,whereas the rhyodacite crystallized at 730–760°C andlog f_O2 = NNO + 1·3 to NNO + 1·9. Mixing betweenthe two magmas caused precipitation of 0·1–0·2wt % magmatic sulfides and an associated decrease in the Cucontent of the silicate melt from 300–500 ppm to lessthan 20 ppm. Quantitative modeling suggests that temporal storageof ore-metals in magmatic sulfides does not significantly enhancethe amount of copper ultimately available to ore-forming hydrothermalfluids. Magmatic sulfides are therefore not vital to the formationof porphyry-Cu deposits, unless a mechanism is required thatholds back ore-forming metals until late in the evolution ofthe volcanic–plutonic system. KEY WORDS: porphyry-Cu; sulfur; sulfides; magma mixing; LA-ICP-MS     

Decompression and H<Subscript>2</Subscript>O exsolution driven crystallization and fractionation: development of a new model for low-pressure fractional crystallization in calc-alkaline magmatic systems

Magma ascent, decompression-induced H₂O exsolution and crystallization is now recognized as an important process in hydrous subduction zone magmas. During the course of such a process calculations suggest that the ascent rate of a degassing and crystallizing mafic magma will be greater than crystal settling velocities. Thus, any crystals formed as a consequence of volatile exsolution will remain suspended in the magma. If the magma erupts before the percentage of suspended crystals reaches the critical crystallinity value for mafic magma (~55 vol.%) it will produce the commonly observed crystal rich island arc basalt lava. If the magma reaches its critical crystallinity before it erupts then it will stall within the crust. Extension of compaction experiments on a 55 vol.% sand-Karo syrup suspension at different temperatures (and liquid viscosities) to the likely viscosities of interstitial andesitic to dacitic liquid within such a stalled magma suggest that small amounts (up to ~10%) can be expelled on a time scale of 1–10 years. The expelled liquid can create a new intermediate to silicic body of magma that is related to the original mafic magma via fractional crystallization. The short time scale for liquid expulsion indicate that decompression-induced H₂O exsolution and crystallization can be an important mechanism for fractional crystallization. Based on this assumption a general model of decompression-induced crystallization and fractionation is proposed that explains many of the compositional, mineralogical and textural features of Aleutian (and other andesites).     

The geochemistry of volatile species in melt inclusions and sulfide minerals from Izu-Oshima volcano, Japan

Olivine-hosted melt inclusions in the O95 pyroclastic layer of Izu-Oshima volcano, Japan are basaltic to basaltic-andesitic in composition. The negative correlation between SiO₂ and H₂O in melt inclusions and reverse compositional zoning observed in olivine and other mineral phenocrysts is inferred to arise from mixing between a highly evolved and a less evolved magma. The latter is characterized by the highest S (0.15 wt.%) and H₂O (3.4 wt.%) concentrations among those described in reports of previous studies. The S⁶⁺/S_total ratios in melt inclusions were 0.64?–?0.73, suggesting a relatively high oxidation state (NNO + 0.87 at 1150°C). The presence of pyrrhotites, which are found only in titanomagnetite microlites, suggests that sulfide saturation occurred during microlite growth under at a sulfur fugacity (log fS₂) value of around + 0.5 for T = 1060°C. The groundmass glass compositions are more evolved (andesitic composition) than any melt inclusions containing high amounts of Cl (0.13 wt.%) but negligible H₂O (0.20 wt.%) and S (< 70 ppm), suggesting that Cl was retained in the magma, in contrast to S and H₂O, which degassed strongly during magma effusion.     

Lower mantle diamonds from Rio Soriso (Juina area,Mato Grosso,Brazil)

The morphology, colour, fluorescence, cathodoluminescence, nitrogen content and aggregation state, internal structure and mineral inclusions have been studied for 69 alluvial diamonds from the Rio Soriso (Juina area, Mato Grosso State, Brazil). Nitrogen in most diamonds (53%) is fully aggregated as B centres, but there is also a large proportion of N-free stones (38%). A strong positive correlation between nitrogen and IR-active hydrogen concentrations is observed. The diamonds contain (in order of decreasing abundance) ferropericlase, CaSi-perovskite, magnetite, MgSi-perovskite, pyrrhotite, olivine, SiO₂, perovskite, tetragonal almandine-pyrope phase and some other minerals represented by single grains. The Rio Soriso diamond suite is subdivided into several subpopulations that originated in upper and lower mantle of ultramafic and mafic compositions, with the largest subgroup forming in the ultramafic lower mantle. Analysed ferropericlase grains are enriched in Fe (Mg#=0.43–0.89), which is ascribed to their origin in the lowermost mantle. The Juina kimberlites may be unique in sampling the material from depths below 1,700 km that ascended in a plume formed at the core–mantle boundary.Electronic Supplementary Material  Supplementary material is available for this article at

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