Mobility of trace elements and leaching rates of rhyolitic glass shards from some New Zealand tephra deposits

It is shown that glass shards from volcanic eruptions of known age are useful in natural analogue studies connected with nuclear waste disposal. They may be sequentially leached in bulk with HF and the hydration layer thickness determined. If they have also been irradiated with neurons in a reactor, some elemental profile information is available at the same time. Applying this to New Zealand volcanic glass shards gave as many as 15 different fractions, and information about the distribution of up to 16 trace elements. Those shards from a 22 ka eruption yielded hydration rates of ∼2.5 × 10⁻¹¹ g/cm²/d while rates from a 340 ka eruption were 1.5 × 10⁻¹² −1.2 × 10⁻¹¹ g/cm²/d. The percentage of the total mass hydrated ranged between 5 and 35%. As found in some other studies, many elements accumulate on the surface of the shards, particularly Cr, Co and Fe, but it is shown here that they mostly originate in surrounding groundwater rather than the bulk glass. Rubidium and Cs tend to be removed instead. There was no obvious correlation between degree of hydration and the environment of deposition. The use of glass shards from volcanic eruptions is recommended for such studies because they are ubiquitous, and occurrence is less dependent on local geology than for some sample types.     

Testing the reliability of the JEOL FEGSEM 6500F electron microprobe for quantitative major element analysis of glass shards from rhyolitic tephra

Coulter, S. E., Pilcher, J. R., Hall, V. A., Plunkett, G. & Davies, S. M. 2009: Testing the reliability of the JEOL FEGSEM 6500F electron microprobe for quantitative major element analysis of glass shards from rhyolitic tephra. Boreas , 10.1111/j.1502-3885.2009.00113.x. ISSN 0300-9483.
Electronprobe microanalysis is now widely adopted in tephra studies as a technique for determining the major element geochemistry of individual glass shards. Accurate geochemical characterization is crucial for enabling robust tephra-based correlations; such information may also be used to link the tephra to a specific source and often to a particular eruption. In this article, we present major element analyses for rhyolitic natural glass standards analysed on three different microprobes and the new JEOL FEGSEM 6500F microprobe at Queen's University Belfast. Despite the scatter in some elements, good comparability is demonstrated among data yielded from this new system, the previous Belfast JEOL-733 Superprobe, the JEOL-8200 Superprobe (Copenhagen) and the existing long-established microprobe facility in Edinburgh. Importantly, our results show that major elements analysed using different microprobes and variable operating conditions allow two high-silica glasses to be discriminated accurately.     

Correlation and characterisation of individual glass shards from tephra deposits using trace element laser ablation ICP‐MS analyses: current status and future potential

Laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) is a high spatial resolution analytical method which has been applied to the analysis of silicic tephras. With current instrumentation, around 30 trace elements can be determined from single glass shards as small as ～ 40 µm, separated from tephra deposits. As a result of element fractionation during the ablation process using a 266 nm laser, a relatively complex calibration strategy is required. Nonetheless, such a strategy gives analyses which are accurate (typically within ±5%) and have an analytical precision which varies from ～ ±2% at 100 ppm, to ～ ±15% at 1 ppm. Detection limits for elements used in correlation and discrimination studies are well below 1 ppm. Examples of the application of trace element analysis by LA‐ICP‐MS in tephra studies are presented from the USA, New Zealand and the Mediterranean. Improvements in instrumental sensitivity in recent years have the potential to lower detection limits and improve analytical precision, thus allowing the analysis of smaller glass shards from more distal tephras. Laser systems operating at shorter wavelengths (e.g. 193 nm) are now more widely available, and produce a much more controllable ablation in glasses than 266 nm lasers. Crater sizes of <10 µm are easily achieved, and at 193 nm many of the elemental fractionation issues which mar longer wavelengths are overcome. By coupling a short wavelength laser to a modern ICP‐MS it should be possible to determine the trace element composition of glass shards as small as 20 µm and, providing sample preparation issues can be overcome, the determination of the more abundant trace elements in glass shards as small as 10 µm is within instrumental capabilities. This will make it possible to chemically fingerprint tephra deposits which are far from their sources, and will greatly extend the range over which geochemical correlation of tephras can be undertaken. Copyright © 2007 John Wiley & Sons, Ltd.     

Electron microprobe analysis of glass shards from tephra assigned to set W,Mount St. Helens,Washington

We have extended the fallout areas for each of two members of tephra-set W, erupted from Mount St. Helens about 1500 ad, by several hundred kilometers beyond the limits mapped in 1975. We traced one member (We) east into Idaho, and the other (Wn) northeast into British Columbia. After using stratigraphic and petrographic observations to assign more than 100 tephra samples to set W, we found 26 of these, selected for chemical analysis, to be closely similar in content of Ca, Fe, and K in glass shards. But improved homogeneity was evident when the 26 sampling localities for tephra W were segregated geographically, east vs. northeast of the volcano. When Ca:Fe:K proportions were plotted on a ternary diagram, there was no overlap of the plotting areas for these two groups of tephra W samples. Without such data, tephra layers We and Wn are currently separable only from stratigraphic and geographic information. Partial glass analysis is also an aid, along with stratigraphic position and petrographic characteristics, in distinguishing tephra W from associated tephra layers. These include tephra layers T and Yn from Mount St. Helens, as well as older tephra layers from Mount Mazama and Glacier Peak.     

Standard chemical‐based tephra extraction methods significantly alter the geochemistry of volcanic glass shards

The chemical compositions of tephra shards are widely utilised in a myriad of disciplines, including volcanology, petrology, tephrochronology, palaeoecology and climate studies. Previous research has raised concerns over the possible chemical alteration of microscopic (<100 µm) volcanic glass shards through standard extraction procedures, such as the widely used acid digestion method. This study subjects 10 samples of well‐characterised volcanic glasses ranging from basalt to rhyolite to three common methods used in the extraction of volcanic material from lake sediments and peats. The major element geochemistry of each sample was analysed and compared with a control group. The results of this test indicate that basaltic and andesitic glasses are highly susceptible to chemical alteration, particularly to the concentrated corrosive materials used in acid and base digestion techniques. PERMANOVA analysis of the variation within groups suggests that the oxides most susceptible to variation are alkalis from groups I and II (K₂O, Na₂O, CaO, MgO) and SiO₂, and the most stable oxides are Al₂O₃ and FeO. Felsic glasses are considerably less susceptible to alteration by both acidic (HCl, HNO₃, H₂SO₄) and alkaline (KOH) digestions. Our findings have important implications for interpreting the geochemistry of volcanic glasses. Copyright © 2019 John Wiley & Sons, Ltd.     

Toward a comprehensive upper quaternary tephra and ignimbrite stratigraphy in New Zealand using electron microprobe analysis of glass shards

New Zealand Quaternary marine and terrestrial sequences contain numerous tephras, or volcanic-ash horizons, that are the distal correlatives of voluminous welded ignimbrite sheets, erupted from central North Island. Electron microprobe analyses of glass shards from the distal tephras demonstrate their homogeneity and are shown to identify each tephra examined. By matching tephras from stratigraphically controlled sequences, the first comprehensive tephra stratigraphy spanning from 50,000 to 700,000 yr ago and covering the New Zealand region is advanced.Analyses on glass shards from the unwelded base of ignimbrite sheets are comparable to the distal tephra analyses and allow correlation between ignimbrites and to the distal tephras. The better exposed tephra record constrains the number of separate eruptive events and the stratigraphy of the ignimbrites, both of which were previously confused by lack of outcrop.Samples from pumiceous marine sediments were found to contain two or more chemically distinct populations of glass. The pumice is in cross-bedded sands or sand lenses within conglomerate, attesting to a shallow high-energy environment where reworking could occur. However, each glass population could be matched to older, known tephras.     

Trace-element geochemistry of individual glass shards of the Old Crow tephra and the age of the Delta glaciation, central Alaska

Two widespread tephra deposits constrain the age of the Delta Glaciation in central Alaska. The Old Crow tephra (ca. 140,000 ± 10,000 yr), identified by electron microprobe and ion microprobe analyses of individual glass shards, overlies an outwash terrace coeval with the Delta glaciation. The Sheep Creek tephra (ca. 190,000 yr) is reworked in alluvium of Delta age. The upper and lower limiting tephra dates indicate that the Delta glaciation occurred during marine oxygen isotope stage 6. We hypothesize that glaciers in the Delta River Valley reached their maximum Pleistocene extent during this cold interval because of significant mid-Pleistocene tectonic uplift of the east-central Alaska Range.     

Recognition and characterisation of high-grade ignimbrites from the Neoproterozoic rhyolitic volcanism in southernmost Brazil

Neoproterozoic magmatism in southern Brazil is associated with translithospheric shear belts and strike-slip basins in a post-collisional setting related to the last stages of the Brasilian-Pan African Orogenic Cycle. It evolved from an association of high-K calc-alkaline, leucocratic-peraluminous and continental tholeiitic magmas, to an association with shoshonitic magmas and, eventually, to an association with magmas of the sodic mildly alkaline series. This magmatism varies from metaluminous to peralkaline and exhibits alkaline sodic affinity. A large volcanism is related to this alkaline sodic magmatism and is named the Acampamento Velho Formation. This unit was coeval with subaerial siliciclastic sedimentation in post-collisional basins preserved in the region. The Acampamento Velho Formation consists of pyroclastic and effusive volcanic deposits, which are mainly silicic, emplaced under subaerial conditions. The best exposures of this volcanism occur on the Ramada and Taquarembó plateaus, located southwest of Rio Grande do Sul in southernmost Brazil. The pyroclastic flow deposits are composed mainly of juvenile fragments such as pumices, shards and crystal fragments. Welding is very effective in these units. High-grade ignimbrites occur at the base and intermediate portions of the deposits and rheoignimbrites are observed at the top. The pre-eruptive temperature calculations, which were obtained at the saturation of zircon, revealed values between 870 °C and 978 °C for Taquarembó Plateau and 850 °C–946 °C for Ramada Plateau. The calculated viscosity values vary from 6.946 to 8.453 log η (Pas) for the rheoignimbrites and 7.818 to 10.588 log η (Pas) for the ignimbrites. Zr contents increase toward the top of the pyroclastic sequence, which indicates an increase in peralkalinity and determines the reduction in viscosity for clasts at the upper portions of the flows. The patterns of the structures of the ignimbrites and rheoignimbrites in the Taquarembó and Ramada plateaus accords well with successive pyroclastic flows that halts en masse. In this model the entire pyroclastic flow halts en masse, so complex vertical changes in grain size and composition are interpreted as recording deposition from successive discrete pyroclastic flows. The stratification observed in intermediate units in Taquarembó Plateau might reflect in this case variation in eruptive dynamics and short pauses.     

日本樱岛火山灰玻璃碎屑形态特征研究

火山灰年代学是控制地层年代最简单可靠的直接手段,近年来在磁性地层、构造演化和古气候环境、考古等研究中被广泛重视和应用,经常成为最关键的要素。然而对其在地层中的识别常常产生较大分歧,制约了对年代的控制及与此相关的许多科学问题的解决。火山玻璃作为火山灰中的常见和标签物质,是识别火山灰最直接可靠的材料。日本强烈的第四纪火山活动和清晰连续的火山灰沉积在这方面具有代表性。本文利用光学显微镜和扫描电镜,对日本樱岛第四纪晚期典型火山灰中的火山玻璃形态和表面结构特征进行观察分析,总结出火山玻璃碎屑的外部形貌为独特、醒目的各种玻璃碎片状,呈各种大小和形态的带有气孔的曲面或弧面尖棱角状颗粒,如锋利的长条状、各种多边形粒状、片状（月牙状、三角状、多边形状等）和三交面状等,表面特征为各种与火山喷发炸裂作用相关的光滑或弱贝壳状断口的曲面,及与火山喷气有关的各种孔洞、管槽、小圆坑、椭圆形坑和眼状坑。其中眼状坑和三交面状这两种特殊表面形态分别只在安山质和流纹质火山灰中出现,为准确识别中-酸性火山灰及其类型提供了微观形态学鉴定标志。     

Hydration of rhyolitic glass during weathering as characterized by IR microspectroscopy

The mechanism and rate of hydration of rhyolitic glass during weathering were studied. Doubly polished thin sections of two rhyolites with different duration of weathering (Ohsawa lava: 26,000 yr, Awanomikoto lava: 52,000 yr) were prepared. Optical microscope observation showed that altered layers had developed along the glass surfaces. IR spectral line profile analysis was conducted on the glass sections from the surface to the interior for a length of 250 μm and the contents of molecular H₂O (H₂O_m), OH species (OH) and total water (H₂O_t) were determined. The diffusion profile of H₂O_m in Ohsawa lava extends beyond the layer observed by optical microscope. The content of H₂O_m in the hydrated region is much higher than that of OH species. Thus, the reaction from H₂O_m to OH appears to be little and H₂O_m is the dominant water species moving into the glass during weathering. Based on the concentration profiles, the diffusion coefficients of H₂O_m(D_H2Om) and H₂O_t(D_H2Ot) were determined to be 2.8 × 10⁻¹⁰ and 3.4 × 10⁻¹⁰ μm² s⁻¹ for Ohsawa lava, and 5.2 × 10⁻¹¹ and 4.1 × 10⁻¹¹ μm² s⁻¹ for Awanomikoto lava, respectively. The obtained D_H2Om during weathering are more than 2-3 orders of magnitude larger than the diffusion coefficient at ∼20 °C that is extrapolated from the diffusivity data for >400 °C. This might suggest that the mechanism of water transport is different at weathering conditions and >400 °C.     

Compositional variation in magma through early neogene in the Northeast Indian Ocean: A testimony from glass shards

We report unusual occurrence of glass shards with diverse morphologies and compositions in the volcanic ash associated with the early Neogene marine stratigraphic succession (early Miocene to early middle Miocene) of Andaman-Nicobar Islands, Northeast Indian Ocean. These small, ash-size (200 to 800 μm) broken pieces of glass shards when viewed under Scanning Electron Microscope (SEM), represent distinctive — platy, sickle, bicuspate, concentric, angular, horn shape and slivers with broken angular bubble wall — morphologies. Glass shards are colourless. But, a few are grey or reddish-brown, indicate high Fe content. Chilled, juvenile, angular and blocky shards show fragments of highly viscous, silicic magma. Spindle and ribbon-shape shards form from a low viscosity basalt and rhyolite. Electron Probe Micro Analyzer (EPMA) was used to measure low concentration variations of major oxides within individual amorphous silicate solid glass shards whose disordered atomic structure is that of a liquid derived from a silicate melt. Major elemental chemistry of early Miocene glass shards from Colebrook island show low silica, alkalis, high FeO_(T) MgO and CaO, whereas, early middle Miocene glass shards from Inglis island show high silica, alkalis, low FeO_(T), MgO and CaO contents. These data-sets when plotted on ternary TotalAlkali-Silica and Na₂O+K₂O-MgO-FeO_(T) diagrams show that their data plots lie within the basaltic-andesite, tephri-phonolite, rhyolite and trachyte fields. These glass shards which were present in the provenance, formed by explosive eruption of lavas, ranging in composition from basalt to rhyolite with andesite/ basalt-andesite being the most common magma types erupted sub-areally, implying island arc type of tectono-magmatic setting for the formation of these lavas. However, more evolutionary variant rhyolite was most likely formed by crystal fractionation.     

Magnetic characterisation and correlation of a Younger Dryas tephra in North Atlantic marine sediments

A technique for identifying non‐visible basaltic tephra‐rich horizons of Younger Dryas (YD)/Greenland Stadial (GS) 1 age in northeast Atlantic sediments using rapid, non‐destructive magnetic measurements is presented. Three high‐resolution marine sediment cores have been studied in an E–W transect across the Hebridean margin: St Kilda Basin (MD95‐2007), Barra Fan (MD95‐2006) and Rockall Trough (MD04‐2822). Magnetic susceptibilities and remanent magnetisations were measured at contiguous 1 cm resolution on bulk sediments. In all three cores, an interval with higher proportions of hard magnetic minerals coincides with a clearly defined peak in basaltic tephra shard (>250 µm) counts, which can be constrained to the early part of the YD/GS1 based on faunal climate proxies. Electron microprobe analyses of the magnetically distinct basaltic tephra interval, in all three cores, displays the same major element geochemistry as published for the Vedde basaltic (I Tab. 1), i.e. sourced from the Icelandic volcano Katla. The identification of transitional alkalic basaltic tephras within marine sediments could potentially be facilitated by magnetic analysis as a useful chronostratigraphic screening tool. Copyright © 2009 John Wiley & Sons, Ltd.     

Late Pleistocene Eifel eruptions: insights from clinopyroxene and glass geochemistry of tephra layers from Eifel Laminated Sediment Archive sediment cores

The Eifel Laminated Sediment Archive (ELSA), which comprises several cores from maar lakes, includes numerous tephra layers spanning the last 140 000 years. The sediment cores are dated by ¹⁴C and thermoluminescence as well as tuned to Greenland stadial–interstadial successions. Within the last glacial cycle, the Eifel Volcanic Fields are source to several widespread tephra layers, namely the Laacher See, Eltville, Rambach and Rocourt Tephra. However, a corresponding source volcano was so far only identified for the Laacher See Tephra. In this study we use glass and clinopyroxene geochemistry to link the remaining tephra layers to possible eruption centers within the West and East Eifel Volcanic Fields: while we demonstrate that the Eltville Tephra originated from an earlier eruption of the Laacher See Volcano at 24 300 a bp from within the East Eifel Volcanic Field, the Rambach and Rocourt Tephras are sourced from the West Eifel Volcanic Field and erupted from Wartgesberg at 27 900 a bp and Pulvermaar at 75 000 a bp , respectively. Phases of volcanic activity peaked at 10 000–30 000 and 60 000–80 000 a bp and were thus erupted around the temperature minima of the last glacial cycle. The longest phase of dormancy between individual vents was around 30 000 years long, within the last interglacial.     

Tephrological implications of beam size—sample‐size effects in electron microprobe analysis of glass shards

This paper concerns the potential consequences of varying procedures for the determination of tephra geochemistry by electron microprobe. Application of electron probe microanalysis to tephrostratigraphical methods has increasingly facilitated the resolution and refinement of Quaternary chronology associated with records of proxy‐environmental or proxy‐climatic change. The geographical range over which tephras are recovered has expanded significantly with the identification and analysis of crypto (or hidden) tephras in areas far removed from tephra sources. These tephras are dominated by glass shards, which, in many distal environments, may be either small in size (μm) or may be highly pumiceous with low glass:void ratios and thin (<10 μm) shard walls. We demonstrate that reducing the size of the electron beam used to analyse shard geochemistry cannot be used reliably to permit analysis of thin glass walls. This approach distorts the geochemical data, creating analytical differences that may generate inappropriate tephrogeochemical fingerprints. Additional distortion of the geochemical fingerprint in the form of hybrid analyses may be encountered in glass fragments containing micron‐sized crystalline phases such as feldspar. Copyright © 2001 John Wiley & Sons, Ltd.     

Redox state of iron in peralkaline rhyolitic glass/melt: X-ray absorption micro-spectroscopy experiments at high temperature

Assessing the ferric-ferrous ratio in magmas prior to eruption remains a challenging task. X-ray absorption near-edge structure (μXANES) spectra were collected at the iron K-edge in water-rich peralkaline silicic melt/glass inclusions trapped in quartz. These experiments were carried out between 800 and 20 °C. The chemical environment of iron was also determined in the naturally quenched samples (glass inclusions and matrix glass) and in the peralkaline rhyolitic reference glasses, with variable [Fe³⁺ / ∑Fe] ratios.In the reference glasses, both the intensity of the pre-peaks (Fe²⁺, Fe³⁺) and site geometry of iron change as the oxidation state increases. Fourfold-coordinated Fe³⁺ prevails in highly oxidised peralkaline silicic glasses, using alkalis for charge balance. The position of the pre-edge centroid of the 1s-3d transition correlates with the Fe³⁺ / ΣFe ratios that allowed calibration of the redox state of iron of our natural samples.At high temperatures, Fe²⁺ dominates in the pre-edge structure of melt inclusions. Upon cooling down to 20 °C, the intensity of the Fe³⁺ peak increases, the centroid position of the pre-edge features shifts by nearly 0.5 eV and the main edge moves slightly towards higher energies. The slower the cooling rate, the higher the ferric iron contribution. Iterative μXANES experiments performed on the same samples show that the process is reversible. However, this apparent oxidation of iron upon cooling is an artefact of changes in Fe coordination. It implies that the [Fe³⁺ / ΣFe] ratio of glassy samples, measured at 20 °C, may be overestimated by a factor > 1.7, and that this ratio cannot be reliably retrieved by probing naturally cooled glass inclusions, and most silicate glasses. High temperature μXANES experiments led first to an assessment of the ferric-ferrous ratio in the water-rich peralkaline melt in pre-eruptive magmatic conditions and second to the determination of the corresponding oxygen fugacity at 740 °C.     

Distinction between the Youngest Toba Tuff and Oldest Toba Tuff from northern Sumatra based on the area density of spontaneous fission tracks in their glass shards

Determination of the area density of spontaneous fission tracks (ρ_s) in glass shards of Toba tephra is a reliable way to distinguish between the Youngest Toba Tuff (YTT) and the Oldest Toba Tuff (OTT). The ρ_s values for YTT, uncorrected for partial track fading, range from 70 to 181 tracks/cm² with a weighted mean of 108 ± 5 tracks/cm², based on 15 samples. Corrected ρ_s values for YTT are in the range of 77–140 tracks/cm² with a weighted mean of 113 ± 8 tracks/cm², within the range of uncorrected ρ_s values. No significant difference in ρ_s exists between YTT samples collected from marine and continental depositional settings. The uncorrected ρ_s for OTT is 1567 ± 114 tracks/cm² so that confusion with YTT is unlikely.     

Paleoecology of two marine oxygen isotope stage 7 sites correlated by the Sheep Creek tephra, northwestern North America

Pollen analysis at two sites, correlated by the presence of the 190,000 yr-old Sheep Creek tephra, documents fluctuations in vegetation and climate consistent with this date and indicates that the records span marine oxygen isotope stage 7 and the stage 6/7 transition. Dawson Cut, near Fairbanks, Alaska, provides a 5.2-m-long pollen record of interglacial boreal forest succeeded by shrub tundra and then forest/tundra. Ash Bend, Stewart River, central Yukon, provides a 9.5-m-long record of interglacial boreal forest succeeded by forest/tundra, shrub tundra, and herbaceous tundra. The replacement of forest at both sites by more open or tundra vegetation indicates warm interglacial conditions giving way to cold and arid climate. It is not clear whether stage 7 was warmer than the present. The warm-cool-warm climate oscillation evident at both sites may correlate to Lake Baikal substages 7a, 7b, and 7c. Sheep Creek tephra fell on forest/tundra vegetation.     

Hekla 1947, 1845, 1510 and 1158 tephra in Finland: challenges of tracing tephra from moderate eruptions

Several cryptotephra layers that originate from Icelandic volcanic eruptions with a volcanic explosivity index (VEI) of ≤ 4 and tephra volumes of < 1 km³ have previously been identified in Northern Europe, albeit within a restricted geographical area. One of these is the Hekla 1947 tephra that formed a visible fall-out in southern Finland. We searched for the Hekla 1947 tephra from peat archives within the previously inferred fall-out zone but found no evidence of its presence. Instead, we report the first identification of Hekla 1845 and Hekla 1510 cryptotephra layers outside of Iceland, the Faroe Islands, Ireland and the UK. Additionally, Hekla 1158 tephra was found in Finland for the first time. Our results confirm that Icelandic eruptions of moderate size can form cryptotephra deposits that are extensive enough to be used in inter-regional correlations of environmental archives and carry a great potential for refining regional tephrochronological frameworks. Our results also reveal that Icelandic tephra has been dispersed into Finnish airspace at least seven times during the past millennium and in addition to a direct eastward route the ash clouds can travel either via a northerly or a southerly transport pathway.     

Petrogenesis of a basalt-rhyolite tephra from the west-central Afar,Ethiopia

The Cindery Tuff is an unusual tephra fall deposit that contains evidence for the mixing of basaltic and rhyolitic liquids prior to eruption. It contains clear rhyolitic glass shards together with brown basaltic glass spheres and a broadly bimodal phenocryst assemblage. Brown glasses are ferrobasaltic in composition and are similar to the voluminous Pliocene tholeiites of the surrounding west-central Afar volcanic field; both are enriched in the light rare earth and incompatible elements and possess higher ⁸⁷Sr/⁸⁶Sr and lower ¹⁴³Nd/¹⁴⁴Nd than MORB. Rhyolitic glasses are subalkaline and, compared to the basaltic glasses, are strongly depleted in the compatible elements and enriched in the incompatible elements. Both glass types have similar incompatible element and isotopic ratios, and with the rhyolite glass showing a 2-fold parallel enrichment in rare earth element abundances over the basaltic glass. These observations suggest that the two glasses are genetically related.Rare glasses with intermediate compositions occur as phenocryst melt inclusions, as mantles on phenocrysts and as free pumice clasts. Their major element contents do not point to an origin by simple hybrid mixing of the basaltic and rhyolitic melts. Rather, major element mixing calculations indicate formation of the intermediate and rhyolite melts by fractionation of the observed phenocryst assemblage, using a starting composition of the observed basaltic glass. Model calculations from trace element data, though lacking from the intermediate glasses, support fractional crystallization. The bimodal mineral assemblage argues against an immiscible liquid origin for the contrasting glass compositions.