Intra- and Intercrystalline Oxygen Isotope Variations in Minerals from Basalts and Peridotites

Igneous phenocrysts commonly exhibit zoning in major and trace element composition, reflecting (and potentially constraining) the differentiation and/or mixing histories of their parent melts. To date, little work has been done characterizing zonation of oxygen isotopes in minerals from mafic and ultramafic rocks. We present 259 ion probe (CAMECA ims-1280) measurements of δ^(18)O in 34 natural magmatic and mantle olivines and pyroxenes from five hand samples from diverse igneous environments. We compare δ^(18)O variations with zonation in other elements [especially P; analyzed by electron microprobe analysis (EMPA) and nano-secondary ionization mass spectrometry (nanoSIMS)]. There is generally a close (average within ~0·1–0·2 ‰) agreement between average δ^(18)O values of olivines measured by SIMS (standardized against San Carlos olivine) and independently known values for bulk separates from the same samples measured by laser fluorination. These data demonstrate that current ion microprobe techniques are not only precise but also accurate enough for study of sub-per-mil oxygen isotope variations in silicates (within ~0·2 ‰), provided samples are prepared and analyzed following strict guidelines. All but one of the 34 studied grains are homogeneous in δ^(18)O within a small multiple of analytical precision [estimated ±0·2‰, 1σ for most data; poorer for a subset of measurements made on small (~5 µm) spots]. This population of isotopically homogeneous grains includes some with oscillatory micrometer-scale P banding. The lack of δ^(18)O variations suggests that whatever factors lead to this common mode of trace element zonation have no detectable effect on melt–crystal partitioning of oxygen isotopes. Large (2‰) oxygen isotope variations are observed in one olivine glomerocryst from Mauna Kea, Hawaii. This glomerocryst contains P-rich domains that are either equant or skeletal or feathery in outline, and these P-rich domains are systematically low in δ^(18)O compared with adjacent, later-grown, P-poor olivine. This unusual oxygen isotope zonation pattern might reflect a kinetic fractionation during nucleation and growth of the cores of some olivine phenocrysts. We tested this hypothesis through measurements of δ^(18)O distributions in synthetic olivines grown at a range of rates and exhibiting diverse patterns of P zoning. These synthetic olivines are homogeneous in δ^(18)O, within the limits of our analyses (± 0·3–0·4‰ in this case) and show no connection between P zonation and oxygen isotope heterogeneity. We therefore think it more plausible that unusual O isotope zonation in the Mauna Kea glomerocryst reflects addition of a low-δ^(18)O component to some Hawaiian magmas just before nucleation of olivine. More generally, this study demonstrates the utility of modern SIMS techniques for in situ study of the subtle (~1‰ range) oxygen isotope variations characteristic of common mafic and ultramafic rocks

Correlations and zoning patterns of phosphorus and chromium in olivine from H chondrites and the LL chondrite Semarkona

Phosphorus zoning is observed in olivines in high-FeO (type IIA) chondrules in H chondrites over the entire range of petrologic grades: H3.1–H6. Features in P concentrations such as oscillatory and sector zoning, and high P cores are present in olivines that are otherwise unzoned in the divalent cations. Aluminum concentrations are low and not significantly associated with P zoning in chondrule olivines. In highly unequilibrated H chondrites, phosphorus zoning is generally positively correlated with Cr. Atomic Cr:P in olivine is roughly 1:1 (3:1 for one zone in one olivine in RC 075), consistent with Cr^(3+) charge-balancing P^(5+) substituting for Si^(4+). Normal igneous zonation involving the dominant chrome species Cr^(2+) was observed only in the LL3.0 chondrite Semarkona. In more equilibrated chondrites (H3.5–H3.8), Cr spatially correlated with P is occasionally observed but it is diffuse relative to the P zones. In H4–H6 chondrites, P-correlated Cr is absent. One signature of higher metamorphic grades (≥H3.8) is the presence of near matrix olivines that are devoid of P oscillatory zoning. The restriction to relatively high metamorphic grade and to grains near the chondrule–matrix interface suggests that this is a response to metasomatic processes. We also observed P-enriched halos near the chondrule–matrix interface in H3.3–H3.8 chondrites, likely reflecting the loss of P and Ca from mesostasis and precipitation of Ca phosphate near the chondrule surface. These halos are absent in equilibrated chondrites due to coarsening of the phosphate and in unequilibrated chondrites due to low degrees of metasomatism. Olivines in type IA chondrules show none of the P-zoning ubiquitous in type IIA chondrules or terrestrial igneous olivines, likely reflecting sequestration of P in reduced form within metallic alloys and sulfides during melting of type IA chondrules

The Stability of Zirconia-Saturated Perovskite and Conditions in the Early Solar System

Perovskite and tazheranite (cubic zirconia) are among the most refractory oxides in nebular vapors [1] and important repositories for several refractory elements whose concentrations can potentially be used to constrain the environments of formation. There are numerous studies on the phase relations and thermodynamic properties of zirconias containing Al, Ca, Mg, Sc, Ti, and the REE [e.g., 2-4], but meteoritic zirconia is rare [5]. Meteoritic perovskite is much more common [e.g., 5-9], but there are few constraints on thermodynamic properties of the relevant solid solutions. Here, we describe experiments to determine the partitioning of minor elements between perovskite and zirconia of variable Zr/Ti; the results will be used to constrain thermodynamic modeling for the solid solutions represented by meteoritic perovskite

Sulfur speciation in lunar apatite

Apatite incorporates several volatile elements (including S, as SO_4 ^(2-)) and can provide a record of magmatic volatile evolution. Recent measurements of volatiles in apatite from Apollo sample 14053.241 revealed 300-450 ppm S. Although many lunar melts have sufficient S for sulfide saturation, the observed S content of lunar apatite is surprising because lunar samples (especially 14053) are highly reduced (≤ IW) and are thus expected to contain little SO_4 ^(2-). One possibility is that there are micro-environments in late-stage lunar melts that are more oxidized than one would infer from conditions recorded by other components of these rocks. Alternatively, it may be that S^(2-) substitutes for F+Cl+OH in lunar apatite: S^(2—)bearing apatite has been synthesized, but to our knowledge has not been observed in nature

Volatile and major element zonation within melt inclusions: A natural diffusion experiment

The diffusivities of volatile elements in silicate melts significantly impact petrological processes [e.g. 1, 2]. Although many studies of volatile diffusion in silicic melts have been undertaken, there have been few studies in basaltic melts [e.g. 3], and most of these have concentrated on the diffusion of only one or two elements in each experiment

Comparison of Experimental vs Theoretical Abundances of ¹³CH₃D and ¹²CH₂D₂ for Isotopically Equilibrated Systems from 1 to 500 °C

Methane is produced and consumed via numerous microbial and chemical reactions in atmospheric, hydrothermal, and magmatic reactions. The stable isotopic composition of methane has been used extensively for decades to constrain the source of methane in the environment. A recently introduced isotopic parameter used to study the formation temperature and formational conditions of methane is the measurement of molecules of methane with multiple rare, heavy isotopes (‘clumped’) such as ¹³CH₃D and ¹²CH₂D₂. In order to place methane clumped-isotope measurements into a thermodynamic reference frame that allows calculations of clumped-isotope based temperatures (geothermometry) and comparison between laboratories, all past studies have calibrated their measurements using a combination of experiment and theory based on the temperature dependence of clumped isotopologue distributions for isotopically equilibrated systems. These have previously been performed at relatively high temperatures (>150˚C). Given that many natural occurrences of methane form below these temperatures, previous calibrations require extrapolation when calculating clumped-isotope based temperatures outside of this calibration range. We provide a new experimental calibration of the relative equilibrium abundances of ¹³CH₃D and ¹²CH₂D₂ from 1–500˚C using a combination of γ-Al₂O₃ and Ni-based catalysts and compare them to new theoretical computations using Path Integral Monte Carlo (PIMC) methods and find 1:1 agreement (within ± 1 standard error) for the observed temperature dependence of clumping between experiment and theory over this range. This demonstrates that measurements, experiments, and theory agree from 1–500°C providing confidence in the overall approaches. Polynomial fits to PIMC computations, which are considered the most rigorous theoretical approach available, are given as follows (valid T ≥ 270 K): ∆¹³CH₃D≅1000×ln(K¹³CH₃D)= 1.47348×10¹⁹/T⁷ - 2.08648×10¹⁷/T⁶ + 1.19810×10¹⁵/T⁵ - 3.54757×10¹²/T⁴ +5.54476×10⁹/T³ – 3.49294×10⁶/T² + 8.89370×10₂/T ∆¹²CH₂D₂≅1000×ln(8/3×K¹²CH₂D₂)= -9.67634×10¹⁵/T⁶ + 1.71917×10¹⁴/T⁵ - 1.24819×10¹²/T⁴ + 4.30283×10⁹/T3 -4.48660×10⁶/T² + 1.86258×10³/T. We additionally compare PIMC computations to those performed utilizing traditional approaches that are the basis of most previous calibrations (Bigeleisen, Mayer, and Urey model, BMU) and discuss the potential sources of error in the BMU model relative to PIMC computations

Chemical zonation in olivine-hosted melt inclusions

Significant zonation in major, minor, trace, and volatile elements has been documented in naturally glassy olivine-hosted melt inclusions from the Siqueiros Fracture Zone and the Galapagos Islands. Components with a higher concentration in the host olivine than in the melt (e.g., MgO, FeO, Cr_2O_3, and MnO) are depleted at the edges of the zoned melt inclusions relative to their centers, whereas except for CaO, H_2O, and F, components with a lower concentration in the host olivine than in the melt (e.g., Al_2O_3, SiO_2, Na_2O, K_2O, TiO_2, S, and Cl) are enriched near the melt inclusion edges. This zonation is due to formation of an olivine-depleted boundary layer in the adjacent melt in response to cooling and crystallization of olivine on the walls of the melt inclusions, concurrent with diffusive propagation of the boundary layer toward the inclusion center. Concentration profiles of some components in the melt inclusions exhibit multicomponent diffusion effects such as uphill diffusion (CaO, FeO) or slowing of the diffusion of typically rapidly diffusing components (Na_2O, K_2O) by coupling to slow diffusing components such as SiO_2 and Al_2O_3. Concentrations of H_2O and F decrease toward the edges of some of the Siqueiros melt inclusions, suggesting either that these components have been lost from the inclusions into the host olivine late in their cooling histories and/or that these components are exhibiting multicomponent diffusion effects. A model has been developed of the time-dependent evolution of MgO concentration profiles in melt inclusions due to simultaneous depletion of MgO at the inclusion walls due to olivine growth and diffusion of MgO in the melt inclusions in response to this depletion. Observed concentration profiles were fit to this model to constrain their thermal histories. Cooling rates determined by a single-stage linear cooling model are 150–13,000 °C h^(−1) from the liquidus down to ~1,000 °C, consistent with previously determined cooling rates for basaltic glasses; compositional trends with melt inclusion size observed in the Siqueiros melt inclusions are described well by this simple single-stage linear cooling model. Despite the overall success of the modeling of MgO concentration profiles using a single-stage cooling history, MgO concentration profiles in some melt inclusions are better fit by a two-stage cooling history with a slower-cooling first stage followed by a faster-cooling second stage; the inferred total duration of cooling from the liquidus down to ~1,000 °C ranges from 40 s to just over 1 h. Based on our observations and models, compositions of zoned melt inclusions (even if measured at the centers of the inclusions) will typically have been diffusively fractionated relative to the initially trapped melt; for such inclusions, the initial composition cannot be simply reconstructed based on olivine-addition calculations, so caution should be exercised in application of such reconstructions to correct for post-entrapment crystallization of olivine on inclusion walls. Off-center analyses of a melt inclusion can also give results significantly fractionated relative to simple olivine crystallization. All melt inclusions from the Siqueiros and Galapagos sample suites exhibit zoning profiles, and this feature may be nearly universal in glassy, olivine-hosted inclusions. If so, zoning profiles in melt inclusions could be widely useful to constrain late-stage syneruptive processes and as natural diffusion experiments

Formation temperatures of thermogenic and biogenic methane

Methane is an important greenhouse gas and energy resource generated dominantly by methanogens at low temperatures and through the breakdown of organic molecules at high temperatures. However, methane-formation temperatures in nature are often poorly constrained. We measured formation temperatures of thermogenic and biogenic methane using a “clumped isotope” technique. Thermogenic gases yield formation temperatures between 157° and 221°C, within the nominal gas window, and biogenic gases yield formation temperatures consistent with their comparatively lower-temperature formational environments (<50°C). In systems where gases have migrated and other proxies for gas-generation temperature yield ambiguous results, methane clumped-isotope temperatures distinguish among and allow for independent tests of possible gas-formation models

The science of clinical practice: disease diagnosis or patient prognosis? Evidence about "what is likely to happen" should shape clinical practice.

BACKGROUND: Diagnosis is the traditional basis for decision-making in clinical practice. Evidence is often lacking about future benefits and harms of these decisions for patients diagnosed with and without disease. We propose that a model of clinical practice focused on patient prognosis and predicting the likelihood of future outcomes may be more useful. DISCUSSION: Disease diagnosis can provide crucial information for clinical decisions that influence outcome in serious acute illness. However, the central role of diagnosis in clinical practice is challenged by evidence that it does not always benefit patients and that factors other than disease are important in determining patient outcome. The concept of disease as a dichotomous 'yes' or 'no' is challenged by the frequent use of diagnostic indicators with continuous distributions, such as blood sugar, which are better understood as contributing information about the probability of a patient's future outcome. Moreover, many illnesses, such as chronic fatigue, cannot usefully be labelled from a disease-diagnosis perspective. In such cases, a prognostic model provides an alternative framework for clinical practice that extends beyond disease and diagnosis and incorporates a wide range of information to predict future patient outcomes and to guide decisions to improve them. Such information embraces non-disease factors and genetic and other biomarkers which influence outcome. SUMMARY: Patient prognosis can provide the framework for modern clinical practice to integrate information from the expanding biological, social, and clinical database for more effective and efficient care