Iron isotope fractionation and the oxygen fugacity of the mantle

The oxygen fugacity of the mantle exerts a fundamental influence on mantle melting, volatile speciation, and the development of the atmosphere. However, its evolution through time is poorly understood. Changes in mantle oxidation state should be reflected in the Fe3+/Fe2+ of mantle minerals, and hence in stable iron isotope fractionation. Here it is shown that there are substantial (1.7 per mil) systematic variations in the iron isotope compositions (delta57/54Fe) of mantle spinels. Spinel delta57/54Fe values correlate with relative oxygen fugacity, Fe3+/sigmaFe, and chromium number, and provide a proxy of changes in mantle oxidation state, melting, and volatile recycling.     

Sulfur isotopic composition of cenozoic seawater sulfate

A continuous seawater sulfate sulfur isotope curve for the Cenozoic with a resolution of approximately 1 million years was generated using marine barite. The sulfur isotopic composition decreased from 19 to 17 per mil between 65 and 55 million years ago, increased abruptly from 17 to 22 per mil between 55 and 45 million years ago, remained nearly constant from 35 to approximately 2 million years ago, and has decreased by 0.8 per mil during the past 2 million years. A comparison between seawater sulfate and marine carbonate carbon isotope records reveals no clear systematic coupling between the sulfur and carbon cycles over one to several millions of years, indicating that changes in the burial rate of pyrite sulfur and organic carbon did not singularly control the atmospheric oxygen content over short time intervals in the Cenozoic. This finding has implications for the modeling of controls on atmospheric oxygen concentration.     

Primitive boron isotope composition of the mantle

Boron isotope ratios are homogeneous in volcanic glasses of oceanic island basalts [-9.9 +/- 1.3 per mil, relative to standard NBS 951 (defined by the National Bureau of Standards)], whereas mid-oceanic ridge basalts (MORBs) and back-arc basin basalts (BABBs) show generally higher and more variable ratios. Melts that have assimilated even small amounts of altered basaltic crust show significant variations in the boron isotope ratios. Assimilation may thus account for the higher boron ratios of MORBs and BABBs. A budget of boron between mantle and crust implies that the primitive mantle had a boron isotope ratio of -10 +/- 2 per mil and that this ratio was not fractionated significantly during the differentiation of the mantle.     

Cryptic grain-scale heterogeneity of oxygen isotope ratios in metamorphic magnetite

Oxygen isotope ratios measured by ion microprobe in magnetite from granulite-facies marble of the Adirondack Mountains, New York, range from +2 to +11 per mil (standard mean ocean water) across a single grain that measures 3 millimeters by 5 millimeters. Low values are concentrated in irregular domains near the grain boundary but also occur in the grain's interior. In contrast, grains 1 millimeter in diameter that are from a second nearby sample show no significant heterogeneity, except within 10 micrometers of the grain boundary. These data, including large gradients of up to 9 per mil per 10 micrometers, provide important new constraints on the nature and origins of intragrain isotopic heterogeneity and on oxygen isotope thermometry. The differences between these magnetite grains result from contrasting mechanisms of isotope exchange with fluids after the peak of regional metamorphism. Volume diffusion of oxygen through the crystal structure of magnetite contributed to isotope exchange in the rims of small grains, but larger grains are crosscut by healed cracks that are not readily detected and that short-circuited diffusion.     

Water, hydrogen, deuterium, carbon, carbon-13, and oxygen-18 content of selected lunar material

The water content of the breccia is 150 to 455 ppm, with a deltaD from-580 to -870 per mil. Hydrogen gas content is 40 to 53 ppm with a deltaD of -830 to -970 per mil. The CO(2) is 290 to 418 ppm with delta (13)C = + 2.3 to + 5.1 per mil and delta(18)O = 14.2 to 19.1 per mil. Non-CO(2) carbon is 22 to 100 ppm, delta(13)C = -6.4 to -23.2 per mil. Lunar dust is 810 ppm H(2)O (D = 80 ppm) and 188 ppm total carbon(delta(13)C = -17.6 per mil). The (18)O analyses of whole rocks range from 5.8 to 6.2 per mil. The temperature of crystallization of type B rocks is 1100 degrees to 1300 degrees C, based on the oxygen isotope fractionation between coexisting plagioclase and ilmenite.     

Stable-carbon isotope ratios as a measure of marine versus terrestrial protein in ancient diets

The stable-carbon isotope ratios for the flesh of marine and terrestrial animals from Canada's Pacific coast differ by 7.9 +/- 0.4 per mil, reflecting the approximately 7 per mil difference between oceanic and atmospheric carbon. This difference is passed on to human consumers. The carbon isotopic values (delta(13)C) for human collagen thus yield direct information on the relative amounts of marine and terrestrial foods in prehistoric diets.     

Oxygen isotopes: experimental vapor fractionation and variations in tektites

High-temperature (about 2800 degrees C) vapor fractionation of a silicate glass that originally contained 82 percent by weight of SiO(2) resulted in a decrease of the silica content to 45 percent. Oxygen isotope analyses show that the O(18)/O(16) ratio increased from 13.80 per mil in the starting material to 14.47 and 15.03 per mil in the residuum. This suggests that bediasites, which also exhibit an increase in this ratio with decreasing content of silica, have been subjected to a process of vapor fractionation.     

Stable nitrogen isotope ratios of bone collagen reflect marine and terrestrial components of prehistoric human diet

The delta 15N values of bone collagen from Eskimos and from Northwest Coast Indians dependent on salmon fishing are about 10 per mil more positive than those from agriculturalists in historic times. Among prehistoric humans, two groups dependent on marine food sources show bone collagen delta 15N values that are 4 to 6 per mil more positive than those from two agricultural groups. The nitrogen isotope ratios of bone collagen from prehistoric inhabitants of the Bahamas are anomalously low for reasons that relate to the biogeochemical cycle of nitrogen in coral reefs.     

Carbon isotope fractionation in the Fischer-tropsch synthesis and in meteorites

Carbon dioxide and organic compounds made by a Fischer-Tropsch reaction at 400 degrees K show a kinetic isotope fractionation of 50 to 100 per mil, similar to that observed in carbonaceous chondrites. This result supports the view that organic compounds in meteorites were produced by catalytic reactions between carbon monoxide and hydrogen in the solar nebula.     

Oxygen isotope ratios in eclogites from kimberlites

The oxygen isotope compositions (delta(18)O) of eclogitic xenoliths from the Roberts Victor kimberlite range from 2 to 8 per mil relative to SMOW (standard mean ocean water). This surprising variation appears to be due to fractional crystallization: the eclogites rich in oxygen-18 represent early crystal accumulates; the eclogites poor in oxygen-18 represent residual liquids. Crystal-melt partitioning probably exceeded 3 per mil and is interpreted to be pressure-dependent. Anomalous enrichment of oxygen-18 in cumulate eclogites relative to ultramafic xenoliths suggests that crystal-melt partitioning increased after melt-formation but prior to crystallization.     

Oxygen-18 content of atmospheric precipitation during last 11,000 years in the Great Lakes region

Freshwater lake marl and mollusks from Indiana show variations in ratios of oxygen-18 to oxygen-16 of a few per mil during the Postglacial. For the last 9000 years these variations are about 1 per mil for properly selected lake sediments. Thus the oxygen isotope composition of atmospheric precipitation appears relatively stable over this interval, indicating stationary atmospheric circulation patterns over the Great Lakes region. A reduction in oxygen-18 content around 10,000 years ago corresponds with the climate change indicated by pollen profiles. Large systematic differences were found between carbon-13 and oxygen-18 content of marl and mollusks.     

Oxygen isotope constraints on the origin of impact glasses from the cretaceous-tertiary boundary

Laser-extraction oxygen isotope and major element analyses of individual glass spherules from Haitian Cretaceous-Tertiary boundary sediments demonstrate that the glasses fall on a mixing line between an isotopically heavy (delta(18)O = 14 per mil) high-calcium composition and an isotopically light (delta(18)O = 6 per mil) high-silicon composition. This trend can be explained by melting of heterogeneous source rocks during the impact of an asteroid (or comet) approximately 65 million years ago. The data indicate that the glasses are a mixture of carbonate and silicate rocks and exclude derivation of the glasses either by volcanic processes or as mixtures of sulfate-rich evaporate and silicate rocks.     

Carbon-13/carbon-12 isotope fractionation of organic matter associated with uranium ores induced by alpha irradiation

Analyses of stable carbon isotopes from two sample suites from sandstone uranium (tabular) ores show interesting variations. Organic carbon associated with high-grade uranium ore is heavy (delta(13)C = -16.9 to -19.6 per mil, where delta(13)C = (13)C/(12)C relative to the Pee Dee belemnite standard) relative to the adjacent lower-grade samples (-22.7 to -26.4 per mil). It is suggested that the heavy isotopic values for the are samples are related to a radiation and chemical isotope effect that has occurred mainly because of an alpha-radiation dose of 10(11) rads.     

Short-lived oxygen diffusion during hot, deep-seated meteoric alteration of anorthosite

Heterogeneous oxygen isotope compositions of plagioclase from the Boehls Butte anorthosite include some of the most oxygen-18-depleted values (to -16 per mil) reported for plagioclase in meta-igneous rocks and indicate high-temperature (T > 500 degrees C) isotopic exchange between plagioclase and nearly pristine meteoric fluid. Retrograde reaction-enhanced permeability assisted influx of meteoric-hydrothermal fluids into the deep-seated anorthosite. Isotopic gradients of about 14 per mil over 600 micrometers in single crystals require short-lived (about 10(4) years) diffusional exchange of oxygen and locally large effective water:rock ratios, followed by rapid loss of water and cessation of oxygen diffusion in the anorthosite.     

Abiotic pyrite formation produces a large Fe isotope fractionation

The iron isotope composition of sedimentary pyrite has been proposed as a potential proxy to trace microbial metabolism and the redox evolution of the oceans. We demonstrate that Fe isotope fractionation accompanies abiotic pyrite formation in the absence of Fe(II) redox change. Combined fractionation factors between Fe(II)(aq), mackinawite, and pyrite permit the generation of pyrite with Fe isotope signatures that nearly encapsulate the full range of sedimentary δ(56)Fe(pyrite) recorded in Archean to modern sediments. We propose that Archean negative Fe isotope excursions reflect partial Fe(II)(aq) utilization during abiotic pyrite formation rather than microbial dissimilatory Fe(III) reduction. Late Proterozoic to modern sediments may reflect greater Fe(II)(aq) utilization and variations in source composition.     

Unexpected changes to the global methane budget over the past 2000 years

We report a 2000-year Antarctic ice-core record of stable carbon isotope measurements in atmospheric methane (delta13CH4). Large delta13CH4 variations indicate that the methane budget varied unexpectedly during the late preindustrial Holocene (circa 0 to 1700 A.D.). During the first thousand years (0 to 1000 A.D.), delta13CH4 was at least 2 per mil enriched compared to expected values, and during the following 700 years, an about 2 per mil depletion occurred. Our modeled methane source partitioning implies that biomass burning emissions were high from 0 to 1000 A.D. but reduced by almost approximately 40% over the next 700 years. We suggest that both human activities and natural climate change influenced preindustrial biomass burning emissions and that these emissions have been previously understated in late preindustrial Holocene methane budget research.     

Oxygen isotope ratios in trees reflect mean annual temperature and humidity

Values of the oxygen isotope ratios (delta(18)O) in tree-ring cellulose closely reflect the delta(18)O values in atmospheric precipitation and hence mean annual temperature. The change in delta(18)O in cellulose is 0.41 per mil per degree Celsius for selected near-coastal stations. The values of delta(18)O in precipitation and cellulose also change with altitude, as demonstrated for Mount Rainier, Washington. A temperature lapse rate of 5.2 degrees +/- 0.5 degrees C per 1000 meters calculated from cellulose delta(18)O values agrees with the accepted mean annual lapse rate of 5 degrees C per 1000 meters for this region. Cellulose delta(18)O values and delta(18)O values of carbon dioxide equilibrated with leaf water differ by a fixed 16 per mil.     

Vertical distribution and isotopic composition of living planktonic foraminifera in the Western north atlantic

Thirteen species of planktonic foraminifera collected with vertically stratified zooplankton tows in the slope water, Gulf Stream cold core ring, and northern Sargasso Sea show significant differences in their vertical distributions in the upper 200 meters of these different hydrographic regimes. Gulf Stream cold core rings may be responsible for a southern displacement of the faunal boundary associated with the Gulf Stream when reconstructed from the deep-sea sediment record. Oxygen isotope analyses of seven species reveal that nonspinose species (algal symbiont-barren) apparently calcify in oxygen isotope equilibrium, whereas spinose species usually calcify out of oxygen isotope equilibrium by approximately -0.3 to -0.4 per mil in delta(18)O values. The isotope data indicate that foraminifera shells calcify in depth zones that are significantly narrower than the overall vertical distribution of a species would imply.     

Pore Fluid Constraints on the Temperature and Oxygen Isotopic Composition of the Glacial Ocean

Pore fluids from the upper 60 meters of sediment 3000 meters below the surface of the tropical Atlantic indicate that the oxygen isotopic composition (delta18O) of seawater at this site during the last glacial maximum was 0.8 ± 0.1 per mil higher than it is today. Combined with the delta18O change in benthic foraminifera from this region, the elevated ratio indicates that the temperature of deep water in the tropical Atlantic Ocean was 4°C colder during the last glacial maximum. Extrapolation from this site to a global average suggests that the ice volume contribution to the change in delta18O of foraminifera is 1.0 per mil, which partially reconciles the foraminiferal oxygen isotope record of tropical sea surface temperatures with estimates from Barbados corals and terrestrial climate proxies.     

Relation between long-term trends of oxygen-18 isotope composition of precipitation and climate

Stable isotope ratios of oxygen ((18)O/(16)O) and hydrogen (D/H) in water have long been considered powerful indicators of paleoclimate. However, quantitative interpretation of isotope variations in terms of climate changes is hampered by a limited understanding of physical processes controlling the global isotope behavior. Analysis was conducted of time series of (18)O content (delta (18)O) of monthly precipitation and surface air temperature available through the International Atomic Energy Agency-World Meteorological Organization global network, "Isotopes in Precipitation." This study indicates that long-term changes of isotopic composition of precipitation over mid-and high-latitude regions during the past three decades closely followed long-term changes of surface air temperature with the average 8180-temperature coefficient around 0.6 per mil per degree Celsius.