Millennial timescale resolution of rhyolite magma recharge at Tarawera volcano: insights from quartz chemistry and melt inclusions

Most rhyolite eruption episodes of Tarawera volcano have emitted several physiochemically distinct magma batches (∼1–10 km³). These episodes were separated on a millennial timescale. The magma batches were relatively homogeneous in temperature and composition at pumice scale (>4 cm), but experienced isolated crystallisation histories. At the sub-cm scale, matrix glasses have trace element compositions (Sr, Ba, Rb) that vary by factors up to 2.5, indicating incomplete mixing of separate melts. Some quartz-hosted melt inclusions are depleted in compatible trace elements (Sr, Ti, Ba) compared to enclosing matrix glasses. This could reflect re-melting of felsic crystals deeper in the crystal pile. Individual quartz crystals display a variety of cathodoluminescence brightness and Ti zoning patterns including rapid changes in melt chemistry and/or temperature (∼50–100°C), and point to multi-cycle crystallisation histories. The Tarawera magma system consisted of a crystal-rich mass containing waxing and waning melt pockets that were periodically recharged by silicic melts driven by basaltic intrusion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Canadian Shield brine from the Con Mine, Yellowknife, NT, Canada: Noble gas evidence for an evaporated Palaeozoic seawater origin mixed with glacial meltwater and Holocene recharge

Dissolved noble gas concentrations were measured in high salinity (270 g/L) Ca(Na)-Cl groundwaters from the Con Mine, Yellowknife, Canada in an effort to discriminate between two possible origins, as either a brine generated by evaporative enrichment in a Paleozoic inland sea, or marine water concentrated by freezing during glacial times. Major ion and isotope geochemistry indicate that brines from the deepest level remain relatively undisturbed by mixing with modern water introduced by mining. Mixing calculations are used to quantify fractions of brine, glacial meltwater and modern water. From this, noble gas concentrations were corrected for excess air with Ne and normalized to 100% brine solution. Over-pressuring of helium and argon in the brine provide age constraints based on the accumulation of geogenic ⁴He and ⁴⁰Ar. Radiogenic age calculations together with the local geological history suggest brine emplacement during early Palaeozoic time, likely during the Devonian when evaporitic inland seas existed in this region. The concentrations of the atmospherically derived noble gases in the brine fraction (Kr = 1.4E-8, Xe = 8.5E-10 cc_STP/cc_H2O) are close to atmospheric equilibrium for brine at 25 °C (Kr = 7.3E-9, Xe = 8.0E-10 cc_STP/cc_H2O), but are far lower than would be expected for closed-system concentration of seawater by freezing (Kr = 2.8E-6, Xe = 4.2E-7 cc_STP/cc_H2O). Thus, despite the complicated mixing history of the brine, the atmospheric and geogenic noble gases provide strong evidence for an origin as air-equilibrated brine from evaporated Paleozoic seawater, which infiltrated via density displacement through existing fractures and faults into the Canadian Shield.     

Isotopic variations of dissolved copper and zinc in stream waters affected by historical mining

Zinc and Cu play important roles in the biogeochemistry of natural systems, and it is likely that these interactions result in mass-dependent fractionations of their stable isotopes. In this study, we examine the relative abundances of dissolved Zn and Cu isotopes in a variety of stream waters draining six historical mining districts located in the United States and Europe. Our goals were to (1) determine whether streams from different geologic settings have unique or similar Zn and Cu isotopic signatures and (2) to determine whether Zn and Cu isotopic signatures change in response to changes in dissolved metal concentrations over well-defined diel (24-h) cycles.Average δ⁶⁶Zn and δ⁶⁵Cu values for streams varied from +0.02‰ to +0.46‰ and −0.7‰ to +1.4‰, respectively, demonstrating that Zn and Cu isotopes are heterogeneous among the measured streams. Zinc or Cu isotopic changes were not detected within the resolution of our measurements over diel cycles for most streams. However, diel changes in Zn isotopes were recorded in one stream where the fluctuations of dissolved Zn were the largest. We calculate an apparent separation factor of ∼0.3‰ (^66/64Zn) between the dissolved and solid Zn reservoirs in this stream with the solid taking up the lighter Zn isotope. The preference of the lighter isotope in the solid reservoir may reflect metabolic uptake of Zn by microorganisms. Additional field investigations must evaluate the contributions of soils, rocks, minerals, and anthropogenic components to Cu and Zn isotopic fluxes in natural waters. Moreover, rigorous experimental work is necessary to quantify fractionation factors for the biogeochemical reactions that are likely to impact Cu and Zn isotopes in hydrologic systems. This initial investigation of Cu and Zn isotopes in stream waters suggests that these isotopes may be powerful tools for probing biogeochemical processes in surface waters on a variety of temporal and spatial scales.     

Reactions of the feldspar surface with metal ions: Sorption of Pb(II), U(VI) and Np(V), and surface analytical studies of reaction with Pb(II) and U(VI)

Feldspar minerals are thermodynamically unstable in the near-surface environment and their surfaces are well known to react readily with aqueous solutions, leading to incongruent dissolution at low pH values, but congruent dissolution at neutral and high pH values. Interactions with mineral surfaces are an important control on the environmental transport of trace elements and detrital feldspars are abundant in soils and sediments. However, the interactions of metal ions in solution with the reacting feldspar surface have not been widely explored. The interactions of Pb(II), U(VI) and Np(V) ions with the feldspar surface have therefore been studied. Lead is taken up by the microcline surface at pH 6 and 10, but no uptake could be measured at pH 2. There was measurable uptake of Pb(II) on the plagioclase surface at pH 2, 6 and 10. Uptake always increased with pH. In most conditions, Pb(II) reacts through cation exchange process although, at high pH, a discrete phase, probably hydrocerrusite, is observed by atomic force microscopy (AFM) to precipitate on the plagioclase surface. Supersaturation with hydrocerrusite in these conditions is expected from thermodynamic calculations. Uptake of uranyl ion , generally through surface complex formation, could only be measured at pH 6 and 10. At pH 6 and an initial U(VI) concentration above 21.0 μM, precipitation of becquerelite (Ca[(UO₂)₃O₂(OH)₃]₂·8H₂O), identified by AFM and characterised by grazing incidence X-ray diffraction and X-ray photoelectron spectroscopy, is observed on plagioclase. The U(VI) concentration range in which becquerelite precipitation begins (dissolved U(VI) 1-5 μM) is consistent with that predicted from thermodynamic modelling. On plagioclase feldspar, secondary ion mass spectrometry showed diffusion of uranium into the altered surface layer. Uptake of the neptunyl ion (Np(V)) was found at pH 6 and 10 for microcline and at pH 2, 6 and 10 for plagioclase, and was generally lower than uptake of U(VI). By combining batch sorption experiments with imaging and surface analysis, and thermodynamic modelling, it has been possible to gain a mechanistic insight into the reactions of the feldspar surface with metal ions in solution.     

Seismic Properties of Anita Bay Dunite: an Exploratory Study of the Influence of Water

As a pilot study of the role of water in the attenuation ofseismic waves in the Earth's upper mantle, we have performeda series of seismic-frequency torsional forced-oscillation experimentson a natural (Anita Bay) dunite containing accessory hydrousphases, at high temperatures to 1300°C and confining pressure(P_c) of 200 MPa, within a gas-medium high-pressure apparatus.Both oven-dried and pre-fired specimens wrapped in Ni–Fefoil within the (poorly) vented assembly were recovered essentiallydry after 50–100 h of annealing at 1300°C followedby slow staged cooling. The results for those specimens indicatebroadly similar absorption-band viscoelastic behaviour, butwith systematic differences in the frequency dependence of strain-energydissipation Q^–1, attributed to differences in the smallvolume fraction of silicate melt and its spatial distribution.In contrast, it has been demonstrated that a new assembly involvinga welded Pt capsule retains aqueous fluid during prolonged exposureto high temperatures—allowing the first high-temperaturetorsional forced-oscillation measurements under high aqueousfluid pore pressure P_f. At temperatures >1000°C, a markedreduction in shear modulus, without concomitant increase inQ^–1, is attributed to the widespread wetting of grainboundaries resulting from grain-scale hydrofracturing and themaintenance of conditions of low differential pressure P_d =P_c – P_f . Staged cooling from 1000°C is accompaniedby decreasing P_f and progressive restoration of significantlypositive differential pressure resulting in a microstructuralregime in which the fluid on grain boundaries is increasinglyrestricted to arrays of pores. The more pronounced viscoelasticbehaviour observed within this regime for the Pt-encapsulatedspecimen compared with the essentially dry specimens may reflectboth water-enhanced solid-state relaxation and the direct influenceof the fluid phase. The scenario of overpressurized fluids andhydrofracturing in the Pt-encapsulated dunite specimen may havesome relevance to the high Q^–1 and low-velocity zonesobserved in subduction-zone environments. The outcomes of thisexploratory study indicate that the presence of water can havea significant effect on the seismic wave attenuation in theupper mantle and provide the foundation for more detailed studieson the role of water. KEY WORDS: seismic wave attenuation; water; dunite; hydrous mineral; shear modulus; viscoelasticity; olivine; grain-scale hydrofracturing     

Predicting twenty-first century recession of architectural limestone in European cities

Cities of the twenty-first century will expose buildings to environments that are quite different from those experienced over preceding periods. The recent reduction in sulfur dioxide in cities and continued pressure to lower the emissions of combustion generated pollutants creates a potential for climate induced deterioration, by contrast, to be more important. Given that climate will likely change over the next hundred years, recession rates of calcareous stones have been predicted for Oviedo (Spain), Paris and Prague over the period 1981–2099. This can give guidance as to the likely change in balance of future threat. The Lipfert, ICP, and MULTI-ASSESS functions were used to calculate recession from estimates of climate and air quality. It is likely that under a continued decline or stable levels of pollution, recession rates having reached low values will remain largely unchanged over the coming century, despite likely changes in climate. Although the functions adopted disagree in a quantitative sense, there is evidence that they were reasonably concordant in the last decades of the twentieth century. In a cleaner future their different underlying assumptions lead to poorer agreement.     

How effective are plant macrofossils as a proxy for macrophyte presence? The case of <Emphasis Type="Italic">Najas flexilis</Emphasis> in Scotland

Preventing biodiversity loss is a key aim of modern conservation, and paleolimnology can inform conservation strategies for target species and habitats where other data are unavailable. Care must be taken to fully understand the possibilities and limits of such techniques, particularly where they concern single species. This study uses plant and seed distribution data to inform macrofossil reconstructions of the rare macrophyte Najas flexilis (Slender Naiad) in Scotland, UK. It answers three questions: (a) How does the location of N. flexilis seeds in the surface sediments relate to the distribution of N. flexilis plants? (b) How do the numbers of seeds in surface sediments correlate with % cover of N. flexilis plants across lakes with differing N. flexilis abundances? (c) What are the implications of these findings for paleolimnology? Percentage N. flexilis cover and number of N. flexilis seeds in surface sediments were recorded at ~100 sample points at each of three sites; one where the species was abundant, one where it was occasional and one where it was extinct. At all sites, N. flexilis seeds were present in surface sediments across the entire lake. No correlation between % cover N. flexilis and the number of seeds in surface sediments was found within individual sites. The distribution of seeds in these lakes appeared to be related to multiple environmental and ecological variables including latitude and longitude (proxies for water currents). This is attributed to the ability of seed-bearing N. flexilis plants to fragment and float large distances on water. Between sites, there was a significant difference in the mean seed counts, with higher mean seed counts corresponding to higher abundances of N. flexilis plants. It is concluded that N. flexilis is likely to be well represented in sediment cores taken from any location within a basin, but that care should be taken when inferring changes in N. flexilis abundance from changes in the numbers of seeds in sediment samples. This work demonstrates that the reproductive ecology (number of seeds produced and dispersal mechanisms) is an important factor to consider when attempting reconstructions of single aquatic plant populations from macrofossil records.     

Dynamics of the α-β phase transitions in quartz and cristobalite as observed by in-situ high temperature 29Si and 17O NMR

Relaxation times (T₁) and lineshapes were examined as a function of temperature through the - transition for ²⁹Si in a single crystal of amethyst, and for ²⁹Si and ¹⁷O in cristobalite powders. For single crystal quartz, the three ²⁹Si peaks observed at room temperature, representing each of the three differently oriented SiO₄ tetrahedra in the unit cell, coalesce with increasing temperature such that at the - transition only one peak is observed. ²⁹Si T₁'s decrease with increasing temperature up to the transition, above which they remain constant. Although these results are not uniquely interpretable, hopping between the Dauphiné twin related configurations, ₁ and ₂, may be the fluctuations responsible for both effects. This exchange becomes observable up to 150° C below the transition, and persists above the transition, resulting in -quartz being a time and space average of ₁ and ₂. ²⁹Si T₁'s for isotopically enriched powdered cristobalite show much the same behavior as observed for quartz. In addition, ¹⁷O T₁'s decrease slowly up to the - transition at which point there is an abrupt 1.5 order of magnitude drop. Fitting of static powder ¹⁷O spectra for cristobalite gives an asymmetry parameter () of 0.125 at room T, which decreases to <0.040 at=" the=" transition=" temperature.=" the=" electric=" field=" gradient=" (efg)=" and=" chemical=" shift=" anisotropy=" (csa),=" however,=" remain=" the=" same,=" suggesting=" that=" the=" decrease=" in="> is caused by a dynamical rotation of the tetrahedra below the transition. Thus, the mechanisms of the - phase transitions in quartz and cristobalite are similar: there appears to be some fluctuation of the tetrahedra between twin-related orientations below the transition temperature, and the -phase is characterized by a dynamical average of the twin domains on a unit cell scale.     

Development and Extension of An Aggregated Scale Model: Part 2 – Extensions to ASMITA

Whilst much attention has been given to models that describe wave, tide and sediment transport processes in sufficient detail to determine the local changes in bed level over a relatively detailed representation of the bathymetry, far less attention has been given to models that consider the problem at a much larger scale (e.g. that of geomorphological elements such as a tidal flat and tidal channel). Such aggregated or lumped models tend not to represent the processes in detail but rather capture the behaviour at the scale of interest. One such model developed using the concept of an equilibrium concentration is the Aggregated Scale Morphological Interaction between Tidal basin and Adjacent coast (ASMITA). In a companion paper (Part 1), we detail the original model and provide some new insights into the concepts of equilibrium, and horizontal and vertical exchange that are key components of this modelling approach. In this paper, we summarise a range of developments that have been undertaken to extend the original model concept, to illustrate the flexibility and power of the conceptual framework. However, adding detail progressively moves the model in the direction of the more detailed process-based models and we give some consideration to the boundary between the two.