Nami Kitchen

Oxygen-isotope evidence for recycled crust in the sources of mid-ocean-ridge basalts

Mid-ocean-ridge basalts (MORBs) are the most abundant terrestrial magmas and are believed to form by partial melting of a globally extensive reservoir of ultramafic rocks in the upper mantle. MORBs vary in their abundances of incompatible elements (that is, those that partition into silicate liquids during partial melting) and in the isotopic ratios of several radiogenic isotope systems. These variations define a spectrum between ‘depleted’ and ‘enriched’ compositions, characterized by respectively low and high abundances of incompatible elements. Compositional variations in the sources of MORBs could reflect recycling of subducted crustal materials into the source reservoir, or any of a number of processes of intramantle differentiation. Variations in 18O/16O (principally sensitive to the interaction of rocks with the Earths hydrosphere) offer a test of these alternatives. Here we show that 18O/16O ratios of MORBs are correlated with aspects of their incompatible-element chemistry. These correlations are consistent with control of the oxygen-isotope and incompatible-element geochemistry of MORBs by a component of recycled crust that is variably distributed throughout their upper mantle sources.

Melt mixing and crystallization under Theistareykir, northeast Iceland

Analysis of the compositions of crystals and melt inclusions from a suite of 40 gabbroic and wehrlitic nodules in a single eruptive body provides a record of concurrent mixing and crystallization of melts under NE Iceland. The crystals in the nodules have a similar range of compositions to those found as phenocrysts in the flow, and many of the nodules may have been generated by crystallization of a magma with a similar composition to that of the host flow. While plagioclase is only present in nodules where the average forsterite content of olivines is 0.8 GPa and is in agreement with estimates of crystallization pressures for the host basalt. The relationship between the compositional variability of melt inclusions and the forsterite content of the host olivine is revealed by REE analyses of over 120 melt inclusions. The degree of variability in REE concentrations and REE/Yb ratios decreases with falling forsterite content of the host olivine, as expected if melt mixing and fractional crystallization are operating together. The standard deviation of the REEs falls by a factor of ~4 between Fo90 and Fo87. This change in olivine composition can be produced by crystallization of 20% which occurs on cooling of ~50°C. The relative rates of mixing, cooling and crystallization may provide constraints upon the dynamics of magma bodies. The oxygen isotopic composition of olivines from the nodules and phenocrysts is highly variable (δ18O from 3.3–5.2 per mil) and shows little correlation with the forsterite content of the olivine. The full range of oxygen isotope variation is present in olivines with Fo89–90, and the low δ18O signal is associated with melts of high Mg# and La/Yb. Such geochemical relationships cannot be produced by assimilation of low Mg# crustal materials alone, and may reflect oxygen isotopic variation within the mantle source. The geochemistry of the melt inclusions and their host crystals can be accounted for by fractional melting of a mantle source with variable composition, followed by concurrent mixing and crystallization beneath the Moho.

Oxygen isotope evidence for the origin of chemical variations in lavas from Theistareykir volcano in Iceland’s northern volcanic zone

Oxygen isotope ratios in phenocrysts from recent Theistareykir lavas (Iceland) are consistently ^(18)O-depleted relative to common terrestrial basalts (e.g. δ^(18)O olivine=4.7–4.1‰) and correlate with geochemical indices of ‘enrichment’ (e.g. K_2O/TiO_2; La/Sm) and major element indices of differentiation (e.g. Mg#; CaO/Na_2O). The sense of these correlations is that decreasing δ^(18)O is accompanied by increasing ‘enriched’ geochemical signatures and an increasing extent of differentiation. These trends are similar to (although more subtle than) those defined by highly differentiated and contaminated Icelandic andesites, dacites and rhyolites. The trends we observe are consistent with models in which primary recent Theistareykir magmas are highly ‘depleted’ in their incompatible element geochemistry and similar in δ^(18)O to common terrestrial basalts; differentiation of these magmas is accompanied by contamination by the low δ^(18)O, and on average more ‘enriched’ rocks of the Icelandic crust to produce the observed spectrum in δ^(18)O and other geochemical indices. Our results suggest that geochemical variations among recent Theistareykir lavas are only indirect constraints on the composition and dynamics of the Iceland plume. Extrapolation of the geochemical trends we observe to oxygen isotope compositions within the range of common oceanic basalts suggests that primary recent Theistareykir magmas are exceptionally depleted (e.g. La/Sm=0.2–0.5), indicating unusually high degrees and/or multiple stages of melting of their sources.

D/H ratios of atmospheric H2 in urban air: Results using new methods for analysis of nano-molar H2 samples

We present the results of a study of the concentration and D/H ratio of molecular hydrogen from air in the Los Angeles Basin and adjacent San Gabriel Mountains. These data define a mixing relationship in dimensions of D/H ratio vs. 1/(H_2) which constrains the δD_(VSMOW) of unpolluted winter air in this region to be ca. +100 to +125 ‰ and that of urban H2 sources to be ca. −270 ‰. This study makes use of a new method for measuring the deuterium content of molecular hydrogen in small samples (∼100 to 500 cc) of air, which we describe in detail. The method consists of an off-line separation of H_2 followed by introduction to the mass spectrometer in a continuous flow of He. Off-line, all components of an atmospheric gas sample, with the exception of He, H_2, and Ne are condensed by exposure to a cold-trap held at 30 Kelvin. This separation is followed by cryo-transfer of non-condensable gases to a small volume molecular sieve finger, with assist from a mercury piston pump. At the mass spectrometer, the sample is put in line with a continuous flow of He where it is focused on to an additional column of molecular sieve before subsequent introduction into the ion source. Analyses of DH/H_2 ratio have accuracy and precision of ±4 to 7 per mil. Comparison of sample peak area to peak areas of standards of known size allows for determination of H_2 concentration with accuracy and precision of ∼±5%, relative. The method reduces sample size and processing time by several orders of magnitude compared to previous methods, allowing for sampling at proportionately higher spatial and temporal resolution.

Concentration and δD of molecular hydrogen in boreal forests: Ecosystem‐scale systematics of atmospheric H2

We examined the concentration and δD of atmospheric H2 in a boreal forest in interior Alaska to investigate the systematics of high latitude soil uptake at ecosystem scale. Samples collected during nighttime inversions exhibited vigorous H_2 uptake, with concentration negatively correlated with the concentration of CO_2 (−0.8 to −1.2 ppb H_2 per ppm CO_2) and negatively correlated with δD of H_2. We derived H_2 deposition rates of between 2 to 12 nmol m^(−2) s^(−1). These rates are comparable to those observed in lower latitude ecosystems. We also derive an average fractionation factor, α = D:H_(residual)/D:H_(consumed) = 0.94 ± 0.01 and suggestive evidence that α depends on forest maturity. Our results show that high northern latitude soils are a significant sink of molecular hydrogen indicating that the record of atmospheric H_2 may be sensitive to changes in climate and land use.

Oxygen isotope geochemistry of the second HSDP core

Oxygen isotope ratios were measured in olivine phenocrysts (~1 mm diameter), olivine microphenocrysts (generally ~100–200 µm diameter), glass, and/or matrix from 89 samples collected from depths down to 3079.7 m in the second, and main, HSDP core (HSDP-2). Olivine phenocrysts from 11 samples from Mauna Loa and 34 samples from the submarine section of Mauna Kea volcano have delta18O values that are similar to one another (5.11 ± 0.10‰, 1sigma, for Mauna Loa; 5.01 ± 0.07‰, for submarine Mauna Kea) and within the range of values typical of olivines from oceanic basalts (delta18O of ~5.0 to 5.2‰). In contrast, delta18O values of olivine phenocrysts from 20 samples taken from the subaerial section of Mauna Kea volcano (278 to 1037 mbsl) average 4.79 ± 0.13‰. Microphenocrysts in both the subaerial (n = 2) and submarine (n = 24) sections of Mauna Kea are on average ~0.2‰ lower in delta18O than phenocrysts within the same stratigraphic interval; those in submarine Mauna Kea lavas have an average delta18O of 4.83 ± 0.11‰. Microphenocrysts in submarine Mauna Kea lavas and phencrysts in Mauna Loa lavas are the only population of olivines considered in this study that are typically in oxygen isotope exchange equilibrium with coexisting glass or groundmass. These data confirm the previous observation that the stratigraphic boundary between Mauna Loa and Mauna Kea lavas defines a shift from “normal” to unusually low delta18O values. Significantly, they also document that the distinctive 18O-depleted character of subaerial Mauna Kea lavas is absent in phenocrysts of submarine Mauna Kea lavas. Several lines of evidence suggest that little if any of the observed variations in delta18O can be attributed to subsolidus alteration or equilibrium fractionations accompanying partial melting or crystallization. Instead, they reflect variable proportions of an 18O-depleted source component or contaminant from the lithosphere and/or volcanic edifice that is absent in or only a trace constituent of subaerial Mauna Loa lavas, a minor component of submarine Mauna Kea lavas, and a major component of subaerial Mauna Kea lavas. Relationships between the delta18O of phenocrysts, microphenocrysts, and glass or groundmass indicate that this component (when present) was added over the course of crystallization-differentiation. This process must have taken place in the lithosphere and most likely at depths of between ~5 and 15 km. We conclude that the low-delta18O component is either a contaminant from the volcanic edifice that was sampled in increasingly greater proportions as the volcano drifted off the center of the Hawaiian plume or a partial melt of low-delta18O, hydrothermally altered perdotites in the shallow Pacific lithosphere that increasingly contributed to Mauna Kea lavas near end of the volcanos shield building stage. The first of these alternatives is favored by the difference in delta18O between subaerial and submarine Mauna Kea lavas, whereas the second is favored by systematic differences in radiogenic and trace element composition between higher and lower delta18O lavas.

Hydrogen-isotope analysis of nanomole (picoliter) quantities of H2O

We describe a technique for on-line reduction of water vapor carried in a He stream followed by continuous-flow mass spectrometry of evolved H_2 gas. This technique is appropriate for analysis of D/H ratios of ∼10^(−9) to ∼5 × 10^(−8) moles of water and has an external precision (1σ) typically varying between ±1.0 and 2.0‰. For specific ranges in sample size, temperature of the reduction reaction, and method of introducing evolved vapor into the mass spectrometer, this technique involves negligible analytical corrections (∼0 to 3‰) beyond those inherent to gas-source mass spectrometry of molecular hydrogen. We present an analysis of the D/H ratio of water released by stepped heating of a 10-mg fragment of the Shergottite-Nahklite-Chassignite meteorite ALH84001 and ∼1 to 2 μg of a terrestrial hydrous mineral (thermonatrite) as examples of possible applications making use of this technique.

Experimental constraints on the stable-isotope systematics of CO2 ice/vapor systems and relevance to the study of Mars

Variations in the isotopic compositions of oxygen, hydrogen, and carbon in the near-surface environment of Mars are likely influenced by condensation, evaporation, and sublimation of major volatile species (H_2O, CO_2). We present here an experimental study of the fractionations of ^(18)O/^(16)O and ^(13)C/^(12)C ratios between CO_2 ice and vapor at conditions relevant to the present near-surface of Mars; these experiments constrain isotopic variations generated by the current Martian CO_2 condensation/sublimation cycle. Oxygen-isotope fractionation between ice and vapor (Δ_(ice-vapor) = 1000 · 1n ([^(18)O_(ice)/^(16)O_(ice)] / [^(18)O_(vapor)/^(16)O_(vapor)]) varies approximately linearly vs. 1/T between temperatures of 150 and 130 K (from 4.2 and 7.5 ‰, respectively). Carbon isotopes are unfractionated (Δ^(13)C_(ice-vapor) ≤ 0.2‰) at temperatures ≥ 135 K and only modestly fractionated (Δ^(13)C_(ice-vapor) ≤ 0.4‰) at temperatures between 135 and 130 K. Martian atmospheric volumes that are residual to high extents of condensation (i.e., at high latitudes during the winter) may vary in δ^(18)O by up to tens of per mil, depending on the scales and mechanisms of ice/vapor interaction and atmospheric mixing. Precise (i.e., per mil level) examination of the Martian atmosphere or ices could be used as a tool for examining the Martian climate; at present such precision is only likely to be had from laboratory study of returned samples or substantial advances in the performance of mass spectrometers on landers and/or orbital spacecraft. Oxygen-isotope fractionations accompanying the CO_2 condensation/sublimation cycle may play a significant role in the oxygen-isotope geochemistry of secondary phases formed in SNC meteorites, in particular as a means of generating ^(18)O-depleted volatile reservoirs.