Experimental determination of Pb partitioning between sulfide melt and basalt melt as a function of P, T and X

© 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 Geochimica et Cosmochimica Acta 185 (2016): 9-20, doi:10.1016/j.gca.2016.01.030.We have measured the partition coefficient of Pb (KdPb) between FeS melt and basalt melt at temperatures of 1250–1523 °C, pressures of 1.0–3.5 GPa and oxygen fugacities at iron–wustite and wustite–magnetite. The total observed range of KdPb is 4.0–66.6, with a strong negative dependence on pressure and a strong negative dependence on FeO of the silicate melt (Fe+2 only). The FeO control was constrained over a wide range of FeO (4.2–39.5%). We found that the effect of oxygen fugacity can be subsumed under the FeO control parameter. Prior work has established the lack of a significant effect of temperature (Kiseeva and Wood, 2015; Li and Audétat, 2015). Our data are parameterized as: KdPb = 4.8 + (512 − 119*P in GPa)*(1/FeO − 0.021). We also measured a single value of KdPb between clinopyroxene and basalt melt at 2.0 GPa of 0.020 ± 0.001. This experimental data supports the “natural” partitioning of Pb measured on sulfide globules in MORB (Patten et al., 2013), but not the low KdPb of ∼3 inferred from sulfides in abyssal peridotites by Warren and Shirey (2012). It also quantitatively affirms the modeling of Hart and Gaetani (2006) with respect to using sulfide to buffer the canonical Nd/Pb ratio for MORB and OIB (Hofmann, 2003). For the low FeO and pressure of segregation typical of MORB, KdPb ∼ 45, and the Nd/Pb ratio of erupted basalts will be the same as the Nd/Pb ratio of the mantle source. The remaining puzzle is why MORB and OIB have the same Nd/Pb when they clearly have different FeO and pressure of melt segregation.This work would not have been done without the support of NSF, through Grant EAR-0635530.2017-02-1

Ta'u and Ofu/Olosega volcanoes : the “Twin Sisters” of Samoa, their P, T, X melting regime, and global implications

Author Posting. © American Geophysical Union, 2014. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry, Geophysics, Geosystems 15 (2014): 2301–2318, doi:10.1002/2013GC005221.The Samoan islands of Ta'u and Ofu/Olosega (Ofol hereafter) are single shield volcanoes that have erupted alkali basalt for the past 70 and 440 kyr, respectively. They are 20 km apart, and are the easternmost subaerial expressions of the Samoan plume. The isotopic data for these islands are published; we report here the first major and trace element data for Ofol. The two islands are similar isotopically and in trace elements. Their high 3He/4He marks them as being a FOZO mantle end-member. By comparing data from both volcanoes, we test the efficacy of melting models in constraining the mantle compositions and their P-T of melting. We show that the mantle sources are similar, with spidergrams that peak at Ta (4× BSE), and Lu ∼0.5× BSE. Melts and mantle sources both have Lu/Hf ratios that are too low to support measured 176Hf/177Hf ratios, pointing to a young enrichment event in the mantle source. Degrees of melting are 6.5% for Ta'u and 5.2% for Ofol. P-T of melting show a wide, overlapping range, but define a precise array; average values are 1475°C—77 km for Ta'u and 1550°C—110 km for Ofol. The deepest P-T estimate is 4.2 GPa and 1550°C. The P-T array is either a melting adiabat, or a mixing line of melts equilibrated at various depths. Kinetic modeling shows melt re-equilibration will be likely for ascent velocities (m/yr) less than 40/(conduit radius in cm)2. P-T estimates for melting may typically be minimum values.We thank the National Science Foundation for their many years of support of our studies in Samoa (OCE- 0351437, EAR-0509891, EAR-0652707, EAR-0318137, OCE-1153894).2014-12-0

Age and geochemistry of the mafic sills, ODP site 1276, Newfoundland margin

Author Posting. © Elsevier B.V., 2006. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Chemical Geology 235 (2006): 222-237, doi:10.1016/j.chemgeo.2006.07.001.Site 1276, Leg 210 of the Ocean Drilling Program, was located on the Newfoundland margin in seismically-defined ~128 Ma “transitional” crust just west of presumed oceanic crust, and the M3 magnetic anomaly. The goal of drilling on this non-volcanic margin was to study the rifting, nature of basement, and post-rift sedimentation in the Newfoundland-Iberia rift. Drilling of this 1739m hole was terminated 90-160 meters above basement, in the lower of a doublet of alkaline diabase sills. We have carried out geochemical studies of the sill complex, in the hopes that they will provide proxy information regarding the nature of the underlying basement. Excellent 40Ar/39Ar plateau ages were obtained for the two sills: upper sill ~105.3 Ma; lower sill ~97.8 Ma. Thus the sills are substantially younger than the presumed age of the seafloor at site 1276 (~128 Ma), and were intruded beneath substantial sediment overburden (250 m for the upper, older sill, and 575 m for the lower younger sill). While some of the geochemistry of the sills has been compromised by alteration, the “immobile” trace elements show these sills to be hawaiites, differentiated from an enriched alkaline or basanitic parentage. Sr, Nd and Pb isotopes are suggestive of an enriched hotspot/plume mantle source, with a possible “added” component of continental material. These sills unequivocally were not derived from typical MORB (asthenospheric) upper mantle.Funding for this research was provided by JOI/USSSP 261855 and NSF-EAR0509891

Reconciling the shadow of a subduction signature with rift geochemistry and tectonic environment in Eastern Marie Byrd Land, Antarctica

Basalt-trachyte volcanoes in the Marie Byrd Land (MBL) Cenozoic province lie along the Amundsen Sea coast on the north flank of the West Antarctic rift. Basalts here are characterized by OIB-like geochemistry, restricted ranges of 87Sr/86Sr (0.702535–0.703284) and 143Nd/144Nd (0.512839–0.513008) and a wide range of 206Pb/204Pb (19.357–20.934). Basalts at three MBL volcanoes display two anomalies compared with the above and with all other basalts in West Antarctica. They include 143Nd/144Nd (0.512778–0.512789) values at Mt. Takahe and Mt. Siple that are 2σ lower than other West Antarctic basalts, and Ba/Nb, Ba/La, and Ba/Th values at Mt. Murphy and Mt. Takahe that are 3–8 times higher than normal OIB. Isotope and trace element data do not support crustal and lithospheric mantle contamination, or the presence of residual mantle amphibole or phlogopite as explanations of these anomalies. The apparent coincidence of these anomalies with the site of a pre-Cenozoic convergence zone along the Gondwanaland margin suggests a subduction influence. Major episodes of subduction and granitic plutonism took place in MBL during the Devonian, Permian, and Late Cretaceous. Relicts in the source region, of components from these subducted slabs, provide a credible explanation for the uncoupling of Ba from other large ion lithophile elements (LILE), for its erratic distribution, and for the anomalously low 143Nd/144Nd at Mt. Takahe. The last episode of subduction ended ~ 85 Ma, and was followed by continental break-up, rifting and lithospheric attenuation that produced the West Antarctic rift as we know it today. Thus, the enigmatic geochemical signatures in these three volcanoes seem to have been preserved roughly 61–85 m.y. after subduction ended. New calculations of source melting depth and a new determination of lithospheric thickness suggest that the source of the anomalies resides in a fossil mélange diapir that rose from the Cretaceous subducting slab, became attached to the base of the lithosphere at 80–100 km depth, and remained there during the subsequent plate motion and source remobilization history of this region

Scale length of mantle heterogeneities : constraints from helium diffusion

Author Posting. © Elsevier B.V., 2008. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Earth and Planetary Science Letters 269 (2008): 508-517, doi:10.1016/j.epsl.2008.03.010.A model of coupled He production/diffusion is used to constrain the question of whether Earth’s peridotitic mantle contains ubiquitous mesoscale veins or slabs of other lithologies. The high diffusion rates of helium preclude survival of He isotope heterogeneities on scales smaller than a few tens of meters, especially if they represent long term in-growth of 4He in the mantle. For 1.5 Gy residence times, and a diffusion coefficient of 10-10 m2/sec, 0.5 km slabs or 2 km cylinders will lose >90% of in-grown 4He. However, substantial 3He/4He variations may persist in slabs or be induced in adjacent mantle, depending on initial He, U and Th contents. We have modeled three cases of 3He/4He equilibration between mantle domains: an ocean crust (OC) slab in depleted upper mantle (DMM) or in enriched mantle (BSE), and a BSE slab in DMM. For a 1 km OC slab in DMM (8 Ra today), the slab today will have 3He/4He of only 3 Ra, and will have influenced the surrounding mantle with 4He for >7 km on either side. The average 3He/4He of this mixed zone will be <7 Ra, even when sampled by melts over a total width of 20-50 km. For the case of a 1 km BSE slab in DMM (8 Ra today), the slab will be 37 Ra today, and will have infected a mantle domain >16 km wide. Even with a 60 km melt sampling width, the average 3He/4He will be >15 Ra. Slabs may lose their He signature by diffusion, but their presence will be recorded in the surrounding mantle. We have evaluated 3 along-axis N-MORB ridge-crest data sets in this context (MAR 25.7-26.5°S; EPR 19-23°S; SWIR 16-24°E), with a view to defining scale-lengths of He isotope variability. The average 3He/4He variability for these 3 areas is very small, and independent of spreading rate: 0.13, 0.19 and 0.21 Ra (±1σ). Since these ridges range from ultraslow to very fast-spreading, the variability in size of along-axis magma chambers will lead inevitably to various scales of melt averaging. We conclude that these ridge areas are not sampling mantle that contains enriched veins or recycled oceanic crust slabs of significant size (> tens of meters). It appears difficult to sustain a view of the upper mantle as a ubiquitous mixture of veins and depleted matrix, with MORB always representing an averaging of this mixture.We are grateful for the consistent support of NSF that made this work possible (EAR - 0509891 to SRH; OCE - 0525864 to MDK)

FOZO, HIMU, and the rest of the mantle zoo

Author Posting. © American Geophysical Union, 2005. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 6 (2005): Q05007, doi:10.1029/2004GC000824.The parameter μ describes the 238U/204Pb ratio of an Earth reservoir. Mantle domains labeled HIMU (high μ) originally defined reservoirs with highly radiogenic Pb isotope ratios observed in basalts from a select number of ocean islands, St. Helena in the Atlantic Ocean and the Cook-Austral islands in the South Pacific Ocean. While some authors use the term HIMU in this original sense, others refer to HIMU as a widespread component in many mid-ocean ridge and ocean island basalt (MORB and OIB) sources. Here we show that highly radiogenic Pb isotope signatures in MORB and OIB originate from two different sources. In addition to the classical HIMU component observed at St. Helena and the South Pacific (named HIMU in the following), we define a component with slightly less radiogenic Pb but significantly more radiogenic Sr isotope signatures. This component lies at the extension of the (Atlantic and Pacific) MORB array in a Sr-Pb isotope ratio diagram and is argued to be a ubiquitous component in MORB and many OIB sources. The inferred role of this component in the mantle and its inferred genetic origin closely resemble those originally suggested for a mantle component termed FOZO by Hart and coworkers. By redefining the composition, the origin, and the role of FOZO in the mantle, we establish a simple conceptual framework that explains the isotopic variability in both MORB and OIB with the lowest number of components. OIB are grouped into HIMU-type OIB and basalts from islands that diverge from the MORB-FOZO array toward various isotopically “enriched” compositions (EM). The apparent ubiquity of FOZO in the mantle and the calculated isotopic evolution of compositionally diverse MORB suggest that normal mantle melting and continuous subduction and aging of that crust during recycling through the mantle are the dominant causes of the MORB-FOZO array. In contrast to FOZO, HIMU-type OIB are quite rare, and if an origin by recycling of oceanic crust is also postulated, the production of HIMU sources has to be a special and rare combination of age and composition of subduction-modified recycled oceanic crust.This work is partially supported by the Deutsche Forschungsgmeinschaft (DFG grant STR853/1 to A.S)

Mineral ages and metamorphism

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Geology and Geophysics, 1960.Vita.Includes bibliographical references (leaves 208-218).Stanley Robert Hart.Ph.D

Generating derivative structures: Algorithm and applications

We present an algorithm for generating all derivative superstructures--for arbitrary parent structures and for any number of atom types. This algorithm enumerates superlattices and atomic configurations in a geometry-independent way. The key concept is to use the quotient group associated with each superlattice to determine all unique atomic configurations. The run time of the algorithm scales linearly with the number of unique structures found. We show several applications demonstrating how the algorithm can be used in materials design problems. We predict an altogether new crystal structure in Cd-Pt and Pd-Pt, and several new ground states in Pd-rich and Pt-rich binary systems