Oxygen Isotope Variations of Basaltic Lavas and Upper Mantle Rocks

This chapter summarizes the oxygen isotope geochemistry of terrestrial basalts and their mantle sources, including the conceptual framework for interpreting such data and the phenomenology of known variations. In particular, the first section outlines the motivations for and first-order results of oxygen isotope studies of terrestrial and lunar basalts over the last 30 years; the second section reviews oxygen isotopic fractionations among phases relevant for studying basalts and mantle rocks; the third summarizes variations in δ^(18)O of various crustal rocks that may contribute to the petrogenesis of basalts either as subducted source components or lithospheric contaminants; and the final and longest section describes observed oxygen isotope variations of major classes of terrestrial basalts and related mantle nodules with an emphasis on data generated within the last six years using laser-based fluorination techniques. In the interests of brevity, I do not describe in detail methods for oxygen isotope analysis or changes in δ^(18)O of volcanic rocks caused by sub-solidus alteration; however, these issues are important practical considerations for anyone studying oxygen isotope compositions of basalts and interested readers are directed to the following references: analytical methods: Sharp (1990), Mattey and Macpherson (1993), and Valley et al. (1995); basalt alteration: Muehlenbachs (1986), Alt (1993), and Staudigel et al. (1995)

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

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 volcano's 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

Oxygen isotope composition of the Phanerozoic ocean and a possible solution to the dolomite problem

The ^(18)O/^(16)O of calcite fossils increased by ∼8‰ between the Cambrian and present. It has long been controversial whether this change reflects evolution in the δ^(18)O of seawater, or a decrease in ocean temperatures, or greater extents of diagenesis of older strata. Here, we present measurements of the oxygen and ‟clumped” isotope compositions of Phanerozoic dolomites and compare these data with published oxygen isotope studies of carbonate rocks. We show that the δ^(18)O values of dolomites and calcite fossils of similar age overlap one another, suggesting they are controlled by similar processes. Clumped isotope measurements of Cambrian to Pleistocene dolomites imply crystallization temperatures of 15–158 °C and parent waters having δ^(18)O_(VSMOW) values from −2 to +12‰. These data are consistent with dolomitization through sediment/rock reaction with seawater and diagenetically modified seawater, over timescales of 100 My, and suggest that, like dolomite, temporal variations of the calcite fossil δ^(18)O record are largely driven by diagenetic alteration. We find no evidence that Phanerozoic seawater was significantly lower in δ^(18)O than preglacial Cenozoic seawater. Thus, the fluxes of oxygen–isotope exchange associated with weathering and hydrothermal alteration reactions have remained stable throughout the Phanerozoic, despite major tectonic, climatic and biologic perturbations. This stability implies that a long-term feedback exists between the global rates of seafloor spreading and weathering. We note that massive dolomites have crystallized in pre-Cenozoic units at temperatures >40 °C. Since Cenozoic platforms generally have not reached such conditions, their thermal immaturity could explain their paucity of dolomites

Constraining the Origin of the Jupiter Trojans by In Situ Measurement of Volatiles, Minerals, and Ices

As the KISS Trojans program comes to a close, we report here on our achievements in this venture that began with a KISS workshop in 2012, “In Situ Science and Instrumentation for Primitive Bodies”. The original workshop brought together a diverse group (see Appendix B) that set out to tackle an ambitious goal – to find a way to test predictions of dynamical models (such as the Nice model, named after the founding research group in Nice, France), that have recently led to a radically new understanding of solar system formation. We aimed to do so through interdisciplinary collaboration between the planetary dynamics communities that have formulated (and largely dominated discussion of) these new ideas, and the meteoritics and cosmochemistry communities who would no doubt be involved in any in situ mission to an outer solar system body

Eiler receives 2002 James B. Macelwane Medal

John M. Eiler was awarded the 2002 James B. Macelwane Medal at the AGU Fall Meeting Honors Ceremony. The medal is given for significant contributions to the geophysical sciences by a young scientist of outstanding ability

Constraints on the formation and diagenesis of phosphorites using carbonate clumped isotopes

The isotopic composition of apatites from sedimentary phosphorite deposits has been used previously to reconstruct ancient conditions on the surface of the earth. However, questions remain as to whether these minerals retain their original isotopic composition or are modified during burial and lithification. To better understand how apatites in phosphorites form and are diagenetically modified, we present new isotopic measurements of δ^(18)O values and clumped-isotope-based (Δ_(47)) temperatures of carbonate groups in apatites from phosphorites from the past 265 million years. We compare these measurements to previously measured δ^(18)O values of phosphate groups from the same apatites. These results indicate that the isotopic composition of many of the apatites do not record environmental conditions during formation but instead diagenetic conditions. To understand these results, we construct a model that describes the consequences of diagenetic modification of phosphorites as functions of the environmental conditions (i.e., temperature and δ^(18)O values of the fluids) during initial precipitation and subsequent diagenesis. This model captures the basic features of the dataset and indicates that clumped-isotope-based temperatures provide additional quantitative constraints on both the formational environment of the apatites and subsequent diagenetic modification. Importantly, the combination of the model with the data indicates that the δ^(18)O values and clumped-isotope temperatures recorded by phosphorites do not record either formation or diagenetic temperatures, but rather represent an integrated history that includes both the formation and diagenetic modification of the apatites

Introduction

Geological models of subduction zones impact thinking about many of the central problems in the structure, dynamics, chemistry, and history of the solid earth. Should those models change, the effects will reach across the earth sciences. We are currently in the midst of such a change, brought on by several causes. First, the earth science community recently began an organized, multi-disciplinary study of subduction zones by way of the National Science Foundation's "Margins initiative." This has improved the quality of our descriptions of key focus areas and should continue to do so for the next several years. Less purposefully but of equal importance, several of the debates in subduction zone research have evolved in recent years, making us revisit both recent and old observations in a new light. This book consists of descriptions of these advances, written by the some of the leading participants. I describe the origin and organization of the book in the preface; here I review the context of previous thought regarding convergent margins, with particular focus on the link between tectonics and magmatism, and point out questions raised in the following chapters

Measurement of rare isotopologues of nitrous oxide by high-resolution multi-collector mass spectrometry

Rationale: Bulk and position-specific stable isotope characterization of nitrous oxide represents one of the most powerful tools for identifying its environmental sources and sinks. Constraining ^(14)N^(15)N^(18)O and ^(15)N^(14)N^(18)O will add two new dimensions to our ability to uniquely fingerprint N_2O sources. Methods: We describe a technique to measure six singly and doubly substituted isotopic variants of N2O, constraining the values of δ^(15)N, δ^(18)O, ∆^(17)O, ^(15)N site preference, and the clumped isotopomers ^(14)N^(15)N^(18)O and ^(15)N^(14)N^(18)O. The technique uses a Thermo MAT 253 Ultra, a high-resolution multi-collector gas source isotope ratio mass spectrometer. It requires 8–10 hours per sample and ~10 micromoles or more of pure N_2O. Results: We demonstrate the precision and accuracy of these measurements by analyzing N_2O brought to equilibrium in its position-specific and clumped isotopic composition by heating in the presence of a catalyst. Finally, an illustrative analysis of biogenic N_2O from a denitrifying bacterium suggests that its clumped isotopic composition is controlled by kinetic isotope effects in N_2O production. Conclusions: We developed a method for measuring six isotopic variants of N_2O and tested it with analyses of biogenic N_2O. The added isotopic constraints provided by these measurements will enhance our ability to apportion N_2O sources