Water in the Oceanic Lithosphere: Salt Lake Crater Xenoliths, Oahu, Hawaii

Water can be present in nominally anhydrous minerals of peridotites in the form of hydrogen bonded to structural oxygen. Such water in the oceanic upper mantle could have a significant effect on its physical and chemical properties. However, the water content of the MORB source has been inferred indirectly from the compositions of basalts. Direct determinations on abyssal peridotites are scarce because they have been heavily hydrothermally altered. Here we present the first water analyses of minerals from spinel peridotite xenoliths of Salt Lake Crater, Oahu, Hawaii, which are exceptionally fresh. These peridotites are thought to represent fragments of the Pacific oceanic lithosphere that was refertilized by alkalic Hawaiian melts. A few have unradiogenic Os and radiogenic Hf isotopes and may be fragments of an ancient (~2 Ga) depleted and recycled lithosphere. Water contents in olivine (Ol), orthopyroxene (Opx), and clinopyroxene (Cpx) were determined by FTIR spectrometry. Preliminary H_{2}O contents show ranges of 8-10 ppm for Ol, 151-277 ppm for Opx, and 337-603 ppm for Cpx. Reconstructed bulk rock H_{2}O contents range from 88-131 ppm overlapping estimates for the MORB source. Water contents between Ol minerals of the same xenolith are heterogeneous and individual OH infrared bands vary within a mineral with lower 3230 cm^{-1} and higher 3650-3400 cm^{-1} band heights from core to edge. This observation suggests disturbance of the hydrogen in Ol likely occurring during xenolith entrainment to the surface. Pyroxene water contents are higher than most water contents in pyroxenes from continental peridotite xenoliths and higher than those of abyssal peridotites. Cpx water contents decrease with increasing degree of depletion (e.g. increasing Fo in Ol and Cr# in spinel) consistent with an incompatible behavior of water. However Cpx water contents also show a positive correlation with LREE/HREE ratios and LREE concentrations consistent with refertilization. Opx water contents increase with increasing degree of depletion and decrease with LREE/HREE ratios which is inconsistent with the incompatible behavior of H. Calculated water contents of melts in equilibrium with Cpx or Opx range from 1.4 to 3.8 wt % which is higher than that of all Hawaiian lavas. Calculated melts in equilibrium with Cpx and Opx have variable but mostly high H_{2}O/Ce ratios (194 to 1146) consistent with those of rejuvenated stage lavas from Niihau and the South Arch volcanic field, but unlike the drier shield building stage tholeiites. Whether the high water contents recorded in Salt Lake Crater xenoliths were acquired before and/or during interaction of the oceanic lithosphere with the Hawaiian plume will be discussed

The Paradox of a Wet (High H2O) and Dry (Low H2O/Ce) Mantle: High Water Concentrations in Mantle Garnet Pyroxenites from Hawaii

Water dissolved as trace amounts in anhydrous minerals has a large influence on the melting behavior and physical properties of the mantle. The water concentration of the oceanic mantle is inferred from the analyses of Mid-Ocean Ridge Basalt (MORB) and Oceanic Island Basalt (OIB). but there is little data from actual mantle samples. Moreover, enriched mineralogies (pyroxenites, eclogites) are thought as important sources of heterogeneity in the mantle, but their water concentrations and their effect on the water budget and cycling in the mantle are virtually unknown. Here, we analyzed by FTIR water in garnet clinopyroxenite xenoliths from Salt Lake Crater, Oahu, Hawaii. These pyroxenites are high-pressure (>20kb) crystal fractionates from alkalic melts. The clinopyroxenes (cpx) have 260 to 576 ppm wt H2O, with the least differentiated samples (Mg#>0.8) in the 400-500 ppm range. Orthopyroxene (opx) contain 117-265 ppm H2O, about half of that of cpx, consistent with other natural sample studies, but lower than cpx/opx equilibrium from experimental data. The pyroxenite cpx and opx H2O concentrations are at the high-end of on-and off-craton peridotite xenolith concentrations and those of Hawaiian spinel peridotites. In contrast, garnet has extremely low water contents (<5ppm H2O). There is no correlation between H2O in cpx and lithophile element concentrations. Phlogopite is present in some samples, and its modal abundance shows a positive correlation in Mg# with cpx, implying equilibrium. However, there is no correlation between H2O concentrations and or the presence of phlogopite. These data imply that cpx and opx may be at water saturation, far lower than experimental data suggest. Reconstructed bulk rock pyroxenite H2O ranges from 200-460 ppm (average 331 +/- 75 ppm), 2 to 8 times higher than H2O estimates for the MORB source (50-200 ppm), but in the range of E-MORB, OIB and the source of rejuvenated Hawaiian magmas. The average bulk rock pyroxenite H2O/Ce is 69 +/-35, lower than estimates of the MORB source (approx 150) or FOZO, C (200-250) mantle component, but consistent with "dry" EM sources (<100). These data suggest that a metasomatized, refertilized oceanic lithosphere that contains pyroxenitic veins (e.g. the lower part of an oceanic plate, where ascending melts can become trapped and crystallize), will have both higher water concentrations and low H2O/Ce, and may contribute to EM-type OIB sources, like that of Samoa basalts. Therefore, a low H2O/Ce mantle source may not necessarily be "dry"

Iron isotope tracing of mantle heterogeneity within the source regions of oceanic basalts

Mineralogical variations in the Earth's mantle and the relative proportions of peridotitic versus enriched and potentially crustally-derived pyroxenitic domains within the mantle have important implications for mantle dynamics, magma generation, and the recycling of surface material back into the mantle. Here we present iron (Fe) stable isotope data (δ57Fe, deviation in 57Fe/54Fe from the IRMM-014 standard in parts per thousand) for peridotite and garnet–pyroxenite xenoliths from Oahu, Hawaii and explore Fe isotopes as tracer of both peridotitic and pyroxenitic components in the source regions of oceanic basalts. The pyroxenites have δ57Fe values that are heavy (0.10 to 0.27‰) relative to values for mid-ocean ridge and ocean island basalts (MORB; OIB; View the MathML sourceδFe57∼0.16‰) and the primitive mantle (PM; View the MathML sourceδFe57∼0.04‰). Pyroxenite δ57Fe values are positively correlated with bulk pyroxenite titanium and heavy rare earth element (REE) abundances, which can be interpreted in terms of stable isotope fractionation during magmatic differentiation and pyroxene cumulate formation. In contrast, the peridotites have light δ57Fe values (−0.34 to 0.14‰) that correlate negatively with degree of melt depletion and radiogenic hafnium isotopes, with the most depleted samples possessing the most radiogenic Hf isotope compositions and lightest δ57Fe values. While these correlations are broadly consistent with a scenario of Fe isotope fractionation during partial melting, where isotopically heavy Fe is extracted into the melt phase, leaving behind low-δ57Fe peridotite residues, the extent of isotopic variation is far greater than predicted by partial melting models. One possibility is derivation of the samples from a heterogeneous source containing both light-δ57Fe (relative to PM) and heavy-δ57Fe components. While pyroxenite is a viable explanation for the heavy-δ57Fe component, the origin of the depleted light-δ57Fe component is more difficult to explain, as melting models predict that even large (>30%) degrees of melt extraction do not generate strongly fractionated residues. Multiple phases of melt extraction or other processes, such as metasomatism, melt percolation or the assimilation of xenocrystic olivine with light δ57Fe values may need to be invoked to explain these light δ57Fe values; a caveat to this is that these processes must either preserve, or generate correlations between δ57Fe and Hf isotopes. Published variations in δ57Fe in mantle melting products, such as MORB and OIB, are also greater than predicted by melting models assuming derivation from δ57Fe-homogeneous mantle. For example, OIB from the Society and Cook-Austral islands, which have radiogenic Pb and Sr isotope compositions indicative of recycled components such as subduction modified, low-Pb oceanic crust and terrigenous sediments have heavy mean δ57Fe values (∼0.21‰∼0.21‰) significantly distinct to those of other OIB and MORB, which could explained by the presence of heavy-δ57Fe pyroxenite cumulate or pyroxenitic melt components, whereas large degree partial melts, such as komatiites and boninites, display light Fe-isotopic compositions which may reflect sampling of refractory, light-δ57Fe mantle components. Iron stable isotopes may therefore provide a powerful new means of fingerprinting mineralogical variations within the Earth's mantle and identifying the mineralogy of depleted and enriched components within the source regions of volcanic rocks

Deepwater expansion and enhanced remineralization in the eastern equatorial Pacific during the last glacial maximum

Author Posting. © American Geophysical Union, 2018. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography and Paleoclimatology 33 (2018): 563-578, doi:10.1029/2017PA003221.Published estimates of the radiocarbon content of middepth waters suggest a decrease in ventilation in multiple locations during the last glacial maximum (LGM; 24.0–18.1 ka). Reduced glacial ventilation would have allowed respired carbon to accumulate in those waters. A subsequent deglacial release of this respired carbon reservoir to the atmosphere could then account for the observed increases in atmospheric CO2 and decline in atmospheric radiocarbon content. However, age model error and a release of 14C‐depleted mantle carbon have also been cited as possible explanations for the observed middepth radiocarbon depletions, calling into question the deep ocean's role in storing respired carbon during the LGM. Joint measurements of benthic foraminiferal carbon isotope values (δ13C) and cadmium/calcium (Cd/Ca) ratios provide a method for isolating the air‐sea component of a water mass from changes in remineralization. Here we use benthic foraminiferal δ13C and Cd/Ca records from the eastern equatorial Pacific to constrain changes in remineralization and water‐mass mixing over the last glacial‐interglacial transition. These records are complemented with elemental measurements of the authigenic coatings of foraminifera to monitor postdepositional changes in bottom water properties. Our results suggest an increase of deep waters at midwater depths consistent with a shoaling of the boundary between the upper and lower branches of Southern Ocean overturning circulation. Additionally, our records demonstrate increased organic matter remineralization in middepth waters during the LGM, suggesting that respired carbon did accumulate in middepth waters under periods of reduced ventilation.National Science foundation Grant Number: OCE‐09563682018-11-1

Transition-Metal Ion Exchange Using Poly(ethylene glycol) Oligomers as Solvents

Poly(ethylene glycol) oligomers have been found to be effective as alternative solvents for the ion exchange of Mn2þ , Fe2 þ , and Co2þ into hydrated and dehydrated Zeolite X (Na80Al80Si112- O384 3 nH2O). When attempted in aqueous solutions, the exchange of these cations quickly leads to destruction of the zeolite structure within 1-2 exchange cycles. However, in PEG oligomer solvents, the structure can be maintained and exchanges of 48% (Co2þ ), 80% (Mn2þ ), and 91% (Fe2þ ) are observed after one cycle under hydrated conditions. When rigorous steps are taken to remove all water from the zeolite before exchange, absorption of the oligomers into the zeolite pores is promoted, which hinders ion exchange; a maximum of 6% exchange is seen under dehydrated conditions. However, improved catalytic efficiency toward NO decomposition is observed for these samples, with turnover frequencies of 0.0237 s-1 for Dehyd Na/Mn-X oligomer, 0.0213 s-1 for Dehyd Na/Fe-X oligomer, and 0.0190 s-1 for Dehyd Na/Co-X oligomer. Use of these PEG oligomers as reaction media has also been expanded to the ion exchange of layered oxides such as Dion-Jacobson perovskite phases

The composition and distribution of the rejuvenated component across the Hawaiian plume: Hf-Nd-Sr-Pb isotope systematics of Kaula lavas and pyroxenite xenoliths

Rejuvenated volcanism refers to the reemergence of volcanism after a hiatus of 0.5-2 Ma following the voluminous shield building stage of Hawaiian volcanoes. The composition of the rejuvenated source and its distribution relative to the center of the plu

Post-Rift Magmatic Evolution of the Eastern North American “Passive-Aggressive” Margin

Understanding the evolution of passive margins requires knowledge of temporal and chemical constraints on magmatism following the transition from supercontinent to rifting, to post-rifting evolution. The Eastern North American Margin (ENAM) is an ideal study location as several magmatic pulses occurred in the 200 My following rifting. In particular, the Virginia-West Virginia region of the ENAM has experienced two postrift magmatic pulses at ∼152 Ma and 47 Ma, and thus provides a unique opportunity to study the long-term magmatic evolution of passive margins. Here we present a comprehensive set of geochemical data that includes new Ar/ Ar ages, major and trace-element compositions, and analysis of radiogenic isotopes to further constrain their magmatic history. The Late Jurassic volcanics are bimodal, from basanites to phonolites, while the Eocene volcanics range from picrobasalt to rhyolite. Modeling suggests that the felsic volcanics from both the Late Jurassic and Eocene events are consistent with fractional crystallization. Sr-Nd-Pb systematics for the Late Jurassic event suggests HIMU and EMII components in the magma source that we interpret as upper mantle components rather than crustal interaction. Lithospheric delamination is the best hypothesis for magmatism in Virginia/West Virginia, due to tectonic instabilities that are remnant from the long-term evolution of this margin, resulting in a “passive-aggressive” margin that records multiple magmatic events long after rifting ended

Emerging airborne contaminants in India : Platinum Group Elements from catalytic converters in motor vehicles

© The Author(s), 2016. This is the author's version of the work and is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Applied Geochemistry 75 (2016): 100-106, doi:10.1016/j.apgeochem.2016.10.006.Platinum Group Element (PGE) pollution on the Indian subcontinent is a growing concern because vehicle sales in India have rapidly increased over the last decade, and it is well known that automobile catalytic converters are one of the major source of anthropogenic PGE in the environment. Despite the rapid growth of the Indian automobile industry, the sources and magnitude of PGE contamination in Indian airborne particles are unknown. In this study we report PGE and mercury (Hg) concentrations, as well as osmium isotope ratios (187Os/188Os) of airborne particles (PM10) collected in Kanpur, a large industrial city in India. We estimate that 61±22%, 32±24%, and 7±3% of the total Os fraction are derived from eroding upper continental crust, catalytic converters fitted in the exhaust system of motor vehicles, and fossil fuel combustion, respectively. Only one sample had a ten times higher (~76%) than average contribution from fossil fuel. Unlike Os, Pt is predominantly (84±10%) derived from anthropogenic sources. Platinum Group Element and Hg concentrations are not well correlated. However, the highest concentration of particulate Hg corresponds to the most radiogenic 187Os/188Os isotope ratios (4.6). Our results further indicated that PGE/Ir ratios could be successfully used to quantify the relative proportions of natural and anthropogenic PGE sources in aerosol samples. Since PGE and Hg data on Indian environmental samples are scarce, this study provides an interpretive framework that calls for additional assessments of PGE and Hg concentrations in environmental samples from India.I.S. acknowledges an Indian Institute of Technology Kanpur Initiation Grant that supported this research.2018-10-2

Evidence for Dry Carbonatite Metasomatism in the Oceanic Lithosphere from Peridotite Xenoliths of Samoa and Lanzarote

Water in Earths mantle affects processes like magmatism and plate tectonics. Experiments show that CO2-rich fluids lower the water solubility in olivine, implying that CO2-rich melts/fluids may dehydrate the lithosphere during metasomatism. To test this hypothesis, we report water concentrations (by polarized FTIR) of olivines, orthopyroxenes (OPX) and clinopyroxenes (CPX) from Savaii (Samoa) and Lanzarote (Canary Islands) peridotite xenoliths with evidence of carbonatite metasomatism. Savaii peridotites are highly depleted harzburgites and dunites with spinel Cr# (Cr/(Cr+Al)) ranging from 0.4 to 0.76 (estimated degree of melting: 191.5%). Strong Light Rare Earth Element (LREE) enrichments with Ti and Zr depletions in OPX and CO2-rich fluid inclusions (via Raman spectroscopy) are consistent with carbonatite metasomatism. Olivine, OPX and reconstructed bulk rock water concentrations (0.67-3.8, 17-89 and 4-26 ppm H2O, respectively) are low and show no apparent relationship with extent of carbonatite metasomatism. Calculated water concentrations of melts in equilibrium with Savaii OPX (OPX/melt partitioning of water 0.0063 to 0.011) are, on average (0.540.32 wt% H2O), lower than host Samoan lavas (0.63 to 1.5 wt% H2O), despite the LREE enrichments in OPX. Lanzarote peridotites are also highly depleted (degree of melting from spinel Cr#: 171.8%).Water concentrations are low in olivines (1.7-5.3 ppm H2O) and variable in pyroxenes (OPX: 42-103 ppm H2O; CPX: 105-301 ppm H2O), and show no apparent correlation with indicators of carbonatite metasomatism. Both Savaii and Lanzarote peridotites show negative correlations between water and degree of melting (i.e. Mg/(Mg+Fe), Cr#), suggesting melt depletion rather than metasomatism may have influenced their water concentrations. Calculated water concentrations of melts in equilibrium with Lanzarote CPX (average 1.90.75 wt% H2O; CPX/melt partitioning of water 0.011 to 0.012) are similar to those for Western Canaries lavas (average 1.80.31 wt%; CPX/melt partitioning of water 0.016 to 0.021) inferred from their CPX phenocrysts. However, calculated Ce concentrations in such melts (352 to 378 ppm; CPX/melt partitioning of Ce 0.07) are an order of magnitude greater than the lavas, and similar to carbonatites. This leads to H2O/Ce to be an order of magnitude lower in the inferred melts (26 to 57) than estimates for Western Canary lavas (280150). These low H2O/Ce ratios may suggest H2O loss from CPX during ascent, but the lack of strong water diffusion gradients in Lanzarote minerals does not support this. Instead we hypothesize that carbonatite metasomatism resulted in greater enrichment of Ce over H2O. Assuming carbonatite magmas are water rich, this implies a lower partitioning of water between minerals and melts during metasomatism, as suggested by experiments. Our data suggests carbonatite metasomatism does not result in significant re-hydration of the lithosphere, in contrast to silicate metasomatism as previously observed in Hawaiian peridotites

Shelf Inputs and Lateral Transport of Mn, Co, and Ce in the Western North Pacific Ocean

The margin of the western North Pacific Ocean releases redox-active elements like Mn, Co, and Ce into the water column to undergo further transformation through oxide formation, scavenging, and reductive dissolution. Near the margin, the upper ocean waters enriched in these elements are characterized by high dissolved oxygen, low salinity, and low temperature, and are a source of the North Pacific Intermediate Water. High dissolved concentrations are observed across the Western Subarctic Gyre, with a rapid decrease in concentrations away from the margin and across the subarctic-subtropical front. The particulate concentrations of Mn, Co, and Ce are also high in the subarctic surface ocean and enriched relative to Ti and trivalent rare earth elements. Furthermore, the particles enriched in Mn, Co, and Ce coincide at the same depth range, suggesting that these elemental cycles are coupled through microbial oxidation in the subarctic gyre as the waters travel along the margin before being subducted at the subarctic-subtropical front. Away from the margin, the Mn, Co, and Ce cycles decouple, as Mn and Ce settle out as particles while dissolved Co is preserved and transported within the North Pacific Intermediate Water into the central North Pacific Ocean