On the nature of pressure‐induced coordination changes in silicate melts and glasses

Progressive decreases in the Si‐O‐Si angles between corner‐shared silicate tetrahedra in glasses and melts with increasing pressure can lead to arrangements of oxygen atoms that can be described in terms of edge‐ or face‐shared octahedra. This mechanism of compression can account for the gradual, continuous increases in melt and glass densities from values at low pressure that indicate dominantly tetrahedral coordination of Si to values at several tens of GPa that suggest higher coordination. It also can explain the unquenchable nature of octahedrally coordinated Si in glasses, the absence of spectroscopically detectable octahedrally coordinated Si in glasses until they are highly compressed, the gradual and reversible transformation from tetrahedral to octahedral coordination in glasses once the transformation is detectable spectroscopically, and the fact that this transformation takes place in glass at room temperature. It may also have relevance to pressure‐induced transformations from crystalline to glassy phases, the difficulty in retrieving some metastable high pressure crystalline phases at low pressure, and the observed differences between the pressures required for phase transformations in shock wave experiments on glasses and crystals

Measurement of water in rhyolitic glasses; calibration of an infrared spectroscopic technique

A series of natural rhyolitic obsidians were analyzed for their total water contents by a vacuum extraction technique. The grain size of the crushed samples can significantly affect these analyses. Coarse powders must be used in order to avoid surface-correlated water. These analyses were used to calibrate infrared spectroscopic measurements of water in glass using several infrared and near-infrared absorption bands. We demonstrate that infrared spectroscopy can yield precise determinations of not only total dissolved water contents, but also the concentrations of individual H-bearing species in natural and synthetic rhyolitic glasses on spots as small as a few tens of micrometers in diameter

A Numerical Treatment of Melt/Solid Segregation: Size of the Eucrite Parent Body and Stability of the Terrestrial Low-Velocity Zone

Crystal sinking to form cumulates and melt percolation toward segregation in magma pools can be treated with modifications of Stokes' and Darcy's laws, respectively. The velocity of crystals and melt depends, among other things, on the force of gravity (g) driving the separations and the cooling time of the environment. The increase of g promotes more efficient differentiation, whereas the increase of cooling rate limits the extent to which crystals and liquid can separate. The rate at which separation occurs is strongly dependent on the proportion of liquid that is present. As a result, cumulate formation is a process with a negative feedback; the more densely aggregated the crystals become, the slower the process can proceed. In contrast, melt accumulation is a process with a positive feedback; partial accumulation of melt leads to more rapid accumulation of subsequent melt. This positive feedback can cause melt accumulation to run rapidly to completion once a critical stability limit is passed. The observation of cumulates and segregated melts among the eucrite meteorites is used as a basis for calculating the g (and planet size) required to perform these differentiations. The eucrite parent body was probably at least 10-100 km in radius. The earth's low velocity zone (LVZ) is shown to be unstable with respect to draining itself of excess melt if the melt forms an interconnecting network. A geologically persistent LVZ with a homogeneous distribution of melt can be maintained with melt fractions only on the order of 0.1% or less

Oxygen isotope ratios in olivine from the Hawaii Scientific Drilling Project

Oxygen isotope ratios of olivine in 23 tholeiites from the Hawaii Scientific Drilling Project (HSDP) core (15 from Mauna Kea, 8 from Mauna Loa) and three samples of outcropping subaerial or dredged submarine Mauna Kea lavas have been measured by laser fluorination. The δ^(18)O values are 4.6–5.4 ‰, confirming previous observations that some Hawaiian lavas are derived from sources with δ^(18)O values lower than typical upper mantle (δ^(18)Oolivine ≈ 5.2±0.2 ‰). The Mauna Kea-Mauna Loa transition marks a shift from δ^(18)O values lower than the mantle average in Mauna Kea olivines (∼4.8) to more typical mantle values in Mauna Loa olivines. Lavas containing olivines with δ^(18)O values similar to the typical upper mantle are associated with more “primitive” or less depleted radiogenic isotope characteristics; i.e., with higher ^3He/^4He (>13 Ra), higher ^(87)Sr/^(86)Sr (>0.7036) and lower є_(Nd) (<6.5), and with ^(206)Pb/^(204)Pb ratios less than -18.3. These relationships indicate that the δ^(18)O values of the relatively enriched source components of the Hawaiian plume sampled by Mauna Loa lavas are comparable to (or greater than) the mantle average. This conclusion is supported by δ^(18)O values of olivine from other high ^3He/^4He islands, which are also comparable to the upper mantle average. The low δ^(18)O values in Hawaiian lavas are derived from a source having more MORB-like, or depleted, He, Nd, and Sr isotope ratios, but more radiogenic Pb than is seen in the Mauna Loa lavas Assimilation of ^(18)O-depleted lower oceanic crust from the underlying Pacific crust by hot, MgO-rich parental magmas or melting of older, recycled oceanic crust entrained in the Hawaiian plume are both possible sources of this ^(18)O-depleted, MORB-like component in Hawaiian magmas

Deep drilling into a Hawaiian volcano

Hawaiian volcanoes are the most comprehensively studied on Earth. Nevertheless, most of the eruptive history of each one is inaccessible because it is buried by younger lava flows or is exposed only below sea level. For those parts of Hawaiian volcanoes above sea level, erosion typically exposes only a few hundred meters of buried lavas (out of a total thickness of up to 10 km or more).Available samples of submarine lavas extend the time intervals of individual volcanoes that can be studied. However, the histories of individual Hawaiian volcanoes during most of their ~1-million-year passages across the zone of melt production are largely unknown

Petrography and petrology of the Hawaii Scientific Drilling Project lavas: Inferences from olivine phenocryst abundances and compositions

The Mauna Loa (ML) and Mauna Kea (MK) lavas recovered by the Hawaii Scientific Drilling Project (HSDP) include aphyric to highly olivine-phyric basalts. The average olivine phenocryst abundance in the reference suite of ML flows is 14.5 vol % (vesicle-free and weighted by the flow thickness), while the average abundances of olivine in the reference suites of the MK alkalic and tholeiitic basalts are 1.1 and 14.0 vol %, respectively. Plagioclase and augite phenocrysts are rare in the ML and MK tholeiites, but the MK alkalic basalts can have up to 4 vol % plagioclase phenocrysts. Strained olivine grains, thought to represent disaggregated dunite xenoliths from the cumulate pile within the magma chamber(s), are ubiquitous in the drill core lavas. These deformed grains can comprise up to 50 % of the modal olivine in a given rock. Olivine core compositions in the lavas span forsterite contents of 80.4–90.7 (median 88.8, ML tholeiites), 75.8–86.6 (median 85.8, MK alkalic basalts), and 76.3–90.5 (median 88.0 mol %, MK tholeiites). Olivines with core compositions in the range Fo_(89–90.5) are present in tholeiitic lavas with a wide range of whole-rock MgO contents (9–30 wt %). Strained and unstrained olivines completely overlap in composition as do the compositions of spinels (100*Cr/(Cr+Al) ∼59–72; Mg# = 100*Mg/(Mg+Fe^(2+)) ∼40–66) present as inclusions in the olivine phenocrysts. The presence of Fo_(90.5) olivine in the HSDP lavas requires magmas with ∼16 wt % MgO in the ML and MK plumbing systems. Rare dunite xenoliths are also present in the drill core lavas. While compositionally homogeneous within a given xenolith, the six xenoliths contain olivines that span a wide range of forsterite contents (78.3–89.2 mol %). Spinels in these xenoliths are chrome-rich, have Mg# between 31 and 66, and define two populations on the basis of TiO_2 contents. Whole-rock compositions for the ML and MK tholeiites define olivine control lines on MgO-oxide diagrams, and the relationship between whole-rock MgO and olivine phenocryst abundance in these lavas suggests that the lavas with >12 wt % MgO have accumulated olivine. Comparing the weighted bulk composition of all of the MK tholeiites in the drill core with a calculated parental magma suggests that, on average, the MK tholeiites entrained most of the olivine phenocrysts that crystallized from their parental liquids. Although deformed olivines in Hawaiian lavas are widely thought to represent disaggregated dunite xenoliths, none of the majoror minor-element data on the strained or unstrained olivine phenocrysts suggest that the strained olivines in the HSDP lavas are exotic. We suggest that most of the olivine phenocrysts in a given flow, whether strained or unstrained, are closely related to the evolved liquid that now forms the groundmass. This is consistent with observed correlations between isotopic systems measured on olivine separates (e.g., O, He) and isotopic systems dominated by groundmass (e.g., Nd, Pb)

Introduction to special section: Hawaii Scientific Drilling Project

Intraplate or "hot spot" volcanic island chains, exemplified by Hawaii, play an important role in plate tectonic theory as reference points for absolute plate motions, but the origin of these volcanoes is not explained by the plate tectonic paradigm [Engebretson et al., 1985; Molnar and Stock, 1987; Morgan, 1971, 1981, 1983; Wilson, 1963]. The most widely held view is that these chains of volcanoes form from magma generated by decompression melting of localized, buoyant upwellings in the mantle [Ribe and Christensen, 1994; Richards et al., 1988; Sleep, 1990; Watson and McKenzie, 1991] . These upwellings, or "plumes," are believed to originate at boundary layers in the mantle (e.g., at the core-mantle boundary or near the boundary at-670 km between the upper and lower mantle), and the cause of the buoyancy may be both compositional and thermal [Campbell and Griffiths, 1990; Griffiths, 1986; Richards et al., 1988; Watson and McKenzie, 1991]. Mantle plumes are responsible for about 10% of the Earth's heat loss and constitute an important mechanism for cycling mass from the deep mantle to the Earth's surface. Studies of the chemical and isotopic compositions of lavas from intraplate volcanoes, especially ocean island volcanoes, have contributed significantly to our knowledge of magma genesis in the mantle [Carmichael et al., 1974; Macdonald et al., 1983] and the compositional heterogeneity of the mantle [Allègre et al., 1983; Hart, 1988; Hart et al., 1986; Kurz et al., 1983]. Of particular importance is the identification of distinct compositional end members in the mantle, the origin and distribution of which provide insight into the long-term differentiation of the mantle-crust system, the recycling of oceanic crust and continental sediment into the mantle, and the history of the lithosphere [Allègre et al., 1995; Farley et al., 1992; Hart, 1988; Hofmann and White, 1982; McKenzie and O'Nions, 1983; Weaver, 1991; Zindler and Hart, 1986]

Degassing history of water, sulfur, and carbon in submarine lavas from Kilauea volcano, Hawaii

Major, minor, and dissolved volatile element concentrations were measured in tholeiitic glasses from the submarine portion (Puna Ridge) of the east rift zone of Kilauea Volcano, Hawaii. Dissolved H_(2)O and S concentrations display a wide range relative to nonvolatile incompatible elements at all depths. This range cannot be readily explained by fractional crystallization, degassing of H20 and S during eruption on the seafloor, or source region heterogeneities. Dissolved C0_2 concentrations, in contrast, show a positive correlation with eruption depth and typically agree within error with the solubility at that depth. We propose that most magmas along the Puna Ridge result from (I) mixing of a relatively volatile-rich, undegassed component with magmas that experienced low pressure (perhaps subaerial) degassing during which substantial H_(2)O, S, and C0_2 were lost, followed by (2) fractional crystallization of olivine, clinopyroxene, and plagioclase from this mixture to generate a residual liquid; and (3) further degassing, principally of C0_2 for samples erupted deeper than 1000 m, during eruption on the seafloor. The degassed end member may form at upper levels of the summit magma chamber (assuming less than lithostatic pressure gradients), during residence at shallow levels in the crust, or during sustained summit eruptions. The final phase of degassing during eruption on the seafloor occurs slowly enough to achieve melt/vapor equilibrium during exsolution of the typically CO_(2)-rich vapor phase. We predict that average Kilauean primary magmas with 16% MgO contain ~0.47 wt% H_(2)O, ~900 ppm S, and have δD values of ~-30 to -40‰. Our model predicts that submarine lavas from wholly submarine volcanoes (i.e., Loihi), for which there is no opportunity to generate the degassed end member by low pressure degassing, will be enriched in volatiles relative to those from volcanoes whose summits have breached the sea surface (i.e., Kilauea and Mauna Loa)

The Origin and Significance of Reverse Zoning in Melilite from Allende Type B Inclusions

In many Type B Allende inclusions, melilite is reversely-zoned over restricted portions of each crystal. Textural relationships and the results of dynamic crystallization experiments suggest that the reverselyzoned intervals in these Type melilites result from the co-precipitation of melilite with clinopyroxene from a melt, prior to the onset of anorthite precipitation. When clinopyroxene begins to precipitate, the Al/Mg ratio of the melt rises, causing the crystallizing melilite to become more gehlenitic, an effect which is negated by crystallization of anorthite. Because the equilibrium crystallization sequence in these liquids is anorthite before pyroxene, melilite reverse zoning can occur only when anorthite nucleation is suppressed relative to pyroxene. This has been achieved in our experiments at cooling rates as low as 0.5°C/hour. Our experiments further indicate, however, that reverse zoning does not form at cooling rates ≥50°C/hour , probably because the clinopyroxene becomes too Al-rich to drive up the Al/Mg ratio of the liquid. Type inclusions with reversely-zoned melilites must have cooled at rates greater than those at which anorthite begins to crystallize before clinopyroxene but <50°C/hour. Such rates are far too slow for the Type droplets to have cooled by radiation into a nebular gas but are much faster than the cooling rate of the solar nebula itself. One possibility is that Type B's formed in local hot regions within the nebula, where their cooling rate was equal to that of their surrounding gas. Other possibilities are that their cooling rates reflect their movement along nebular temperature gradients or the influence of a heat source. The sun or viscous drag on inclusions as they moved through the nebular gas are potential candidates for such heat sources