Titanium and water-rich metamorphic olivine in high-pressure serpentinites from the Voltri Massif (Ligurian Alps, Italy): evidence for deep subduction of high-field strength and fluid-mobile elements

Titanium- and water-rich metamorphic olivine (Fo 86-88) is reported from partially dehydrated serpentinites from the Voltri complex, Ligurian Alps. The rocks are composed of mostly antigorite and olivine in addition to magnetite, chlorite, clinopyroxene and Ti-clinohumite. In situ secondary ion mass spectrometry (SIMS) data show that metamorphic olivine has very high and strongly correlated H2O (up to 0.7 wt%) and TiO2 contents (up to 0.85 wt%). Ti-rich olivine shows colourless to yellow pleochroism. Olivine associated with Ti-clinohumite contains low Ti, suggesting that Ti-rich olivine is not the breakdown product of Ti-clinohumite. Fourier transform infrared spectroscopy (FTIR) absorption spectra show peaks of serpentine, Ti-clinohumite and OH-related Si vacancies. Combining FTIR and SIMS data, we suggest the presence of clustered planar defects or nanoscale exsolutions of Ti-clinohumite in olivine. These defects or exsolutions contain more H2O (x similar to 0.1 in the formula 4Mg(2)SiO(4)center dot(1-x)Mg(OH, F)(2)center dot xTiO(2)) than Ti-clinohumite in the sample matrix (x = 0.34-0.46). In addition to TiO2 and H2O, secondary olivine contains significant Li (2-60 ppm), B (10-20 ppm), F (10-130 ppm) and Zr (0.9-2.1 ppm). It is enriched in B-11 (delta B-11 = +17 to +23 parts per thousand). Our data indicate that secondary olivine may play a significant role in transporting water, high-field strength and fluid-mobile elements into the deeper mantle as well as introduce significant B isotope anomalies. Release of hydrogen from H2O-rich olivine subducted into the deep mantle may result in strongly reduced mantle domains.OAIID:oai:osos.snu.ac.kr:snu2014-01/102/0000043439/1SEQ:1PERF_CD:SNU2014-01EVAL_ITEM_CD:102USER_ID:0000043439ADJUST_YN:YEMP_ID:A076886DEPT_CD:3345CITE_RATE:3.476FILENAME:de hoog et al-14-cmp-titanium- and water-ric.pdfDEPT_NM:지구환경과학부SCOPUS_YN:NCONFIRM:

Boron isotope record of peak metamorphic ultrahigh-pressure and retrograde fluid–rock interaction in white mica (Lago di Cignana, Western Alps)

This study presents boron (B) concentration and isotope data for white mica from (ultra)high-pressure (UHP), subduction-related metamorphic rocks from Lago di Cignana (Western Alps, Italy). These rocks are of specific geological interest, because they comprise the most deeply subducted rocks of oceanic origin worldwide. Boron geochemistry can track fluid–rock interaction during their metamorphic evolution and provide important insights into mass transfer processes in subduction zones. The highest B contents (up to 345 μg/g B) occur in peak metamorphic phengite from a garnet–phengite quartzite. The B isotopic composition is variable (δ11B = − 10.3 to − 3.6%) and correlates positively with B concentrations. Based on similar textures and major element mica composition, neither textural differences, prograde growth zoning, diffusion nor a retrograde overprint can explain this correlation. Modelling shows that B devolatilization during metamorphism can explain the general trend, but fails to account for the wide compositional and isotopic variability in a single, well-equilibrated sample. We, therefore, argue that this trend represents fluid–rock interaction during peak metamorphic conditions. This interpretation is supported by fluid–rock interaction modelling of boron leaching and boron addition that can successfully reproduce the observed spread in δ11B and [B]. Taking into account the local availability of serpentinites as potential source rocks of the fluids, the temperatures reached during peak metamorphism that allow for serpentine dehydration, and the high positive δ11B values (δ11B = 20 ± 5) modelled for the fluids, an influx of serpentinite-derived fluid appears likely. Paragonite in lawsonite pseudomorphs in an eclogite and phengite from a retrogressed metabasite have B contents between 12 and 68 μg/g and δ11B values that cluster around 0% (δ11B = − 5.0 to + 3.5). White mica in both samples is related to distinct stages of retrograde metamorphism during exhumation of the rocks. The variable B geochemistry can be successfully modelled as fluid–rock interaction with low-to-moderate (< 3) fluid/rock ratios, where mica equilibrates with a fluid into which B preferentially partitions, causing leaching of B from the rock. The metamorphic rocks from Lago di Cignana show variable retention of B in white mica during subduction-related metamorphism and exhumation. The variability in the B geochemical signature in white mica is significant and enhances our understanding of metamorphic processes and their role in element transfer in subduction zones

Hydrous Phase Relations and Trace Element Partitioning Behaviour in Calcareous Sediments at Subduction-Zone Conditions

We report the results of experiments on two natural marine sediments with different carbonate contents (calcareous clay: CO2 = 6·1 wt %; marl: CO2 = 16·2 wt %) at subduction-zone conditions (3 GPa, 750-1200°C). Water (7-15 wt %) was added to the starting materials to simulate the effects of external water addition from within the subducting slab. The onset of melting is at 760°C in water-rich experiments; melt becomes abundant by 800°C. In contrast, the onset of melting in published, water-poor experiments occurs at variable temperatures with the production of significant melt fractions being restricted to more than 900°C (phengite-out). The different solidus temperatures (Tsolidus) can be ascribed to variable fluid XH2O [H2O/(CO2 + H2O)], which, in turn, depends on bulk K2O, H2O and CO2. Partial melts in equilibrium with residual garnet, carbonate, quartz/coesite, epidote, rutile, kyanite, phengite, and clinopyroxene are granitic in composition, with substantial dissolved volatiles. Supersolidus runs always contain both silicate melt and solute-rich fluid, indicating that experimental conditions lie below the second critical endpoint in the granite-H2O-CO2 system. Carbonatite melt coexists with silicate melt and solute-rich fluid above 1100°C in the marl. The persistence of carbonate to high temperature, in equilibrium with CO2-rich hydrous melts, provides a mechanism to both supply CO2 to arc magmas and recycle carbon into the deep Earth. The trace element compositions of the experimental glasses constrain the potential contribution of calcareous sediment to arc magmas. The presence of residual epidote and carbonate confers different trace element characteristics when compared with the trace element signal of Ca-poor marine sediments (e.g. pelagic clays). Notably, epidote retains Th and light rare earth elements, such that some melts derived from calcareous sediments have elevated Ba/Th and U/Th, and low La/SmPUM, thereby resembling fluids conventionally ascribed to altered oceanic crust. Our results emphasize the importance of residual mineralogy, rather than source lithology, in controlling the trace element characteristics of slab-derived fluid

Paediatric Acute Respiratory Distress Syndrome Neuromuscular Blockade study (PAN-study):a phase IV randomised controlled trial of early neuromuscular blockade in moderate-to-severe paediatric acute respiratory distress syndrome

BACKGROUND: Paediatric acute respiratory distress syndrome (PARDS) is a manifestation of severe, life-threatening lung injury necessitating mechanical ventilation with mortality rates ranging up to 40–50%. Neuromuscular blockade agents (NMBAs) may be considered to prevent patient self-inflicted lung injury in PARDS patients, but two trials in adults with severe ARDS yielded conflicting results. To date, randomised controlled trials (RCT) examining the effectiveness and efficacy of NMBAs for PARDS are lacking. We hypothesise that using NMBAs for 48 h in paediatric patients younger than 5 years of age with early moderate-to-severe PARDS will lead to at least a 20% reduction in cumulative respiratory morbidity score 12 months after discharge from the paediatric intensive care unit (PICU). METHODS: This is a phase IV, multicentre, randomised, double-blind, placebo-controlled trial performed in level-3 PICUs in the Netherlands. Eligible for inclusion are children younger than 5 years of age requiring invasive mechanical ventilation with positive end-expiratory pressure (PEEP) ≥ 5 cm H(2)O for moderate-to-severe PARDS occurring within the first 96 h of PICU admission. Patients are randomised to continuous infusion of rocuronium bromide or placebo for 48 h. The primary endpoint is the cumulative respiratory morbidity score 12 months after PICU discharge, adjusted for confounding by age, gestational age, family history of asthma and/or allergy, season in which questionnaire was filled out, day-care and parental smoking. Secondary outcomes include respiratory mechanics, oxygenation and ventilation metrics, pulmonary and systemic inflammation markers, prevalence of critical illness polyneuropathy and myopathy and metrics for patient outcome including ventilator free days at day 28, length of PICU and hospital stay, and mortality DISCUSSION: This is the first paediatric trial evaluating the effects of muscular paralysis in moderate-to-severe PARDS. The proposed study addresses a huge research gap identified by the Paediatric Acute Lung Injury Consensus Collaborative by evaluating practical needs regarding the treatment of PARDS. Paediatric critical care practitioners are inclined to use interventions such as NMBAs in the most critically ill. This liberal use must be weighed against potential side effects. The proposed study will provide much needed scientific support in the decision-making to start NMBAs in moderate-to-severe PARDS. TRIAL REGISTRATION: ClinicalTrials.govNCT02902055. Registered on September 15, 2016

Multi-stage subduction-related metasomatism recorded in whiteschists from the Dora-Maira Massif, Western Alps

Whiteschists from the Dora-Maira massif (Western Alps, Italy) are Mg and K-rich metasomatised granites which experienced ultra-high pressure metamorphism and fluid-rock interaction during Alpine continental subduction. The sources and timing of fluid infiltration are a source of significant debate. In this study we present boron (B) isotopes and other fluid-mobile trace element (FME) concentrations in various generations of phengite from whiteschists and their country rock protoliths to investigate the sources and timing of metasomatic fluid influx. Reconstructed bulk rock concentrations based on modal data and mineral compositions indicate that significant amounts B and other FME were added to the rock during prograde metamorphism, but that this fluid influx postdates the main Mg metasomatic event. High B concentrations (150–350 µg/g) and light δ11B values (-16 to -4 ‰) recorded in phengite point to a B-rich sediment-derived fluid as the main source of B in the whiteschists. Further redistribution of FME during metamorphism was associated with breakdown of hydrous minerals such as talc, phlogopite and ellenbergerite. The source of the Mg-rich fluids cannot be constrained based on the B data in phengite, since its signature was overprinted by the later main B metasomatic event. Rare tourmaline-bearing whiteschists record additional information about B processes. Tourmaline δ11B values (-6 to +1 ‰) are in isotopic equilibrium with similar fluids to those recorded in most phengite, but phengites in tourmaline-bearing samples records anomalous B isotope compositions that reflect later redistribution of B. This study demonstrates the utility of in situ analyses in unravelling complex fluid-rock interaction histories, where whole rock analyses make it difficult to distinguish between different stages of fluid-rock interaction. Polymetasomatism may result in decoupling of different isotopic systems, thus complicating their interpretation. The Dora-Maira whiteschists interacted with multiple generations of fluids during subduction and therefore may represent a long-lived fluid pathway

Gliotoxin, identified from a screen of fungal metabolites, disrupts 7SK snRNP, releases P-TEFb, and reverses HIV-1 latency

A leading pharmacological strategy toward HIV cure requires "shock" or activation of HIV gene expression in latently infected cells with latency reversal agents (LRAs) followed by their subsequent clearance. In a screen for novel LRAs, we used fungal secondary metabolites as a source of bioactive molecules. Using orthogonal mass spectrometry (MS) coupled to latency reversal bioassays, we identified gliotoxin (GTX) as a novel LRA. GTX significantly induced HIV-1 gene expression in latent ex vivo infected primary cells and in CD4+ T cells from all aviremic HIV-1+ participants. RNA sequencing identified 7SK RNA, the scaffold of the positive transcription elongation factor b (P-TEFb) inhibitory 7SK small nuclear ribonucleoprotein (snRNP) complex, to be significantly reduced upon GTX treatment of CD4+ T cells. GTX directly disrupted 7SK snRNP by targeting La-related protein 7 (LARP7), releasing active P-TEFb, which phosphorylated RNA polymerase II (Pol II) C-terminal domain (CTD), inducing HIV transcription

Cadmium and phosphate in coastal Antarctic seawater: Implications for Southern Ocean nutrient cycling

Cadmium is a biologically important trace metal that co-varies with phosphate (PO43- or Dissolved Inorganic Phosphate, DIP) in seawater. However, the exact nature of Cd uptake mechanisms and the relationship with phosphate and other nutrients in global oceans remain elusive. Here, we present a time series study of Cd and PO43- from coastal Antarctic seawater, showing that Cd co-varies with macronutrients during times of high biological activity even under nutrient and trace metal replete conditions. Our data imply that Cd/PO43- in coastal surface Antarctic seawater is higher than open ocean areas. Furthermore, the sinking of some proportion of this high Cd/PO43- water into Antarctic Bottom Water, followed by mixing into Circumpolar Deep Water, impacts Southern Ocean preformed nutrient and trace metal composition. A simple model of endmember water mass mixing with a particle fractionation of Cd/P (aCd–P) determined by the local environment can be used to account for the Cd/PO43- relationship in different parts of the ocean. The high Cd/PO43- of the coastal water is a consequence of two factors: the high input from terrestrial and continental shelf sediments and changes in biological fractionation with respect to P during uptake of Cd in regions of high Fe and Zn. This implies that the Cd/PO43- ratio of the Southern Ocean will vary on glacial–interglacial timescales as the proportion of deep water originating on the continental shelves of the Weddell Sea is reduced during glaciations because the ice shelf is pinned at the edge of the continental shelf. There could also be variations in biological fractionation of Cd/P in the surface waters of the Southern Ocean on these timescales as a result of changes in atmospheric inputs of trace metals. Further variations in the relationship between Cd and PO43- in seawater arise from changes in population structure and community requirements for macro- and micronutrients