Mantle heterogeneity during the formation of the North Atlantic Igneous Province: Constraints from trace element and Sr-Nd-Os-O isotope systematics of Baffin Island picrites

Sr-Nd-Os-O isotope and major and trace element data from ~62 Ma picrites from Baffin Island constrain the composition of mantle sources sampled at the inception of North Atlantic Igneous Province (NAIP) magmatism. We recognize two compositional types. Depleted (N-type) lavas have low 87Sr/86Sri (0.702990–0.703060) and 187Os/188Osi (0.1220–0.1247) and high 143Nd/144Ndi (0.512989–0.512999) and are depleted in incompatible elements relative to primitive mantle. Enriched (E-type) lavas have higher 87Sr/86Sri (0.703306–0.703851) and 187Os/188Osi (0.1261–0.1303), lower 143Nd/144Ndi (0.512825–0.512906), and incompatible element concentrations similar to, or more enriched than, primitive mantle. There is also a subtle difference in oxygen isotope composition; E-type lavas are marginally lower in δ18Oolivine value (5.16–4.84‰) than N-type lavas (5.15–5.22‰). Chemical and isotopic variations between E- and N-type lavas are inconsistent with assimilation of crust and/or subcontinental lithospheric mantle and appear to instead reflect mixing between melts derived from two distinct mantle sources. Strontium-Nd-O isotope compositions and incompatible trace element abundances of N-type lavas suggest these are largely derived from the depleted upper mantle. The 187Os/188Osi ratios of N-type lavas can also be explained by such a model but require that the depleted upper mantle had γOs of approximately −5 to −7 at 62 Ma. This range overlaps the lowest γOs values measured in abyssal peridotites. Baffin Island lava compositions are also permissive of a model involving recharging of depleted upper mantle with 3He-rich material from the lower mantle (Stuart et al., Nature, 424, 57–59, 2003), with the proviso that recharge had no recognizable effect on the lithophile trace element and Sr-Nd-Os-O isotope composition. The origin of the enriched mantle component sampled by Baffin Island lavas is less clear but may be metasomatized and high-temperature-altered recycled oceanic lithosphere transported within the proto Iceland plume. Differences between Baffin Island lavas and modern Icelandic basalts suggest that a range of enriched and depleted mantle sources have been tapped since the inception of magmatism in the province. Similarities between Baffin Island lavas erupted and those of similar age from East and West Greenland also suggest that the enriched component in Baffin Island lavas may have been sampled by lavas erupted over a wide geographic range

Seconds after impact: Insights into the thermal history of impact ejecta from diffusion between lechatelierite and host glass in tektites and experiments

Tektites contain inclusions of lechatelierite, nearly pure SiO_2 glass formed by quenching of quartz grains melted during hypervelocity impacts. We report the discovery in a tektite of chemically zoned boundary layers (ca 20 μm) between lechatelierite and host felsic glass. These boundary layers in tektites formed by chemical diffusion between molten silicainclusions (quenched to lechatelierite on cooling) and surrounding felsic melt. We reproduced the details of these boundary layers via experiments on mixtures of powdered natural tektite plus quartz grains heated to 1800–2400 °C for 1–120 s using an aerodynamic levitation laser heating furnace. The results of these experiments were used to provide quantitative constraints on possible thermal histories of the natural sample. The experiments successfully reproduced all major aspects of the concentration profiles from the natural sample including diffusion length scale, strong asymmetry of the concentration profiles with respect to the Matano plane (due to the strong concentration dependence of the diffusivities of all oxides on SiO_2 content), similarities in lengths of the diffusive profiles (due to control by the diffusion of SiO_2 on the diffusivity of the other oxides), and differences in the shapes of the profiles among the oxides (including a maximum in the diffusion profile of K_2O due to uphill diffusion). The characteristic lengths of all non-alkali oxide profiles are proportional to t from which diffusivities and activation energies can be derived; these results are consistent with measurements in melts with lower SiO_2 contents and at lower temperatures reported in the literature. We also fit the experimental profiles of SiO_2 and Al_2O_3 using simple formulations of the dependence of their diffusivities on SiO_2 content and temperature, yielding results similar to those obtained from the t dependence of the characteristic profile lengths. The quantitative characterization of diffusion in boundary layers based on our experiments allow us to set limits on the thermal history of the natural tektite in which the boundary layers were discovered. If the interdiffusion between the silica and felsic melts occurred at constant temperature, the duration of heating experienced by the natural tektite we studied depends on temperature; possible solutions include heating at ∼2000 °C for ∼70 s, −2400 °C for ∼3 s. We also explored non-isothermal, asymptotic cooling histories; for a maximum temperature of 2400 °C, a characteristic cooling time scale of ∼50 s is implied, whereas, for 2000 °C, the time scale is ∼1400 s. Further, a maximum temperature of ∼2360 °C yields an effective diffusive time scale of ∼5 s, a cooling time scale of ∼90 s, and a cooling rate at the glass transition temperature of ∼5 °C/s; results that are consistent with independent estimates of cooling time scales for ∼1 cm clasts (Xu and Zhang, 2002), as well as cooling rates at the glass transition temperature (Wilding et al., 1996) – thus satisfying all currently available relevant data. More complex T-t paths are possible and can also be modeled using our experimental results and compared with and used as tests of the accuracy of physical models of tektite-forming impact events

The clumped-isotope geochemistry of exhumed marbles from Naxos, Greece

Exhumation and accompanying retrograde metamorphism alter the compositions and textures of metamorphic rocks through deformation, mineral–mineral reactions, water–rock reactions, and diffusion-controlled intra- and inter-mineral atomic mobility. Here, we demonstrate that these processes are recorded in the clumped- and single-isotope (δ^(13)C and δ^(18)O) compositions of marbles, which can be used to constrain retrograde metamorphic histories. We collected 27 calcite and dolomite marbles along a transect from the rim to the center of the metamorphic core-complex of Naxos (Greece), and analyzed their carbonate single- and clumped-isotope compositions. The majority of Δ_(47) values of whole-rock samples are consistent with exhumation- controlled cooling of the metamorphic complex. However, the data also reveal that water–rock interaction, deformation driven recrystallization and thermal shock associated with hydrothermal alteration may considerably impact the overall distribution of Δ_(47) values. We analyzed specific carbonate fabrics influenced by deformation and fluid–rock reaction to study how these processes register in the carbonate clumped-isotope system. Δ_(47) values of domains drilled from a calcite marble show a bimodal distribution. Low Δ_(47_ values correspond to an apparent temperature of 260 °C and are common in static fabrics; high Δ_(47) values correspond to an apparent temperature of 200 °C and are common in dynamically recrystallized fabrics. We suggest that the low Δ_(47) values reflect diffusion-controlled isotopic reordering during cooling, whereas high Δ_(47) values reflect isotopic reordering driven by dynamic recrystallization. We further studied the mechanism by which dynamic recrystallization may alter Δ_(47) values by controlled heating experiments. Results show no significant difference between laboratory reactions rates in the static and dynamic fabrics, consistent with a mineral-extrinsic mechanism, in which slip along crystal planes was associated with atomic-scale isotopic reordering in the calcite lattice. An intrinsic mechanism (enhanced isotopic reordering rate in deformed minerals) is contraindicated by these experiments. We suggest that Δ_(47) values of dynamically recrystallized fabrics that form below the diffusion-controlled blocking-temperature for calcite constrain the temperature of deformation. We find that Δ_(47)-based temperatures of static fabrics from Naxos marbles are ∼60–80 °C higher than commonly observed in slowly cooled metamorphic rocks, and would suggest cooling rates of ∼10^5°C Myr^(−1). A similar thermal history is inferred for dolomite marbles from the core vicinity, which preserve apparent temperatures up to 200 °C higher than a typical blocking temperature (∼300 °C). This finding could be explained by a hydrothermal event driving a brief thermal pulse and locally resetting Δ_(47) values. Rapid cooling of the core-complex region is consistent with a compilation of published cooling ages and a new apatite U–Th/He age, associating the thermal event with the emplacement of a granodiorite pluton at ∼12 Ma

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

Test and Delivery of the Chemin Mineralogical Instrument for Mars Science Laboratory

The CheMin mineralogical instrument on MSL will return quantitative powder X-ray diffraction data (XRD) and qualitative X-ray fluorescence data (XRF; 14<Z<92) from scooped soil samples and drilled rock powders collected on the Mars surface. The geometry of the source, sample, and detector is shown. A transmission geometry was chosen so that diffracted intensities in the low-20 region (5-15 deg), important for phyllosilicate identification, could be detected

Using the Abitibi Greenstone Belt to Understand Martian Hydrothermal Systems and the Potential for Biosignature Preservation in High Temperature Aqueous Environments

Metabolic bone diseases like osteoporosis result from the disruption of normal bone mineral balance (BMB) resulting in bone loss. During spaceflight astronauts lose substantial bone. Bed rest provides an analog to simulate some of the effects of spaceflight; including bone and calcium loss and provides the opportunity to evaluate new methods to monitor BMB in healthy individuals undergoing environmentally induced-bone loss. Previous research showed that natural variations in the Ca isotope ratio occur because bone formation depletes soft tissue of light Ca isotopes while bone resorption releases that isotopically light Ca back into soft tissue (Skulan et al, 2007). Using a bed rest model, we demonstrate that the Ca isotope ratio of urine shifts in a direction consistent with bone loss after just 7 days of bed rest, long before detectable changes in bone mineral density (BMD) occur. The Ca isotope variations tracks changes observed in urinary N-teleopeptide, a bone resorption biomarker. Bone specific alkaline phosphatase, a bone formation biomarker, is unchanged. The established relationship between Ca isotopes and BMB can be used to quantitatively translate the changes in the Ca isotope ratio to changes in BMD using a simple mathematical model. This model predicts that subjects lost 0.25 +/- 0.07% (+/- SD) of their bone mass from day 7 to day 30 of bed rest. Given the rapid signal observed using Ca isotope measurements and the potential to quantitatively assess bone loss; this technique is well suited to study the short-term dynamics of bone metabolism

Basaltic Soil of Gale Crater: Crystalline Component Compared to Martian Basalts and Meteorites

A significant portion of the soil of the Rocknest dune is crystalline and is consistent with derivation from unweathered basalt. Minerals and their compositions are identified by X-ray diffraction (XRD) data from the CheMin instrument on MSL Curiosity. Basalt minerals in the soil include plagioclase, olivine, low- and high-calcium pyroxenes, magnetite, ilmenite, and quartz. The only minerals unlikely to have formed in an unaltered basalt are hematite and anhydrite. The mineral proportions and compositions of the Rocknest soil are nearly identical to those of the Adirondack-class basalts of Gusev Crater, Mars, inferred from their bulk composition as analyzed by the MER Spirit rover

First X-Ray Diffraction Results from Mars Science Laboratory: Mineralogy of Rocknest Aeolian Bedform at Gale Crater

Numerous orbital and landed observations of the martian surface suggest a reasonably uniform martian soil composition, likely as a result of global aeolian mixing [1, 2]. Chemical data for martian soils are abundant [e.g., 2, 3], and phase information has been provided by lander thermal emission and Moessbauer spectroscopic measurements [3, 4, 5, 6]. However, until now no X-ray diffraction (XRD) data were available for martian soil nor has XRD ever been used on another body apart from Earth. XRD is generally considered the most definitive method for determining the crystalline phases in solid samples, and it is the method of choice for determining mineralogy. CheMin s first XRD analysis on Mars coincided with the 100th anniversary of the discovery of X-ray diffraction by von Laue. Curiosity delivered scooped samples of loose, unconsolidated material ("soil") acquired from an aeolian bedform at the Rocknest locality to instruments in the body of the rover (the laboratory). Imaging shows that the soil has a range of particle sizes, of 1-2 mm and smaller, presumably representing contributions from global, regional, and local sources

Detecting Nanophase Weathering Products with CheMin: Reference Intensity Ratios of Allophane, Aluminosilicate Gel, and Ferrihydrite

X-ray diffraction (XRD) data collected of the Rocknest samples by the CheMin instrument on Mars Science Laboratory suggest the presence of poorly crystalline or amorphous materials [1], such as nanophase weathering products or volcanic and impact glasses. The identification of the type(s) of X-ray amorphous material at Rocknest is important because it can elucidate past aqueous weathering processes. The presence of volcanic and impact glasses would indicate that little chemical weathering has occurred because glass is highly susceptible to aqueous alteration. The presence of nanophase weathering products, such as allophane, nanophase iron-oxides, and/or palagonite, would indicate incipient chemical weathering. Furthermore, the types of weathering products present could help constrain pH conditions and identify which primary phases altered to form the weathering products. Quantitative analysis of phases from CheMin data is achieved through Reference Intensity Ratios (RIRs) and Rietveld refinement. The RIR of a mineral (or mineraloid) that relates the scattering power of that mineral (typically the most intense diffraction line) to the scattering power of a separate mineral standard such as corundum [2]. RIRs can be calculated from XRD patterns measured in the laboratory by mixing a mineral with a standard in known abundances and comparing diffraction line intensities of the mineral to the standard. X-ray amorphous phases (e.g., nanophase weathering products) have broad scattering signatures rather than sharp diffraction lines. Thus, RIRs of X-ray amorphous materials are calculated by comparing the area under one of these broad scattering signals with the area under a diffraction line in the standard. Here, we measured XRD patterns of nanophase weathering products (allophane, aluminosilicate gel, and ferrihydrite) mixed with a mineral standard (beryl) in the CheMinIV laboratory instrument and calculated their RIRs to help constrain the abundances of these phases in the Rocknest samples