The H<Subscript>2</Subscript>O solubility of alkali basaltic melts: an experimental study

Experiments were conducted to determine the water solubility of alkali basalts from Etna, Stromboli and Vesuvius volcanoes, Italy. The basaltic melts were equilibrated at 1,200°C with pure water, under oxidized conditions, and at pressures ranging from 163 to 3,842 bars. Our results show that at pressures above 1 kbar, alkali basalts dissolve more water than typical mid-ocean ridge basalts (MORB). Combination of our data with those from previous studies allows the following simple empirical model for the water solubility of basalts of varying alkalinity and fO₂ to be derived: \textH ₂ \textO( \textwt% ) = \text H ₂ \textO_\textMORB ( \textwt% ) + ( 5.84 ×10 ^{- 5} *\textP - 2.29 ×10 ^{- 2} ) ×( \textNa₂ \textO + \textK₂ \textO )( \textwt% ) + 4.67 ×10 ^{- 2} ×\Updelta \textNNO - 2.29 ×10 ^{- 1} {\text{H}}_{ 2} {\text{O}}\left( {{\text{wt}}\% } \right) = {\text{ H}}_{ 2} {\text{O}}_{\text{MORB}} \left( {{\text{wt}}\% } \right) + \left( {5.84 \times 10^{ - 5} *{\text{P}} - 2.29 \times 10^{ - 2} } \right) \times \left( {{\text{Na}}_{2} {\text{O}} + {\text{K}}_{2} {\text{O}}} \right)\left( {{\text{wt}}\% } \right) + 4.67 \times 10^{ - 2} \times \Updelta {\text{NNO}} - 2.29 \times 10^{ - 1} where H₂O_MORB is the water solubility at the calculated P, using the model of Dixon et al. (1995). This equation reproduces the existing database on water solubilities in basaltic melts to within 5%. Interpretation of the speciation data in the context of the glass transition theory shows that water speciation in basalt melts is severely modified during quench. At magmatic temperatures, more than 90% of dissolved water forms hydroxyl groups at all water contents, whilst in natural or synthetic glasses, the amount of molecular water is much larger. A regular solution model with an explicit temperature dependence reproduces well-observed water species. Derivation of the partial molar volume of molecular water using standard thermodynamic considerations yields values close to previous findings if room temperature water species are used. When high temperature species proportions are used, a negative partial molar volume is obtained for molecular water. Calculation of the partial molar volume of total water using H₂O solubility data on basaltic melts at pressures above 1 kbar yields a value of 19 cm³/mol in reasonable agreement with estimates obtained from density measurements.     

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     

The mechanisms of water diffusion in polymerized silicate melts

Diffusion of water was experimentally investigated for melts of albitic (Ab) and quartz-orthoclasic (Qz₂₉Or₇₁, in wt %) compositions with water contents in the range of 0 to 8.5 wt % at temperatures of 1100 to 1200 °C and at pressures of 1.0 and 5.0 kbar. Apparent chemical diffusion coefficients of water (D _water) were determined from concentration-distance profiles measured by FTIR microspectroscopy. Under the same P-T condition and water content the diffusivity of water in albitic, quartz-orthoclasic and haplogranitic (Qz₂₈Ab₃₈ Or₃₄, Nowak and Behrens, this issue) melts is identical within experimental error. Comparison to data published in literature indicates that anhydrous composition only has little influence on the mobility of water in polymerized melts but that the degree of polymerization has a large effect. For instance, D_water is almost identical for haplogranitic and rhyolitic melts with 0.5–3.5 wt % water at 850 °C but it is two orders of magnitude higher in basaltic than in haplogranitic melts with 0.2–0.5 wt % water at 1300 °C. Based on the new water diffusivity data, recently published in situ near-infrared spectroscopic data (Nowak 1995; Nowak and Behrens 1995), and viscosity data (Schulze et al. 1996) for hydrous haplogranitic melts current models for water diffusion in silicate melts are critically reviewed. The NIR spectroscopy has indicated isolated OH groups, pairs of OH groups and H₂O molecules as hydrous species in polymerized silicate melts. A significant contribution of isolated OH groups to the transport of water is excluded for water contents above 10 ppm by comparison of viscosity and water diffusion data and by inspection of concentration profiles from trace water diffusion. Spectroscopic measurements have indicated that the interconversion of H₂O molecules and OH pairs is relatively fast in silicate glasses and melts even at low temperature and it is inferred that this reaction is an active step for migration of water. However, direct jumps of H₂O molecules from one cavity within the silicate network to another one can not be excluded. Thus, we favour a model in which water migrates by the interconversion reaction and, possibly, small sequences of direct jumps of H₂O molecules. In this model, immobilization of water results from dissociation of the OH pairs. Assuming that the frequency of the interconversion reaction is faster than that of diffusive jumps, OH pairs and water molecules can be treated as a single diffusing species having an effective diffusion coefficient . The shape of curves of D_water versus water content implies that increases with water content. The change from linear to exponential dependence of D_water between 2 and 3 wt % water is attributed to the influence of the dissociation reaction at low water content and to the modification of the melt structure by incorporation of OH groups. Received: 26 March 1996 / Accepted: 23 August 1996     

Petrological and experimental evidence for differentiation of water-rich magmas beneath St. Kitts,Lesser Antilles

St. Kitts lies in the northern Lesser Antilles, a subduction-related intraoceanic volcanic arc known for its magmatic diversity and unusually abundant cognate xenoliths. We combine the geochemistry of xenoliths, melt inclusions and lavas with high pressure–temperature experiments to explore magma differentiation processes beneath St. Kitts. Lavas range from basalt to rhyolite, with predominant andesites and basaltic andesites. Xenoliths, dominated by calcic plagioclase and amphibole, typically in reaction relationship with pyroxenes and olivine, can be divided into plutonic and cumulate varieties based on mineral textures and compositions. Cumulate varieties, formed primarily by the accumulation of liquidus phases, comprise ensembles that represent instantaneous solid compositions from one or more magma batches; plutonic varieties have mineralogy and textures consistent with protracted solidification of magmatic mush. Mineral chemistry in lavas and xenoliths is subtly different. For example, plagioclase with unusually high anorthite content (An_≤100) occurs in some plutonic xenoliths, whereas the most calcic plagioclase in cumulate xenoliths and lavas are An₉₇ and An₉₅, respectively. Fluid-saturated, equilibrium crystallisation experiments were performed on a St. Kitts basaltic andesite, with three different fluid compositions (XH₂O = 1.0, 0.66 and 0.33) at 2.4 kbar, 950–1025 °C, and fO₂ = NNO ? 0.6 to NNO + 1.2 log units. Experiments reproduce lava liquid lines of descent and many xenolith assemblages, but fail to match xenolith and lava phenocryst mineral compositions, notably the very An-rich plagioclase. The strong positive correlation between experimentally determined plagioclase-melt Kd_Ca–Na and dissolved H₂O in the melt, together with the occurrence of Al-rich mafic lavas, suggests that parental magmas were water-rich (> 9 wt% H₂O) basaltic andesites that crystallised over a wide pressure range (1.5–6 kbar). Comparison of experimental and natural (lava, xenolith) mafic mineral composition reveals that whereas olivine in lavas is predominantly primocrysts precipitated at low-pressure, pyroxenes and spinel are predominantly xenocrysts formed by disaggregation of plutonic mushes. Overall, St. Kitts xenoliths and lavas testify to mid-crustal differentiation of low-MgO basalt and basaltic andesite magmas within a trans-crustal, magmatic mush system. Lower crustal ultramafic cumulates that relate parental low-MgO basalts to primary, mantle -derived melts are absent on St. Kitts.     

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.     

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.     

Generation of calc-alkaline andesite of the Tatun volcanic group (Taiwan) within an extensional environment by crystal fractionation

The Pliocene–Pleistocene northern Taiwan volcanic zone (NTVZ) is located within a trench-arc–back-arc basin and oblique arc–continent collision zone. Consequently the origin and tectonic setting of the andesitic rocks within the NTVZ and their relation to other circum-Pacific volcanic island-arc systems is uncertain. Rocks collected from the Tatun volcanic group (TTVG) include basaltic to andesitic rocks. The basalt is compositionally similar to within-plate continental tholeiites whereas the basaltic andesite and andesite are calc-alkaline; however, all rocks show a distinct depletion of Nb-Ta in their normalized incompatible element diagrams. The Sr-Nd isotope compositions of the TTVG rocks are very similar and have a relatively restricted range (i.e. I_Sr = 0.70417–0.70488; εNd_(T) = +2.2 to +3.1), suggesting that they are derived directly or indirectly from the same mantle source. The basalts are likely derived by mixing between melts from the asthenosphere and a subduction-modified subcontinental lithospheric mantle (SCLM) source, whereas the basaltic andesites may be derived by partial melting of pyroxenitic lenses within the SCLM and mixing with asthenospheric melts. MELTS modelling using a starting composition equal to the most primitive basaltic andesite, shallow-pressure (i.e. ≤1 kbar), oxidizing conditions (i.e. FMQ +1), and near water saturation will produce compositions similar to the andesites observed in this study. Petrological modelling and the Sr-Nd isotope results indicate that the volcanic rocks from TTVG, including the spatially and temporally associated Kuanyinshan volcanic rocks, are derived from the same mantle source and that the andesites are the product of fractional crystallization of a parental magma similar in composition to the basaltic andesites. Furthermore, our results indicate that, in some cases, calc-alkaline andesites may be generated by crystal fractionation of mafic magmas derived in an extensional back-arc setting rather than a subduction zone setting.     

Magmatic processes that generated the rhyolite of Glass Mountain, Medicine Lake volcano, N. California

Glass Mountain consists of a 1 km³, compositionally zoned rhyolite to dacite glass flow containing magmatic inclusions and xenoliths of underlying shallow crust. Mixing of magmas produced by fractional crystallization of andesite and crustal melting generated the rhyolite of Glass Mountain. Melting experiments were carried out on basaltic andesite and andesite magmatic inclusions at 100, 150 and 200 MPa, H₂O-saturated with oxygen fugacity controlled at the nickel-nickel oxide buffer to provide evidence of the role of fractional crystallization in the origin of the rhyolite of Glass Mountain. Isotopic evidence indicates that the crustal component assimilated at Glass Mountain constitutes at least 55 to 60% of the mass of erupted rhyolite. A large volume of mafic andesite (2 to 2.5 km³) periodically replenished the magma reservoir(s) beneath Glass Mountain, underwent extensive fractional crystallization and provided the heat necessary to melt the crust. The crystalline residues of fractionation as well as residual liquids expelled from the cumulate residues are preserved as magmatic inclusions and indicate that this fractionation process occurred at two distinct depths. The presence and composition of amphibole in magmatic inclusions preserve evidence for crystallization of the andesite at pressures of at least 200 MPa (6 km depth) under near H₂O-saturated conditions. Mineralogical evidence preserved in olivine-plagioclase and olivine-plagioclase-high-Ca clinopyroxene-bearing magmatic inclusions indicates that crystallization under near H₂O-saturated conditions also occurred at pressures of 100 MPa (3 km depth) or less. Petrologic, isotopic and geochemical evidence indicate that the andesite underwent fractional crystallization to form the differentiated melts but had no chemical interaction with the melted crustal component. Heat released by the fractionation process was responsible for heating and melting the crust. Received: 26 March 1996 / Accepted: 14 November 1996     

Oxygen diffusion in basalt and andesite melts: experimental results and discussion of chemical versus tracer diffusion

Chemical diffusion coefficients for oxygen in melts of Columbia River basalt (Ice Harbor Dam flow) and Mt. Hood andesite have been determined at 1 atm. The diffusion model is that of sorption or desorption of oxygen into a sphere of uniform initial concentration from a constant and semi-infinite atmosphere. The experimental design utilizes a thermogravimetric balance to monitor the rate of weight change arising from the response of the sample redox state to an imposed fO₂. Oxygen diffusion coefficients are approximately an order-ofmagnitude greater for basaltic melt than for andesitic melt. At 1260° C, the oxygen diffusion coefficients are: D=1.65×10^–6cm²/s and D=1.43×10^–7cm²/s for the basalt and andesite melts, respectively. The high oxygen diffusivity in basaltic melt correlates with a high ratio of nonbridging oxygen/tetrahedrally coordinated cations, low melt viscosity, and high contents of network-modifying cations. The dependence of the oxygen diffusion coefficient on temperature is: D=36.4exp(–51,600±3200/RT)cm²/s for the basalt and D=52.5exp(–60,060±4900/RT)cm²/s for the andesite (R in cal/deg-mol; T in Kelvin). Diffusion coefficients are independent of the direction of oxygen diffusion (equilibrium can be approached from extremely oxidizing or reducing conditions) and thus, melt redox state. Characteristic diffusion distances for oxygen at 1260° C vary from 10^-2 to 10² m over the time interval of 1 to 10⁶ years. A compensation diagram shows two distinct trends for oxygen chemical diffusion and oxygen tracer diffusion. These different linear relationships are interpreted as supporting distinct oxygen transport mechanisms. Because oxygen chemical diffusivities are generally greater than tracer diffusivities and their Arrhenius activation energies are less, transport mechanisms involving either molecular oxygen or vacancy diffusion are favored.     

H2O diffusion in dacitic and andesitic melts

The diffusion of water in dacitic and andesitic melts was investigated at temperatures of 1458 to 1858 K and pressures between 0.5 and 1.5 GPa using the diffusion couple technique. Pairs of nominally dry glasses and hydrous glasses containing between 1.5 and 6.3 wt.% dissolved H₂O were heated for 60 to 480 s in a piston cylinder apparatus. Concentration profiles of hydrous species (OH groups and H₂O molecules) and total water (C_H2Ot = sum of OH and H₂O) were measured along the cylindrical axis of the diffusion sample using IR microspectroscopy. Electron microprobe traverses show no significant change in relative proportions of anhydrous components along H₂O profiles, indicating that our data can be treated as effective binary interdiffusion between H₂O and the rest of the silicate melt. Bulk water diffusivity (D_H2Ot) was derived from profiles of total water using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between D_H2Ot and C_H2Ot. In dacitic melts D_H2Ot is proportional to C_H2Ot up to 6 wt.%. In andesitic melts the dependence of D_H2Ot on C_H2Ot is less pronounced. A pressure effect on water diffusivity could not be resolved for either dacitic or andesitic melt in the range 0.5 to 1.5 GPa. Combining our results with previous studies on water diffusion in rhyolite and basalt show that for a given water content D_H2Ot increases monotonically with increasing melt depolymerization at temperatures >1500 K. Assuming an Arrhenian behavior in the whole compositional range, the following formulation was derived to estimate D_H2Ot (m²/s) at 1 wt.% H₂O_t in melts with rhyolitic to andesitic composition as a function of T (K), P (MPa) and S (wt.% SiO₂):

     

Sulphur solubility in andesitic to basaltic melts: implications for Hekla volcano

The solubility of sulphur in sulphide-saturated, H₂O-bearing basaltic–andesitic and basaltic melts from Hekla volcano (Iceland) has been determined experimentally at 1,050°C, 300 and 200 MPa, and redox conditions with oxygen fugacity (logfO₂) between QFM−1.2 and QFM+1.1 (QFM is a quartz–fayalite–magnetite oxygen buffer) in the systems containing various amounts of S and H₂O. The S content of the H₂O-rich glasses saturated with pyrrhotite decreases from 2,500 ppm in basalt to 1,500 ppm in basaltic andesite at the investigated conditions. Furthermore, the reduction of water content in the melt at pyrrhotite saturation and fixed T, P and redox conditions leads to a decrease in S concentration from 2,500 to 1,400 ppm for basaltic experiments (for H₂O decrease from 7.8 to 1.4 wt%) and from 1,500 to 900 ppm (for H₂O decrease from 6.7 to 1.7 wt%) for basaltic andesitic experiments. Our experimental data, combined with silicate melt inclusion investigations and the available models on sulphide saturation in mafic magmas, indicate that the parental basaltic melts of Hekla were not saturated with respect to sulphide. During magmatic differentiation, the S content in the residual melts increased and might have reached sulphide saturation with 2,500 ppm dissolved S. With further magma crystallization, the S concentration in the melt was controlled by the sulphide saturation of the magma, decreasing from ~2,500 to 900 ppm S.     

Experimental investigations of the role of H2O in calc-alkaline differentiation and subduction zone magmatism

Phase relations of natural aphyric high-alumina basalts and their intrusive equivalents were determined through rock-melting experiments at 2 kb, H₂O-saturated with fO₂ buffered at NNO. Experimental liquids are low-MgO high-alumina basalt or basaltic andesite, and most are saturated with olivine, calcic plagioclase, and either high-calcium pyroxene or hornblende (±magnetite). Cr-spinel or magnetite appear near the liquidus of wet high-alumina basalts because H₂O lowers the appearance temperature of crystalline silicates but has a lesser effect on spinel. As a consequence, experimental liquids follow calcalkaline differentiation trends. Hornblende stability is sensitive to the Na₂O content of the bulk composition as well as to H₂O content, with the result that hornblende can form as a near liquidus mineral in wet sodic basalts, but does not appear until liquids reach andesitic compositions in moderate Na₂O basalts. Therefore, the absence of hornblende in basalts with low-to-moderate Na₂O contents is not evidence that those basalts are nearly dry. Very calcic plagioclase (>An₉₀) forms from basaltic melts with high H₂O contents but cannot form from dry melts with normal are Na₂O and CaO abundances. The presence of anorthite-rich plagioclase in high-alumina basalts indicates high magmatic H₂O contents. In sum, moderate pressure H₂O-saturated phase relations show that magmatic H₂O leads to the early crystallization of spinel, produces calcic plagioclase, and reduces the total proportion of plagioclase in the crystallizing assemblage, thereby promoting the development of the calc-alkaline differentiation trend.     

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.     

Calc-alkaline, Shoshonitic, and Primitive Tholeiitic Lavas from Monogenetic Volcanoes near Crater Lake, Oregon

Quaternary monogenetic volcanism in the High Cascades of Oregonis manifested by cinder cones, lava fields, and small shields.Near Crater Lake caldera, monogenetic lava compositions include:low-K (as low as 0?09% K₂O) high-alumina olivine tholeiite (HAOT);medium-K. calc-alkaline basalt, basaltic andesite, and andesite;and shoshonitic basaltic andesite (2?1% K₂O, 1750 ppm Sr at54% SiO₂). Tholeiites have MORB-like trace element abundancesexcept for elevated Sr, Ba, and Th and low high field strengthelements (HFSE), and they represent near-primary liquids. Theyare similar to HAOTs from the Cascades and adjacent Basin andRange, and to many primitive basalts from intraoceanic arcs.Calc-alkaline lavas show a well-developed arc signature of highlarge-ion lithophile elements (LILE) and low HFSE. Their Zrand Hf concentrations are at least partly decoupled from thoseof Nb and Ta; HREE are low relative to HAOT. Incompatible elementabundances and ratios vary widely among basaltic andesites.Some calc-alkaline lavas vented near Mount Mazama contain abundantgabbroic microxcnoliths, and are basaltic andesitic magmas contaminatedwith olivine gabbro. A calc-alkaline basalt and a few basaltic andesites have MgOand compatible trace element contents that suggest only minorfractionation. There appears to be a compositional continuumbetween primitive tholeiitic and calc-alkaline lavas. Compositionalvariation within suites of comagmatic primitive lavas, boththoleiitic and calc-alkaline, mainly results from differentdegrees of partial melting. Sources of calc-alkaline primarymagmas were enriched in LILE and LREE by a subduction componentand contained residual garnet, whereas sources of HAOTs hadlower LILE and LREE concentrations and contained residual clinopyroxene.High and variable LILE and LREE contents of calc-alkaline lavasreflect variations in fluid-transported subduction componentadded to the mantle wedge, degree of partial melting, and possiblyalso interaction with rocks or partial melts in the lower crust. Andesites were derived from calc-alkaline basaltic andesitesby fractionation of plagioclase+augite+magnetite+apatite ? orthopyroxeneor olivine, commonly accompanied by assimilation. Many andesitesare mixtures of andesitic or dacitic magma and a basaltic orbasaltic andesitic component, or are contaminated with gabbroicmaterial. Mingled basalt, andesite, and dacite of Williams Craterformed by multi-component, multi-stage mixing of basaltic andesiticmagma, gabbro, and dacitic magma. The wide range of compositionsvented from monogenetic volcanoes near Crater Lake is a resultof the thick crust coupled with mild tectonic extension superimposedon a subduction-related magmatic arc.     

Water speciation and diffusion in haploandesitic melts at 743-873 K and 100 MPa

Water is an important volatile component in andesitic eruptions and deep-seated andesitic magma chambers. We report an investigation of H₂O speciation and diffusion by dehydrating haploandesitic melts containing ?2.5 wt.% water at 743-873 K and 100 MPa in cold-seal pressure vessels. FTIR microspectroscopy was utilized to measure species [molecular H₂O (H₂O_m) and hydroxyl group (OH)] and total H₂O (H₂O_t) concentration profiles on the quenched glasses from the dehydration experiments. The equilibrium constant of the H₂O speciation reaction H₂O_m+O?2OH, K = (X_OH)²/(X_H2OmX_O) where X means mole fraction on a single oxygen basis, in this Fe-free andesite varies with temperature as ln K = 1.547-2453/T where T is in K. Comparison with previous speciation data on rhyolitic and dacitic melts indicates that, for a given water concentration, Fe-free andesitic melt contains more hydroxyl groups. Water diffusivity at the experimental conditions increases rapidly with H₂O concentration, contrary to previous H₂O diffusion data in an andesitic melt at 1608-1848 K. The diffusion profiles are consistent with the model that molecular H₂O is the diffusion species. Based on the above speciation model, H₂O_m and H₂O_t diffusivity (in m²/s) in haploandesite at 743-873 K, 100 MPa, and H₂O_t ? 2.5 wt.% can be formulated as

     

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.     

Petrology and geochemistry of Early Tertiary volcanism of the Mendejin area,Iran, and implications for magma genesis and tectonomagmatic setting

The Mendejin area, NW Iran, is part of the western Alborz-Azarbaijan zone which is one of the most structurally—and magmatically-active zones of Iran. Volcanic rocks with calc-alkaline and, locally, alkaline features cover an extensive part of this zone. The Mendejin volcanic rocks, Eocene-Oligocene in age, include tuffs and volcanoclastic rocks of dacite, andesite, basaltic andesite, and basalt composition. Felsic (andesite, dacite, and rhyodacite) and basic rocks (basalt, basaltic andesite and andesite) commonly occur in successive layers. This alternation along with multiple occurrences of various types of tuffs suggests prolonged and successive magmatic activity during Eocene-Oligocene in NW Iran. Fractional crystallization has been the most important factor controlling geochemical characteristics of the magma. However, absence of linear correlations on variation diagrams of some immobile elements (such as Al₂O₃, TiO₂, P₂O₅ and Ga) and poorly-developed trends on variation diagrams of Na₂O, MgO, MnO, CaO, Fe₂O₃, Nb, Nd, Y, La, Ce, Th, Hf, Sc, Zn, V, Ni and Co versus SiO₂ indicate that, other than crystal (olivine, pyroxene, plagioclase, biotite, hornblende, zircon, monazite and apatite) fractionation, crustal processes (such as assimilation) have also affected the chemistry of the Mendejin magma. It appears that the basic magma has originated from the mantle whereas the felsic magma resulted from modification in the mantle-derived magma by assimilation in an active continental margin.     

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     

Primitive basalts and andesites from the Mt. Shasta region,N. California: products of varying melt fraction and water content

Quaternary volcanism in the Mt. Shasta region has produced primitive magmas [Mg/(Mg+Fe^*)>0.7, MgO>8 wt% and Ni>150 ppm] ranging in composition from high-alumina basalt to andesite and these record variable extents ofmelting in their mantle source. Trace and major element chemical variations, petrologic evidence and the results of phase equilibrium studies are consistent with variations in H₂O content in the mantle source as the primary control on the differences in extent of melting. High-SiO₂, high-MgO (SiO₂=52% and MgO=11 wt%) basaltic andesites resemble hydrous melts (H₂O=3 to 5 wt%) in equilibrium with a depleted harzburgite residue. These magmas represent depletion of the mantle source by 20 to 30 wt% melting. High-SiO₂, high-MgO (SiO₂=58% and MgO=9 wt%) andesites are produced by higher degrees of melting and contain evidence for higher H₂O contents (H₂O=6 wt%). High-alumina basalts (SiO₂=48.5% and Al₂O₃=17 wt%) represent nearly anhydrous low degree partial melts (from 6 to 10% depletion) of a mantle source that has been only slightly enriched by a fluid component derived from the subducted slab. The temperatures and pressures of last equilibration with upper mantle are 1200°C and 1300°C for the basaltic andesite and basaltic magmas, respectively. A model is developed that satisfies the petrologic temperature constraints and involves magma generation whereby a heterogeneous distribution of H₂O in the mantle results in the production of a spectrum of mantle melts ranging from wet (calc-alkaline) to dry (tholeiitic).     

H2O diffusion models in rhyolitic melt with new high pressure data

Water diffusion in silicate melts is important for understanding bubble growth in magma, magma degassing and eruption dynamics of volcanos. Previous studies have made significant progress on water diffusion in silicate melts, especially rhyolitic melt. However, the pressure dependence of H₂O diffusion is not constrained satisfactorily. We investigated H₂O diffusion in rhyolitic melt at 0.95–1.9 GPa and 407–1629 °C, and 0.2–5.2 wt.% total water (H₂O_t) content with the diffusion-couple method in a piston-cylinder apparatus. Compared to previous data at 0.1–500 MPa, H₂O diffusivity is smaller at higher pressures, indicating a negative pressure effect. This pressure effect is more pronounced at low temperatures. Assuming H₂O diffusion in rhyolitic melt is controlled by the mobility of molecular H₂O (H₂O_m), the diffusivity of H₂O_m (D_H2Om) at H₂O_t ≤ 7.7 wt.%, 403–1629 °C, and ≤ 1.9 GPa is given by

D_H2Om=D₀exp(aX),