Experimental study into the petrogenesis of crystal-rich basaltic to andesitic magmas at Arenal volcano

Arenal volcano is nearly unique among arc volcanoes with its 42 year long (1968–2010) continuous, small-scale activity erupting compositionally monotonous basaltic andesites that also dominate the entire, ~7000 year long, eruptive history. Only mineral zoning records reveal that basaltic andesites are the result of complex, open-system processes deriving minerals from a variety of crystallization environments and including the episodic injections of basalt. The condition of the mafic input as well as the generation of crystal-rich basaltic andesites of the recent, 1968–2010, and earlier eruptions were addressed by an experimental study at 200 MPa, 900–1,050 °C, oxidizing and fluid-saturated conditions with various fluid compositions [H₂O/(H₂O + CO₂) = 0.3–1]. Phase equilibria were determined using a phenocryst-poor (~3 vol%) Arenal-like basalt (50.5?wt% SiO₂) from a nearby scoria cone containing olivine (Fo₉₂), plagioclase (An₈₆), clinopyroxene (Mg# = 82) and magnetite (X_ulvö = 0.13). Experimental melts generally reproduce observed compositional trends among Arenal samples. Small differences between experimental melts and natural rocks can be explained by open-system processes. At low pressure (200 MPa), the mineral assemblage as well as the mineral compositions of the natural basalt were reproduced at 1,000 °C and high water activity. The residual melt at these conditions is basaltic andesitic (55 wt% SiO₂) with 5 wt% H₂O. The evolution to more evolved magmas observed at Arenal occurred under fluid-saturated conditions but variable fluid compositions. At 1,000 °C and 200 MPa, a decrease of water content by approximately 1 wt% induces significant changes of the mineral assemblage from olivine + clinopyroxene + plagioclase (5 wt% H₂O in the melt) to clinopyroxene + plagioclase + orthopyroxene (4 wt% H₂O in the melt). Both assemblages are observed in crystal-rich basalt (15 vol%) and basaltic andesites. Experimental data indicate that the lack of orthopyroxene and the presence of amphibole, also observed in basaltic andesitic tephra units, is due to crystallization at nearly water-saturated conditions and temperatures lower than 950 °C. The enigmatic two compositional groups previously known as low- and high-Al₂O₃ samples at Arenal volcano may be explained by low- and high-pressure crystallization, respectively. Using high-Al as signal of deeper crystallization, first magmas of the 1968–2010 eruption evolved deep in the crust and ascent was relatively fast leaving little time for significant compositional overprint by shallower level crystallization.     

Crystallization of oxidized, moderately hydrous arc basalt at mid- to lower-crustal pressures: implications for andesite genesis

This study focuses on the production of convergent margin calc-alkaline andesites by crystallization–differentiation of basaltic magmas in the lower to middle crust. Previous experimental studies show that dry, reduced, subalkaline basalts differentiate to tholeiitic (high Fe/Mg) daughter liquids, but the influences of H₂O and oxidation on differentiation are less well established. Accordingly, we performed crystallization experiments at controlled oxidized fO₂ (Re–ReO₂ ≈ ΔNi–NiO + 2) on a relatively magnesian basalt (8.7 wt% MgO) typical of mafic magmas erupted in the Cascades near Mount Rainier, Washington. The basalt was synthesized with 2 wt% H₂O and run at 900, 700, and 400 MPa and 1,200 to 950 °C. A broadly clinopyroxenitic crystallization interval dominates near the liquidus at 900 and 700 MPa, consisting of augite + olivine + orthopyroxene + Cr-spinel (in decreasing abundance). With decreasing temperature, plagioclase crystallizes, Fe–Ti-oxide replaces spinel, olivine dissolves, and finally amphibole appears, producing gabbroic and then amphibole gabbroic crystallization stages. Enhanced plagioclase stability at lower pressure narrows the clinopyroxenitic interval and brings the gabbroic interval toward the liquidus. Liquids at 900 MPa track along Miyashiro’s (Am J Sci 274(4):321–355, 1974) tholeiitic versus calc-alkaline boundary, whereas those at 700 and 400 MPa become calc-alkaline at silica contents ≥56 wt%. This difference is chiefly due to higher temperature appearance of magnetite (versus spinel) at lower pressures. Although the evolved liquids are similar in many respects to common calc-alkaline andesites, the 900 and 700 MPa liquids differ in having low CaO concentrations due to early and abundant crystallization of augite, with the result that those liquids become peraluminous (ASI: molar Al/(Na + K + 2Ca) > 1) at ≥61 wt% SiO₂, similar to liquids reported in other studies of the high-pressure crystallization of hydrous basalts (Müntener and Ulmer in Geophys Res Lett 33(21):L21308, 2006). The lower-pressure liquids (400 MPa) have this same trait, but to a lesser extent due to more abundant near-liquidus plagioclase crystallization. A compilation of >6,500 analyses of igneous rocks from the Cascades and the Sierra Nevada batholith, representative of convergent margin (arc) magmas, shows that ASI increases continuously and linearly with SiO₂ from basalts to rhyolites or granites and that arc magmas are not commonly peraluminous until SiO₂ exceeds 69 wt%. These relations are consistent with plagioclase accompanying mafic silicates over nearly all the range of crystallization (or remelting). The scarcity of natural peraluminous andesites shows that progressive crystallization–differentiation of primitive basalts in the deep crust, producing early clinopyroxenitic cumulates and evolved liquids, does not dominate the creation of intermediate arc magmas or of the continental crust. Instead, mid- to upper-crustal differentiation and/or open-system processes are critical to the production of intermediate arc magmas. Primary among the open-system processes may be extraction of highly evolved (granitic, rhyolitic) liquids at advanced degrees of basalt solidification (or incipient partial melting of predecessor gabbroic intrusions) and mixing of such liquids into replenishing basalts. Furthermore, if the andesitic-composition continents derived from basaltic sources, the arc ASI–SiO₂ relation shows that the mafic component returned to the mantle was gabbroic in composition, not pyroxenitic.     

Experimental phase relations of a low MgO Aleutian basaltic andesite at XH2O = 0.7–1

We conducted melting experiments on a low MgO (3.29 wt.%) basaltic andesite (54.63 wt.% SiO₂) from Westdahl volcano, Alaska, at XH₂O = 0.7–1 and fO₂ ~ Ni–NiO, at pressures = 0.1–180 MPa and temperatures = 900–1,200 °C. We examine the evolution of the melt along a liquid line of descent during equilibrium crystallization at high H₂O and fO₂ conditions, starting from a high FeOt/MgO, low MgO basaltic andesite. Ti-magnetite formed on the liquidus regardless of XH₂O, followed by clinopyroxene, plagioclase, amphibole, and orthopyroxene. We observe slight but significant differences in the phase stability curves between the XH₂O = 1 and 0.7 experiments. Early crystallization of Ti-magnetite and suppression of plagioclase at higher pressures and temperatures resulted in strongly decreasing melt FeOt/MgO with increasing SiO₂, consistent with a “calc-alkaline” compositional trend, in agreement with prior phase equilibria studies on basalt at similar H₂O and fO₂. Our study helps quantify the impact of small amounts of CO₂ and high fO₂ on the evolution of melts formed during crystallization of a low MgO basaltic andesite magma stored at mid- to shallow crustal conditions. Like the prior studies, we conclude that H₂O strongly influences melt evolution trends, through stabilization of Ti-magnetite on the liquidus and suppression of plagioclase at high P–T conditions.     

Amphibole stability in primitive arc magmas: effects of temperature,H<Subscript>2</Subscript>O content,and oxygen fugacity

The water-saturated phase relations have been determined for a primitive magnesian andesite (57 wt% SiO₂, 9 wt% MgO) from the Mt. Shasta, CA region over the pressure range 200–800 MPa, temperature range of 915–1,070 °C, and oxygen fugacities varying from the nickel–nickel oxide (NNO) buffer to three log units above NNO (NNO+3). The phase diagram of a primitive basaltic andesite (52 wt% SiO₂, 10.5 wt% MgO) also from the Mt. Shasta region (Grove et al. in Contrib Miner Petrol 145:515–533; 2003) has been supplemented with additional experimental data at 500 MPa. Hydrous phase relations for these compositions allow a comparison of the dramatic effects of dissolved H₂O on the crystallization sequence. Liquidus mineral phase stability and appearance temperatures vary sensitively in response to variation in pressure and H₂O content, and this information is used to calibrate magmatic barometers-hygrometers for primitive arc magmas. H₂O-saturated experiments on both compositions reveal the strong dependence of amphibole stability on the partial pressure of H₂O. A narrow stability field is identified where olivine and amphibole are coexisting phases in the primitive andesite composition above 500 MPa and at least until 800 MPa, between 975–1,025 °C. With increasing H₂O pressure (\({P}_{\text {H}_2{\rm O}}\)), the temperature difference between the liquidus and amphibole appearance decreases, causing a change in chemical composition of the first amphibole to crystallize. An empirical calibration is proposed for an amphibole first appearance barometer-hygrometer that uses Mg# of the amphibole and \(f_{\text {O}_2}\):

$$ P_{\text{H}_{2}{\rm O}}({\rm MPa})=\left[{\frac{{\rm Mg\#}}{52.7}}-0.014 * \Updelta {\rm NNO}\right]^{15.12} $$

This barometer gives a minimum \({P}_{\text{H}_{2}{\rm O}}\) recorded by the first appearance of amphibole in primitive arc basaltic andesite and andesite. We apply this barometer to amphibole antecrysts erupted in mixed andesite and dacite lavas from the Mt. Shasta, CA stratocone. Both high H₂O pressures (500–900 MPa) and high pre-eruptive magmatic H₂O contents (10–14 wt% H₂O) are indicated for the primitive end members of magma mixing that are preserved in the Shasta lavas. We also use these new experimental data to explore and evaluate the empirical hornblende barometer of Larocque and Canil (2010).

     

Deep Fractionation of Clinopyroxene in the East Pacific Rise 13°N: Evidence from High MgO MORB and Melt Inclusions

Mid-ocean ridge basalts (MORBs) from East Pacific Rise (EPR) 13°N are analysed for major and trace elements, both of which show a continuous evolving trend. Positive MgO–Al2O3 and negative MgO–Sc relationships manifest the cotectic crystallization of plagioclase and olivine, which exist with the presence of plagioclase and olivine phenocrysts and the absence of clinopyroxene phenocrysts. However, the fractionation of clinopyroxene is proven by the positive correlation of MgO and CaO. Thus, MORB samples are believed to show a “clinopyroxene paradox”. The highest magnesium-bearing MORB sample E13-3B (MgO=9.52%) is modelled for isobaric crystallization with COMAGMAT at different pressures. Observed CaO/Al2O3 ratios can be derived from E13-3B only by fractional crystallization at pressure >4 ±1 kbar, which necessitates clinopyroxene crystallization and is not consistent with cotectic crystallization of olivine plus plagioclase in the magma chamber (at pressure ~1 kbar). The initial compositions of the melt inclusions, which could represent potential parental magmas, are reconstructed by correcting for post-entrapment crystallization (PEC). The simulated crystallization of initial melt inclusions also produce observed CaO/Al2O3 ratios only at >4±1 kbar, in which clinopyroxene takes part in crystallization. It is suggested that MORB magmas have experienced clinopyroxene fractionation in the lower crust, in and below the Moho transition zone. The MORB magmas have experienced transition from clinopyroxene+plagioclase+olivine crystallization at >4±1 kbar to mainly olivine+plagioclase crystallization at <1 kbar, which contributes to the explanation of the “clinopyroxene paradox”.     

Limestone assimilation by basaltic magmas: an experimental re-assessment and application to Italian volcanoes

The results of an experimental study of limestone assimilation by hydrated basaltic magmas in the range 1,050–1,150°C, 0.1–500 MPa are reported. Alkali basalts doped with up to 19 wt% of Ca, Mg-carbonates were equilibrated in internally heated pressure vessels and the resulting phase relationships are described. The major effects of carbonate incorporation are: (1) generation of CO₂-rich fluid phases; (2) change in liquidus phase equilibria; the crystallization of Ca-rich clinopyroxene is favored and the other phases (e.g. olivine, plagioclase), present in the absence of carbonate assimilation, are consumed. As a consequence of the massive clinopyroxene crystallization, the residual melt is strongly silica-depleted and becomes nepheline-normative. Compositional and mineralogical evolutions observed in Mt. Vesuvius eruptive products match those documented in our experiments with added carbonates, suggesting the possibility that carbonate assimilation increased during the last 25 ka of activity. In Central-Southern Italy, carbonate assimilation at shallow levels probably superimposes on deeper source heterogeneities.     

H<Subscript>2</Subscript>O solubility in basalt at upper mantle conditions

This study presents a new experimental approach for determining H₂O solubility in basaltic melt at upper mantle conditions. Traditional solubility experiments are limited to pressures of ~600 MPa or less because it is difficult to reliably quench silicate melts containing greater than ~10 wt% dissolved H₂O. To overcome this limitation, our approach relies on the use of secondary ion mass spectrometry to measure the concentration of H dissolved in olivine and on using the measured H in olivine as a proxy for the concentration of H₂O in the co-existing basaltic melt. The solubility of H₂O in the melt is determined by performing a series of experiments at a single pressure and temperature with increasing amounts of liquid H₂O added to each charge. The point at which the concentration of H in the olivine first becomes independent of the amount of initial H₂O content of the charge (added + adsorbed H₂O) indicates its solubility in the melt. Experiments were conducted by packing basalt powder into a capsule fabricated from San Carlos olivine, which was then pressure-sealed inside a Ni outer capsule. Our experimental results indicate that at 1000 MPa and 1200 °C, the solubility of H₂O in basaltic melt is 20.6 ± 0.9 wt% (2 × standard deviation). This concentration is considerably higher than predicted by most solubility models but defines a linear relationship between H₂O fugacity and the square of molar H₂O solubility when combined with solubility data from lower pressure experiments. Further, our solubility determination agrees with melting point depression determined experimentally by Grove et al. (2006) for the H₂O-saturated peridotite solidus at 1000 MPa. Melting point depression calculations were used to estimate H₂O solubility in basalt along the experimentally determined H₂O-saturated peridotite solidus. The results suggest that a linear relationship between H₂O fugacity and the square of molar solubility exists up to ~1300 MPa, where there is an inflection point and solubility begins to increase less strongly with increasing H₂O fugacity.     

Cumulate xenoliths from St. Vincent, Lesser Antilles Island Arc: a window into upper crustal differentiation of mantle-derived basalts

In order to shed light on upper crustal differentiation of mantle-derived basaltic magmas in a subduction zone setting, we have determined the mineral chemistry and oxygen and hydrogen isotope composition of individual cumulus minerals in plutonic blocks from St. Vincent, Lesser Antilles. Plutonic rock types display great variation in mineralogy, from olivine–gabbros to troctolites and hornblendites, with a corresponding variety of cumulate textures. Mineral compositions differ from those in erupted basaltic lavas from St. Vincent and in published high-pressure (4–10 kb) experimental run products of a St. Vincent high-Mg basalt in having higher An plagioclase coexisting with lower Fo olivine. The oxygen isotope compositions (δ¹⁸O) of cumulus olivine (4.89–5.18‰), plagioclase (5.84–6.28‰), clinopyroxene (5.17–5.47‰) and hornblende (5.48–5.61‰) and hydrogen isotope composition of hornblende (δD = −35.5 to −49.9‰) are all consistent with closed system magmatic differentiation of a mantle-derived basaltic melt. We employed a number of modelling exercises to constrain the origin of the chemical and isotopic compositions reported. δ¹⁸O_Olivine is up to 0.2‰ higher than modelled values for closed system fractional crystallisation of a primary melt. We attribute this to isotopic disequilibria between cumulus minerals crystallising at different temperatures, with equilibration retarded by slow oxygen diffusion in olivine during prolonged crustal storage. We used melt inclusion and plagioclase compositions to determine parental magmatic water contents (water saturated, 4.6 ± 0.5 wt% H₂O) and crystallisation pressures (173 ± 50 MPa). Applying these values to previously reported basaltic and basaltic andesite lava compositions, we can reproduce the cumulus plagioclase and olivine compositions and their associated trend. We conclude that differentiation of primitive hydrous basalts on St. Vincent involves crystallisation of olivine and Cr-rich spinel at depth within the crust, lowering MgO and Cr₂O₃ and raising Al₂O₃ and CaO of residual melt due to suppression of plagioclase. Low density, hydrous basaltic and basaltic andesite melts then ascend rapidly through the crust, stalling at shallow depth upon water saturation where crystallisation of the chemically distinct cumulus phases observed in this study can occur. Deposited crystals armour the shallow magma chamber where oxygen isotope equilibration between minerals is slowly approached, before remobilisation and entrainment by later injections of magma.     

The Role of CaCO<Subscript>3</Subscript> Reactions in the Contemporary Oceanic CO<Subscript>2</Subscript> Cycle

The present analysis adjusts previous estimates of global ocean CaCO₃ production rates substantially upward, to 133 × 10¹² mol yr^?1 plankton production and 42 × 10¹² mol yr^?1 shelf benthos production. The plankton adjustment is consistent with recent satellite-based estimates; the benthos adjustment includes primarily an upward adjustment of CaCO₃ production on so-called carbonate-poor sedimentary shelves and secondarily pays greater attention to high CaCO₃ mass (calcimass) and turnover of shelf communities on temperate and polar shelves. Estimated CaCO₃ sediment accumulation rates remain about the same as they have been for some years: ~20 × 10¹² mol yr^?1 on shelves and 11 × 10¹² mol yr^?1 in the deep ocean. The differences between production and accumulation of calcareous materials call for dissolution of ~22 × 10¹² mol yr^?1 (~50 %) of shelf benthonic carbonate production and 122 × 10¹² mol yr^?1 (>90 %) of planktonic production. Most CaCO₃ production, whether planktonic or benthonic, is assumed to take place in water depths of <100 m, while most dissolution is assumed to occur below this depth. The molar ratio of CO₂ release to CaCO₃ precipitation (CO₂↑/CaCO₃↓) is <1.0 and varies with depth. This ratio, Ψ, is presently about 0.66 in surface seawater and 0.85 in ocean waters deeper than about 1000 m. The net flux of CO₂ associated with CaCO₃ reactions in the global ocean in late preindustrial time is estimated to be an apparent influx from the atmosphere to the ocean, of +7 × 10¹² mol C yr^?1, at a time scale of 10²–10³ years. The CaCO₃-mediated influx of CO₂ is approximately offset by CO₂ release from organic C oxidation in the water column. Continuing ocean acidification will have effects on CaCO₃ and organic C metabolic responses to the oceanic inorganic C cycle, although those responses remain poorly quantified.     

Deep pre-eruptive storage of silicic magmas feeding Plinian and dome-forming eruptions of central and northern Dominica (Lesser Antilles) inferred from volatile contents of melt inclusions

Volatiles contribute to magma ascent through the sub-volcanic plumbing system. Here, we investigate melt inclusion compositions in terms of major and trace elements, as well as volatiles (H₂O, CO₂, SO₂, F, Cl, Br, S) for Quaternary Plinian and dome-forming dacite and andesite eruptions in the central and the northern part of Dominica (Lesser Antilles arc). Melt inclusions, hosted in orthopyroxene, clinopyroxene and plagioclase are consistently rhyolitic. Post-entrapment crystallisation effects are limited, and negligible in orthopyroxene-hosted inclusions. Melt inclusions are among the most water-rich yet recorded (≤?8 wt% H₂O). CO₂ contents are generally low (<?650 ppm), although in general the highest pressure melt inclusion contain the highest CO₂. Some low-pressure (<?3 kbars) inclusions have elevated CO₂ (up to 1100–1150 ppm), suggestive of fluxing of shallow magmas with CO₂-rich fluids. CO₂-trace element systematics indicate that melts were volatile-saturated at the time of entrapment and can be used for volatile-saturation barometry. The calculated pressure range (0.8–7.5 kbars) indicates that magmas originate from a vertically-extensive (3–27 km depth) storage zone within the crust that may extend to the sub-Dominica Moho (28 km). The vertically-extensive crustal system is consistent with mush models for sub-volcanic arc crust wherein mantle-derived mafic magmas undergo differentiation over a range of crustal depths. The other volatile range of composition for melt inclusions from the central part is F (75–557 ppm), Cl (1525–3137 ppm), Br (6.1–15.4 ppm) and SO₂ (<?140 ppm), and for the northern part it’s F (92–798 ppm), Cl (1506–4428 ppm), Br (not determined) and SO₂ (<?569; one value at 1015 ppm). All MIs, regardless of provenance, describe the same Cl/F correlation (8.3?±?2.7), indicating that the magma source at depth is similar. The high H₂O content of Dominica magmas has implications for hazard assessment.     

Amphibole megacrysts as a probe into the deep plumbing system of Merapi volcano,Central Java,Indonesia

Amphibole has been discussed to potentially represent an important phase during early chemical evolution of arc magmas, but is not commonly observed in eruptive arc rocks. Here, we present an in-depth study of metastable calcic amphibole megacrysts in basaltic andesites of Merapi volcano, Indonesia. Radiogenic Sr and Nd isotope compositions of the amphibole megacrysts overlap with the host rock range, indicating that they represent antecrysts to the host magmas rather than xenocrysts. Amphibole-based barometry suggests that the megacrysts crystallised at pressures of >500 MPa, i.e., in the mid- to lower crust beneath Merapi. Rare-earth element concentrations, in turn, require the absence of magmatic garnet in the Merapi feeding system and, therefore, place an uppermost limit for the pressure of amphibole crystallisation at ca. 800 MPa. The host magmas of the megacrysts seem to have fractionated significant amounts of amphibole and/or clinopyroxene, because of their low Dy/Yb ratios relative to the estimated compositions of the parent magmas to the megacrysts. The megacrysts’ parent magmas at depth may thus have evolved by amphibole fractionation, in line with apparently coupled variations of trace element ratios in the megacrysts, such as e.g., decreasing Zr/Hf with Dy/Yb. Moreover, the Th/U ratios of the amphibole megacrysts decrease with increasing Dy/Yb and are lower than Th/U ratios in the basaltic andesite host rocks. Uranium in the megacrysts’ parent magmas, therefore, may have occurred predominantly in the tetravalent state, suggesting that magmatic fO₂ in the Merapi plumbing system increased from below the FMQ buffer in the mid-to-lower crust to 0.6–2.2 log units above it in the near surface environment. In addition, some of the amphibole megacrysts experienced dehydrogenation (H₂ loss) and/or dehydration (H₂O loss), as recorded by their variable H₂O contents and D/H and Fe³⁺/Fe²⁺ ratios, and the release of these volatile species into the shallow plumbing system may facilitate Merapi’s often erratic eruptive behaviour.     

The evolution of the mantle source beneath Mt. Etna (Sicily,Italy): from the 600 ka tholeiites to the recent trachybasaltic magmas

ABSTRACT

The spatial/temporal proximity of Mt. Etna to the Hyblean Plateau and the Aeolian slab makes the discussion on the nature of its mantle source/s extremely controversial. In this study, a detailed geochemical overview of the entire Mt. Etna evolutionary sequence and a comparison with the magmatism of the Hyblean Plateau was proposed to: (i) simulate the composition of Mt. Etna tholeiitic to alkaline primitive magmas in equilibrium with a fertile mantle source; (ii) model the nature, composition and evolution of the mantle source from the tholeiitic stage (600 ka) to present magmatism. According to our simulations, two amphibole + phlogopite-bearing spinel lherzolite sources are able to explain the wide range of Etnean primary magmas. The enrichment in LILE, ⁸⁷Sr/⁸⁶Sr, Rb and H₂O of the magmas emitted after 1971 (but also discontinuously generated in both historic and prehistoric times) are caused by different melting proportions of amphibole and phlogopite in a modally and compositionally homogeneous mantle domain, with melting degrees analogous to those required to produce magmas erupted prior to 1971. The behaviour of the hydrous phases during melting could be ascribed to a variable H₂O/CO₂ activity in the mantle source, in turn related to the heat/fluxes supply from the asthenospheric upwelling beneath Mt. Etna. All these considerations, strengthened by numerical models, are then merged to review the complex Pliocene/Lower Pleistocene to present day’s geodynamic evolution of eastern Sicily.     

Contrasting compositional trends of rocks and olivine-hosted melt inclusions from Cerro Negro volcano (Central America): implications for decompression-driven fractionation of hydrous magmas

Melt inclusions in olivine Fo_83–72 from tephras of 1867, 1971 and 1992 eruptions of Cerro Negro volcano represent a series of basaltic to andesitic melts of narrow range of MgO (5.6–8 wt %) formed by ~46 wt % fractional crystallization of olivine (~6 wt %), plagioclase (~27 wt %), pyroxene (~13 wt %) and magnetite (<1 wt %) from primitive basaltic melt (average SiO₂ = 49 wt %, MgO = 7.6 wt %, H₂O = 6 wt %) as it ascended to the surface from the depth of about 14 km. The crystallization occurred at increasing liquidus temperature from 1,050 to 1,090 °C in the pressure range from 400 to 50 MPa and was induced by release of mixed H₂O–CO₂ fluid from the melt at decreasing pressure. Matrix glass compositions fall at the high-Si end of the melt inclusion trend and represent the final stage of melt crystallization during and after eruption. The bulk compositions of erupted Cerro Negro magmas (tephras and lavas) range from high- to low-MgO (3–10 wt %) basalts, which form a compositional array crossing the trend of melt inclusions so that virtually no rock from Cerro Negro has composition akin to true melt represented by the inclusions. The variations of the bulk magma (rocks) and melt (melt inclusions) compositions can be generated in a dyke connecting a deep primitive magma reservoir with the Cerro Negro edifice. While the melt inclusions represent the compositional trend of instantaneous melts along the magma pathway at decreasing pressure and H₂O content, occurrence of low-Mg to high-Mg basalts reflects the process of phenocryst re-distribution in progressively evolving melt. The crystallization scenario is anticipated to operate everywhere in dykes feeding basaltic volcanoes and can explain the predominance of plagioclase-rich high-Al basalts in island arc as well as typical compositional variations of magmas during single eruptions.     

Mineralogy and proposed P-T paths of basaltic lavas from Rabaul caldera,Papua New Guinea

Rabaul caldera is a large volcanic depression at the north-east tip of New Britain, Papua New Guinea. The lavas range in composition from basalt to rhyolite and have a calc-alkalic affinity but also display features typical of tholeiites, including moderate absolute iron enrichment in flows cropping out around the caldera. The basalts contain phenocrysts of plagioclase and clinopyroxene with less abundant olivine and titanomagnetite. In the basaltic andesites olivine is rare, while orthopyroxene and titanomagnetite are common along with plagioclase and clinopyroxene. Orthopyroxene is also found mantling olivine in some of the basalts while in both rock types pigeonitic augite is a fairly common constituent of the groundmass. Plagioclase in both basalt and basaltic andesite often exhibits sieve texture and analysis of the glass blebs show them to be of similar composition to the bulk rock. Phenocrystic clinopyroxene is a diopsidic augite in both basalt and basaltic andesite. Al₂O₃ content of the clinopyroxene is moderately high (4%) and often shows considerable variation in any one grain. Calculations show that the microphenocrysts probably crystallised near the surface, while phenocrysts crystallised at around 7 kb (21 km). Neither the basalts nor the basaltic andesites would have been in equilibrium at any geologically reasonable P and T with quartz eclogite. Equilibration between mantle peridotite and a. typical Rabaul basaltic liquid could have occurred around 35 kb and 1270 °C. A basaltic andesite liquid yields a temperature of 1263 °C and a pressure of 28 kb for equilibration with mantle peridotite.Partial melting of sufficient volumes of mantle peridotite at these P's and T's requires about 15% H₂O, but there is no evidence that these magmas ever contained large amounts of water. It is proposed that the Rabaul magmas were initially generated by partial melting of subducted lithosphere and subsequently modified by minor partial melting as they passed through the overlying mantle peridotite.     

The effect of alkalis and polymerization on the solubility of H<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> in alkali-rich silicate melts

The effect of alkalis on the solubility of H₂O and CO₂ in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with H₂O/(H₂O + CO₂) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in H₂O solubility (melt equilibrated with pure H₂O fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO₂ content in melts equilibrated with CO₂-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/T = 0.17) to 0.45 wt % for shoshonite (NBO/T = 0.38) to 0.90 wt % for AH2 (NBO/T = 0.55). The highest CO₂ contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/T, CO₂ solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO₂ solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO₂ solubility at 500 MPa and 1,100–1,300 °C in various silicate melts as a function of the NBO/T, (Na + K)/∑cations and Na/(Na + K) parameters: \({\text{wt}}\% \;{\text{CO}}_{2} = - 0.246 + 0.014\exp \left( {6.995 \cdot \frac{\text{NBO}}{T}} \right) + 3.150 \cdot \frac{{{\text{Na}} + {\text{K}}}}{{\varSigma {\text{cations}}}} + 0.222 \cdot \frac{\text{Na}}{{{\text{Na}} + {\text{K}}}}.\) This model is valid for melt compositions with NBO/T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz–fayalite–magnetite buffer and above.     

CO<Subscript>2</Subscript> mineralization of natural wollastonite into porous silica and CaCO<Subscript>3</Subscript> powders promoted via membrane electrolysis

CO₂ is a greenhouse gas, whose emissions threaten the existence of human beings. Its inherently safe sequestration can be performed via CO₂ mineralization, which is relatively slow under natural conditions. In this work, an energy-saving membrane electrolysis technique was proposed for accelerating the CO₂ mineralization of wollastonite into SiO₂ and CaCO₃ products. The electrolysis process involved splitting NH₄Cl into HCl and NH₃·H₂O via hydrogen oxidation and water reduction at the anode and cathode of the electrolytic system, respectively. In contrast to the chlor-alkali electrolysis, this method did not involve Cl^? oxidation and the standard potential of the anode was reduced. Additionally, NH₄Cl was used as the electrolyte instead of NaCl; as a result, the generation of NH₃·H₂O instead of NaOH occurred in the catholyte and the cathodic pH dramatically decreased, thus reducing the cathodic potential for hydrogen evolution. The observed changes led to a 73.5% decrease in the energy consumption. Moreover, after the process of CO₂ mineralization was optimized, SiO₂ with a specific surface area of 221.8 m² g^?1 and CaCO₃ with a purity of 99.9% were obtained.     

Fractional crystallization of primitive,hydrous arc magmas: an experimental study at 0.7 GPa

Differentiation of mantle-derived, hydrous, basaltic magmas is a fundamental process to produce evolved intermediate to SiO₂-rich magmas that form the bulk of the middle to shallow continental and island arc crust. This study reports the results of fractional crystallization experiments conducted in a piston cylinder apparatus at 0.7 GPa for hydrous, calc-alkaline to arc tholeiitic magmas. Fractional crystallization was approached by synthesis of starting materials representing the liquid composition of the previous, higher temperature experiment. Temperatures ranged from near-liquidus at 1,170 °C to near-solidus conditions at 700 °C. H₂O contents varied from 3.0 to more than 10 wt%. The liquid line of descent covers the entire compositional range from olivine–tholeiite (1,170 °C) to high-silica rhyolite (700 °C) and evolves from metaluminous to peraluminous compositions. The following crystallization sequence has been established: olivine → clinopyroxene → plagioclase, spinel → orthopyroxene, amphibole, titanomagnetite → apatite → quartz, biotite. Anorthite-rich plagioclase and spinel are responsible for a marked increase in SiO₂-content (from 51 to 53 wt%) at 1,040 °C. At lower temperatures, fractionation of amphibole, plagioclase and Fe–Ti oxide over a temperature interval of 280 °C drives the SiO₂ content continuously from 53 to 78 wt%. Largest crystallization steps were recorded around 1,040 °C and at 700 °C. About 40 % of ultramafic plutonic rocks have to crystallize to generate basaltic–andesitic liquids, and an additional 40 % of amphibole–gabbroic cumulate to produce granitic melts. Andesitic liquids with a liquidus temperature of 1,010 °C only crystallize 50 % over an 280 °C wide range to 730 °C implying that such liquids form mobile crystal mushes (<50 % crystals) in long-lived magmatic systems in the middle crust, allowing for extensive fractionation, assimilation and hybridization with periodic replenishment of more mafic magmas from deeper magma reservoirs.     

Petrogenesis of Sierra Nevada plutons inferred from the Sr, Nd, and O isotopic signatures of mafic igneous complexes in Yosemite Valley, California

Mafic complexes in the central Sierra Nevada batholith record valuable geochemical information regarding the role mafic magmas play in arc magmatism and the generation of continental crust. In the intrusive suite of Yosemite Valley, major and trace element compositions of the hornblende-bearing gabbroic rocks from the Rockslides mafic complex and of the mafic dikes in the North America Wall are compositionally similar to high-alumina basalt. Of these rocks, two samples have higher Ni and Cr abundances as well as higher ε_Nd values than previously recognized for the intrusive suite. Plagioclase crystals in rocks from the North America Wall and the Rockslides have prominent calcic cores and sharply defined sodic rims, a texture commonly associated with mixing of mafic and felsic magmas. In situ analyses of ⁸⁷Sr/⁸⁶Sr in plagioclase show no significant isotopic difference from the cores to the rims of these grains. We propose that the high ⁸⁷Sr/⁸⁶Sr (~0.7067) and low ε_Nd (~?3.4) of bulk rocks, the homogeneity of ⁸⁷Sr/⁸⁶Sr in plagioclase, and the high δ¹⁸O values of bulk rocks (6.6–7.3 ‰) and zircon (Lackey et al. in J Petrol 49:1397–1426, 2008) demonstrate that continental crust was assimilated into the sublithospheric mantle-derived basaltic precursors of the mafic rocks in Yosemite Valley. Contamination (20–40 %) likely occurred in the lower crust as the magma differentiated to high-alumina basalt prior to plagioclase (and zircon) crystallization. As a consequence, the isotopic signatures recorded by whole rocks, plagioclase, and zircon do not represent the composition of the underlying lithospheric mantle. We conclude that the mafic and associated felsic members of the intrusive suite of Yosemite Valley represent 60–80 % new additions to the crust and include significant quantities of recycled ancient crust.     

Textural and compositional evidence for magma mixing and its mechanism,Abu volcano group,southwestern Japan

Quaternary basalts, andesites and dacites from the Abu monogenetic volcano group, SW Japan, (composed of more than 40 monogenetic volcanoes) show two distinct chemical trends especially on the FeO^*/MgO vs SiO₂ diagram. One trend is characterized by FeO^*/MgO-enrichment with a slight increase in SiO₂ content (Fe-type trend), whereas the other shows a marked SiO₂-enrichment with relatively constant FeO^*/MgO ratios (Si-type trend). The Fe-type trend is explained by fractional crystallization with subtraction of olivine and augite from a primitive alkali basalt magma. Rocks of the Si-type trend are characterized by partially melted or resorbed quartz and sodic plagioclase phenocrysts and/or fine-grained basaltic inclusions. They are most likely products of mixing of a primitive alkali basalt magma containing olivine phenocrysts with a dacite magma containing quartz, sodic plagioclase and hornblende phenocrysts. Petrographic variation as well as chemical variation from basalt to dacite of the Si-type trend is accounted for by various mixing ratios of basalt and dacite magmas. Pargasitic hornblende and clinopyroxene phenocrysts in andesite and dacite may have crystallized from basaltic magma during magma mixing. Olivine and spinel, and quartz, sodic plagioclase and common hornblende had crystallized in basaltic and dacitic magmas, respectively, before the mixing. Within a lava flow, the abundance of basaltic inclusions decreases from the area near the eruptive vent towards the perimeter of the flow, and the number of resorbed phenocrysts varies inversely, suggesting zonation in the magma chamber.The mode of mixing changes depending on the mixing ratio. In the mafic mixture, basalt and dacite magmas can mix in the liquid state (liquid-liquid mixing). In the silicic mixture, on the other hand, the basalt magma was quenched and formed inclusions (liquid-solid mixing). During mixing, the disaggregated basalt magma and the host dacite magma soon reached thermal equilibrium. Compositional homogenization of the mixed magma can occur only when the equilibrium temperature is sufficiently above the solidus of the basalt magma. The Si-type trend is chemically and petrographically similar to the calc-alkalic trend. Therefore, a calc-alkalic trend which is distinguished from a fractional crystallization trend (e.g. Fe-type trend) may be a product of magma mixing.     

The origin of island arc high-alumina basalts

A detailed examination of the hypothesis that high-alumina basalts (HAB) in island arcs are primary magmas derived by 50–60% partial melting of subducted ocean crust eclogite shows that this model is unlikely to be viable. Evidence suggests that the overwhelming majority of arc HAB are porphyritic lavas, enriched in Al₂O₃ either by protracted prior crystallization of olivine and clinopyroxene, or by plagioclase phenocryst accumulation in magmas of basaltic andesite to dacite composition. Experimentally-determined phase relationships of such plagioclase-enriched (non-liquid) compositions have little bearing on the petrogenesis of arc magmas, and do not rule out the possibility that arc HAB can be derived by fractionation of more primitive arc lavas. Although models invoking eclogite-melting can match typical arc HAB REE patterns, calculations indicate that the Ni and Cr contents of proposed Aleutian primary HAB are many times lower than such models predict. In contrast, Ni vs Sc and Cr vs Sc trends for arc HAB are readily explained by olivine (+Cr-sp) and clinopyroxene-dominated fractionation from more primitive arc magmas. GENMIX major element modelling of several HAB compositions as partial melts of MORB eclogite, using appropriate experimentally (26–34 kb)-determined garnet and omphacite compositions yields exceptionally poor matches, especially for CaO, Na₂O, MgO and Al₂O₃. These mismatches are easily explained if the HAB are plagioclase-accumulative. Groundmasses of arc HAB are shown to vary from basaltic andesite to dacite in composition. Crystal fractionation driving liquid compositions toward dacite involves important plagioclase separation, resulting in development of significant negative Eu anomalies in more evolved lavas. Plagioclase accumulation in such evolved liquids tends to diminish or eliminate negative Eu anomalies. Therefore, the absence of positive Eu anomaly in a plagioclase-phyric HAB does not indicate that plagioclase has not accumulated in that lava. In addition, we show that plagioclase phenocrysts in arc HAB are not in equilibrium with the liquids in which they were carried (groundmass). Exceptional volumes of picrite and olivine basalt occur in the Solomons and Vanuatu arcs; the presence in lavas from these and other arcs (Aleutian, Tonga) of olivine phenocrysts to Fo₉₄, finds no ready explanation in the primary eclogite-derived HAB model. We suggest that most lavas in intra-oceanic arcs are derived from parental magmas with >10% MgO; fractionation of olivine (+Cr-sp) and clinopyroxene drives liquids to basalt compositions with <7% MgO, but plagioclase nucleation is delayed by their low but significant (<1%?) H₂O contents. Thus evolved liquid compositions in the basaltic andesite—andesite range may achieve relatively high Al₂O₃ contents (<17.5%). The majority of arc basalts, however, have Al₂O₃ contents in excess of 18%, reflecting plagioclase accumulation. We give new experimental data to show that HAB liquids may be generated by anhydrous, low-degree (<10%) partial melting of peridotite at P<18 kb. Relative to arc HAB, these experimental melts have notably higher Mg#(69–72) and are in equilibrium with olivine Fo_87–89. Only further detailed trace element modelling will show if they might be parental magmas for some arc HAB.