Petrogenesis of Tholeiitic Lavas from the Submarine Hana Ridge, Haleakala Volcano, Hawaii

Hana Ridge, the longest submarine rift zone in the Hawaiianisland chain, extending from Maui 140 km to the ESE, has a complexmorphology compared with other Hawaiian rift zones. A totalof 108 rock specimens have been collected from the submarineHana Ridge by six submersible dives. All of the rocks (76 bulkrocks analyzed) are tholeiitic basalts or picrites. Their majorelement compositions, together with distinctively low Zr/Nb,Sr/Nb, and Ba/Nb, overlap those of Kilauea lavas. In contrast,the lavas forming the subaerial Honomanu shield are intermediatein composition between those of Kilauea and Mauna Loa. The compositionalcharacteristics of the lavas imply that clinopyroxene and garnetwere important residual phases during partial melting. The compositionsof olivine and glass (formerly melt) inclusions imply that regardlessof textural type (euhedral, subhedral–undeformed, deformed)olivine crystallized from host magmas. Using the most forsteriticolivine (Fo_90·6) and partition coefficients     

Chemical compositions of Kilauea east-rift lava, 1968-1971

The major element chemical compositions of lava from four eruptionson the east rift zone of Kilauea between August 1968 and October1971 reflect three petrologic processes:

1. Production of chemically distinct batches of magma in the mantle.
2. Separation of olivine, augite, and plagioclase from liquidduringflow in the rift-zone conduits.
3. Mixing of differentmagmas during ascent to the surface.

Chemically none of the four Kilauea east-rift eruptions matchesthe preceding summit eruption in Halemaumau that ended in July1968. The Mauna Ulu eruption, May 1969 to October 1971 (thelast of flie east-rift eruptions), can be divided into fiveolivine-controlled and chemically distinct variants. Three ofthese characterize the first seven months of the eruption andare closest in composition to the 1967–8 Halemaumau eruption.Variants 4 and 5 were erupted later and have compositions thatare distinctly different from that of the 1967–8 eruption.Major differences are higher Al₂O₃ (0?15–0?23 per cent),and lower K₂O (0?07–0?10 per cent) and TiO₂ (0?12–0?23per cent) in variants 4 and 5 at the same MgO content. Somelavas from eruptions in August and October 1968 and February1969, have olivine-controlled magma compositions that are identicalto mixtures of Mauna Ulu variants 1–3 and the 1967–8composition. This observation fits an hypothesis advanced earlierby T. L. Wright and R. S. Fiske that magmas in the central magmachamber become mixed with magmas in the rift zone and can beidentified as mixing components of rift eruption magmas beforethey appear as distinctive magmas in summit eruptions. Lavas representing mixing of olivine-controlled magma with differentiatedmagma were erupted in October 1968, February 1969, and in Mayand December 1969. The changes in amount of K₂O and TiO₂ during the latter partof the 1969–71 Mauna Ulu eruption are the reverse of theoverall secular change in composition of Kilauea summit lavasfrom pre-1750 through 1967–8. The K₂O and TiO₂ contentsof the latest overflows during the 1969–71 Mauna Ulu eruption(April 1971) are comparable to that of lava erupted at Kilaueasummit prior to 1750. The changing chemistry of Kilauea magma is found to be of useas a ‘tracer’ in the complex Kilauea conduit system.Application of these data to older lava sequences is difficulbecause of the complexity of the processes controlling lavacomposition and the absence of detailed information about thetime-space chemical variation during individual eruptions.     

Trace element abundances of high-MgO glasses from Kilauea, Mauna Loa and Haleakala volcanoes, Hawaii

We performed an ion-microprobe study of eleven high-MgO (6.7–14.8 wt%) tholeiite glasses from the Hawaiian volcanoes Kilauea, Mauna Loa and Haleakala. We determined the rare earth (RE), high field strength, and other selected trace element abundances of these glasses, and used the data to establish their relationship to typical Hawaiian shield tholeiite and to infer characteristics of their source. The glasses have trace element abundance characteristics generally similar to those of typical shield tholeiites, e.g. L(light)REE/H(heavy)REE_C1 < 1. The Kilauea and Mauna Loa glasses, however, display trace and major element characteristics that cross geochemical discriminants observed between Kilauea and Mauna Loa shield lavas. The glasses contain a blend of these discriminating chemical characteristics, and are not exactly like the typical shield lavas from either volcano. The production of these hybrid magmas likely requires a complexly zoned source, rather than two unique sources. When corrected for olivine fractionation, the glass data show correlations between CaO concentration and incompatible trace element abundances, indicating that CaO may behave incompatibly during melting of the tholeiite source. Furthermore, the tholeiite source must contain residual garnet and clinopyroxene to account for the variation in trace element abundances of the Kilauea glasses. Inversion modeling indicates that the Kilauea source is flat relative to C1 chondrites, and has a higher bulk distribution coefficient for the HREE than the LREE. Received: 4 February 1997 / Accepted: 27 August 1997     

Volatile element zonation in Campanian Ignimbrite magmas (Phlegrean Fields, Italy): evidence from the study of glass inclusions and matrix glasses

The distribution of H₂O, F, Cl and S in the Campanian Ignimbrite (CI) magma chamber was investigated through study of primary glass inclusions and matrix glasses from pumices of the Plinian fall deposit. The eruption, fed by trachytic to phono-trachytic magmas, mainly produced a trachytic non-welded to partially welded tuff, underlain by a minor cogenetic fallout deposit. The entire chemical variability of the eruptive products is well represented in the pumices of the Plinian fall deposit, which we divide into a basal Lower Fall Unit (LFU) and an overlying Upper Fall Unit (UFU). Primary glass inclusions were only found in clinopyroxenes associated with the LFU pumice and contain a mean of 1.60ǂ.32 wt% H₂O (analysed by FTIR), 0.11ǂ.08 wt% F, 0.37ǂ.03 wt% Cl and 0.08ǂ.04 wt% SO₃ (EMP analysis); CO₂ concentrations were below the FTIR detection limit (10-20 ppm). The coexisting matrix glasses contain similar amounts of halogens and sulfur but less water (~0.60 wt%). Partially degassed matrix glasses from UFU pumices contain a mean of 0.30ǂ.02 H₂O, 0.28ǂ.10 F, 0.04ǂ.02 SO₃ and 0.80ǂ.04 wt% Cl. To reconstruct the total amount of volatiles dissolved in the most evolved trachytes we have used experimental solubility data and mass balance calculations concerning the amount of crystal fractionation required to produce the most evolved trachyte from the least evolved trachyte; these yield an estimated pre-eruptive magma volatile content (H₂O + Cl + F) of ~5.5 wt% for the most evolved magmas. On the basis of new determinations of Cl solubility limits in hydrous trachytic melts coexisting with an aqueous fluid phase + hydrosaline melt (brine), we suggest that the upper part of the magma chamber which fed the CI eruption was fluid(s) saturated and at a minimum depth of ~2 km. Variations in eruptive style (Plinian fallout, pyroclastic flows) do not appear to be related to significant variations in pre-eruptive volatile contents.     

Volatiles in Basaltic Glasses from Loihi Seamount, Hawaii: Evidence for a Relatively Dry Plume Component

New H₂O, CO₂ and S concentration data for basaltic glasses fromLoihi seamount, Hawaii, allow us to model degassing, assimilation,and the distribution of major volatiles within and around theHawaiian plume. Degassing and assimilation have affected CO₂and Cl but not H₂O concentrations in most Loihi glasses. Waterconcentrations relative to similarly incompatible elements inHawaiian submarine magmas are depleted (Loihi), equivalent (Kilauea,North Arch, Kauai–Oahu), or enriched (South Arch). H₂O/Ceratios are uncorrelated with major element composition or extentor depth of melting, but are related to position relative tothe Hawaiian plume and mantle source region composition, consistentwith a zoned plume model. In front of the plume core, overlyingmantle is metasomatized by hydrous partial melts derived fromthe Hawaiian plume. Downstream from the plume core, lavas tapa depleted source region with H₂O/Ce similar to enriched Pacificmid-ocean ridge basalt. Within the plume core, mantle components,thought to represent subducted oceanic lithosphere, have waterenrichments equivalent to (KEA) or less than (KOO) that of Ce.Lower H₂O/Ce in the KOO component may reflect efficient dehydrationof the subducting oceanic crust and sediments during recyclinginto the deep mantle. KEY WORDS: basalt; Hawaii; mantle; plumes; volatiles     

Volatiles in basaltic magmas of ocean islands and their mantle sources: I. Melt compositions deduced from melt inclusions and glasses in the rocks

Statistical analysis of a data bank of the compositions of glasses and melt inclusions in minerals from ocean-island basalts. The initial database contains more than 45 000 published analyses of ocean-island igneous rocks from around the world. Much attention was given to the contents of volatiles (H₂O, Cl, F, and S) and their ratios to one another and to nonvolatile components of close incompatibility (Ti, P, K, and Ce). The average compositions of melt inclusions are similar to those of glasses of the rocks, including volatiles, with consideration for a somewhat higher degree (by approximately 20%) of the differentiation of glasses. The average compositions of ocean-island melts differ from those of mid-ocean basalts in having wider variations and elevated contents of some of the most incompatible elements (Sr, Nb, Ta, Ba, U, Th, and others), as well as H₂O, F, and Cl. Based on the correlation of volatiles to one another and to incompatible elements, three groups of ocean-island basalts are distinguished: (I) low-K, P, Ti magma compositions approximating mid-ocean ridge magmas, (II) high-K, Ce, P, and Ti magmas that resemble continental rift magmas but differ from them in low H₂O content, and (III) high-K, H₂O, Ce, P, and Ti magmas close to continental rift magma. All three types of the melts were found only in the Hawaiian Archipelago, whereas other ocean islands are dominated by any one of these types. The distinguished melt types presumably reflect the differences (heterogeneity) in the compositions of the sources.     

Petrology of Submarine Lavas from Kilauea's Puna Ridge, Hawaii

We have studied 30 quenched tholeiitic lava flows recoveredby 20 dredge hauls and one submersible dive along Puna Ridge,the submarine part of the East Rift Zone of Kilauea Volcano,Hawaii Glass grains from numerous additional flows were recoveredin turbidite sands cored in the Hawaiian Trough. These quenchedlavas document variable primary magma compositions; olivineand multiphase crystallization and fractionation; degassing;wall-rock stoping and assimilation; mixing in the crustal reservoirand the rift zone; entrainment of olivine xenocrysts from ahot, ductile, olivine cumulate body; and disruption of gabbrowallrocks in the rift zone. Glass grains in turbidite sands contain up to 15•0wt% MgO,in contrast to < 7•0wt% MgO for the sampled glass rindson lavas. The most forsteritic olivine phenocryst (F0₉₀₇) isin equilibrium with primary Kilauea liquid containing an average16•5 wt% MgO, but ranging from 13•4 to 18•4%.Lavas and glass grains have more restricted P₂O₅/K₂O and TiO₂/K₂Othan glass inclusions in olivine, because more diverse liquidstrapped as glass inclusions are mixed and homogenized beforeeruption. Variable trace element compositions in glass grainsand whole rocks indicate that the primary liquids form by partialmelting of mantle sources retaining clinopyroxene and garnet. Orthopyroxene xenocrysts formed at moderate pressures provideevidence for a sub-crustal staging zone. Chromite and olivinecrystallize in the crustal magma reservoir as the liquid coolsfrom an average 1346C to 1170C. Low viscosities of the primaryliquids (04 Pas) facilitate olivine settling, and the crystallizedolivine forms an olivine cumulate body at the base of the reservoir.Olivine is deformed as the hot ductile dunite body flows downand away from the summit. This flow drives instability of theHilina landslide on Kilauea. Dikes intrude the dunite, and magmaflowing through the dikes disaggregates and entrains olivinexenocrysts in Puna Ridge magmas. Primary liquids pond at or near the base of Kilauea's crustalreservoir because they are denser than more fractionated liquidsthat occupy the upper parts of the reservoir. The sulfur andwater contents of glass rinds indicate that fractionated liquidsnear the top of the reservoir degas at low pressure, a processthat increases their density and causes them to sink to levelswhere they mix with resident undegassed, near-primary liquid.The fractionated liquids near the top of the magma reservoiracquire excess Cl, owing to assimilation of hydrothermally alteredroofrocks. Magma flowing into the rift zone encounters and mixes with low-temperature,multiphase-fractionated melt. The mixed magmas typically containrare orthopyroxene, plagioclase as sodic as andesine, olivineas fayalitic as F0₇₅ and Fe-rich augite derived from the fractionatedmagma. Magma flowing through dikes also dislodged fragmentsof gabbroic wallrocks that occur as xenoliths. The interrelations in the Kilauean submarine lavas between hostglass and glass inclusion compositions, volatile contents andmineral chemistry reveal an extraordinarily complex sequenceof petrogenetic processes and events that are difficult or impossibleto determine in subaerial Kilauea lavas because of crystallization,reequilibration and degassing during or after their eruption. KEY WORDS: submarine lavas; petrology; Kilauea; Hawaii; magma mixing ^*Corresponding authorPresent address: Rosentiel School of Marine and Atmospheric Science, Division of Marine Geology and Geophysics, University of Miami, 4600 Rickenbacker Causeway, Miami, FL 33149-1098, USA     

Volatiles in pillow rim glasses from Loihi and Kilauea volcanoes,Hawaii

Volatiles and major elements in submarine glasses from Loihi seamount and Kilauea volcano. Hawaii were analyzed by high temperature mass spectrometry and the electron microprobe. Loihi glasses are subdivided into three groups: tholeiitic, transitional and alkali basalts. The glasses are evolved: Mg numbers range from 48–58. The alkalic lavas are the most evolved.Total volatiles range from 0.73 to 1.40 wt.%. H₂O shows a positive linear correlation with K₂O content [H₂O = 0.83 (± .09) K₂O + 0.08 (± .06)]. Concentrations of H₂O are higher in the alkalic lavas, but Cl and F abundances are highly variable. Variations in ratios of incompatible elements (K₂O, P₂O₅, H₂O) indicate that each group was derived from a distinct source. CO₂ contents range from 0.05 to 0.19 wt.% but show no systematic correlation with rock type or Mg #. A well-defined decrease in glass CO₂ content with increasing vesicularity is shown by the alkalic lavas. CO₂ may have been outgassed from the tholeiitic and transitional magmas prior to eruption during storage in a shallow magma chamber. Reduced carbon species (CO and CH₄) were found in small amounts in most of the alkalic samples. Although the redox histories of Hawaiian lavas are poorly known, these new data indicate the presence of a reduced source for Loihi magmas.The Kilauea tholeiitic glasses are evolved (Mg # 48.3 to 55) and have higher H₂O contents (av. 0.54 wt.%) than Loihi tholeiites (av. 0.42 wt.%) at the same Mg # (~55). Cl is distinctly lower in Kilauea glasses (0.01 wt.%) compared to Loihi glasses (0.09 wt.%). The data indicate significant source differences for the two volcanoes, consistent with results of other geochemical studies.Loihi tholeiites have distinctly higher ³He/⁴He ratios than Kilauea tholeiites and are the highest measured in submarine basalts (KURZ et al., 1983). These high ratios have been used to invoke a primitive source for Loihi basalts. The high Cl content of these basalts, the highest we have ever measured in submarine basalts, may be a fingerprint of this primitive source, as previously noted for Icelandic basalts (Schillinget al. 1980).     

Petrology, geochemistry, S, Cl and F abundances, and S oxidation state of sideromelane glass shards from Pleistocene ash layers north and south of Gran Canaria (ODP Leg 157)

Major elements, S, F, Cl concentrations and relative proportions of S⁶⁺ to total S were analyzed with electron microprobe in sideromelane glass shards from Pleistocene volcaniclastic sediments drilled during ODP Leg 157. Glasses are moderately to strongly evolved and represent a spectrum from alkali basalt, basanite and nephelinite through hawaiite, mugearite and tephrite to phonolitic tephrite. Measured S⁶⁺/ΣS (0.03–0.98) and calculated Fe²⁺/Fe³⁺ (2.5–5.8) ratios in the melt yield preeruptive redox conditions ranging from NNO−1.4 to NNO+2.1. The morphology of the glass shards, variations of S and Cl concentrations (0.010–0.127 wt% S, 0.018–0.129 wt% Cl), calculated preeruptive temperatures (1030–1200 °C) and oxygen fugacities suggest that glasses deposited even within the same ash layers have diverse origin and may have resulted from both submarine and subaerial eruptions. Most vesicle-free glasses are characterized by high concentrations of S and represent undegassed or slightly degassed submarine lavas, whereas vesiculated glasses with low concentrations of S and Cl are strongly degassed and can be ascribed to the eruptions in shallow water or on land. Sideromelane glass shards at Sites 953 are thought to have resulted from submarine eruptions northeast of Gran Canaria, glasses at Site 954 represent mostly volcaniclastic material of shallow water submarine and subaerial eruptions on Gran Canaria and Tenerife, and glasses deposited at Site 956 resulted from submarine or explosive eruptions on Tenerife. Received: 8 April 1997 / Accepted: 27 October 1997     

Volatiles in Submarine Basaltic Glasses from the Northern Kerguelen Plateau (ODP Site 1140): Implications for Source Region Compositions, Magmatic Processes, and Plateau Subsidence

Submarine pillow basalts (34 Ma) recovered from the NorthernKerguelen Plateau at ODP Site 1140 contain abundant unalteredglass, providing the first opportunity to measure the volatilecontents of tholeiitic basaltic magmas related to the Kerguelenmantle plume. The glasses have La/Sm and Nb/Zr ratios that varyfrom values similar to Southeast Indian Ridge (SEIR) MORB (Unit1), to slightly more enriched (Unit 6), to values transitionalbetween SEIR MORB and basaltic magmas formed by melting of theKerguelen plume (Units 2 and 3). Volatile contents for glassesin Units 1 and 6 are similar to depleted mid-ocean ridge basalt(MORB) values (0·25–0·27 wt % H₂O, 1240–1450ppm S, 42–54 ppm Cl). In contrast, H₂O contents are higherfor the enriched glasses (Unit 2, 0·44 wt % H₂O; Unit3, 0·69 wt %), as are S (1500 ppm) and Cl (146–206ppm). Cl/K ratios for all glasses are relatively low (0·03–0·04),indicating that assimilation of hydrothermally altered materialdid not occur during shallow-level crystallization. H₂O/Ce forthe enriched glasses (Units 2 and 3) is significantly lowerthan Pacific and South Atlantic MORB values, suggesting thatlow H₂O/Ce may be an inherent characteristic of the Kerguelenplume source. Vapor saturation pressures calculated using theH₂O and CO₂ contents of the glasses indicate that     

Ferric/ferrous ratios in 1984 Mauna Loa lavas: a contribution to understanding the oxidation state of Hawaiian magmas

Ferric/ferrous ratios have been used to estimate the oxygen fugacity of lavas erupted in 1984 on Mauna Loa Volcano, Hawaii. Rapidly quenched lavas erupted close to vents are less oxidized than rapidly quenched lavas scooped from lava flows several kilometers away from the vents. These results demonstrate that sampling is of critical importance in determining the oxidation state of lava. The oxidation state of the vent lavas, below or at magnetite–wüstite (MW), is significantly lower than that previously reported for Hawaiian lavas (~FMQ). Similarly, rapidly quenched lavas from the ongoing Kilauea eruption and Loihi seamount, all have oxygen fugacities that are close to MW and on the low side of the range previously reported for Hawaiian lavas. From this we conclude that the initial oxygen fugacity of parental Hawaiian magmas is close to MW, not FMQ, and that previous estimates of the oxidation state of Hawaiian lavas may have been too high. This implies that the plume source of these magmas is also at or below MW, but not as reduced as the mantle source of mid-ocean ridge basalts. Additionally, Mauna Loa lavas appear to be slightly more reduced than Kilauea or Loihi lavas, perhaps indicating heterogeneous oxidation within the Hawaiian plume.     

An Experimental Study of Water and Carbon Dioxide Solubilities in Mid-Ocean Ridge Basaltic Liquids. Part II: Applications to Degassing

Degassing processes in basaltic magmas rich in both water andcarbon dioxide can be modeled using the solubilities of theendmember systems and the assumption of Henry's law. Suitesof vapor-saturated basaltic melts having a range of initialCO₂/H₂O ratios and erupted over a narrow depth interval willdefine negatively sloped arrays on an H₂O vs CO₂ plot. It isimportant that all of the major volatile species be consideredsimultaneously when interpreting trends in dissolved volatilespecies concentrations in magmas. Based on measured concentrations of water and carbon dioxidein basaltic glasses, the composition of the vapor phase at 1200°Cthat could coexist with a basaltic melt and the pressure atwhich it would be vapor saturated can be calculated. The rangein vapor compositions in equilibrium with submarine basaltsreflects the range in water contents in the melts characteristicof each environment. The ranges in the molar proportion of CO₂in vapor phases (X_CO2) calculated to be in equilibrium withsubmarine tholeiitic glasses are 0•93–1•00 formid-ocean ridge basalts (MORB), 0•60–0•99 forglasses from Kilauea [representative of ocean island basalts(OIB)] and 0–0•94 for glasses from back-arc basins(BABB). MORB glasses from spreading centers ranging from slow(e.g. the Mid-Atlantic Ridge) to fast (e.g. East Pacific Rise,9–13°N) are commonly supersaturated with respect toCO₂-rich vapor, resulting from magma ascent rates so rapid thatmagmas erupt on the sea-floor without having been fully degassedby bubble nucleation and growth during ascent. In contrast tothe MORB glasses, volatile contents in submarine glasses fromKilauea are consistent with having been in equilibrium witha vapor phase containing 60–100 mol% CO₂ at the pressureof eruption, reflecting differences in average magma transportrates during eruptions at mid-ocean ridges and hotspot volcanoes. Degassing during decompression of tholeiitic basaltic magmais characterized by strong partitioning of CO₂ into the vaporphase. During open system degassing, CO₂ is rapidly removedfrom the melt with negligible loss of water, until a pressureis reached at which the melt is in equilibrium with nearly purewater vapor. From this pressure downward, the water contentof the melt follows the water solubility curve. During closedsystem degassing, water and CO₂ contents in vapor-saturatedbasaltic magmas will depend strongly on the vapor compositionas determined by the initial volatile concentrations. Deviationfrom open system behavior, toward lower dissolved H₂O and CO₂saturation concentrations at a given pressure, will be greatestin melts having high total volatile concentrations and highCO₂:H₂O ratios. Closed system degassing of basaltic melts havingthe low initial H₂O and CO₂ contents typical of MORB and OIB,however, are similar to the open system case. KEY WORDS: mid-ocean ridge basalts; water and carbon dioxide solubility; degassing     

The emergence of a Galápagos shield volcano, Roca Redonda

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

Cooling rates of basaltic hyaloclastites and pillow lava glasses from the HSDP2 drill core

Cooling rates have been determined for basaltic glasses from different depths of the submarine section of the drill core recovered in the 1999 phase of Hawaii Scientific Drilling Project (HSDP2). The glasses include degassed blocky hyaloclastite clasts and undegassed pillow rims. The degassed glassy clasts were generated in subaerial or shallow submarine environments, during explosive interactions between lava and seawater, before eventual deposition under water. The volatile contents of the glassy pillow rims are consistent with eruption and quenching in water several hundred metres deep. The cooling rates have been calculated from the calorimetric properties of the glass across the glass transition. The heat capacity (c_p) of each sample was measured during several cycles of heating from room temperature to temperatures above their glass transition using a differential scanning calorimeter (DSC). Their compositions did not change during the thermal treatment, a prerequisite for successful c_p measurements, although the glasses with higher H₂O contents became more opaque and their mid-IR spectra changed. Each c_p-T path exhibits the now classic features of the glass transition; glassy and liquid states separated by a hysteresis marking the transition. After experiencing the same experimental thermal history the glass transition occurs at lower temperatures in glasses with higher H₂O contents. Except for one sample, the c_p-T path measured on initial heating also releases energy stored during the natural quench, which is not recovered during subsequent experimental cooling. The energy stored in the HSDP2 glasses is much less than that observed in hyperquenched natural and synthetic glasses. Even so, the Tool-Narayanaswamy enthalpy relaxation geospeedometer, usually used to determine the cooling rates in volcanic glasses, is unable to deal with this energy release. For those samples that exhibit this feature an alternative method, developed for hyperquenched glasses, is applied. This uses the energy released to calculate T_f, from which the cooling rate is calculated. The degassed blocky hyaloclastite clasts exhibit cooling rates 0.1-72.2 K s⁻¹, while the undegassed pillow rims span 0.2-46.4 K s⁻¹. The fastest cooling rates are consistent with the cooling of lava bodies in seawater. The wide variation for both types of glass could reflect quenching at different distances from the basalt-seawater interface. However, for the degassed hyaloclastite clasts the range could indicate that the clasts were generated by different processes operating during the explosive interaction between lava and seawater in the littoral zone. In the undegassed pillow lavas, glassy rims may have been reheated, giving rise to more complex, slower, thermal histories, as a result of latent heat released during the crystallisation of pillow interiors, or flow replenishment. Both types of glass may also have experienced reheating from succeeding flows or deposits. Compared to deep-sea limu o Pele hyaloclastite fragments, whose hyperquench rates indicate simultaneous cooling and fragmentation, the shallow blocky hyaloclastite clasts may have formed during post-cooling brittle fragmentation.     

Isotope Compositions of Submarine Hana Ridge Lavas, Haleakala Volcano, Hawaii: Implications for Source Compositions, Melting Process and the Structure of the Hawaiian Plume

We report Sr, Nd, and Pb isotope compositions for 17 bulk-rocksamples from the submarine Hana Ridge, Haleakala volcano, Hawaii,collected by three dives by ROV Kaiko during a joint Japan–USHawaiian cruise in 2001. The Sr, Nd, and Pb isotope ratios forthe submarine Hana Ridge lavas are similar to those of Kilauealavas. This contrasts with the isotope ratios from the subaerialHonomanu lavas of the Haleakala shield, which are similar toMauna Loa lavas or intermediate between the Kilauea and MaunaLoa fields. The observation that both the Kea and Loa componentscoexist in individual shields is inconsistent with the interpretationthat the location of volcanoes within the Hawaiian chain controlsthe geographical distribution of the Loa and Kea trend geochemicalcharacteristics. Isotopic and trace element ratios in Haleakalashield lavas suggest that a recycled oceanic crustal gabbroiccomponent is present in the mantle source. The geochemical characteristicsof the lavas combined with petrological modeling calculationsusing trace element inversion and pMELTS suggest that the meltingdepth progressively decreases in the mantle source during shieldgrowth, and that the proportion of the recycled oceanic gabbroiccomponent sampled by the melt is higher in the later stagesof Hawaiian shields as the volcanoes migrate away from the centralaxis of the plume. KEY WORDS: submarine Hana Ridge; isotope composition; melting depth; Hawaiian mantle plume     

Diabasic intrusion and lavas,segregation veins,and magma differentiation at Kahoolawe volcano,Hawaii

A mafic sill-like intrusion, ~5?×?30 m, exposed along the eastern shoreline of Kahoolawe Island, Hawaii, represents tholeiitic magma emplaced as diabase among caldera-filling lavas. It differentiated from ~7.8 wt.% MgO to yield low-MgO (2.9 wt.%) vesicular segregation veins. We examined the intrusion for whole-rock and mineral compositions for comparison to Kahoolawe caldera-fill lavas (some also diabasic), to the Uwekahuna laccolith (Kilauea), and to gabbros, diabases, and segregations and oozes of other tholeiitic shield volcanoes (e.g., Mauna Loa and Kilauea lava lakes). We also evaluate this extreme differentiation in terms of MELTS modeling, using parameters appropriate for Hawaiian crystallization environments. Kahoolawe intrusion diabase samples have major and trace element abundances and plagioclase, pyroxene, and olivine compositions in agreement with those in gabbros and diabases of other volcanoes. However, the intrusion samples are at the low-MgO end of the large MgO range formed by the collective comparative samples, as many of those have between 8 and 20 wt.% MgO. The intrusion’s segregation vein has SiO₂ 53.4 wt.%, TiO₂ 3.2 wt.%, FeO 13.5 wt.%, Zr 350 ppm, and La 16 ppm. It plots in compositional fields formed by other Hawaiian segregations and oozes that have MgO <5 wt.%—fields that show large variances, such as factor of ~2 differences for incompatible element abundances accompanying SiO₂ from ~49 to 59 wt.%. Our MELTS modeling assesses the Kahoolawe intrusion as differentiating from ~8 wt.% MgO parent magma beginning along oxygen buffers equivalent to FMQ and FMQ-2, having magmatic H₂O of 0.15 and 0.7 wt.% (plus traces of CO₂ and S), and under 100 and 500 bars pressure. Within these parameters, MELTS calculates that <3 wt.% MgO occurs at ~1,086 to 1,060 °C after ~48 to 63 % crystallization, whereby the lesser crystallization percentages and lower temperatures equate to higher magmatic H₂O, leading to high SiO₂, ~56–58 wt.%. To contrast, greater crystallization is calculated for lower H₂O, for which it achieves less SiO₂, <55 wt.%. While MELTS reliably predicts SiO₂ approaching 58 wt.% for differentiation beyond <4 wt.% MgO, and shows that Kahoolawe intrusion’s segregations and those of Kilauea and Mauna Loa are all reasonably accommodated by the modeled parameters and SiO₂ differentiation curves, MELTS fails where it predicts that Fe enrichment is more robust under FMQ than FMQ-2 buffers. That failure not withstanding, MELTS differentiation from liquidus temperatures ~1,205–1,185 °C (depending on the various parameters) gradually increases fO₂ (up to ~0.4 log units, as normalized to FMQ) until magnetite crystallizes at ~1,090–1,085 °C, which reduces absolute fO₂ ~1 to 1.5 log units. The modeled Kahoolawe intrusion, then, exemplifies how tholeiitic magma differentiation can produce extreme SiO₂ and incompatible element compositions, and how Hawaiian segregations from shallow intrusions and lava lakes can be generally modeled under compositional and physical parameters appropriate for Hawaiian tholeiitic magmatism.     

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     

Environments of Crystallization and Compositional Diversity of Mauna Loa Xenoliths

Two picrite flows from the SW rift zone of Mauna Loa containxenoliths of dunite, harzburgite, lherzolite, plagioclase-bearinglherzolite and harzburgite, troctolite, gabbro, olivine gabbro,and gabbronorite. Textures and olivine compositions precludea mantle source for the xenoliths, and rare earth element concentrationsof xenoliths and clinopyroxene indicate that the xenolith sourceis not old oceanic crust, but rather a Hawaiian, tholeiitic-stagemagma. Pyroxene compositions, phase assemblages and texturalrelationships in xenoliths indicate at least two different crystallizationsequences. Calculations using the pMELTS algorithm show thatthe two sequences result from crystallization of primitive MaunaLoa magmas at 6 kbar and 2 kbar. Independent calculations ofolivine Ni–Fo compositional variability in the plagioclase-bearingxenoliths over these crystallization sequences are consistentwith observed olivine compositional variability. Two parentsof similar bulk composition, but which vary in Ni content, arenecessary to explain the olivine compositional variability inthe dunite and plagioclase-free peridotitic xenoliths. Xenolithsprobably crystallized in a small magma storage area beneaththe rift zone, rather than the large sub-caldera magma reservoir.Primitive, picritic magmas are introduced to isolated rift zonestorage areas during periods of high magma flux. Subsequenteruptions reoccupy these areas, and entrain and transport xenolithsto the surface. KEY WORDS: xenolith; Hawaii; volcano plumbing; mineral composition; picrite     

Temporal helium isotopic variations within Hawaiian volcanoes: Basalts from Mauna Loa and Haleakala

Helium isotope ratios in basalts spanning the subaerial eruptive history of Mauna Loa and Haleakala vary systematically with eruption age. In both volcanoes, olivine mineral separates from the oldest samples have the highest ³He/⁴He ratios. The Haleakala samples studied range in age from roughly one million years to historic time, while the Mauna Loa samples are radiocarbon dated flows younger than 30.000 years old. The Honomanu tholeiites are the oldest samples from Haleakala and have ³He/⁴ ratios that range from 13 to 16.8× atmospheric, while the younger Kula and Hana series alkali basalts all have ³He/⁴ close to 8×atmospheric. A similar range is observed on Mauna Loa; the oldest samples (roughly 30,000 years) have ³He/⁴ ratios of 15 to 20 × atmospheric, with a relatively smooth decrease to 8 × atmospheric with decreasing age. The consistent trend of decreasing ³He/⁴He ratio with time in both volcanoes, coherence between the helium and Sr and Nd isotopes (for Haleakala), and the similarity of ³He/⁴ in the late stage basalts to depleted mid-ocean ridge basalt (MORB) helium, argue against the decrease being the result of radiogenic ingrowth of ⁴He. The data strongly suggest an undegassed (i.e., high ³He/(Th + U)) mantle source for the early shield building stages of Hawaiian volcanism. and are consistent with the hotspot/mantle plume model. The data are difficult to reconcile with models for Hawaiian volcanism that require recycled oceanic crust or derivation from a MORB-related upper mantle source. We interpret the decrease in ³He/⁴ with volcano evolution to result from an increasing involvement of depleted mantle and/or lithosphere during the late stages of Hawaiian volcanism.     

Estimation of the average contents of H2O, Cl, F, and S in the depleted mantle on the basis of the compositions of melt inclusions and quenched glasses of mid-ocean ridge basalts

Using our database of the compositions of melt inclusions and quenched glasses of basaltic magmas from mid-ocean ridges (MORB), the average concentrations and ratios of H₂O, Cl, F, S, K₂O, Ce, and Dy were determined in these magmas. Assuming that the concentration ratios of volatile components to K₂O are constant in the MORB magmas and their sources (depleted mantle, DM), and taking an average K₂O content in the DM of 72 ppm, the following average contents were estimated for the DM: 158 ppm H₂O, 6.6 ppm Cl, and 8.3 ppm F. Using an S/Dy ratio of 212 for MORB melts and a Dy concentration of 0.531 ppm in the DM, the concentration of S in the DM was estimated as 113 ppm. Our value for the average content of Cl is much higher than estimates obtained by other authors. This discrepancy could be due either to the assimilation of crustal (and hydrospheric) Cl by MORB magmas or to the deep mantle recycling of Cl. The latter mechanism is supported by the statistically significant positive correlation of Cl with K₂O, H₂O, and F. Such a correlation is not consistent with the hypothesis of basaltic magma contamination by seawater-derived chloride brines. Similar to other surface processes, the assimilation of crustal material operates within the existing global correlations and disturbs them. Based on the average integrated degree of mantle melting and the average degree of MORB magma differentiation (0.05), the average contents of potassium and volatile components in N-MORB and E-MORB mantle sources were estimated as 39 and 126 ppm K₂O, 103 and 197 ppm H₂O, 4.0 and 10.7 ppm Cl, and 3.9 and 9.1 ppm F, respectively. It is not likely that normal MORB magmas can be derived from depleted mantle that experienced a previous partial melting event (for instance, during the extraction of the primordial continental crust in the Early Precambrian), which was referred to as the ultradepleted mantle. Ordinary (not ultradepleted) MORB magmas can be derived either by the melting of a zone enriched DM (for instance, progressively enriched in incompatible components with depth), which is hardly possible, or by the continuous addition (mixing) of an enriched component to the ultradepleted mantle at the expense of sediments and crustal materials involved in deep recycling.