Expanding the application of the Eu-oxybarometer to the lherzolitic shergottites and nakhlites: Implications for the oxidation state heterogeneity of the Martian interior

Experimentally rehomogenized melt inclusions from the nakhlite Miller Range 03346 (MIL 03346) and the lherzolitic shergottite Allan Hills 77005 (ALH 77005) have been analyzed for their rare earth element (REE) concentrations in order to characterize the early melt compositions of these Martian meteorites and to calculate the oxygen fugacity conditions they crystallized under. D(Eu/Sm)pyroxene/melt values were measured at 0.77 and 1.05 for ALH 77005 and MIL 03346, respectively. These melts and their associated whole rock compositions have similar REE patterns, suggesting that whole rock REE values are representative of those of the early melts and can be used as input into the pyroxene Eu-oxybarometer for the nakhlites and lherzolitic shergottites. Crystallization fO_2 values of IW + 1.1 (ALH 77005) and IW + 3.2 (MIL 03346) were calculated. Whole rock data from other nakhlites and lherzolitic shergottites was input into the Eu-oxybarometer to determine their crystallization fO_2 values. The lherzolitic shergottites and nakhlites have fO_2 values that range from IW + 0.4 to 1.6 and from IW + 1.1 to 3.2, respectively. These values are consistent with some previously determined fO_2 estimates and expand the known range of fO_2 values of the Martian interior to four orders of magnitude. The origins of this range are not well constrained. Possible mechanisms for producing this spread in fO_2 values include mineral/melt fractionation, assimilation, shock effects, and magma ocean crystallization processes. Mineral/melt partitioning can result in changes in fO_2 from the start to the finish of crystallization of 2 orders of magnitude. In addition, crystallization of a Martian magma ocean with reasonable initial water content results in oxidized, water-rich, late-stage cumulates. Sampling of these oxidized cumulates or interactions between reduced melts and the oxidized material can potentially account for the range of fO_2 values observed in the Martian meteorites

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

Identifying cryptotephra units using correlated rapid, nondestructive methods: VSWIR spectroscopy, X-ray fluorescence, and magnetic susceptibility

Understanding the frequency, magnitude, and nature of explosive volcanic eruptions is essential for hazard planning and risk mitigation. Terrestrial stratigraphic tephra records can be patchy and incomplete due to subsequent erosion and burial processes. In contrast, the marine sedimentary record commonly preserves a more complete historical record of volcanic activity as individual events are archived within continually accumulating background sediments. While larger tephra layers are often identifiable by changes in sediment color and/or texture, smaller fallout layers may also be present that are not visible to the naked eye. These cryptotephra are commonly more difficult to identify and often require time-consuming and destructive point counting, petrography, and microscopy work. Here we present several rapid, nondestructive, and quantitative core scanning methodologies (magnetic susceptibility, visible to shortwave infrared spectroscopy, and XRF core scanning) which, when combined, can be used to identify the presence of increased volcaniclastic components (interpreted to be cryptotephra) in the sedimentary record. We develop a new spectral parameter (BDI1000VIS) that exploits the absorption of the 1 µm near-infrared band in tephra. Using predetermined mixtures, BDI1000VIS can accurately identify tephra layers in concentrations >15–20%. When applied to the upper ∼270 kyr record of IODP core U1396C from the Caribbean Sea, and verified by traditional point counting, 29 potential cryptotephra layers were identified as originating from eruptions of the Lesser Antilles Volcanic Arc. Application of these methods in future coring endeavors can be used to minimize the need for physical disaggregation of valuable drill core material and allow for near-real-time recognition of tephra units, both visible and cryptotephra.Keywords: spectroscopy, tephrochronology, magnetic susceptibility, identification, cryptotephraKeywords: spectroscopy, tephrochronology, magnetic susceptibility, identification, cryptotephr

Compositional Characterization of Glassy Volcanic Material From VNIR and MIR Spectra Using Partial Least Squares Regression Models

<p>This is supporting data for the paper titled "Compositional Characterization of Glassy Volcanic Material From VNIR and MIR Spectra Using Partial Least Squares Regression Models" by Leight et al. (submitted to JGR-P 11/23). Table S1 lists each spectrum used to train PLS models, its source, and which training datasets the spectrum was included in. Zip files contain the MIR and VNIR PLS model files. Model files are .asc, and can be run using the code at Ytsma, (2022), https://doi.org/10.5281/zenodo.7347345. </p&gt