Investigation of acidic dissolution of mixed clays between pH 1.0 and −3.0 using Si and Al X-ray absorption near edge structure

Although widely investigated in relation to acid mine drainage systems at pH > 1.0, we know little about the impact of sulfuric acid (H₂SO₄) on the geochemistry and mineralogy of clays at pH < 1.0 (including negative pH values). Thus, laboratory batch experiments were conducted on three mixed clay samples with different mass ratios of phyllosilicates (smectite, illite, and kaolinite) to investigate the impact of H₂SO₄ from pH 1.0 to −3.0 for exposure periods of 14, 90, 180, and 365 days. Si and Al K- and L_2,3-edge X-ray absorption near edge structure (XANES) spectroscopy were employed on these samples to determine the chemical and structural changes that occur during acidic dissolution of phyllosilicates that cannot be distinguished using X-ray diffraction analyses. A series of silicate, phyllosilicate, and Al-bearing standard compounds were also studied to provide an explanation for the observed changes in the clay samples. The Si XANES results indicated the preferential dissolution of the phyllosilicates (pH ? 1.0, t ? 14 d), the persistence of quartz even at pH ? −3.0 and t ? 365 d, and the formation of an amorphous silica-like phase that was confined to the surface layer of the altered clay samples at pH ? 0.0 and t ? 90 d). Al XANES results demonstrated dissolution of Al-octahedral layers (pH ? 1.0, t ? 14 d), the persistence of four-fold relative to six-fold coordinated Al, and the precipitation of an Al-SO₄-rich phase (pH ? −1.0, t ? 90 d). An existing conceptual model of phyllosilicate dissolution under extremely acidic conditions was modified to include the results of this study.     

Aims and implementation in British urban and regional planning

Failure to fully understand or recognise crucial but culturally-determined British dimensions has led to confusion and error even among the British geographers in understanding and contributing to, urban and regional planning. This point assumes more rather than less significance in the context of a discussion between British and Soviet geographers. This paper therefore examines in part one, three fundamental features of the British system of urban and regional planning and then proceeds in part two to focus on the aims and their implementation. It concludes with a reference to the nature of the relationship between planning and geography.     

Rapid incorporation of lipids into macromolecules during experimental decay of invertebrates: Initiation of geopolymer formation

Diagenetic alteration is critical for the preservation of fossil cuticles of plant and animal origin and to the formation of kerogen. The process takes place over millions of years, but the stage at which it is initiated is not known. Laboratory decay experiments were carried out on shrimps, scorpions and cockroaches to monitor changes in the chitin–protein of the arthropod cuticle and associated lipids. The cockroach and scorpion exoskeleton remained largely unaltered morphologically, but the shrimp experienced rapid decomposition within a month, which progressed through the 44 week duration of the experiment as revealed using electron microscopy. Mass spectrometry and ¹³C NMR (nuclear magnetic resonance) spectroscopy revealed the association of an n-alkyl component with labile lipids, such as fatty acids with up to 24 carbon atoms, which were incorporated into the decaying macromolecule. The scorpion and cockroach cuticle did not reveal the incorporation of additional lipids, indicating that decay is important in initiating in situ lipid association. This experiment provides evidence that lipids can become associated with carbohydrate and proteinaceous macromolecules during the very early stages of decay, representing the first stage in the transformation process that contributes to the aliphatic rich composition ubiquitous in organic fossils and kerogen.     

Pattern,style and timing of British–Irish Ice Sheet advance and retreat over the last 45 000 years: evidence from NW Scotland and the adjacent continental shelf

Predicting the future response of ice sheets to climate warming and rising global sea level is important but difficult. This is especially so when fast-flowing glaciers or ice streams, buffered by ice shelves, are grounded on beds below sea level. What happens when these ice shelves are removed? And how do the ice stream and the surrounding ice sheet respond to the abruptly altered boundary conditions? To address these questions and others we present new geological, geomorphological, geophysical and geochronological data from the ice-stream-dominated NW sector of the last British–Irish Ice Sheet (BIIS). The study area covers around 45 000 km² of NW Scotland and the surrounding continental shelf. Alongside seabed geomorphological mapping and Quaternary sediment analysis, we use a suite of over 100 new absolute ages (including cosmogenic-nuclide exposure ages, optically stimulated luminescence ages and radiocarbon dates) collected from onshore and offshore, to build a sector-wide ice-sheet reconstruction combining all available evidence with Bayesian chronosequence modelling. Using this information we present a detailed assessment of ice-sheet advance/retreat history, and the glaciological connections between different areas of the NW BIIS sector, at different times during the last glacial cycle. The results show a highly dynamic, partly marine, partly terrestrial, ice-sheet sector undergoing large size variations in response to sub-millennial-scale climatic (Dansgaard–Oeschger) cycles over the last 45 000 years. Superimposed on these trends we identify internally driven instabilities, operating at higher frequency, conditioned by local topographic factors, tidewater dynamics and glaciological feedbacks during deglaciation. Specifically, our new evidence indicates extensive marine-terminating ice-sheet glaciation of the NW BIIS sector during Greenland Stadials 12 to 9 – prior to the main ‘Late Weichselian’ ice-sheet glaciation. After a period of restricted glaciation, in Greenland Interstadials 8 to 6, we find good evidence for rapid renewed ice-sheet build-up in NW Scotland, with the Minch ice-stream terminus reaching the continental shelf edge in Greenland Stadial 5, perhaps only briefly. Deglaciation of the NW sector took place in numerous stages. Several grounding-zone wedges and moraines on the mid- and inner continental shelf attest to significant stabilizations of the ice-sheet grounding line, or ice margin, during overall retreat in Greenland Stadials 3 and 2, and to the development of ice shelves. NW Lewis was the first substantial present-day land area to deglaciate, in the first half of Greenland Stadial 3 at a time of globally reduced sea-level c. 26 kabp , followed by Cape Wrath at c. 24 kabp. The topographic confinement of the Minch straits probably promoted ice-shelf development in early Greenland Stadial 2, providing the ice stream with additional support and buffering it somewhat from external drivers. However, c. 20–19 kabp , as the grounding-line migrated into shoreward deepening water, coinciding with a marked change in marine geology and bed strength, the ice stream became unstable. We find that, once underway, grounding-line retreat proceeded in an uninterrupted fashion with the rapid loss of fronting ice shelves – first in the west, then the east troughs – before eventual glacier stabilization at fjord mouths in NW Scotland by ~17 kabp. Around the same time, ~19–17 kabp , ice-sheet lobes readvanced into the East Minch – possibly a glaciological response to the marine-instability-triggered loss of adjacent ice stream (and/or ice shelf) support in the Minch trough. An independent ice cap on Lewis also experienced margin oscillations during mid-Greenland Stadial 2, with an ice-accumulation centre in West Lewis existing into the latter part of Heinrich Stadial 1. Final ice-sheet deglaciation of NW mainland Scotland was punctuated by at least one other coherent readvance at c. 15.5 kabp , before significant ice-mass losses thereafter. At the glacial termination, c. 14.5 kabp , glaciers fed outwash sediment to now-abandoned coastal deltas in NW mainland Scotland around the time of global Meltwater Pulse 1A. Overall, this work on the BIIS NW sector reconstructs a highly dynamic ice-sheet oscillating in extent and volume for much of the last 45 000 years. Periods of expansive ice-sheet glaciation dominated by ice-streaming were interspersed with periods of much more restricted ice-cap or tidewater/fjordic glaciation. Finally, this work indicates that the role of ice streams in ice-sheet evolution is complex but mechanistically important throughout the lifetime of an ice sheet – with ice streams contributing to the regulation of ice-sheet health but also to the acceleration of ice-sheet demise via marine ice-sheet instabilities.     

The legacy of crystal-plastic deformation in olivine: high-diffusivity pathways during serpentinization

Crystal-plastic olivine deformation to produce subgrain boundaries composed of edge dislocations is an inevitable consequence of asthenospheric mantle flow. Although crystal-plastic deformation and serpentinization are spatio-temporally decoupled, we identified compositional readjustments expressed on the micrometric level as a striped Fe-enriched ( [`(X)]<sub>\textFe</sub> \bar{X}_{\text{Fe}}  = 0.24 ± 0.02 (zones); 0.12 ± 0.02 (bulk)) or Fe-depleted ( [`(X)]_\textFe \bar{X}_{\text{Fe}}  = 0.10 ± 0.01 (zones); 0.13 ± 0.01 (bulk)) zoning in partly serpentinized olivine grains from two upper mantle sections in Norway. Focused ion beam sample preparation combined with transmission electron microscopy (TEM) and aberration-corrected scanning TEM, enabling atomic-level resolved electron energy-loss spectroscopic line profiling, reveals that every zone is immediately associated with a subgrain boundary. We infer that the zonings are a result of the environmental Fe²⁺Mg₋₁ exchange potential during antigorite serpentinization of olivine and the drive toward element exchange equilibrium. This is facilitated by enhanced solid-state diffusion along subgrain boundaries in a system, which otherwise re-equilibrates via dissolution-reprecipitation. Fe enrichment or depletion is controlled by the silica activity imposed on the system by the local olivine/orthopyroxene mass ratio, temperature and the effect of magnetite stability. The Fe-Mg exchange coefficients K_\textD^{\textAtg/\textOl} K_{\text{D}}^{{{\text{Atg}}/{\text{Ol}}}} between both types of zoning and antigorite display coalescence toward exchange equilibrium. With both types of zoning, Mn is enriched and Ni depleted compared with the unaffected bulk composition. Nanometer-sized, heterogeneously distributed antigorite precipitates along olivine subgrain boundaries suggest that water was able to ingress along them. Crystallographic orientation relationships gained via electron backscatter diffraction between olivine grain domains and different serpentine vein generations support the hypothesis that serpentinization was initiated along olivine subgrain boundaries.     

A paper with an interest in rhythm

This paper is a performative effort to move with and through the expressive and theoretical spaces of an interest in rhythm. This interest emerges initially from the middle of an encounter with the 5 Rhythms™, a contemporary somatic practice that uses rhythm to facilitate and catalyse expressive movement. Rather than seeking to excavate representational meaning from an encounter with the practice or using it to critically diagnose the corporeal politics of contemporary society, this paper apprehends the creative movement emerging from an encounter with/in the non-representational, performative potential of the 5 Rhythms™. By becoming a deliberately playful effort to hold onto the lines of movement emergent from the affective, kinaesthetic territories of this practice, the paper works to avoid either falling back upon a representational ethics that stops this movement dead in its tracks or becoming seduced by an aesthetics of weightless escape. This effort draws particular support from Deleuze and Guattari's writing on the refrain, a concept that provides a vehicle through which the lines of an interest in rhythm gain expressive and theoretical consistency. Because the territories of the refrain open onto lines of movement that are as much figural as discursive, the paper works to animate the lines of movement emerging from an encounter with the 5 Rhythms™ through a series of non-representational diagrammatic interventions. Finally, in drawing the diagrammatic lines of this movement in-between, the paper becomes not so much a series of lines about moving, but a series of lines moving about.     

A possible glacially-forced tectonic mechanism for late Neogene surface uplift and subsidence around the North Atlantic

Analysis of old erosion surfaces and estimates of exhumation from apatite fission track data can be used to infer late Neogene surface uplift of Britain, Greenland, Norway and Svalbard of 1–2 km. Subsidence and sedimentation in adjacent offshore basins can be found from interpretation of seismic and well log data. Various mechanisms for surface uplift have been proposed but the underlying cause remains unexplained. Since the multiple glaciations that took place during the late Neogene were a common factor, a possible glacially-forced tectonic mechanism to thicken the crust and produce surface uplift has been investigated. This could result from the relatively slow accumulation of ice that loads the crust as an ice sheet grows during a glacial period, followed by relatively rapid retreat and unloading around its periphery at the end. Unloading could create transient stresses that induce lateral flow in a ductile lower crust to thicken it onshore and produce surface uplift, with associated thinning beneath adjacent offshore basins, producing subsidence. Simple calculations show that the proposed mechanism is feasible and indicate that crustal thickening and surface uplift accumulated from a number of glacial cycles can account for the observed surface uplift, with an acceptable flow rate in the lower crust at the end of each cycle if the viscosity of ductile flow is sufficiently low.     

The influence of negative emission technologies and technology policies on the optimal climate mitigation portfolio

Combining policies to remove carbon dioxide (CO₂) from the atmosphere with policies to reduce emissions could decrease CO₂ concentrations faster than possible via natural processes. We model the optimal selection of a dynamic portfolio of abatement, research and development (R&D), and negative emission policies under an exogenous CO₂ constraint and with stochastic technological change. We find that near-term abatement is not sensitive to the availability of R&D policies, but the anticipated availability of negative emission strategies can reduce the near-term abatement optimally undertaken to meet 2°C temperature limits. Further, planning to deploy negative emission technologies shifts optimal R&D funding from ??carbon-free?? technologies into ??emission intensity?? technologies. Making negative emission strategies available enables an 80% reduction in the cost of keeping year 2100 CO₂ concentrations near their current level. However, negative emission strategies are less important if the possibility of tipping points rules out using late-century net negative emissions to temporarily overshoot the CO₂ constraint earlier in the century.