Oxygen Isotope Evidence for Chemical Interaction of Ki lauea Historical Magmas with Basement Rocks

Klauea historical summit lavas have a wide range in matrix ¹⁸O_VSMOWvalues (4·9–5·6) with lower values in rockserupted following a major summit collapse or eruptive hiatus.In contrast, ¹⁸O values for olivines in most of these lavasare nearly constant (5·1 ± 0·1). The disequilibriumbetween matrix and olivine ¹⁸O values in many samples indicatesthat the lower matrix values were acquired by the magma afterolivine growth, probably just before or during eruption. BothMauna Loa and Klauea basement rocks are the likely sources ofthe contamination, based on O, Pb and Sr isotope data. However,the extent of crustal contamination of Klauea historical magmasis probably minor (< 12%, depending on the assumed contaminant)and it is superimposed on a longer-term, cyclic geochemicalvariation that reflects source heterogeneity. Klauea's heterogeneoussource, which is well represented by the historical summit lavas,probably has magma ¹⁸O values within the normal mid-ocean ridgebasalt mantle range (5·4–5·8) based on thenew olivine ¹⁸O values. KEY WORDS: Hawaii; Klauea; basalt; oxygen isotopes; crustal contamination     

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/(H₂) 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 H₂ 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, H₂, 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/H₂ 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 H₂ 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.     

Paleoclimate reconstruction using carbonate clumped isotope thermometry

Carbonate clumped isotope thermometry is a relatively new paleotemperature proxy based on measurements of the degree of ordering of ¹³C and ¹⁸O into bonds with each other (making the ¹³C¹⁸O¹⁶O₂^?2 ion group) in lattices of carbonate minerals. This technique has several unusual properties that complement existing methods of paleoclimate reconstruction. Most importantly, it is based on a homogeneous isotope exchange equilibrium and thus constrains temperature independent of the isotopic composition of waters from which carbonates grew. This method also appears to be generally insensitive to ‘vital effects’ that compromise many other paleothermometers based on the chemical properties of biominerals or organic matter, at least for those organisms that have been subjected to systematic study to-date (corals and foraminifera); however, discrepancies among some calibrations, particularly at low temperatures, may point toward the existence of vital effects in mollusks and other organisms. This review discusses the principles and calibrations of the technique, its uses in combination with conventional stable isotope measurements to constrain the δ¹⁸O of past waters, preservation of paleotemperatures in ancient materials, as well as current problems in our understanding of calibrations and interlaboratory data comparisons.     

Calibration of the carbonate ‘clumped isotope’ paleothermometer for otoliths

Paleothermometry is an essential tool for understanding past changes in climate. The ‘carbonate clumped isotope thermometer’ is a temperature proxy related to ordering of ¹³C and ¹⁸O in the carbonate lattice (based on measurements of ¹³C¹⁸O¹⁶O in CO₂ produced by acid digestion of carbonate). This thermometer has been previously calibrated for inorganic calcite and aragonitic corals [Ghosh P., Adkins J., Affek H., Balta B., Guo W. F., Schauble E. A., Schrag D., and Eiler J. M. (2006) C-13-O-18 bonds in carbonate minerals: a new kind of paleothermometer. Geochim. Cosmochim. Acta70 (6), 1439-1456]. Here we determine the relationship between growth temperatures of aragonitic fish otoliths and abundances of ¹³C¹⁸O¹⁶O produced by acid digestion of those otoliths. Our calibration is based on analyses of otoliths from six species from four genera of modern fish sampled from a latitudinal transect of the Atlantic Ocean between 54° S and 65° N, plus one species from the tropical western Pacific. The temperatures at which fish otoliths precipitated were estimated by the mean temperature in the waters in which they lived, averaged over their estimated lifetimes. Estimated growth temperatures of our samples vary between 2 and 25 °C. Our results show that the abundance of ¹³C¹⁸O¹⁶O in CO₂ produced by acid digestion of fish otolith aragonite is a function of growth temperature, following the relationship: , where Δ₄₇ is the enrichment, in per mil, of ¹³C¹⁸O¹⁶O in CO₂ relative to the amount expected for a stochastic (random) distribution of isotopes among all CO₂ isotopologues, and T is the temperature in Kelvin. This relationship closely approaches that previously documented for inorganic calcite and aragonitic coral (Ghosh et al., 2006).     

Sub-micron scale distributions of trace elements in zircon

Sub-micron scale zoning of Ti concentrations and correlations between concentrations of Ti and other trace elements (P, Ce, and Y) and cathodoluminescent (CL) banding is observed in natural zircons. Ion images were made using the Caltech Microanalysis Center’s CAMECA NanoSIMS 50L with an O⁻ primary beam focused to ~300 nm on the sample surface. The high spatial resolution of this technique allows for interrogation of chemical variations at or below the scale of CL banding in natural zircons. Images produced in this manner display two types of correlations among Ti, P, Ce, and Y (which appears to be a proxy for CL intensity): strong (correlation coefficients >0.8) and subtle (correlation coefficients ~0.15–0.4). Strongly correlated images, which display Ti variations of ca. a factor of 3 between adjacent CL bands and overall elevated trace element concentrations in CL-dark bands, were found within an oscillatory-zoned, trace element enriched sector of a CL sector-zoned zircon. Three possible causes for such correlations include: temperature-dependent equilibrium partitioning, trace element partitioning limited by diffusion in the host melt and surface-controlled, non-equilibrium growth. Comparison of our data with the expected results of these processes suggests that: (1) Ti partitioning in zircon is dependent upon non-equilibrium effects in addition to temperature and/or (2) the incorporation of elements that co-vary with Ti in zircon (e.g., Y, P and Ce) is also temperature-dependent. Sub-micron scale, high-Ti regions are also found within Proterozoic Adirondack and >4 Ga Jack Hills zircons as well as trace element enrichments (including Ti) along cracks within Jack Hills zircons.     

Chemical fractionation in the silicate vapor atmosphere of the Earth

Despite its importance to questions of lunar origin, the chemical composition of the Moon is not precisely known. In recent years, however, the isotopic composition of lunar samples has been determined to high precision and found to be indistinguishable from the terrestrial mantle despite widespread isotopic heterogeneity in the Solar System. In the context of the giant-impact hypothesis, this level of isotopic homogeneity can evolve if the proto-lunar disk and post-impact Earth undergo turbulent mixing into a single uniform reservoir while the system is extensively molten and partially vaporized. In the absence of liquid–vapor separation, such a model leads to the lunar inheritance of the chemical composition of the terrestrial magma ocean. Hence, the turbulent mixing model raises the question of how chemical differences arose between the silicate Earth and Moon. Here we explore the consequences of liquid–vapor separation in one of the settings relevant to the lunar composition: the silicate vapor atmosphere of the post-giant-impact Earth. We use a model atmosphere to quantify the extent to which rainout can generate chemical differences by enriching the upper atmosphere in the vapor, and show that plausible parameters can generate the postulated enhancement in the FeO/MgO ratio of the silicate Moon relative to the Earth's mantle. Moreover, we show that liquid–vapor separation also generates measurable mass-dependent isotopic offsets between the silicate Earth and Moon and that precise silicon isotope measurements can be used to constrain the degree of chemical fractionation during this earliest period of lunar history. An approach of this kind has the potential to resolve long-standing questions on the lunar chemical composition.     

Ion microprobe evidence for the mechanisms of stable isotope retrogression in high-grade metamorphic rocks

Retrograde interdiffusion is widely proposed as the dominant factor in producing the stable isotopic fractionation among minerals in slowly cooled igneous and metamorphic rocks. Mineral zonation consistent with interdiffusion of stable isotopes has never been directly observed, however, leaving doubt as to the mechanism responsible for the bulk-mineral isotopic compositions commonly measured. Ion microprobe analyses of oxygen isotope ratios in magnetite were combined with conventional bulk mineral analyses and diffusion modeling to document the relationship between mineral zonation and the mechanism of retrogression inferred from bulk mineral data. Two samples of magnetitebearing, quartzo-feldspathic Lyon Mountain gneiss from the Adirondack mountains, N.Y. were studied in detail. Conventional stable isotope analysis of both samples indicates that isotope thermometers are discordant and were reset by as much as 200°C from the estimated peak temperature of 750°C. The relative order of apparent temperatures recorded by various thermometers differs between the two samples, however, with T _qtz-fsp≫T _mt-qtz and T _mt-fsp in one sample and T _qtz-fsp<T _mt-qtz and T _mt-fsp in the other. Diffusion modeling using the Fast Grain Boundary model shows that the former pattern of apparent temperatures is consistent with closed system interdiffusion during cooling, whereas the latter is not. The modeling predicts that 0.5 mm diameter magnetite grains common to this rock type will contain isotopic zonation of 1‰ (rims lower in δ¹⁸O than cores), and that the cores of smaller (0.1 mm) grains will be similarly lower than to the cores of large (0.5 mm) grains. Ion microprobe analysis reveals that the zoning patterns of magnetite grains from the first sample contain clear core to rim zonation in multiple grains (Δcore-rim=1.1±0.4‰) and predicted grain-size vs core composition variations, consistent with diffusion-controlled resetting of bulk mineral fractionations. In contrast, the second sample shows irregular inter-and intra-granular variations over an 8‰ range, consistent with open system alteration. These results provide direct documentation of the importance of interdiffusion in affecting stable isotope distributions in slowly cooled rocks. The correlations of bulk-mineral resetting with zonation show that bulk mineral data, when interpreted with detailed modeling, can be used to determinate what processes controlling retrogression.     

OCO in Earth’s atmosphere

The chemistry and budgets of atmospheric gases are constrained by their bulk stable isotope compositions (e.g., δ¹³C values), which are based on mixing ratios of isotopologues containing one rare isotope (e.g., ¹⁶O¹³C¹⁶O). Atmospheric gases also have isotopologues containing two or more rare isotopes (e.g., ¹⁸O¹³C¹⁶O). These species have unique physical and chemical properties and could help constrain origins of atmospheric gases and expand the scope of stable isotope geochemistry generally. We present the first measurements of the abundance of ¹⁸O¹³C¹⁶O from natural and synthetic sources, discuss the factors influencing its natural distribution and, as an example of its applied use, demonstrate how its abundance constrains the sources of CO₂ in the Los Angeles basin. The concentration of ¹⁸O¹³C¹⁶O in air can be explained as a combination of ca. 1‰ enrichment (relative to the abundance expected if C and O isotopes are randomly distributed among all possible isotopologues) due to enhanced thermodynamic stability of this isotopologue during isotopic exchange with leaf and surface waters, ca. 0.1‰ depletion due to diffusion through leaf stomata, and subtle (ca. 0.05‰) dilution by ¹⁸O¹³C¹⁶O-poor anthropogenic CO₂. Some air samples are slightly (ca. 0.05‰) lower in ¹⁸O¹³C¹⁶O than can be explained by these factors alone. Our results suggest that ¹⁸O¹³C¹⁶O abundances should vary by up to ca. 0.2‰ with latitude and season, and might have measurable sensitivities to stomatal conductances of land plants. We suggest the greatest use of Δ₄₇ measurements will be to “leverage” interpretation of the δ¹⁸O of atmospheric CO₂.     

Timescales and mechanisms of fluid infiltration in a marble: an ion microprobe study

Using a recently developed ion microprobe technique, a detailed oxygen isotope map of calcite grains in a coarse-grained marble has been constructed, supported by trace element (Mn, Sr, Fe) analysis and cathodoluminescence (CL) imaging, in order to constrain scales of oxygen isotope equilibrium, timescales and mechanisms of metamorphic fluid infiltration, and fluid sources and pathways. Results are compared with a previous study of this sample (Wada 1988) carried out using a cryo-microtome technique and conventional oxygen isotope analysis. The marble, from the high temperature/low pressure Hida metamorphic belt in north-central Japan, underwent granulite facies followed by amphibolite facies metamorphic events, the latter associated with regional granite intrusion. The CL imaging indicates two types of calcite, a yellow luminescing (YLC) and a purple luminescing (PLC) variety. The YLC, which occupies grain boundaries, fractures, replacement patches, and most of the abundant deformation twin lamellae, post-dates the dominant PLC calcite and maps out fluid pathways. Systematic relationships were established between oxygen isotope and trace element composition, calcite type and texture, based on 74 ¹⁸O/¹⁶O and 17 trace element analyses with 20–30 μ m spatial resolution. The YLC is enriched in Mn and Fe, and depleted in ¹⁸O and Sr compared to PLC, and is much more ¹⁸O depleted than is indicated from conventional analyses. Results are interpreted to indicate infiltration of ¹⁸O-depleted (metamorphic or magmatic) fluid (initial δ¹⁸O = 9‰–10.5‰) along grain boundaries, fractures and deformation twin lamellae, depleting calcite grains in Sr and enriching them in Mn and Fe. The sample is characterised by gross isotopic and elemental disequilibrium, with important implications for the application of chromatographic theory to constrain fluid fluxes in metacarbonate rocks. Areas of PLC unaffected by “short-circuiting” fluid pathways contain oxygen diffusion profiles of ∼10‰/∼200 μm in grain boundary regions or adjacent to fractures/patches. When correction is made for estimated grain boundary/fracture and profile orientation in 3D, profiles are indistinguishable within error. Modelling of these profiles gives consistent estimates of Dt (where D is the diffusion coefficient and t is time) of ∼0.8 × 10⁻⁸ m², from which, using experimental data for oxygen diffusion in calcite, timescales of fluid transport along grain boundaries at amphibolite facies temperatures of ∼10³ to ∼10⁴ years are obtained. These short timescales, which are much shorter than plausible durations of metamorphism, imply that rock permeabilities may be transiently much higher during fluid flow than those calculated from time integrated fluid fluxes or predicted from laboratory measurements. The preservation of ¹⁸O/¹⁶O profiles requires either rapid cooling rates (∼100–600 °C/million years), or, more plausibly, loss of grain boundary fluid such that a dry cooling history followed the transient passage of fluid. The δ¹⁸O/trace element correlations are also consistent with volume diffusion-controlled transport in the PLC. Fluid transport and element exchange occurred by two inter-related mechanisms on short timescales and on different lengthscales – long-distance flow along cracks, grain boundaries and twin lamellae coupled to ∼200 μm-scale volume diffusion of oxygen. Received: 8 December 1997 / Accepted: 18 May 1998     

Rare sulfur and triple oxygen isotope geochemistry of volcanogenic sulfate aerosols

We present analyses of stable isotopic ratios ¹⁷O/¹⁶O, ¹⁸O/¹⁶O, ³⁴S/³²S, and ³³S/³²S, ³⁶S/³²S in sulfate leached from volcanic ash of a series of well known, large and small volcanic eruptions. We consider eruptions of Mt. St. Helens (Washington, 1980, ∼1 km³), Mt. Spurr (Alaska, 1953, <1 km³), Gjalp (Iceland, 1996, 1998, <1 km³), Pinatubo (Phillipines, 1991, 10 km³), Bishop tuff (Long Valley, California, 0.76 Ma, 750 km³), Lower Bandelier tuff (Toledo Caldera, New Mexico, 1.61 Ma, 600 km³), and Lava Creek and Huckleberry Ridge tuffs (Yellowstone, Wyoming, 0.64 Ma, 1000 km³ and 2.04 Ma 2500 km³, respectively). This list covers much of the diversity of sizes and the character of silicic volcanic eruptions. Particular emphasis is paid to the Lava Creek tuff for which we present wide geographic sample coverage.This global dataset spans a significant range in δ³⁴S, δ¹⁸O, and Δ¹⁷O of sulfate (29‰, 30‰, and 3.3‰, respectively) with oxygen isotopes recording mass-independent (Δ¹⁷O > 0.2‰) and sulfur isotopes exhibiting mass-dependent behavior. Products of large eruptions account for most of‘ these isotopic ranges. Sulfate with Δ¹⁷O > 0.2‰ is present as 1-10 μm gypsum crystals on distal ash particles and records the isotopic signature of stratospheric photochemical reactions. Sediments that embed ash layers do not contain sulfate or contain little sulfate with Δ¹⁷O near 0‰, suggesting that the observed sulfate in ash is of volcanic origin.Mass-dependent fractionation of sulfur isotopic ratios suggests that sulfate-forming reactions did not involve photolysis of SO₂, like that inferred for pre-2.3 Ga sulfates from Archean sediments or Antarctic ice-core sulfate associated with few dated eruptions. Even though the sulfate sulfur isotopic compositions reflect mass-dependent processes, the products of caldera-forming eruptions display a large δ³⁴S range and exhibit fractionation relationships that do not follow the expected equilibrium slopes of 0.515 and 1.90 for ³³S/³²S vs. ³⁴S/³²S and ³⁶S/³²S vs. ³⁴S/³²S, respectively. The data presented here are consistent with modification of a chemical mass-dependent fractionation of sulfur isotopes in the volcanic plume by either a kinetic gas phase reaction of volcanic SO₂ with OH and/or a Rayleigh processes involving a residual Rayleigh reactant—volcanic SO₂ gas, rather than a Rayleigh product. These results may also imply at least two removal pathways for SO₂ in volcanic plumes.Above-zero Δ¹⁷O values and their positive correlation with δ¹⁸O in sulfate can be explained by oxidation by high-δ¹⁸O and high-Δ¹⁷O compounds such as ozone and radicals such as OH that result from ozone break down. Large caldera-forming eruptions have the highest Δ¹⁷O values, and the largest range of δ¹⁸O, which can be explained by stratospheric reaction with ozone-derived OH radicals. These results suggest that massive eruptions are capable of causing a temporary depletion of the ozone layer. Such depletion may be many times that of the measured 3-8% depletion following 1991 Pinatubo eruption, if the amount of sulfur dioxide released scales with the amount of ozone depletion.