Volatile content and degassing processes in the AD 79 magma chamber at Vesuvius (Italy)

The evolution of volatiles in the AD 79 magma chamber at Vesuvius (Italy) was investigated through the study of melt inclusions (MI) in crystals of different origins. FTIR spectroscopy and EMPA were used to measure H₂O, CO₂, S and Cl of the different melts. This allowed us to define the volatile content of the most evolved, phonolitic portion of the magma chamber and of the mafic melts feeding the chamber. MI in sanidine from phonolitic and tephri-phonolitic pumices show systematic differences in composition and volatile content, which can be explained by resorption of the host mineral during syn-eruptive mixing. The pre-eruption content of phonolitic magma appears to have been dominated by H₂O and Cl (respectively 6.0 to 6.5 wt% and 6700 ppm), while magma chamber refilling occurred through the repeated injection of H₂O, CO₂ and S-rich tephritic magmas (respectively 3%, 1500 ppm and 1400 ppm). Strong CO₂ degassing probably occurred during the decompressional path of mafic batches towards the magma chamber, while sulphur was probably released by the magma following crystallization and mixing processes. Water and chlorine strongly accumulated in the magma and reached their solubility limits only during the eruption. Chlorine solubility appears to have been strongly compositionally controlled, and Cl release was inhibited by groundmass crystallization of leucite, which shifted the composition of the residual liquid towards higher Cl solubilities. Received: 28 October 1999 / Accepted: 21 April 2000     

Complex zoning between super-calcic pigeonite and augite from the Graveyard Point sill, Oregon: a record of the interplay between bulk and interstitial liquid fractionation

The 150 m thick late Miocene Graveyard Point sill (GPS) is situated at the Idaho-Oregon border near the southwestern edge of the western Snake River Plain. It records from bottom to top continuous fractional crystallization of a tholeiitic parent magma (lower chilled border, FeO/(FeO+MgO) = 0.59, Ni = 90 ppm) towards granophyres (late pods and dikes, FeO/(FeO+MgO) = 0.98, 78 wt% SiO₂ 3.5 wt% K₂O, <4 ppm Ni) showing a typical trend of Fe and P enrichment. Fractionating minerals are olivine (Fo₇₉-Fo₂), augite (X _Fe = 0.18−0.95), feldspars (An₈₀Or₁-An₁Or₆₂), Fe-Ti oxides (Ti-rich magnetite and ilmenite), apatite and in two samples super-calcic pigeonite (Wo_18–28 Fs_41–54). The granophyres may bear some quartz. Compositionally zoned minerals record a large interval of the fractionation process in every single sample, but this interval changes with stratigraphic height. In super-calcic pigeonite-bearing samples, olivine is scarce or lacking and because super-calcic pigeonite occurs as characteristic overgrowths on augite, its formation is interpreted to be related to the schematic reaction: augite + olivine (component in melt) + SiO₂ (in melt) = pigeonite, that defines the cotectic between augite and pigeonite in olivine-saturated basaltic systems. Line measurements with the electron microprobe reveal that the transition from augite to super-calcic pigeonite is continuous. However, some crystals show an abrupt “reversal” towards augite after super-calcic pigeonite growth. Two processes compete with each other in the GPS: fractional crystallization of the bulk liquid (the bulk melt separates from solids and interstitial liquids in the solidification front) and fractional crystallization of interstitial melt in the solidification front itself. Interplay between those two processes is proposed to account for the observed variations in mineral chemistry and mineral textures. Received: 25 November 1998 / Accepted: 14 June 1999     

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     

Experimental investigation of H2O and Cl− solubilities in F-enriched silicate liquids; implications for volatile saturation of topaz rhyolite magmas

To interpret the degassing of F-bearing felsic magmas, the solubilities of H₂O, NaCl, and KCl in topaz rhyolite liquids have been investigated experimentally at 2000, 500, and ≈1 bar and 700° to 975 °C. Chloride solubility in these liquids increases with decreasing H₂O activity, increasing pressure, increasing F content of the liquid from 0.2 to 1.2 wt% F, and increasing the molar ratio of ((Al + Na + Ca + Mg)/Si). Small quantities of Cl⁻ exert a strong influence on the exsolution of magmatic volatile phases (MVPs) from F-bearing topaz rhyolite melts at shallow crustal pressures. Water- and chloride-bearing volatile phases, such as vapor, brine, or fluid, exsolve from F-enriched silicate liquids containing as little as 1 wt% H₂O and 0.2 to 0.6 wt% Cl at 2000 bar compared with 5 to 6 wt% H₂O required for volatile phase exsolution in chloride-free liquids. The maximum solubility of Cl⁻ in H₂O-poor silicate liquids at 500 and 2000 bar is not related to the maximum solubility of H₂O in chloride-poor liquids by simple linear and negative relationships; there are strong positive deviations from ideality in the activities of each volatile in both the silicate liquid and the MVP(s). Plots of H₂O versus Cl⁻ in rhyolite liquids, for experiments conducted at 500 bar and 910°–930 °C, show a distinct 90° break-in-slope pattern that is indicative of coexisting vapor and brine under closed-system conditions. The presence of two MVPs buffers the H₂O and Cl⁻ concentrations of the silicate liquids. Comparison of these experimentally-determined volatile solubilities with the pre-eruptive H₂O and Cl⁻ concentrations of five North American topaz and tin rhyolite melts, determined from melt inclusion compositions, provides evidence for the exsolution of MVPs from felsic magmas. One of these, the Cerro el Lobo magma, appears to have exsolved alkali chloride-bearing vapor plus brine or a single supercritical fluid phase prior to entrapment of the melt inclusions and prior to eruption. Received: 6 November 1995 / Accepted: 29 January 1998     

Petrogenesis of the amphibole-rich veins from the Lherz orogenic lherzolite massif (Eastern Pyrenees, France): a case study for the origin of orthopyroxene-bearing amphibole pyroxenites in the lithospheric mantle

The Lherz orogenic lherzolite massif (Eastern French Pyrenees) displays one of the best exposures of subcontinental lithospheric mantle containing veins of amphibole pyroxenites and hornblendites. A reappraisal of the petrogenesis of these rocks has been attempted from a comprehensive study of their mutual structural relationships, their petrography and their mineral compositions. Amphibole pyroxenites comprise clinopyroxene, orthopyroxene and spinel as early cumulus phases, with garnet and late-magmatic K₂O-poor pargasite replacing clinopyroxene, and subsolidus exsolution products (olivine, spinel II, garnet II, plagioclase). The original magmatic mineralogy and rock compositions were partly obscured by late-intrusive hornblendites and over a few centimetres by vein–wallrock exchange reactions which continued down to subsolidus temperatures for Mg–Fe. Thermobarometric data and liquidus parageneses indicate that amphibole pyroxenites started to crystallize at P ≥ 13 kbar and recrystallized at P < 12 kbar. The high Al^VI/Al^IV ratio (>1) of clinopyroxenes, the early precipitation of orthopyroxene and the late-magmatic amphibole are arguments for parental melts richer in silica but poorer in water than alkali basalts. Their modelled major element compositions are similar to transitional alkali basalt with about 1–3 wt% H₂O. In contrast to amphibole pyroxenites, hornblendites only show kaersutite as liquidus phase, and phlogopite as intercumulus phase. They are interpreted as crystalline segregates from primary basanitic magmas (mg=0.6; 4–6 wt% H₂O). These latter cannot be related to the parental liquids of amphibole pyroxenites by a fractional crystallization process. Rather, basanitic liquids mostly reused pre-existing pyroxenite vein conduits at a higher structural level (P ≤ 10 kbar). A continuous process of redox melting and/or alkali melt/peridotite interaction in a veined lithospheric mantle is proposed to account for the origin of the Lherz hydrous veins. The transitional basalt composition is interpreted in terms of extensive dissolution of olivine and orthopyroxene from wallrock peridotite by alkaline melts produced at the mechanical boundary layer/thermal boundary layer transition (about 45–50 km deep). Continuous fluid ingress allowed remelting of the deeper veined mantle to produce the basanitic, strongly volatiles enriched, melts that precipitated hornblendites. A similar model could be valid for the few orthopyroxene-rich hydrous pyroxenites described in basalt-hosted mantle xenoliths. Received: 15 September 1999 / Accepted: 31 January 2000     

Volatiles H2O,CO2, and Cl in a subduction related basalt

The products of the 1974 eruption of Fuego, a subduction zone volcano in Guatemala, have been investigated through study of silicate melt inclusions in olivine. The melt inclusions sampled liquids in regions where olivine, plagioclase, magnetite, and augite were precipitating. Comparisons of the erupted ash, groundmass, and melt inclusion compositions suggest that the inclusions represent samples of liquids present in a thermal boundary layer of the magma body. The concentrations of H₂O and CO₂ in glass inclusions were determined by a vacuum fusion manometric technique using individual olivine crystals (Fo77 to Fo71) with glass inclusion compositions that ranged from high-alumina basalt to basaltic andesite. Water, Cl, and K₂O concentrations increased by a factor of two as the olivine crystals became more iron-rich (Fo77 to Fo71) and as the glass inclusions increased in SiO₂ from 51 to 54 wt.% SiO₂. The concentration of H₂O in the melt increased from 1.6 wt.% in the least differentiated liquid to about 3.5% in a more differentiated liquid. Carbon dioxide is about an order of magnitude less abundant than H₂O in these inclusions. The gas saturation pressures for pure H₂O in equilibrium with the melt inclusions, which were calculated from the glass inclusion compositions using the solubility model of Burnham (1979), are given approximately by P(H₂O)(Pa)=(SiO₂−48.5 wt.%) × 1.45 × 10⁷. The concentrations of water in the melt and the gas saturation pressures increased from about 1.5% to 3.5% and from 300 to 850 bars, respectively, during pre-eruption crystallization.     

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).     

Experimental constraints on the effects of pressure and H2O on the fractional crystallization of high-Mg island arc basalt

H₂O-undersaturated melting experiments of synthesized basalt (SiO₂ = 50.7 wt.%, MgO = 8.3 wt.%, Mg# = 60) were conducted at fO₂ corresponding to NNO+1 and NNO−1 to clarify the effects of pressure (2–7 kbar) and H₂O on fractional crystallization in island arcs. H₂O content was ranged from nominally anhydrous to 4.4 wt.%. Differentiation trends, namely the liquid lines of descent, change sensitively according to pressure-H₂O relations. Tholeiitic differentiation trends are reproduced with H₂O ≤ ∼2 wt.% in primary magma. With such quantities of H₂O, fractional crystallization is controlled by olivine + plagioclase at 2 kbar. Increasing the pressure from 2 to ≥4 kbar induces early crystallization of orthopyroxene instead of olivine and therefore SiO₂ enrichment in the residual melts is suppressed. Increasing H₂O (≥ ∼2 wt.% in primary magma) stabilizes clinopyroxene relative to orthopyroxene and/or magnetite. Although the phase relations and proportions strongly depend on fO₂ and H₂O content, differentiation trends are always calc-alkaline.     

Liquidus temperatures and phase compositions in the system Qz-Ab-Or at 5 kbar and very low water activities

Liquidus phase relations have been experimentally determined in the systems Qz-Ab-Or-(H₂O), Qz-Ab-(H₂O) and Qz-Or-(H₂O) at H₂O-undersaturated conditions (a _H2O = 0.07) and P = 5 kbar. Starting materials were homogeneous synthetic glasses containing 1 wt% H₂O. The liquidus temperatures were bracketed by crystallization and dissolution experiments. The results of kinetic studies showed that crushed glasses are the best starting materials to overcome undercooling and to minimize the temperature difference between the lowest temperature of complete dissolution (melting) and the highest temperature at which crystallization can be observed. At P = 5 kbar and a _H2O = 0.07, the Qz-Ab eutectic composition is Qz₃₂Ab₆₈ at 1095 °C (±10 °C) and the Qz-Or eutectic is Qz₃₈Or₆₂ at 1030 °C (±10 °C). The minimum temperature of the ternary system Qz-Ab-Or is 990 °C (±10 °C) and the minimum composition is Qz₃₂Ab₃₅‐ Or₃₃. The Qz content of the minimum composition in the system Qz-Ab-Or-H₂O remains constant with changing a _H2O. The normative Or content, however, increases by approximately 10 wt% with decreasing a _H2O from 1 to 0.07. Such an increase has already been observed in the system Qz-Ab-Or-H₂O-CO₂ at high a _H2O and it is concluded that the use of CO₂ to reduce water activities does not influence the composition of the minima in quartz-feldspar systems. The determined liquidus temperature in melts with 1 wt% H₂O is very similar to that obtained in previous nominally “dry” experiments. This discrepancy is interpreted to be due to problems in obtaining absolutely dry conditions. Thus, the hitherto published solidus and liquidus temperatures for “dry” conditions are probably underestimated. Received: 27 March 1997 / Accepted: 1 October 1997     

Plagioclase-free andesites from Zitácuaro (Michoacán), Mexico: petrology and experimental constraints

Approximately 150 km west of Mexico City in the central part of the Mexican Volcanic Belt (MVB) near Zitácuaro, Mexico, young volcanism has produced shield volcanoes, large volume silicic deposits, and fault-related basalt and andesite lava flows and cinder cones. This paper concerns a small cluster of Pleistocene andesite cones and flows which can be separated into two distinct groups: high-magnesium andesites (>6% MgO, 57–59% SiO₂), conveniently called basaltic andesites, with phenocrysts of orthopyroxene and augite, or augite and olivine; and andesites (60–62% SiO₂, <4.6% MgO), which have phenocrysts of orthopyroxene and augite, and ghosts of relict hornblende. Remarkably, plagioclase phenocrysts are absent, and evenly distributed but sparse (0.5–3.5%) quartz xenocrysts are present in all the lavas. In order to establish the conditions under which early crystallizing plagioclase is suppressed in these lavas, water saturated experiments up to 3 kbars were performed on one of the basaltic andesites. The conditions required to reproduce the phenocryst assemblages (either olivine + augite or opx + augite) are temperatures in excess of 1000 °C, with water saturated liquids (>3 wt%) at pressures of about 1 kbar. Compared to basaltic andesites of western Mexico, the Zitácuaro basaltic andesites have ∼2 wt% lower Al₂O₃ concentrations, which causes plagioclase to precipitate at significantly lower temperatures, and it therefore follows the crystallization sequence: olivine, augite, and orthopyroxene. Based on ubiquitous quartz xenocrysts, with glassy rhyolitic inclusions, a reasonable conclusion is that substantial mixing of a quartz-bearing rhyolitic magma with a parental basaltic andesite has occurred at low pressure (shallow depth), and this would account for the low Al₂O₃ concentrations in the Zitácuaro basaltic andesites. Whatever the mechanism of incorporation, the quartz xenocrysts are evidence of contamination of basaltic magma with more siliceous material, thus making it difficult to use these magmas as indicators of mantle melting processes. Received: 29 July 1997 / Accepted: 29 January 1998     

Crystallization of primitive basaltic magmas at crustal pressures and genesis of the calc-alkaline igneous suite: experimental evidence from St Vincent,Lesser Antilles arc

Near-liquidus crystallization experiments have been carried out on two basalts (12.5 and 7.8 wt% MgO) from Soufriere, St Vincent (Lesser Antilles arc) to document the early stages of differentiation in calc-alkaline magmas. The water-undersaturated experiments were performed mostly at 4 kbar, with 1.6 to 7.7 wt% H₂O in the melt, and under oxidizing conditions (ΔNNO = −0.8 to +2.4). A few 10 kbar experiments were also performed. Early differentiation of primitive, hydrous, high-magnesia basalts (HMB) is controlled by ol + cpx + sp fractionation. Residual melts of typical high-alumina basalt (HAB) composition are obtained after 30–40% crystallization. The role of H₂O in depressing plagioclase crystallization leads to a direct relation between the Al₂O₃ content of the residual melt and its H₂O concentration, calibrated as a geohygrometer. The most primitive phenocryst assemblage in the Soufriere suite (Fo_89.6 olivine, Mg-, Al- and Ti-rich clinopyroxene, Cr–Al spinel) crystallized from near-primary (Mg# = 73.5), hydrous (∼5 wt% H₂O) and very oxidized (ΔNNO = +1.5–2.0) HMB liquids at middle crustal pressures and temperatures from ∼1,160 to ∼1,060°C. Hornblende played no role in the early petrogenetic evolution. Derivative HAB melts may contain up to 7–8 wt% dissolved H₂O. Primitive basaltic liquids at Soufriere, St Vincent, have a wide range of H₂O concentrations (2–5 wt%).     

Origin of calc-alkaline series lavas at Medicine Lake Volcano by fractionation,assimilation and mixing

The results of experimental studies and examination of variations in major elements, trace elements and Sr isotopes indicate that fractionation, assimilation and magma mixing combined to produce the lavas at Medicine Lake Highland. Some characteristics of the compositional differences among the members of the calc-alkalic association (basalt-andesite-dacite-rhyolite) can be produced by fractional crystallization, and a fractionation model reproduces the major element trends. Other variations are inconsistent with a fractionation origin. Elevated incompatible element abundances (K and Rb) observed in lavas intermediate between basalt and rhyolite can be produced through assimilation of a crustal component. An accompanying increase in ⁸⁷Sr/⁸⁶Sr from ∼ 0.07030 in basalt to ∼0.7040 in rhyolite is also consistent with crustal assimilation. The compatible trace element contents (Ni and Sr) of intermediate lavas can not be produced by fractional crystallization, and suggest a magma-mixing origin for some lavas. Unusual phenocryst assemblages and textural criteria in these lavas provide additional evidence for magma mixing. A phase diagram constructed from the low pressure melting experiments identifies a distributary reaction point, where olivine+augite react to pigeonite. Parental basalts reach this point at low pressures and undergo iron-enrichment at constant SiO₂ content. The resulting liquid line of descent is characteristic of the tholeiitic trend. Calc-alkalic differentiation trends circumvent the distributary reaction point by three processes: fractionation at elevated pH₂O, assimilation and magma mixing.     

Microtextures and crystal chemistry in P21/c pigeonites

Summary ?A single-crystal X-ray investigation was performed on crystals of P2₁/c natural pigeonite with varying Ca and Fe^* ( = Fe²⁺ + Mn²⁺) contents, in order to verify the effect of microtextural disorder on structure refinements and to constrain the crystal chemistry of pigeonite. Antiphase domains and exsolution lamellae affect differently the refinement results. In a crystal free of exsolution the structure obtained after refinement with all reflections is an average of that of the antiphase domains and of their boundaries, whereas in an exsolved crystal it represents only the structure of the prevailing pigeonite lamellae. The refinement using only h + k odd reflections seems to give the structure of the Ca-free pigeonite characteristic of the antiphase domains rather than that of Ca-rich domain walls. The ratio of the scale factors in refinements with all reflections and with only h + k odd reflections allows the ratios of the exsolved augite and pigeonite phases to be estimated. The crystal chemistry of the investigated samples follows the trends outlined by data on Ca-free and Fe-free synthetic samples. In particular, it is shown that Ca and Fe^* substitution for Mg induce similar changes in the average structure, i.e. both induce an expansion in the M1 polyhedron and decrease the difference between the M2–O3 distances. Received October 18, 2001; revised version accepted February 15, 2002     

An experimental study of the effects of melt composition on plagioclase-melt equilibria at 5 and 10 kbar: implications for the origin of magmatic high-An plagioclase

An experimental investigation of plagioclase crystallization in broadly basaltic/andesitic melts of variable Ca# (Ca/(Ca+Na)*100) and Al# (Al/(Al+Si)*100) values and H₂O contents has been carried out at high pressures (5 and 10 kbar) in a solid media piston-cylinder apparatus. The H₂O contents of glasses coexisting with liquidus or near-liquidus plagioclases in each experiment were determined via an FTIR spectroscopic technique. This study has shown that melt Ca# and Al#, H₂O content and crystallization pressure all control the composition of liquidus plagioclase. Increasing melt Ca# and Al# increase An content of plagioclase, whereas the effect of increasing pressure is the opposite. However, the importance of the role played by each of these factors during crystallization of natural magmas varies. Melt Ca# has the strongest control on plagioclase An content, but melt Al# also exerts a significant control. H₂O content can notably increase the An content of plagioclase, up to 10 mol % for H₂O-undersaturated melts, and 20 mol % for H₂O-saturated melts. Exceptionally calcic plagioclases (up to An₁₀₀) in some primitive subduction-related boninitic and related rocks cannot be attributed to the presence of the demonstrated amounts of H₂O (up to 3 wt %). Rather, they must be due to the involvement of extremely refractory (CaO/Na₂O>18) magmas in the petrogenesis of these rocks. Despite the refractory nature of some primitive MORB glasses, none are in equilibrium with the most calcic plagioclase (An₉₄) found in MORB. These plagioclases were likely produced from more refractory melts with CaO/Na₂O = 12–15, or from melts with exceptionally high Al₂O₃(>18%). Magmas of appropriate compositions to crystallize these most calcic plagioclases are sometimes found as melt inclusions in near liquidus phenocrysts from these rocks, but are not known among wholerock or glass compositions. The fact that such melts are not erupted as discrete magma batches indicates that they are effectively mixed and homogenized with volumetrically dominant, less refractory magmas. The high H₂O contents (∼ 6 wt%) in some high-Al basaltic arc magmas may be responsible for the existence of plagioclases up to An₉₅ in arc lavas. However, an alternative possibility is that petrogenesis involving melts with abnormally high CaO/Na₂O values (> 8) may account for the presence of highly anorthitic plagioclases in these rocks. Received: 31 August 1993 / Accepted: 20 May 1994     

Depths of Partial Crystallization of H2O-bearing MORB: Phase Equilibria Simulations of Basalts at the MAR near Ascension Island (7 11{degrees}S)

Phase equilibria simulations were performed on naturally quenchedbasaltic glasses to determine crystallization conditions priorto eruption of magmas at the Mid-Atlantic Ridge (MAR) east ofAscension Island (7–11°S). The results indicate thatmid-ocean ridge basalt (MORB) magmas beneath different segmentsof the MAR have crystallized over a wide range of pressures(100–900 MPa). However, each segment seems to have a specificcrystallization history. Nearly isobaric crystallization conditions(100–300 MPa) were obtained for the geochemically enrichedMORB magmas of the central segments, whereas normal (N)-MORBmagmas of the bounding segments are characterized by polybariccrystallization conditions (200–900 MPa). In addition,our results demonstrate close to anhydrous crystallization conditionsof N-MORBs, whereas geochemically enriched MORBs were successfullymodeled in the presence of 0·4–1 wt% H₂O in theparental melts. These estimates are in agreement with direct(Fourier transform IR) measurements of H₂O abundances in basalticglasses and melt inclusions for selected samples. Water contentsdetermined in the parental melts are in the range 0·04–0·09and 0·30–0·55 wt% H₂O for depleted and enrichedMORBs, respectively. Our results are in general agreement (within±200 MPa) with previous approaches used to evaluate pressureestimates in MORB. However, the determination of pre-eruptiveconditions of MORBs, including temperature and water contentin addition to pressure, requires the improvement of magma crystallizationmodels to simulate liquid lines of descent in the presence ofsmall amounts of water. KEY WORDS: MORB; Mid-Atlantic Ridge; depth of crystallization; water abundances; phase equilibria calculations; cotectic crystallization; pressure estimates; polybaric fractionation     

Liquid Lines of Descent of Island Arc Magmas and Genesis of Rhyolites: Evidence from the Shirahama Group, Japan

The Mio-Pliocene Shirahama Group, Izu Peninsula, Central Japan,a well-exposed submarine volcanic arc complex of lava flows,pyroclastic rocks and associated shallow intrusives, is characterizedby a tholeiitic series (basalt to dacite) and a calc-alkalineseries (andesite to dacite). Chemical variations in the tholeiiticseries and calc-alkaline series are consistent with crystalfractionation from basalt and magnesian andesite (boninite),respectively. Crystal–liquid phase relations of thesemagmas have been investigated by study of sample suites fromthese two series. Compositions of liquids in equilibrium withphenocrysts were determined by microprobe grid analyses, inwhich 49 points were averaged in 03 mm 03 mm groundmassareas. The liquid compositions, coupled with the phenocrystmineralogy of the same samples, define the liquid lines of descentof these volcanic arc magmas. Major findings include the following:(1) Crystallization of the tholeiitic series magma is consistentwith early stage crystallization in the simple system Fo–Di–Silica–H₂O,with olivine having a reaction relation to augite and the tholeiiticliquid. (2) The later stage products of the tholeiitic seriesmagma are, however, crystal-poor (<10%) dacites with no maficminerals, suggesting that tholeiitic liquids, hypersthene andaugite were no longer on the cotectic (3) A characteristic ofthe calc-alkaline series magmas is the development of rhyoliticliquids. Hypersthene, augite, plagioclase and Fe–Ti oxideoccur in most calc-alkaline rocks studied, and hornblende andquartz can be found in about half of these. However, their differentiationpaths show that the cotectic relation between quartz and liquidended at a later stage, resulting in the resorption of quartzphenocrysts and ultimately in the formation of quartz-free magmas.(4) The late-stage liquids of both the tholeiitic and calc-alkalineseries have deviated from their cotectics, which cannot be explainedby fractional crystallization alone. The addition of H₂O froman outside system is probably required to explain the differentiationpaths. (5) The formation of chilled margins, the in situ crystallizationof a magma chamber in the solidification zone, and/or the migrationof groundwater into the magma chamber are thought to be likelyprocesses affecting magmas during their migration and intrusioninto the crust. An extreme effect of H₂O addition would be tolower the liquidus temperatures of all precipitating silicatephases far below their restorable range before eruption, resultingin the production of aphyric magmas. Even when a temperaturedecrease in the magma chamber causes a liquid to intersect theliquidus of a pre-existing phase, the addition of H₂O shiftsthe cotectic toward SiO₂, resulting in quartz being the lastphase to crystallize. The resorption of quartz is interpretedto be the result of a liquidus boundary shift caused by theaddition of H₂O. The genesis of aphyric rhyolites is thereforeinferred to result from fractional crystallization followingaddition of H₂0. KEY WORDS: Shirahama Group; Japan; island arc; rhyolite; magma series     

The behavior of chlorine and sulfur during differentiation of the Mt. Somma-Vesuvius magmatic system

Summary Reheated silicate melt inclusions in volcanic rock samples from Mt. Somma-Vesuvius, Italy, have been analyzed for 29 constituents including H₂O, S, Cl, F, B, and P₂O₅. This composite volcano consists of the older Mt. Somma caldera, formed between 14 and 3.55 ka before present, and the younger Vesuvius cone. The melt inclusion compositions provide important constraints on pre-eruptive magma geochemistry, identify relationships that relate to eruption behavior and magma evolution, and provide extensive evidence for magmatic fluid exsolution well before eruption. The melt inclusion data have been categorized by groups that reflect magma compositions, age, and style of eruptions. The data show distinct differences in composition for eruptive products older than 14.0 ka (pre-caldera rocks) versus eruptive products younger than 3.55 ka. Moreover, pre-caldera eruptions were associated with magmas relatively enriched in SiO₂, whereas eruptions younger than 3.55 ka (i.e., the syn- and post-caldera magmas which generated the Somma caldera and the Vesuvius cone) were derived from magmas comparatively enriched in S, Cl, CaO, MgO, P₂O₅, F, and many lithophile trace elements. Melt inclusion data indicate that eruptive behavior at Vesuvius correlates with pre-eruptive volatile enrichments. Most magmas associated with explosive plinian and subplinian events younger than 3.55 ka contained more H₂O, contained significantly more S, and exhibited higher (S/Cl) ratios than syn- and post-caldera magmas which erupted during relatively passive interplinian volcanic phenomena. Received January 10, 2000 Revised version accepted July 17, 2000     

La–SiO<Subscript>2</Subscript> and Yb–SiO<Subscript>2</Subscript> systematics in mid-ocean ridge magmas: implications for the origin of oceanic plagiogranite

Analytical expressions for the variation in D _La and D _Yb with increasing liquid SiO₂ for olivine, plagioclase, augite, hornblende, orthopyroxene, magnetite and ilmenite (Brophy in Contrib Mineral Petrol 2008, online first) have been combined with numerical models of hydrous partial melting, of mid-ocean ridge (MOR) cumulate gabbro melting, and fractional crystallization of slightly hydrous mid-ocean ridge basalt (MORB) magma to assess a melting versus fractionation origin for oceanic plagiogranite. For felsic magmas (>63 wt.% SiO₂) the modeling predicts the following. MOR cumulate gabbro melting should yield constant or decreasing La and constant Yb abundances with increasing liquid SiO₂. The overall abundances should be similar to those in associated mafic magmas. MORB fractional crystallization should yield steadily increasing La and Yb abundances with increasing SiO₂ with overall abundances significantly higher than those in associated mafic magmas. Application to natural occurrences of oceanic plagiogranite indicate that both MOR cumulate gabbro melting and MORB fractionation are responsible. Application of the model results to Icelandic rhyolites strongly support a fractional crystallization rather than a crustal melting origin.     

Evolution of metamorphic volatiles during exhumation of microdiamond-bearing granulites in the Western Gneiss Region, Norway

Fluid inclusions in garnet, kyanite and quartz from microdiamond-bearing granulites in the Western Gneiss Region, Norway, document a conspicuous fluid evolution as the rocks were exhumed following Caledonian high- and ultrahigh-pressure (HP–UHP) metamorphism. The most important of the various fluid mixtures and daughter minerals in these rocks are: (N₂ + CO₂ + magnesian calcite), (N₂ + CO₂ + CH₄ + graphite + magnesian calcite), (N₂ + CH₄), (N₂ + CH₄ + H₂O), (CO₂) and (H₂O + NaCl + CaCl₂ + nahcolite). Rutile also occurs in the N₂ + CO₂ inclusions as a product of titanium diffusion from the garnet host into the fluid inclusions. Volatiles composed of N₂ + CO₂ + magnesian calcite characterise the ambient metamorphic environment between HP–UHP (peak) and early retrograde metamorphism. During progressive decompression, the mole fraction of N₂ increased in the fluid mixtures; as amphibolite-facies conditions were reached, CH₄ and later, H₂O, appeared in the fluids, concomitant with the disappearance of CO₂ and magnesian calcite. Graphite is ubiquitous in the host lithologies and fluid inclusions. Thermodynamic modelling of the metamorphic volatiles in a graphite-buffered C-O-H system demonstrates that the observed metamorphic volatile evolution was attainable only if the f _O2 increased from c. −3.5 (±0.3) to −0.8 (±0.3) log units relative to the FMQ oxygen buffer. External introduction of oxidising aqueous solutions along a system of interconnected ductile shear zones adequately explains the dramatic increase in the f _O2. The oxidising fluids introduced during exhumation were likely derived from dehydration of oceanic crust and continental sediments previously subducted during an extended period of continental collision in conjunction with the Caledonian orogeny. Received: 15 December 1997 / Accepted: 25 May 1998     

Experimental constraints on ultrapotassic magmatism from the Bohemian Massif (durbachite series, Czech Republic)

The equilibrium phase relations of a mafic durbachite (53 wt.% SiO₂) from the Třebíč pluton, representative of the Variscan ultrapotassic magmatism of the Bohemian Massif (338–335 Ma), have been determined as a function of temperature (900–1,100°C), pressure (100–200 MPa), and H₂O activity (1.1–6.1 wt.% H₂O in the melt). Two oxygen fugacity ranges were investigated: close to the Ni–NiO (NNO) buffer and 2.6 log unit above NNO buffer (∆NNO + 2.6). At 1,100°C, olivine is the liquidus phase and co-crystallized with phlogopite and augite at 1,000°C for the whole range of investigated pressure and water content in the melt. At 900°C, the mineral assemblage consists of augite and phlogopite, whereas olivine is not stable. The stability field of both alkali feldspar and plagioclase is restricted to low pressure (100 MPa) at nearly water-saturated conditions (<3–4 wt.% H₂O) and T < 900°C. A comparison between experimental products and natural minerals indicates that mafic durbachites have a near-liquidus assemblage of olivine, augite, Ti-rich phlogopite, apatite and zircon, followed by alkali feldspar and plagioclase, similar to the mineral assemblage of minette magma. Natural amphibole, diopside and orthopyroxene were not reproduced experimentally and probably result from sub-solidus reactions, whereas biotite re-equilibrated at low temperature. The crystallization sequence olivine followed by phlogopite and augite reproduces the sequence inferred in many mica-lamprophyre rocks. The similar fractionation trends observed for durbachites and minettes indicate that mafic durbachites are probably the plutonic equivalents of minettes and that K- and Mg-rich magmas in the Bohemian Massif may have been generated from partial melting of a phlogopite–clinopyroxene-bearing metasomatized peridotite. Experimental melt compositions also suggest that felsic durbachites can be generated by simple fractionation of a more mafic parent and mixing with mantle-derived components at mid crustal pressures.