Microstructural and chemical transformations accompanying deformation of granite in a shear zone at Miéville,Switzerland; with implications for stress corrosion cracking and superplastic flow

At Miéville, in the Aiguilles-Rouges Massif, granitic rocks of the basement are deformed into mylonites within a major subvertical shear zone. The ambient temperature during translation is estimated at 250° C±30° C from fluid inclusion filling temperatures in syntectonic microveins, from ¹⁸O quartzilmenite of+15%, and from mineralogical criteria. Porphyroclasts of both oligoclase and orthoclase feldspar decrease from initial diameters of 20 mm and assume elliptical shapes during progressive deformation, due to recrystallisation of the margins to ultra-fine polygonal grains which extend out from the porphyroclasts in thin trails: the final stable grain size is <5 . The recrystallised feldspar has a composition of the parent porphyroclast,+albite, requiring relative gains of Na and losses of K+Ca compared to the precursor, and implying short range redistribution of the components during deformation. Decrease of free energy associated with the deformation catalysed change in feldspar composition, coupled with stored strain energy in the porphyroclasts may account for recrystallisation to a stable aggregate of ultrafine grain size. The long trails imply exceptionally high ductility, which, coupled with microstructural criteria, and admixture of quartz from neighbouring pure quartz aggregates by grain boundary sliding, is interpreted in terms of superplastic flow. Estimated temperatures of T/T _m0.2 for the inferred superplastic deformation is lower by a factor of 2 than previously recorded for this flow michanism in silicates. The feldspar and quartz probably accomodated grain boundary sliding by intercrystalline diffusion.Biotite responds to deformation by bendgliding, kinking, and recrystallisation in mantles. The reaction of high-Ti parent grains to low-Ti biotite+Fe-muscovite+ ilmenite+chlorite is catalysed at all of these microstructural sites. Progressive deformation of the fine-grained products in the mantles is coupled with steady reaction to low-Fe muscovite+epidote+ sphene+rutile resulting in exceptionally ductile trails, as for the case of feldspar.Biotite grains have pervasive networks of nondisplacive intragranular fractures. At the fracture tips increase of the stress intensity has catalysed the reaction of high-Ti parent grains to low-Ti biotite+muscovite+ ilmenite which occupy the fractures. The fractures propagate and coalesce resulting in mechanical breakdown of the parent grains: these microstructures are believed to be examples of natural stress corrosion cracking. These features are also abundant in feldspar porphyroclasts where at fracture tips orthoclasesecondary orthoclase+albite, and oligoclasesecondary oligoclase+albite. Stress corrosion cracking may be significant in the steady state deformation of crustal rocks at low temperatures when intracrystalline plasticity is not generally dominant.Two way mass balance calculations utilising major and selected trace element data, reveal that deformation of the granite was essentially isochemical, involving average additions of <1 % H₂O+CO₂, at approximately constant specific gravity. The parameters Fe²⁺/Fe and ¹⁸O_{whole rock} maintain relatively constant values across the shear zone, and this also implies limited participation of fluids in the deformation. Alkali elements and titanium display the largest percentage variation during progressive deformation, whereas SiO₂, Al₂O₃, and P₂O₅, together with V, Ni, Cr,Y,Zr, and Nb remain relatively constant. All variations decrease at increasing states of deformation and this is interpreted in terms of mechanical mixing of chemical inhomogeneities of the granite precursor within the shear zone. Constraints imposed by variations in abundance of the relatively immobile elements imply that volume changes accompanying deformation in the shear zone were less than ±10%.     

Does pore water velocity affect the reaction rates of adsorptive solute transport in soils? Demonstration with pore-scale modelling

Modelling adsorptive solute transport in soils needs a number of parameters to describe its reaction kinetics and the values of these parameters are usually determined from batch and displacement experiments. Some experimental results reveal that when describing the adsorption as first-order kinetics, its associated reaction rates are not constants but vary with pore water velocity. Explanation of this varies but an independent verification of each explanation is difficult because simultaneously measuring the spatiotemporal distributions of dissolved and adsorbed solutes in soils is formidable. Pore-scale modelling could play an important role to address this gap and has received increased attention over the past few years. This paper investigated the transport of adsorptive solute in a simple porous medium using pore-scale modelling. Fluid flow through the void space of the medium was assumed to be laminar and in saturated condition, and solute transport consisted of advection and molecular diffusion; the sorption and desorption occurring at the fluid–solid interface were modelled as linear first-order kinetics. Based on the simulated spatiotemporal distribution of dissolved and adsorbed solutes at pore scale, volumetric-average reaction kinetics at macroscopic scale and its associated reactive parameters were measured. Both homogeneous adsorption where the reaction rates at microscopic scale are constant, and heterogeneous adsorption where the reaction rates vary from site to site, were investigated. The results indicate that, in contrast to previously thought, the macroscopic reaction rates directly measured from the pore-scale simulations do not change with pore velocity under both homogeneous and heterogeneous adsorptions. In particular, we found that for the homogeneous adsorption, the macroscopic adsorption remains first-order kinetic and can be described by constant reaction rates, regardless of flow rate; whilst for the heterogeneous adsorption, the macroscopic adsorption kinetics continues not to be affected by flow rate but is no longer first-order kinetics that can be described by constant reaction rates. We discuss how these findings could help explain some contrary literature reports over the dependence of reaction rates on pore water velocity.     

Raman spectroscopy of irradiated organic matter

Raman spectroscopy of a range of irradiated and nonirradiated natural terrestrial bitumens has revealed that radiolytic alteration is generally associated with an increase in structural disorganisation. An interpretational methodology designed to overcome the considerable difficulties in obtaining reproducible, meaningful parameters of structural disorganisation is also presented, and should prove useful for future Raman applications. Raman investigation of a set of bitumens reported to have formed by the radiolytic polymerisation of light hydrocarbons, such as methane, has revealed excessive structural disorganisation, relative to biogenic complex-hydrocarbon-derived bitumens of similar radioelement concentrations, which may indicate the importance of precursor materials on the organic products of irradiation. Variations in the R1 ratio (D1/G band intensity) are found to be the best guide to variations in structural organisation. Comparisons of Raman spectra of the same sample, but produced by different exciting wavelengths, reveal the importance of the selection of a suitable laser wavelength. The results are discussed in terms of analyses of irradiated organic matter in the solar system, especially cometary nuclei and carbonaceous chondrites.     

Geochemistry of a confirmed Precambrian impact ejecta deposit: The Grænsesø spherule layer,South Greenland

Samples from a single outcrop of the Graenseso spherule layer, Midternaes, South Greenland, consist of a spherule‐bearing dolomixtite with matrix‐supported intraclasts up to 1 m in size. In addition to field observations, we performed mineralogical and whole rock geochemical analysis, including electron microprobe, neutron activation analysis, X‐ray fluorescence, and mass spectrometry of the horizon and the overlying and underlying strata. We show that the spherules are petrographically similar to those in the Zaonega spherule layer, Karelia, Russia. Our petrographic and chemical results are consistent with the previous suggestion that the Grænsesø layer correlates with the Zaonega layer, and it is possible that both layers are related to the Vredefort impact event. The samples containing spherules, as well as the overlying rocks, have elevated REEs compared to the underlying pre‐impact layer, suggestive of a new continental source of sediment that may be coincident with the impact event. Zircons separated from the lower part of the Grænsesø spherule layer display complex age patterns suggesting that they have genetically different origins based on distinctly different Th/U ratios. Crystallization ages of all groups are ≥ 2.8 Ga, with ~2.8 Ga representing a time of major crustal growth globally. Therefore, we cannot conclusively determine in this study if the zircons are locally derived or if they are transported with the ejecta. The spherule layer was deposited by a high‐energy, subaqueous debris flow, an origin that is consistent with the hypothesis that the layer was deposited by impact‐induced waves and/or currents.     

Plankton dynamics due to rainfall,eutrophication, dilution,grazing and assimilation in an urbanized coastal lagoon

After a prolonged summer dry period, the effects of a distinctive and continuing rainfall on the nutrients and plankton of an urban coastal lagoon were investigated over 2 months. The lagoon filled up over 5 weeks from <10% of its maximum volume until it broke open to the sea. Nutrients (ammonia and oxidised nitrogen) significantly increased the day after initial rainfall, before returning to pre-rainfall conditions within 5 days. Phytoplankton biomass grew 10 fold within a week after initial rainfall in the 25–30 °C water and declined to near initial levels 2 weeks later. The assemblage of phytoplankton and zooplankton changed dramatically after 1 day and again by 6 days later, gradually returning to the original community by 2 weeks after the initial rainfall. Zooplankton responded within a day with a two fold increase in the adult stages of the calanoid copepod Oithona sp., followed a week later by nauplii and adult Acartia bispinosa. The influx of adult Oithona indicates resting populations that were previously under sampled by our plankton net. The plankton community returned to the initial state by 2 weeks, to being dominated by a centric diatom and A. bispinosa after 5 weeks. Dilution of the lagoon reached a maximum of 0.25 d⁻¹, while growth rates of the phytoplankton population reached a maximum of 1 d⁻¹, and A. bispinosa nauplii growth of 2.5 d⁻¹. Declines in chlorophyll biomass from the maximum 10 μg l⁻¹, at a rate of approximately 10% d⁻¹ are consistent with the modelled uptake by zooplankton. The nutrients from runoff, growth and the influx of new zooplankton into the water column, resulted in a depleted δ¹³C and δ¹⁵N stable isotope signature of A. bispinosa by 2–4 ppt within 1–2 weeks, consistent with diatom growth and the terrestrial supply of depleted nutrients. δ³⁴S of A. bispinosa was enriched by 2 ppt for 1–2 weeks after rainfall, but unlike C and N, returned to pre-rainfall levels by the end of the study period. We suggest that plankton studies in coastal lakes with variable water levels that are not tidally driven, should account for the influence of changes in water levels to help explain data variability.     

Pattern of deglaciation of the last (Late Devensian) Scottish ice sheet: Evidence from ice-marginal deposits in the Dee valley,Northeast Scotland

The mode of deglaciation of the last Scottish ice sheet is assessed from evidence provided by geomorphological mapping and sedimentology. Ice-marginal deposits in the Dee valley have a distinctive morphological expression and a characteristically varied sedimentology that strongly resembles those from subpolar glaciers. The deposits tend to occur in certain topographic situations which can be accounted for by compression of ice near the margin and formation of an ice-cored supraglacial land system. A series of recessional stages of the ice-front can be mapped demonstrating that active retreat occurred. However, additional evidence shows there was probably a thin marginal zone of stagnant ice. Recessional stages are inferred to be stillstands that are considered to be topographically controlled rather than related to climate. Development of the supraglacial land system during deglaciation suggests that the ice sheet had a polythermal basal regime with a cold-based margin. This implies that deglaciation took place in northeast Scotland while the climate remained cold, probably due to a precipitation deficit, which agrees well with chronostratigraphic data.     

Clearwater East impact structure: A re‐interpretation of the projectile type using new platinum‐group element data from meteorites

Abstract— Platinum‐group element (PGE) concentrations and ratios obtained from samples of the Clearwater East impact melt have been used along with other siderophile element ratios to classify the impacting projectile as a carbonaceous chondrite. This is at odds with recent chromium isotope analyses that suggest ordinary chondrite‐type material is present. The present study reviews and reinterprets the available PGE data in the light of new PGE data from meteorites and concludes that the PGE ratios in the impact melt are most consistent with ordinary (possibly type‐L) chondrite source material, not carbonaceous chondrites. Therefore the structure was most probably formed by the impact of an asteroid composed of material similar to ordinary chondrites.     

A machine learning approach for regional geochemical data:Platinum-group element geochemistry vs geodynamic settings of the North Atlantic Igneous Province

Whilst traditional approaches to geochemistry provide valuable insights into magmatic processes such as melting and element fractionation, by considering entire regional data sets on an objective basis using machine learning algorithms(MLAs), we can highlight new facets within the broader data structure and significantly enhance previous geochemical interpretations.The platinum-group element(PGE) budget of lavas in the North Atlantic Igneous Province(NAIP) has been shown to vary systematically according to age, geographic location and geodynamic environment.Given the large multi-element geochemical data set available for the region, MLAs were employed to explore the magmatic controls on these shifting concentrations.The key advantage of using machine learning in analysis is its ability to cluster samples across multi-dimensional(i.e., multi-element)space.The NAIP data set is manipulated using Principal Component Analysis(PCA) and t-Distributed Stochastic Neighbour Embedding(t-SNE) techniques to increase separability in the data alongside clustering using the k-means MLA.The new multi-element classification is compared to the original geographic classification to assess the performance of both approaches.The workflow provides a means for creating an objective high-dimensional investigation on a geochemical data set and particularly enhances the identification of metallogenic anomalies across the region.The techniques used highlight three distinct multi-element end-members which successfully capture the variability of the majority of elements included as input variables.These end-members are seen to fluctuate in prominence throughout the NAIP, which we propose reflects the changing geodynamic environment and melting source.Crucially, the variability of Pt and Pd are not reflected in MLA-based clustering trends, suggesting that they vary independently through controls not readily demonstrated by the NAIP major or trace element data structure(i.e., other proxies for magmatic differentiation).This data science approach thus highlights that PGE(here signalled by Pt/Pd ratio) may be used to identify otherwise localised or cryptic geochemical inputs from the subcontinental lithospheric mantle(SCLM) during the ascent of plume-derived magma, and thereby impact upon the resulting metallogenic basket.