Composition-Induced Variations in SIMS Instrumental Mass Fractionation during Boron Isotope Ratio Measurements of Silicate Glasses

An analytical artefact is reported here related to differences in instrumental mass fractionation between NIST SRM glasses and natural geological glasses during SIMS boron isotope determinations. The data presented demonstrated an average 3.4‰ difference between the NIST glasses and natural basaltic to rhyolitic glasses mainly in terms of their sputtering-induced fractionation of boron isotopes. As no matrix effect was found among basaltic to rhyolitic glasses, instrumental mass fractionation of most natural glass samples can be corrected by using appropriate glass reference materials. In order to confirm the existence of the compositionally induced variations in boron SIMS instrumental mass bias, the observed offset in SIMS instrumental mass bias has been independently reproduced in two laboratories and the phenomenon has been found to be stable over a period of more than one year. This study highlights the need for a close match between the chemical composition of the reference material and the samples being investigated.     

Radiocarbon redating of contaminated samples from a tropical volcano: the Mansion ‘Series’ of St Kitts,West Indies

Heavy rainfall and dense vegetation on tropical volcanoes produce abundant carbonized wood in pyroclastic deposits, in addition to easy contamination of this wood by root systems and soluble humic material. Because the physical nature of the charcoal varies, some samples are more prone to contamination. Two independent studies of the same volcano, Mt Liamuiga on St Kitts in the Lesser Antilles, sometimes using samples from the same carbonized tree, yielded a systematic difference in radiocarbon ages. An exchange of samples and a re-investigation of three physically distinct types of charcoal yielded the following results. Rare, hard, dense charcoal, lacking contamination, which had yielded a spurious age of 2860 years bp, was redated at 1845±58 years bp. Common soft, friable charcoal with good cellular structure proved to be susceptible to contamination. A field decontamination technique utilized by one group seems significant as it yields older ages than when only routine laboratory pre-treatment was used, indicating that the latter technique only partly removes the dried and hard residue produced by the decomposition of modern plant rootlets. A previous date of 24870 years bp obtained from powdery charcoal in a horizon beneath the Mansion Series contradicted ages older than 41000 years bp from common friable charcoal in the lower Mansion Series. The soft powdery charcoal was re-investigated using a sample collected a few centimeters from the original, although field decontamination of this sample was not possible, more extensive laboratory treatment yielded an age of ca. 43000 years bp, again proving that routine laboratory pretreatments are inadequate. A revised geochronology for the Mansion Series is described and a cautionary discussion is presented for the benefit of investigators using radiocarbon ages to date volcanic deposits.     

Formation of the mid-fifteenth century Kuwae caldera (Vanuatu) by an initial hydroclastic and subsequent ignimbritic eruption

In the mid-fifteenth century, one of the largest eruptions of the last 10 000 years occurred in the Central New Hebrides arc, forming the Kuwae caldera (12x6 km). This eruption followed a late maar phase in the pre-caldera edifice, responsible for a series of alternating hydromagmatic deposits and airfall lapilli layers. Tuffs related to caldera formation ( 120 m of deposits on a composite section from the caldera wall) were emitted during two main ignimbritic phases associated with two additional hydromagmatic episodes. The lower hydromagmatic tuffs from the precaldera maar phase are mainly basaltic andesite in composition, but clasts show compositions ranging from 48 to 60% SiO₂. The unwelded and welded ashflow deposits from the ignimbritic phases and the associated intermediate and upper hydromagmatic deposits also show a wide compositional range (60–73% SiO₂), but are dominantly dacitic. This broad compositional range is thought to be due to crystal fractionation. The striking evolution from one eruptive style (hydromagmatic) to the other (magmatic with emission of a large volume of ignimbrites) which occurred either over the tuff series as a whole, or at the beginning of each ignimbritic phase, is the most impressive characteristic of the caldera-forming event. This strongly suggests triggering of the main eruptive phases by magma-water interaction. A three-step model of caldera formation is presented: (1) moderate hydromagmatic (sequences HD 1–4) and magmatic (fallout deposits) activity from a central vent, probably over a period of months or years, affected an area slightly wider than the present caldera. At the end of this stage, intense seismic activity and extrusion of differentiated magma outside the caldera area occurred; (2) unhomogenized dacite was released during a hydromagmatic episode (HD 5). This was immediately followed by two major pyroclastic flows (PFD 1 and 2). The vents spread and intense magma-water interaction at the beginning of this stage decreased rapidly as magma discharge increased. Subsequent collapse of the caldera probably commenced in the southeastern sector of the caldera; (3) dacitic welded tuffs were emplaced during a second main phase (WFD 1–5). At the beginning of this phase, magma-water interaction continued, producing typical hydromagmatic deposits (HD 6). Caldera collapse extended to the northern part of the caldera. Previous C¹⁴ dates and records of explosive volcanism in ice from the south Pole show that the climactic phase of this event occurred in 1452 A.D.     

GGR Critical Review of Analytical Developments in 2004–2005

In 2005 Geostandards and Geoanalytical Research embarked upon a new initiative for its readers. Key researchers in various fields of geoanalytical technique development and their application were identified and invited to provide reviews pertinent to their expertise. As noted in the first of these publications "…instead of revisiting the historical context or decades of development in each analytical technique, the goal here has been to capture a snapshot of "hot topics" across a range of fields as represented in the… literature" (Hergt et al . 2005). Rather than prepare an annual review, a decision was taken earlier this year to provide a biennial summary of progress and accomplishments, in this case for the years 2004–2005. The principal techniques employed in Earth and environmental sciences are covered here, and include laser ablation and multicollector ICP-MS, ICP-AES, thermal ionisation and secondary ion mass spectrometry, as well as neutron activation analysis, X-ray fluorescence and atomic absorption spectrometry. A comprehensive review of the development of reference materials, often essential to these techniques, is also provided. The contributions assembled serve both to keep readers informed of advances they may be unfamiliar with, but also as a means of showcasing examples of the breadth and depth of work being conducted in these fields.     

Reference Materials in Geoanalytical Research -Review for 2004 and 2005

This review gives an overview of the use and development of reference materials of geochemical and environmental interest in the literature of the years 2004 and 2005. In these years the performance of existing methods has been improved and new geochemical applications using new techniques have been developed. Accordingly, there was an increasing need for new reference materials, especially for in situ microanalysis and for precise stable isotope measurements. In addition, there was a notable trend for further characterisation of existing reference materials, mainly for the platinum-group elements. This review focuses on five topics: reference materials for platinum-group elements, reference glasses for in situ microanalysis, zircon reference materials, isotopic reference materials, and the development and certification of reference materials.     

Structural Evolvement of Heating Treatment of Mg/AI-LDH and Preparation of Mineral Mesoporous Materials

Although hydrotalcite, or layered double hydroxides （LDHs）, is not a common mineral, it is an important material that can be easily synthesized in laboratory. In this study, structural evolvement and BET surface area changes of heat treated Mg/AI-LDH is evaluated by XRD, TEM and N2-BET analyses. The results indicate that the magnesium-aluminum LDH with carbonate as interlayer anion, periclase-like oxides was formed at temperatures of 400-800℃. Meanwhile, 2-3 nanometer mesoporous were formed during decomposition of LDH. However, the heat treated samples still preserve the morphology of the original LDH plates. Periclase-like formed from LDH heat treatment may re-hydrolyze and recover the structure of LDH. However, crystallinity of the recovered LDH is lower than that of the original LDH. This heat treatment will result in formation of （Mg, Al）-oxide nano-crystals and nanopores among the nano-crystals. When heating temperature exceeds 1000, the periclase-like （Mg, Al）-oxide is transformed into a composite with periclase （MgO） and spinel phases. The periclase can be re-hydrolyzed and dissolved in HCl solution. After acid treatment, the sample with a high surface area is composed of spinel nano-crystals and nanopores among them. Our results will provide a new and economic way to synthesize mesoporous materials through pathways of phase transformation of precursor materials with different composition.     

Analogue study of particle segregation in pyroclastic density currents, with implications for the emplacement mechanisms of large ignimbrites

Abstract Analogue flume experiments were conducted to investigate the transport and sedimentation behaviour of turbulent pyroclastic density currents. The experimental currents were scaled approximately to the natural environment in three ways: (1) they were fully turbulent; (2) they had a very wide range of particle sizes and associated Rouse numbers (the ratio of particle settling velocity to effective turbulent eddy velocity in the current); and (3) they contained particles of two different densities. Two sets of surge‐type experiments were conducted in a 5 m long, water‐filled lock‐exchange flume at five different volumetric particle concentrations from 0·6% to 23%. In one set (one‐component experiments), the currents contained just dense particles; in the other set (two‐component experiments), they contained both light and dense particles in equal volume proportions. In both sets of experiments, the population of each component had a log‐normal size distribution. In the two‐component experiments, the size range of the light particle population was selected in order to be in hydrodynamic equivalence with that of the dense particles. Dense particles were normally graded, both vertically and downstream, in the deposits from both sets of experiments. The mass loading (normalized to the initial mass of the suspension) and grain size of the dense component in the deposits decreased with distance from the reservoir and were insensitive to initial total particle concentration in the currents. On the other hand, in the two‐component experiments, the light particles were extremely sensitive to concentration. They were deposited in hydrodynamic equivalence with the dense particles from dilute currents, but were segregated efficiently at concentrations higher than a few per cent. With increasing particle concentration, the large, light particles were carried progressively further down the flume because of buoyancy effects. Deposits from the high‐concentration currents exhibited reverse vertical grading of the large, light particles. Efficient segregation of the light component was observed even if the bulk density of the current was less than that of the light particles. In both sets of experiments, marked inflexions in the rate of downstream decline in mass loading and maximum grain size of the dense component can be attributed to the presence of two different particle settling regimes in the flow: (1) particles with Rouse numbers >2·5, which did not respond to the turbulence and settled rapidly; and (2) particles with Rouse numbers <2·5, which followed the turbulent eddies and settled slowly. The results are applied to the transport and sedimentation dynamics of pyroclastic density currents that generate large, widespread ignimbrites. Field data fail to reveal significant departures from aerodynamic equivalence between pumice and lithic clasts in three such ignimbrites: the particulate loads of some large ignimbrites are transported principally in turbulent suspensions of low concentration. In some ignimbrites, the well‐developed inflexions in curves of maximum lithic (ML) size vs. distance can be attributed to the existence of distinct high and low Rouse number particle settling regimes that mark the transition from an overcharged state to one in which the residual particulate load is transported more effectively by turbulence.     

Three types of pyroclastic currents and their deposits: examples from the Vulsini Volcanoes, Italy

This paper deals with ground-hugging, gas–pyroclast currents from explosive volcanic eruptions and their deposits. Key field observations and laboratory determinations are proposed to relate specific deposit types with flow regimes and particle concentration in the transport and depositional systems. Three relevant flow scenarios and corresponding deposit types have been recognized from a survey of pyroclastic successions of the Vulsini Volcanic District (central Italy): (1) dilute, turbulent, pyroclastic currents producing normally or multiply graded beds by direct suspension sedimentation; (2) concentrated bedload regions beneath suspension currents, depositing inversely graded beds by traction carpet sedimentation; (3) self-sustained, high particle concentration, laminar, mass flows developing massive, poorly sorted bodies, with opposite grading of coarse lithic and pumice clasts, overlying fine-grained, inversely graded, basal layers. Main distinguishing criteria include the occurrence and pattern of clast grading, clast–thickness relationships, grain size, ash matrix componentry and pyroclast size–density relationships. Downcurrent and temporal transitions among identified flow scenarios are likely to occur for changing energy conditions and gas–pyroclast ratio both on regional and local scales. The nature and efficiency of magma fragmentation, volatile content, conduit geometry (which determine the characteristics of the erupted mixture and possible lateral blast component at the vent), and the angle of incidence of the column collapse, are suggested as the main factors controlling the generation of one type over the other at flow inception. Dilute, fine-grained, overpressured eruption clouds are thought to favor the formation of low particle concentration turbulent currents. Column collapse over slightly inclined volcano slopes, causing a high degree of compression of the collapsing mixture and of gas expulsion, would favor the generation of high particle concentration pyroclastic currents.     

Determining Q of near-surface materials from Rayleigh waves

High-frequency (≥2 Hz) Rayleigh wave phase velocities can be inverted to shear (S)-wave velocities for a layered earth model up to 30 m below the ground surface in many settings. Given S-wave velocity (V_S), compressional (P)-wave velocity (V_P), and Rayleigh wave phase velocities, it is feasible to solve for P-wave quality factor Q_P and S-wave quality factor Q_S in a layered earth model by inverting Rayleigh wave attenuation coefficients. Model results demonstrate the plausibility of inverting Q_S from Rayleigh wave attenuation coefficients. Contributions to the Rayleigh wave attenuation coefficients from Q_P cannot be ignored when Vs/V_P reaches 0.45, which is not uncommon in near-surface settings. It is possible to invert Q_P from Rayleigh wave attenuation coefficients in some geological setting, a concept that differs from the common perception that Rayleigh wave attenuation coefficients are always far less sensitive to Q_P than to Q_S. Sixty-channel surface wave data were acquired in an Arizona desert. For a 10-layer model with a thickness of over 20 m, the data were first inverted to obtain S-wave velocities by the multichannel analysis of surface waves (MASW) method and then quality factors were determined by inverting attenuation coefficients.     

Reconciling pyroclastic flow and surge: the multiphase physics of pyroclastic density currents

Two end-member types of pyroclastic density current are commonly recognized: pyroclastic surges are dilute currents in which particles are carried in turbulent suspension and pyroclastic flows are highly concentrated flows. We provide scaling relations that unify these end-members and derive a segregation mechanism into basal concentrated flow and overriding dilute cloud based on the Stokes number (S_T), the stability factor (Σ_T) and the dense-dilute condition (D_D). We recognize five types of particle behaviors within a fluid eddy as a function of S_T and Σ_T: (1) particles sediment from the eddy, (2) particles are preferentially settled out during the downward motion of the eddy, but can be carried during its upward motion, (3) particles concentrate on the periphery of the eddy, (4) particles settling can be delayed or ‘fast-tracked’ as a function of the eddy spatial distribution, and (5) particles remain homogeneously distributed within the eddy. We extend these concepts to a fully turbulent flow by using a prototype of kinetic energy distribution within a full eddy spectrum and demonstrate that the presence of different particle sizes leads to the density stratification of the current. This stratification may favor particle interactions in the basal part of the flow and D_D determines whether the flow is dense or dilute. Using only intrinsic characteristics of the current, our model explains the discontinuous features between pyroclastic flows and surges while conserving the concept of a continuous spectrum of density currents.