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 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)

Stable isotope geochemistry

This review is intended principally to be a reasonably comprehensive bibliography. It covers papers by workers in stable isotope geochemistry in the United States that have been published or presented at national meetings since the last quadrennial report. The titles of the papers in the bibliography are in most cases indicative of the general content, so only the highlights are described below

The role of stable isotopes in geochemistries of all types

Although I was surprised by the invitation to write a prefatory chapter for the Annual Review of Earth and Planetary Sciences, I decided to accept this opportunity to write about my experiences as a participant in the isotope geochemistry revolution that occurred 40–50 years ago. My own experiences during the early stages of my life were uniquely intertwined with those of many of the leaders of this revolution, and thus I was allowed to witness and participate in many remarkable changes in the science as a whole. In addition, I thought that my contribution might be of some interest to the members of a younger generation, to help them judge whether a scientific career could be interesting, rewarding, and worth working hard for to accomplish something. This chapter also gives me the opportunity to express my appreciation to some of the teachers, early colleagues, and students whose influences were important in my life

A general moment NRIXS approach to the determination of equilibrium Fe isotopic fractionation factors: application to goethite and jarosite

We measured the reduced partition function ratios for iron isotopes in goethite FeO(OH), potassium-jarosite KFe3(SO4)2(OH)6, and hydronium-jarosite (H3O)Fe3(SO4)2(OH)6, by Nuclear Resonant Inelastic X-Ray Scattering (NRIXS, also known as Nuclear Resonance Vibrational Spectroscopy -NRVS- or Nuclear Inelastic Scattering -NIS) at the Advanced Photon Source. These measurements were made on synthetic minerals enriched in 57Fe. A new method (i.e., the general moment approach) is presented to calculate {\beta}-factors from the moments of the NRIXS spectrum S(E). The first term in the moment expansion controls iron isotopic fractionation at high temperature and corresponds to the mean force constant of the iron bonds, a quantity that is readily measured and often reported in NRIXS studies.Comment: 38 pages, 2 tables, 8 figures. In press at Geochimica et Cosmochimica Acta. Appendix C contains new derivations relating the moments of the iron PDOS to the moments of the excitation probability function measured in Nuclear Resonant Inelastic X-ray Scatterin

Why are variations in bromine isotope compositions in the Earth's history larger than chlorine isotope compositions?

In this paper we discuss the marked discrepancy in global chlorine and bromine isotope variations. While, based on experimentally and theoretically determined fractionation factors, it is expected that bromine isotope variations should be, depending on the process, 2 to 7 times less than chlorine isotope variations it is observed that in formation brines the isotope variations of bromine are at least of the same size as chlorine isotope variations, and regularly even larger. In this paper we argue that this is caused by the fact that oxidation-reduction processes play a more important role in bromine isotope geochemistry than in chlorine isotope geochemistry. Due to the fact that the bromide ion is more easily to oxidise than the chloride ion Rayleigh effects can cause the observed larger variations in bromine isotope geochemistry. In this paper we propose that biochemical reactions (oxidation of bromide ions to methyl bromide) may be the major cause for this effect. Although we do not yet understand the full processes that take place we show that oxidation-reduction processes must be the main effect to explain the differences between the two isotope systems and propose that more research is developed to understand how the processes cause the observed variations

Trace element and isotope geochemistry of Cretaceous-Tertiary boundary sediments: identification of extra-terrestrial and volcanic components

Trace element and stable isotope analyses were performed on a series of sediment samples crossing the Cretaceous-Tertiary (K-T) boundary from critical sections at Aumaya and Sopelano, Spain. The aim is to possibly distinguish extraterrestrial vs. volcanic or authigenic concentration of platinum group and other elements in K-T boundary transitional sediments. These sediments also have been shown to contain evidence for step-wise extinction of several groups of marine invertebrates, associated with negative oxygen and carbon isotope excursions occurring during the last million years of the Cretaceous. These isotope excursions have been interpreted to indicate major changes in ocean thermal regime, circulation, and ecosystems that may be related to multiple events during latest Cretaceous time. Results to date on the petrographic and geochemical analyses of the Late Cretaceous and Early Paleocene sediments indicate that diagenesis has obviously affected the trace element geochemistry and stable isotope compositions at Zumaya. Mineralogical and geochemical analysis of K-T boundary sediments at Zumaya suggest that a substantial fraction of anomalous trace elements in the boundary marl are present in specific mineral phases. Platinum and nickel grains perhaps represent the first direct evidence of siderophile-rich minerals at the boundary. The presence of spinels and Ni-rich particles as inclusions in aluminosilicate spherules from Zumaya suggests an original, non-diagenetic origin for the spherules. Similar spherules from southern Spain (Caravaca), show a strong marine authigenic overprint. This research represents a new approach in trying to directly identify the sedimentary mineral components that are responsible for the trace element concentrations associated with the K-T boundary

d13C pattern of dissolved inorganic carbon in a small granitic catchment: the Strengbach case study (Vosges mountains, France)

The transfers and origins of dissolved inorganic carbon DIC. were studied for a year in a soil–spring–stream system in the Strengbach catchment, Vosges mountains, France. This 80 ha experimental research basin is located on the eastern side of the mountains, at an altitude ranging from 883 to 1146 m.a.s.l. and is mainly covered by spruce 80%.. Brown acid and podzolic soils developed on a granitic basement, and, as a result, the DIC originates solely from CO2 generated by oxidation of soil organic matter. The d13CDIC. in catchment waters is highly variable, from about y22‰ in the springs and piezometers to about y12‰ in the stream at the outlet of the catchment. In the springs, pronounced seasonal variations of d13C exist, with the DIC in isotopic equilibrium with the soil CO that has estimated d13DIC 2 C of about y24‰ in winter and y20‰ in summer. These seasonal variations reflect an isotopic fractionation that seems only induced by molecular diffusion of soil CO2 in summer. In stream water, seasonal variations are small and the relatively heavy DIC y12‰ on average. is a result of isotopic equilibration of the aqueous CO2 with atmospheric CO2

Mantle Source Variations beneath the Eastern Lau Spreading Center and the Nature of Subduction Components in the Lau Basin-Tonga Arc System

New high-density sampling of the Eastern Lau Spreading Center provides constraints on the processes that affect the mantle wedge beneath a back-arc environment, including the effect of the subduction input on basalt petrogenesis and the change in subduction input with distance from the Tonga arc. We obtained trace element and Pb-Sr-Nd isotopic compositions of 64 samples distributed between 20.2 degree S and 22.3 degree S with an average spacing of ~3.6 km. The trace element and isotope variations do not vary simply with distance from the arc and reflect variations in the mantle wedge composition and the presence of multiple components in the subduction input. The mantle wedge composition varies form north to south, owing to the southward migration of Indian-like mantle, progressively replacing the initially Pacific-like mantle wedge. The mantle wedge compositions also require an enriched mid-ocean ridge basalt-like trace element enrichment that has little effect on isotope ratios, suggesting recent low-degree melt enrichment events. The composition of the subduction input added to the mantle wedge is geographically variable and mirrors the changes observed in the Tonga arc island lavas. The combination of the back-arc and arc data allows identification of several components contributing to the subduction input. These are a fluid derived from the altered oceanic crust with a possible sedimentary contribution, a pelagic sediment partial melt, and, in the southern Lau basin, a volcaniclastic sediment partial melt. While on a regional scale, there is a rough decrease in subduction influence with the distance from the arc, on smaller scales, the distribution of the subduction input reflects different mechanisms of the addition of the subduction input to a variable mantle wedge.Earth and Planetary Science