Melting of metasomatized peridotite at 4–6 GPa and up to 1200 °C: an experimental approach

The phase assemblages and compositions in a K-bearing lherzolite + H2O system are determined between 4 and 6 GPa and 850–1200 °C, and the melting reactions occurring at subarc depth in subduction zones are constrained. Experiments were performed on a rocking multi-anvil apparatus. The experiments had around 16 wt% water content, and hydrous melt or aqueous fluid was segregated and trapped in a diamond aggregate layer. The compositions of the aqueous fluid and hydrous melt phases were measured using the cryogenic LA-ICP-MS technique. The residual lherzolite consists of olivine, orthopyroxene, clinopyroxene, and garnet, while diamond (C) is assumed to be inert. Hydrous and alkali-rich minerals were absent from the run products due to preferred dissolution of K2O (and Na2O) to the aqueous fluid/hydrous melt phases. The role of phlogopite in melting relations is, thus, controlled by the water content in the system: at the water content of around 16 wt% used here, phlogopite is unstable and thus does not participate in melting reactions. The water-saturated solidus, i.e., the first appearance of hydrous melt in the K–lherzolite composition, is located between 900 and 1000 °C at 4 GPa and between 1000 and 1100 °C at 5 and 6 GPa. Compositional jumps between hydrous melt and aqueous fluid at the solidus include a significant increase in the total dissolved solids load. All melts/fluids are peralkaline and calcium-rich. The melting reactions at the solidus are peritectic, as olivine, clinopyroxene, garnet, and H2O are consumed to generate hydrous melt plus orthopyroxene. Our fluid/melt compositional data demonstrate that the water-saturated hybrid peridotite solidus lies above 1000 °C at depths greater than 150 km and that the second critical endpoint is not reached at 6 GPa for a K2O–Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O–Cr2O3(–TiO2) peridotite composition.

On the Methyl-Transfer Reaction in Crystalline Methyl 2-(Methylthio)benzenesulfonate: a Thermally Induced Non-Topochemical Solid-State Reaction

The rearrangement of methyl 2-(methylthio)benzenesulfonate (1) to the zwitterionic 2-(dimethyl-sulfonium)benzenesulfonate (2) is known to proceed in solution by intermolecular Me transfers. The same rearrangement has been observed to occur in crystalline 1, but the crystal structure shows that the molecular packing is not conducive to intermolecular Me transfer. The reaction has been carried out with mixed crystals composed of 1 and deuteriomethylated (D6)-l. By fast-atom-bombardment mass spectroscopy, it has been shown that the product consists of a 1:2:1 mixture of the non-, tri-, and hexadeuterated species, the mixture expected, if the solid-state reaction proceeds by intermolecular Me transfers. From this result, together with the slower rates of conversion in the single crystal compared with the melt, it can be concluded that the reaction must occur not topochemically but rather at defects such as microcavities, surfaces, and other irregularities in the ordered crystal arrangement.

Cdk7 is required for full activation of Drosophila heat shock genes and RNA polymerase II phosphorylation in vivo

TFIIH has been implicated in several fundamental cellular processes, including DNA repair, cell cycle progression, and transcription. In transcription, the helicase activity of TFIIH functions to melt promoter DNA; however, the in vivo function of the Cdk7 kinase subunit of TFIIH, which has been hypothesized to be involved in RNA polymerase II (Pol II) phosphorylation, is not clearly understood. Using temperature-sensitive and null alleles of cdk7, we have examined the role of Cdk7 in the activation of Drosophila heat shock genes. Several in vivo approaches, including polytene chromosome immunofluorescence, nuclear run-on assays, and, in particular, a protein-DNA cross-linking assay customized for adults, revealed that Cdk7 kinase activity is required for full activation of heat shock genes, promoter-proximal Pol II pausing, and Pol II-dependent chromatin decondensation. The requirement for Cdk7 occurs very early in the transcription cycle. Furthermore, we provide evidence that TFIIH associates with the elongation complex much longer than previously suspected.

Continuous eclogite melting and variable refertilisation in upwelling heterogeneous mantle

Large-scale tectonic processes introduce a range of crustal lithologies into the Earth's mantle. These lithologies have been implicated as sources of compositional heterogeneity in mantle-derived magmas. The model being explored here assumes the presence of widely dispersed fragments of residual eclogite (derived from recycled oceanic crust), stretched and stirred by convection in the mantle. Here we show with an experimental study that these residual eclogites continuously melt during upwelling of such heterogeneous mantle and we characterize the melting reactions and compositional changes in the residue minerals. The chemical exchange between these partial melts and more refractory peridotite leads to a variably metasomatised mantle. Re-melting of these metasomatised peridotite lithologies at given pressures and temperatures results in diverse melt compositions, which may contribute to the observed heterogeneity of oceanic basalt suites. We also show that heterogeneous upwelling mantle is subject to diverse local freezing, hybridization and carbonate-carbon-silicate redox reactions along a mantle adiabat.

A 600 years warm-season temperature record from varved sediments of Lago Plomo, Northern Patagonia, Chile (47°S)

High-resolution records of calibrated proxy data for the past millennium are fundamental to place current changes into the context of pre-industrial natural forced and unforced variability. Although the need for regional spatially-explicit comprehensive reconstructions is widely recognized, the proxy data sources are still scarce, particularly for the Southern Hemisphere and especially for South America. We present a 600-year long warm season temperature record from varved sediments of Lago Plomo, a proglacial lake of the Northern Patagonian Ice field in Southern Chile (46°59′S, 72°52′W, 203 m a.s.l.). The thickness of the bright summer sediment layer relative to the dark winter layer (measured as total brightness; % reflectance 400–730 nm) is calibrated against warm season SONDJF temperature (1900–2009; r = 0.58, p(aut) = 0.056, RE = 0.52; CE = 0.15, RMSEP = 0.28 °C; five-year triangular filtered data). In Lago Plomo, warm summer temperatures lead to enhanced glacier melt and suspended sediment transport, which results in thicker light summer layers and to brighter sediments. Although Patagonia shows pronounced regional differences in decadal temperature trends and variability, the 600 years temperature reconstruction from Lago Plomo compares favourably with other regional/continental temperature records, but also emphasizes significant regional differences for which no data and information existed so far. These regional differences seem to be real as they are also reflected in modern climate data sets (1900–2010). The reconstruction shows pronounced subdecadal – multidecadal variability with cold phases during parts of the Little Ice Age (16th and 18th centuries) and in the beginning of the 20th century. The most prominent warm phase is the 19th century which is as warm as the second half of the 20th century. The exceptional summer warmth AD 1780–1810 is also found in other archives of Northern Patagonia and Central Chile. Our record shows the delayed 20th century warming in the Southern Hemisphere. The comparison between winter precipitation and summer temperature (inter-seasonal coupling) from Lago Plomo reveals alternating phases with parallel and contrasting decadal trends of winter precipitation and summer temperature (positive and negative running correlations Rwinter PP; summer TT). This observation from the sediment proxy data is also confirmed by two sets of reanalysis data for the 20th century. Reanalysis data show that phases with negative correlations between winter precipitation and summer temperature (e.g., dry winters and warm summers) at Lago Plomo are characteristic for periods when circumpolar Westerly flow is displaced southward and enhanced around 60°S.

Flood triggering in Switzerland: the role of daily to monthly preceding precipitation

Determining the role of different precipitation periods for peak discharge generation is crucial for both projecting future changes in flood probability and for short- and medium-range flood forecasting. In this study, catchment-averaged daily precipitation time series are analyzed prior to annual peak discharge events (floods) in Switzerland. The high number of floods considered – more than 4000 events from 101 catchments have been analyzed – allows to derive significant information about the role of antecedent precipitation for peak discharge generation. Based on the analysis of precipitation times series, a new separation of flood-related precipitation periods is proposed: (i) the period 0 to 1 day before flood days, when the maximum flood-triggering precipitation rates are generally observed, (ii) the period 2 to 3 days before flood days, when longer-lasting synoptic situations generate "significantly higher than normal" precipitation amounts, and (iii) the period from 4 days to 1 month before flood days when previous wet episodes may have already preconditioned the catchment. The novelty of this study lies in the separation of antecedent precipitation into the precursor antecedent precipitation (4 days before floods or earlier, called PRE-AP) and the short range precipitation (0 to 3 days before floods, a period when precipitation is often driven by one persistent weather situation like e.g., a stationary low-pressure system). A precise separation of "antecedent" and "peak-triggering" precipitation is not attempted. Instead, the strict definition of antecedent precipitation periods permits a direct comparison of all catchments. The precipitation accumulating 0 to 3 days before an event is the most relevant for floods in Switzerland. PRE-AP precipitation has only a weak and region-specific influence on flood probability. Floods were significantly more frequent after wet PRE-AP periods only in the Jura Mountains, in the western and eastern Swiss plateau, and at the outlet of large lakes. As a general rule, wet PRE-AP periods enhance the flood probability in catchments with gentle topography, high infiltration rates, and large storage capacity (karstic cavities, deep soils, large reservoirs). In contrast, floods were significantly less frequent after wet PRE-AP periods in glacial catchments because of reduced melt. For the majority of catchments however, no significant correlation between precipitation amounts and flood occurrences is found when the last 3 days before floods are omitted in the precipitation amounts. Moreover, the PRE-AP was not higher for extreme floods than for annual floods with a high frequency and was very close to climatology for all floods. The fact that floods are not significantly more frequent nor more intense after wet PRE-AP is a clear indicator of a short discharge memory of Pre-Alpine, Alpine and South Alpine Swiss catchments. Our study poses the question whether the impact of long-term precursory precipitation for floods in such catchments is not overestimated in the general perception. The results suggest that the consideration of a 3–4 days precipitation period should be sufficient to represent (understand, reconstruct, model, project) Swiss Alpine floods.

The behaviour of incompatible elements during hydrous melting of metasomatized peridotite at 4–6 GPa and 1000 °C–1200 °C

Trace element behavior during hydrous melting of a metasomatized garnet–peridotite was examined at pressures of 4–6 GPa and temperatures of 1000 °C–1200 °C, conditions appropriate for fluid penetrating the mantle wedge atop the subducting slab. Experiments were performed in a rocking multi-anvil apparatus using a diamond-trap setup. The compositions of the fluid and melt phases were measured using the cryogenic LA-ICP-MS technique. The water-saturated solidus of the K-lherzolite composition is located between 900 °C and 1000 °C at 4 GPa and between 1000 °C and 1100 °C at 5 and 6 GPa. The partition coefficients between fluid or melt and clinopyroxene reveal an asymmetric MREE trough with a minimum at Dy. The clinopyroxene in equilibrium with aqueous fluids is characterized by DUfluid–cpx > DThfluid–cpx while DUmelt–cpx tends to be similar to DThmelt–cpx. The partition coefficients between fluid or melt and garnet reveal very strong light to heavy REE fractionation, DLa/DLu from 95 (hydrous melt) to 1600 (aqueous fluid). The LILE are highly incompatible with partition coefficients > 50. The behavior of HFSE are decoupled, with DZr,Hf close to 1 while DNb,Ta > 10. Garnet is characterized by DUmelt/fluid–garnet < DThmelt/fluid–garnet. A comparison of our experimental partitioning results for trivalent cations as well as the results from the literature and the calculations carried out using the lattice strain model adapted to the presence of water in the bulk system indicates that H2O in the fluid or melt phase has a prominent effect on trace element partitioning. Garnet in mantle rocks in equilibrium with an aqueous fluid is characterized by significantly higher Do(3 +) for REE in the X site of the garnet compared with the partitioning values of the optimal cation in garnet in equilibrium with hydrous melts. Our data show for the first time that the change in the nature of the mobile phase (fluid vs. melt) does affect the affinities of trace elements into the garnet crystal at conditions below the second critical endpoint of the system. The same also applies for clinopyroxene, although this is less clear. Consequently, our new data allow for refinements in predictive modeling of element transfer from the slab to the mantle wedge and of possible compositions of metasomatized mantle that sources OIB magmatism.

Apatite as an indicator of fluid salinity: An experimental study of chlorine and fluorine partitioning in subducted sediments

In order to constrain the salinity of subduction zone fluids, piston-cylinder experiments have been conducted to investigate the partitioning behaviour of Cl and F in subducted sediments. These experiments were performed at H2O-undersaturated conditions with a synthetic pelite starting composition containing 800 ppm Cl, over a pressure and temperature range of 2.5–4.5 GPa and 630–900 °C. Repetitive experiments were conducted with 1900 ppm Cl + 1000 ppm F, and 2100 ppm Cl. Apatite represents the most Cl-abundant mineral phase, with Cl concentration varying in the range 0.1–2.82 wt%. Affinity for Cl decreases over the following sequence: aqueous fluid > apatite ⩾ melt > other hydrous minerals (phengite, biotite and amphibole). It was found that addition of F to the Cl-bearing starting composition significantly lowers the Cl partition coefficients between apatite and melt (DClAp–melt) and apatite and aqueous fluid (DClAp–aq). Cl–OH exchange coefficients between apatite and melt (KdCl–OHAp–melt) and apatite and aqueous fluid (KdCl–OHAp–aq) were subsequently calculated. KdCl–OHAp–melt was found to vary from 1 to 58, showing an increase with temperature and a decrease with pressure and displaying a regular decrease with increasing H2O content in melt. Mole fractions of Cl and OH in melt were calculated based on an ideal mixing model for H2O, OH, O, Cl and F. The Cl contents of other hydrous minerals (phengite, biotite and amphibole) fall between 200 and 800 ppm, with resultant Cl partition coefficients from 0.02 to 0.49, appearing independent of the bulk Cl and F content. Preliminary data from this study show that the partitioning behaviour of F is strongly in favour of apatite relative to melt and phengite, with DFAp–melt = 15–51. Apatites from representative eclogite facies metasediments were examined and found to have low Cl contents close to ∼100 ppm. Calculations using our experimentally determined KdCl–OHAp–aq of 0.004 at 2.5 GPa, 630 °C indicate a low salinity character (0.5–2 wt% NaCleq) for the fluid formed during dehydration of subducted oceanic sediment at ∼80 km depth.

The Interplay between Melting, Refertilization and Carbonatite Metasomatism in Off-Cratonic Lithospheric Mantle under Zealandia: an Integrated Major, Trace and Platinum Group Element Study

It is widely accepted that stabilization of the continental crust requires the presence of sub-continental lithospheric mantle. However, the degree of melt depletion required to stabilize the lithosphere and whether widespread refertilization is a significant process remain unresolved. Here, major and trace element, including platinum group elements (PGE), characterization of 40 mantle xenoliths from 13 localities is used to constrain the melt depletion, refertilization and metasomatic history of lithospheric mantle underneath the micro-continent Zealandia. Our previously published Re–Os isotopic data for a subset of these xenoliths indicate Phanerozoic to Paleoproterozoic ages and, reinterpreted with the new major and trace element data presented here, demonstrate that a large volume (>2 million km3) of lithospheric mantle with an age of 1·99 ± 0·21 Ga is present below the much younger crust of Zealandia. A peritectic melting model using moderately incompatible trace elements (e.g. Yb) in bulk-rocks demonstrates that these peridotites experienced a significant range of degrees of partial melting, between 3 and 28%. During subsolidus equilibration clinopyroxene gains significant rare earth elements (REE), which then leads to the underestimation of the degree of partial melting by ≤12% in fertile xenoliths. A new approach taking into account the effects of subsolidus re-equilibration on clinopyroxene composition effectively removes discrepancies in the calculated degree of melting and provides consistent estimates of between 4 and 29%. The estimated amount of melting is independent of the Re–Os model ages of the samples. The PGE patterns record simple melt depletion histories and the retention of primary base metal sulfides in the majority of the xenoliths. A rapid decrease in Pt/IrN observed at c. 1·0 wt % Al2O3 is a direct result of the exhaustion of sulfide in the mantle residue at c. 20–25% partial melting and the inability of Pt to form a stable alloy phase. Major elements preserve evidence for refertilization by a basaltic component that resulted in the formation of secondary clinopyroxene and low-forsterite olivine. The majority of xenoliths show the effects of cryptic metasomatic overprinting, ranging from minor to strong light REE enrichments in bulk-rocks (La/YbN = 0·16–15·9). Metasomatism is heterogeneous, with samples varying from those with weak REE enrichment and notable positive Sr and U–Th anomalies and negative Nb–Ta anomalies in clinopyroxene to those that have extremely high concentrations of REE, Th–U and Nb. Chemical compositions are consistent with a carbonatitic component contributing to the metasomatism of the lithosphere under Zealandia. Notably, the intense metasomatism of the samples did not affect the PGE budget of the peridotites as this was controlled by residual sulfides.

Selective sampling during catastrophic disruption: Mapping the location of reaccumulated fragments in the original parent body

In this paper, we simulate numerically the catastrophic disruption of a large asteroid as a result of a collision with a smaller projectile and the subsequent reaccumulation of fragments as a result of their mutual gravitational attractions. We then investigate the original location within the parent body of the small pieces that eventually reaccumulate to form the largest offspring of the disruption as a function of the internal structure of the parent body. We consider four cases that may represent the internal structure of such a body (whose diameter is fixed at 250 km) in various early stages of the Solar System evolution: fully molten, half molten (i.e., a 26 km-deep outer layer of melt containing half of the mass), solid except a thin molten layer (8 km thick) centered at 10 km depth, and fully solid. The solid material has properties of basalt. We then focus on the three largest offspring that have enough reaccumulated pieces to consider. Our results indicate that the particles that eventually reaccumulate to form the largest reaccumulated bodies retain a memory of their original locations in the parent body. Most particles in each reaccumulated body are clustered from the same original region, even if their reaccumulations take place far away. The extent of the original region varies considerably depending on the internal structure of the parent. It seems to shrink with the solidity of the body. The fraction of particles coming from a given depth is computed for the four cases, which can give constraints on the internal structure of parent bodies of some meteorites. As one example, we consider the ureilites, which in some petrogenetic models are inferred to have formed at particular depths within their parent body. (C) 2014 Elsevier Ltd. All rights reserved.

Volcanic terrain and the possible periglacial formation of "excess ice" at the mid-latitudes of Utopia Planitia, Mars

At the mid-latitudes of Utopia Planitia (UP), Mars, a suite of spatially-associated landforms exhibit geomorphological traits that, on Earth, would be consistent with periglacial processes and the possible freeze-thaw cycling of water. The suite comprises small-sized polygonally-patterned ground, polygon-junction and -margin pits, and scalloped, rimless depressions. Typically, the landforms incise a dark-toned terrain that is thought to be ice-rich. Here, we investigate the dark-toned terrain by using high resolution images from the HiRISE as well as near-infrared spectral-data from the OMEGA and CRISM. The terrain displays erosional characteristics consistent with a sedimentary nature and near-infrared spectra characterised by a blue slope similar to that of weathered basaltic-tephra. We also describe volcanic terrain that is dark-toned and periglacially-modified in the Kamchatka mountain-range of eastern Russia. The terrain is characterised by weathered tephra inter-bedded with snow, ice-wedge polygons and near-surface excess ice. The excess ice forms in the pore space of the tephra as the result of snow-melt infiltration and, subsequently, in-situ freezing. Based on this possible analogue, we construct a three-stage mechanism that explains the possible ice-enrichment of a broad expanse of dark-toned terrain at the mid-latitudes of UP: (1) the dark-toned terrain accumulates and forms via the regional deposition of sediments sourced from explosive volcanism; (2) the volcanic sediments are blanketed by atmospherically-precipitated (H2O) snow, ice or an admixture of the two, either concurrent with the volcanic-events or between discrete events; and, (3) under the influence of high obliquity or explosive volcanism, boundary conditions tolerant of thaw evolve and this, in turn, permits the migration, cycling and eventual formation of excess ice in the volcanic sediments. Over time, and through episodic iterations of this scenario, excess ice forms to decametres of depth. (C) 2015 Elsevier B.V. All rights reserved.

Modeling postglacial vegetation dynamics of temperate forests on the Olympic Peninsula (WA, USA) with special regard to snowpack

Past and future forest composition and distribution in temperate mountain ranges is strongly influenced by temperature and snowpack. We used LANDCLIM, a spatially explicit, dynamic vegetation model, to simulate forest dynamics for the last 16,000 years and compared the simulation results to pollen and macrofossil records at five sites on the Olympic Peninsula (Washington, USA). To address the hydrological effects of climate-driven variations in snowpack on simulated forest dynamics, we added a simple snow accumulation-and-melt module to the vegetation model and compared simulations with and without the module. LANDCLIM produced realistic present-day species composition with respect to elevation and precipitation gradients. Over the last 16,000 years, simulations driven by transient climate data from an atmosphere-ocean general circulation model (AOGCM) and by a chironomid-based temperature reconstruction captured Late-glacial to Late Holocene transitions in forest communities. Overall, the reconstruction-driven vegetation simulations matched observed vegetation changes better than the AOGCM-driven simulations. This study also indicates that forest composition is very sensitive to snowpack-mediated changes in soil moisture. Simulations without the snow module showed a strong effect of snowpack on key bioclimatic variables and species composition at higher elevations. A projected upward shift of the snow line and a decrease in snowpack might lead to drastic changes in mountain forests composition and even a shift to dry meadows due to insufficient moisture availability in shallow alpine soils.