Diffusive over-hydration of olivine-hosted melt inclusions

The pre-eruptive water content of magma is often estimated using crystal-hosted melt inclusions. However, olivine-hosted melt inclusions are prone to post-entrapment modification by H+ diffusion as they re-equilibrate with their external environment. This effect is well established for the case of H+ loss from olivine-hosted inclusions that have cooled slowly in degassed magma. Here we present evidence for the opposite effect: the addition of H+ into inclusions that are held in melts that are enriched in H2O with respect to the trapped melts. The compositional variability in a suite of 211 olivine-hosted inclusions from the Laki and Skuggafjöll eruptions in Iceland's Eastern Volcanic Zone indicates that diffusive H+ gain governs the H2O content of incompatible trace element depleted inclusions. Individual eruptive units contain olivine-hosted inclusions with widely varying incompatible element concentrations but near-constant H2O. Furthermore, over 40% of the inclusions have H2O/Ce>380H2O/Ce>380, significantly higher than the H2O/Ce expected in primary Icelandic melts or mid-ocean ridge basalts (150–280). The fact that the highest H2O/Ce ratios are found in the most incompatible element depleted inclusions indicates that hydration is a consequence of the concurrent mixing and crystallisation of compositionally diverse primary melts. Hydration occurs when olivines containing depleted inclusions with low H2O contents are juxtaposed against more hydrous melts during mixing. Melt inclusions from a single eruption may preserve evidence of both diffusive H+ loss and H+ gain. Trace element data are therefore vital for determining H2O contents of melt inclusions at the time of inclusion trapping and, ultimately, the H2O content of the mantle source regions.This work was supported by NERC grant NE/I012508/1 and a NERC studentship NE/1528277/1 to DAN. MEH acknowledges a Junior Research Fellowship from Murray Edwards College, Cambridge.This is the final published version. It first appeared at http://www.sciencedirect.com/science/article/pii/S0012821X15003647#

Fe-XANES analyses of Reykjanes Ridge basalts: Implications for oceanic crust's role in the solid Earth oxygen cycle

The cycling of material from Earth's surface environment into its interior can couple mantle oxidation state to the evolution of the oceans and atmosphere. A major uncertainty in this exchange is whether altered oceanic crust entering subduction zones can carry the oxidised signal it inherits during alteration at the ridge into the deep mantle for long-term storage. Recycled oceanic crust may be entrained into mantle upwellings and melt under ocean islands, creating the potential for basalt chemistry to constrain solid Earth–hydrosphere redox coupling. Numerous independent observations suggest that Iceland contains a significant recycled oceanic crustal component, making it an ideal locality to investigate links between redox proxies and geochemical indices of enrichment. We have interrogated the elemental, isotope and redox geochemistry of basalts from the Reykjanes Ridge, which forms a 700 km transect of the Iceland plume. Over this distance, geophysical and geochemical tracers of plume influence vary dramatically, with the basalts recording both long- and short-wavelength heterogeneity in the Iceland plume. We present new high-precision Fe-XANES measurements of Fe³⁺/∑Fe on a suite of 64 basalt glasses from the Reykjanes Ridge. These basalts exhibit positive correlations between Fe³⁺/∑Fe and trace element and isotopic signals of enrichment, and become progressively oxidised towards Iceland: fractionation-corrected Fe³⁺/∑Fe increases by ∼0.015 and ΔQFM by ∼0.2 log units. We rule out a role for sulfur degassing in creating this trend, and by considering various redox melting processes and metasomatic source enrichment mechanisms, conclude that an intrinsically oxidised component within the Icelandic mantle is required. Given the previous evidence for entrained oceanic crustal material within the Iceland plume, we consider this the most plausible carrier of the oxidised signal. To determine the ferric iron content of the recycled component ([Fe₂O₃]) we project observed liquid compositions to an estimate of Fe₂O₃ in the pure enriched endmember melt, and then apply simple fractional melting models, considering lherzolitic and pyroxenitic source mineralogies, to estimate [Fe₂O₃] content. Propagating uncertainty through these steps, we obtain a range of [Fe₂O₃] for the enriched melts (0.9–1.4 wt%) that is significantly greater than the ferric iron content of typical upper mantle lherzolites. This range of ferric iron contents is consistent with a hybridised lherzolite–basalt (pyroxenite) mantle component. The oxidised signal in enriched Icelandic basalts is therefore potential evidence for seafloor–hydrosphere interaction having oxidised ancient mid-ocean ridge crust, generating a return flux of oxygen into the deep mantle.OS was supported by a Title A Fellowship from Trinity College, JM through NERC grant NE/J021539/1 and MH acknowledges a Junior Research Fellowship from Murray Edwards College, Cambridge. We acknowledge Diamond Light Source for time on beamline I18 under proposals SP9446, SP9456 and SP12130 and the support during our analytical sessions from beamline scientist Konstantin Ignatyev and principal beamline scientist Fred Mosselmans. The Smithsonian Institution National Museum of Natural History is thanked for their loan of NMNH 117393.This is the final version of the article. It first appeared from Elsevier via http://dx.doi.org/10.1016/j.epsl.2015.07.01

High fluxes of deep volatiles from ocean island volcanoes: Insights from El Hierro, Canary Islands

Basaltic volcanism contributes significant fluxes of volatiles (CO2, H2O, S, F, Cl) to the Earth’s surface environment. Quantifying volatile fluxes requires initial melt volatile concentrations to be determined, which can be accessed through crystal-hosted melt inclusions. However, melt inclusions in volatile-rich mafic alkaline basalts, such as those erupted at ocean islands, often trap partially degassed melts, meaning that magmatic volatile fluxes from these tectonic settings are often significantly underestimated. We have measured major, trace element and volatile concentrations in melt inclusions from a series of young (<20 ka) basanites from El Hierro, Canary Islands. Our melt inclusions show some of the highest CO2 (up to 3600 ppm) and S (up to 4290 ppm) concentrations measured in ocean island basalts to date, in agreement with data from the recent 2011-2012 eruption. Volatile enrichment is observed in melt inclusions with crystallisation-controlled major element compositions and highly variable trace element ratios such as La/Yb. We use volatile-trace element ratios to calculate original magmatic CO2 contents up to 4.2 wt%, which indicates at least 65% of the original CO2 was degassed prior to melt inclusion trapping. The trace element contents and ratios of El Hierro magmas are best reproduced by 1-8% partial melting of a garnet lherzolite mantle source. Our projected CO2 (200-680 ppm) and S (265-450 ppm) concentrations for the source are consistent with upper estimates for primitive mantle. However, El Hierro magmas have elevated F/Nd and F/Cl in comparison with melts from a primitive mantle, indicating that the mantle must also contain a component enriched in F and other volatiles, most probably recycled oceanic lithosphere. Our modelled original magmatic CO2 contents indicates that, per mass unit, volatile fluxes from El Hierro magmas are up to two orders of magnitude greater than from typical mid-ocean ridge basalts and 1.5 to 7 times greater than from recent Icelandic eruptions, indicating large variability in the primary volatile content of magmas formed in di fferent geodynamic settings, or even within di fferent ocean islands. Our results highlight the importance of characterising mantle heterogeneity in order to accurately constrain both short- and long-term magmatic volatile emissions and fluxes from ocean island volcanoes.NERC studentship NE/L002469/1 NERC grant 526 IMF600/101

Volatile and light lithophile elements in high-anorthite plagioclase-hosted melt inclusions from Iceland

Melt inclusions formed during the early stages of magmatic evolution trap primitive melt compositions and enable the volatile contents of primary melts and the mantle to be estimated. However, the syn- and post-entrapment behaviour of volatiles in primitive high-anorthite plagioclase-hosted melt inclusions from oceanic basalts remains poorly constrained. To address this deficit, we present volatile and light lithophile element analyses from a well-characterised suite of nine matrix glasses and 102 melt inclusions from the 10 ka Grímsvötn tephra series (i.e., Saksunarvatn ash) of Iceland’s Eastern Volcanic Zone (EVZ). High matrix glass H$_{2}$O and S contents indicate that eruption-related exsolution was arrested by quenching in a phreatomagmatic setting; Li, B, F and Cl did not exsolve during eruption. The almost uniformly low CO$_{2}$ content of plagioclase-hosted melt inclusions cannot be explained by either shallow entrapment or the sequestration of CO$_{2}$ into shrinkage bubbles, suggesting that inclusion CO$_{2}$ contents were controlled by decrepitation instead. High H$_{2}$O/Ce values in primitive plagioclase-hosted inclusions (182–823) generally exceed values expected for EVZ primary melts ($\sim$180), and can be accounted for by diffusive H2O gain following the entrainment of primitive macrocrysts into evolved and H$_{2}$O-rich melts a few days before eruption. A strong positive correlation between H$_{2}$O and Li in plagioclase-hosted inclusions suggests that diffusive Li gain may also have occurred. Extreme F enrichments in primitive plagioclase-hosted inclusions (F/Nd = 51–216 versus $\sim$15 in matrix glasses) possibly reflect the entrapment of inclusions from high-Al/(Al + Si) melt pools formed by dissolution-crystallisation processes (as indicated by HFSE depletions in some inclusions), and into which F was concentrated by uphill diffusion since F is highly soluble in Al-rich melts. The high S/Dy of primitive inclusions ($\sim$300) indicates that primary melts were S-rich in comparison with most oceanic basalts. Cl and B are unfractionated from similarly compatible trace elements, and preserve records of primary melt heterogeneity. Although primitive plagioclase-hosted melt inclusions from the 10 ka Grímsvötn tephra series record few primary signals in their volatile contents, they nevertheless record information about crustal magma processing that is not captured in olivine-hosted melt inclusions suites.D.A.N. acknowledges support from the Natural Environment Research Council (NE/1528277/1) and the Alexander von Humboldt Foundation. SIMS analyses were supported by a Natural Environment Research Council Ion Microprobe Facility award (IMF508/1013)

Caenorhabditis elegans dnj-14, the orthologue of the DNAJC5 gene mutated in adult onset neuronal ceroid lipofuscinosis, provides a new platform for neuroprotective drug screening and identifies a SIR-2.1-independent action of resveratrol

Adult onset neuronal lipofuscinosis (ANCL) is a human neurodegenerative disorder characterized by progressive neuronal dysfunction and premature death. Recently, the mutations that cause ANCL were mapped to the DNAJC5 gene, which encodes cysteine string protein alpha. We show here that mutating dnj-14, the Caenorhabditis elegans orthologue of DNAJC5, results in shortened lifespan and a small impairment of locomotion and neurotransmission. Mutant dnj-14 worms also exhibited age-dependent neurodegeneration of sensory neurons, which was preceded by severe progressive chemosensory defects. A focussed chemical screen revealed that resveratrol could ameliorate dnj-14 mutant phenotypes, an effect mimicked by the cAMP phosphodiesterase inhibitor, rolipram. In contrast to other worm neurodegeneration models, activation of the Sirtuin, SIR-2.1, was not required, as sir-2.1; dnj-14 double mutants showed full lifespan rescue by resveratrol. The Sirtuin-independent neuroprotective action of resveratrol revealed here suggests potential therapeutic applications for ANCL and possibly other human neurodegenerative diseases

Atom-by-Atom Substitution of Mn in GaAs and Visualization of their Hole-Mediated Interactions

The discovery of ferromagnetism in Mn doped GaAs [1] has ignited interest in the development of semiconductor technologies based on electron spin and has led to several proof-of-concept spintronic devices [2-4]. A major hurdle for realistic applications of (Ga,Mn)As, or other dilute magnetic semiconductors, remains their below room-temperature ferromagnetic transition temperature. Enhancing ferromagnetism in semiconductors requires understanding the mechanisms for interaction between magnetic dopants, such as Mn, and identifying the circumstances in which ferromagnetic interactions are maximized [5]. Here we report the use of a novel atom-by-atom substitution technique with the scanning tunnelling microscope (STM) to perform the first controlled atomic scale study of the interactions between isolated Mn acceptors mediated by the electronic states of GaAs. High-resolution STM measurements are used to visualize the GaAs electronic states that participate in the Mn-Mn interaction and to quantify the interaction strengths as a function of relative position and orientation. Our experimental findings, which can be explained using tight-binding model calculations, reveal a strong dependence of ferromagnetic interaction on crystallographic orientation. This anisotropic interaction can potentially be exploited by growing oriented Ga1-xMnxAs structures to enhance the ferromagnetic transition temperature beyond that achieved in randomly doped samples. Our experimental methods also provide a realistic approach to create precise arrangements of single spins as coupled quantum bits for memory or information processing purposes

Time scales of magma transport and mixing at Kīlauea Volcano, Hawai'i

Modelling of volcanic processes is strongly limited by a poor knowledge of the timescales of storage, mixing and final ascent of magmas into the shallowest portions of volcanic 'plumbing' systems immediately prior to eruption. It is impossible to measure these timescales directly; however, micro-analytical techniques provide indirect estimates based on the extent of diffusion of species through melts and crystals. Here, diffusion in olivine phenocrysts from the 1959 Kīlauea Iki eruption is used to constrain the timing of mixing events in the crustal plumbing system on timescales of months to years before eruption. The timescales derived from zonation of Fe-Mg in olivines, combined with contemporaneous geophysical data suggests mixing occurred on 3 timescales: (1) up to 2 years prior to eruption in the deep storage system, (2), in a shallow reservoir, between incoming hot melts and cooler, resident melt for several weeks to months prior to eruption, and (3), in the conduit and summit reservoir, between the resident magma and cooled surface lava, draining back into the vent on timescales of hours to several days during pauses between episodes. Synchronous inflation of the shallow reservoir with deep earthquake swarms and mixing suggests a fitfully open transcrustal magmatic system prior to and during eruption.We acknowledge NERC studentship funds (I. Sides) and a United States Geological Survey Jack Kleinman grant, which allowed samples for this study to be collected.This is the final version of the article. It first appeared from the Geological Society of America via https://doi.org/10.1130/G37800.

Value of team approach combined with clinical pathway for diabetic foot problems: a clinical evaluation

Aims: To evaluate the effectiveness of management of diabetic foot problems (DFP) by the National University Hospital (NUH) Multidisciplinary Diabetic Foot Team combined with a clinical pathway in terms of average length of stay (ALOS), readmission rates, hospitalisation cost per patient, major reamputation rate, and complication rate. Methods: 939 patients admitted to the Department of Orthopaedic Surgery, NUH, for DFP from 2002 (before team formation) to 2007 (after team formation). It consisted of six cohorts of patients &#x2013; 61 for 2002, 70 for 2003, 148 for 2004, 180 for 2005, 262 for 2006, and 218 for 2007. All patients were managed by the NUH Multidisciplinary Diabetic Foot Team combined with a clinical pathway. Statistical analyses were carried out for five parameters (ALOS, hospitalisation cost per patient, major amputation rate, readmission rate, and complication rate). Results: From 2002 to 2007, the ALOS was significantly reduced from 20.36 days to 12.20 days (p=0.0005). Major amputation rate was significantly reduced from 31.15 to 11.01% (p&#60;0.0005). There was also a significant reduction in complication rate from 19.67 to 7.34% (p=0.005). There were reductions in the hospitalisation cost per patient and readmission rate after formation of the multidisciplinary team but they were not statistically significant. Conclusion: Our evaluation showed that a multidisciplinary team approach combined with the implementation of a clinical pathway in NUH was effective in reducing the ALOS, major amputation rate, and complication rate of DFP

Ferromagnetic Semiconductors: Moving Beyond (Ga,Mn)As

The recent development of MBE techniques for growth of III-V ferromagnetic semiconductors has created materials with exceptional promise in spintronics, i.e. electronics that exploit carrier spin polarization. Among the most carefully studied of these materials is (Ga,Mn)As, in which meticulous optimization of growth techniques has led to reproducible materials properties and ferromagnetic transition temperatures well above 150 K. We review progress in the understanding of this particular material and efforts to address ferromagnetic semiconductors as a class. We then discuss proposals for how these materials might find applications in spintronics. Finally, we propose criteria that can be used to judge the potential utility of newly discovered ferromagnetic semiconductors, and we suggest guidelines that may be helpful in shaping the search for the ideal material.Comment: 37 pages, 4 figure

Degeneracy: a link between evolvability, robustness and complexity in biological systems

A full accounting of biological robustness remains elusive; both in terms of the mechanisms by which robustness is achieved and the forces that have caused robustness to grow over evolutionary time. Although its importance to topics such as ecosystem services and resilience is well recognized, the broader relationship between robustness and evolution is only starting to be fully appreciated. A renewed interest in this relationship has been prompted by evidence that mutational robustness can play a positive role in the discovery of adaptive innovations (evolvability) and evidence of an intimate relationship between robustness and complexity in biology. This paper offers a new perspective on the mechanics of evolution and the origins of complexity, robustness, and evolvability. Here we explore the hypothesis that degeneracy, a partial overlap in the functioning of multi-functional components, plays a central role in the evolution and robustness of complex forms. In support of this hypothesis, we present evidence that degeneracy is a fundamental source of robustness, it is intimately tied to multi-scaled complexity, and it establishes conditions that are necessary for system evolvability