Raman spectroscopy for the discrimination of tephras from the Hekla eruptions of AD 1510 and 1947
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Tephrochronology (the dating of sedimentary sequences using volcanic ash layers) is an important tool for the dating and correlation of sedimentary sequences containing archives and proxies of past environmental change. In addition, tephra layers provide valuable information on the frequency and nature of ash fallout from volcanic activity. Successful tephrochronology is usually reliant on the correct geochemical identification of the tephra which has, until now, been based primarily on the analysis of major element oxide composition of glass shards using electron probe microanalysis (EPMA). However, it is often impossible to differentiate key tephra layers using EPMA alone. For example, the Hekla AD 1947 and 1510 tephras (which are found as visible layers in Iceland and also as ‘crypto-tephra’ microscopic layers in NW Europe) are currently indistinguishable using EPMA. Therefore, other stratigraphic or chronological information is needed for their reliable identification. Raman spectroscopy is commonly used in chemistry, since vibrational information is specific to the chemical bonds and symmetry of molecules, and can provide a fingerprint by which these can be identified. Here, we demonstrate how Raman spectroscopy can be used for the successful discrimination of mineral species in tephra through the analysis of individual glass shards. In this study, we obtained spectra from minerals within the glass shards – we analysed the microlites and intratelluric mineral phases that can definitely be attributed to the tephra shards and the glass itself. Phenocrysts were not analysed as they could be sourced locally from near-site erosion. Raman spectroscopy can therefore be considered a valuable tool for both proximal and distal tephrochronology because of its non-destructive nature and can be used to discriminate Hekla 1510 from Hekla 1947.Keywords:
Tephrochronology
Phenocryst
Volcanic glass
Volcanology
Explosive volcanic eruptions generate plumes of hot gas and quenched molten rock that has been fragmented by the expansion of gas as the magma exits the vent. These fragments are called pyroclasts . The tephra layers are comprised of volcanic glass, crystals, and lithic material. Given that tephra is dispersed over wide areas and forms a geologically instantaneous layer, these tephra layers can be particularly useful for chronology – providing a relative chronology between sites and age if the eruption has been dated using radiometric methods. Correlating volcanic ash layers between sites and to specific eruption deposits preserved at their source volcanoes can be achieved using the composition of the volcanic glass shards. The major and trace element glass compositions remain the same for a specific eruption deposit irrespective of the distance from the vent, and they constitute the chemical fingerprint of the tephra. Volcanic deposits can be dated using many commonly employed radiometric dating methods.
Tephrochronology
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Peléan eruption
Volcanic glass
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This review is intended to highlight recent exciting advances in the study of distal (>100 km from the source) tephra and cryptotephra deposits and their potential application for volcanology. Geochemical correlations of tephra between proximal and distal locations have extended the geographical distribution of tephra over tens of millions square kilometers. Such correlations embark on the potential to reappraise volume and magnitude estimates of known eruptions. Cryptotephra investigations in marine, lake and ice-core records also give rise to continuous chronicles of large explosive eruptions many of which were hitherto unknown. Tephra preservation within distal ice sheets and varved lake sediments permit precise dating of parent eruptions and provide new insight into the frequency of eruptions. Recent advances in analytical methods permit an examination of magmatic processes and the evolution of the whole volcanic belts at distances of hundreds and thousands of kilometers from source. Distal tephrochronology has much to offer volcanology and has the potential to significantly contribute to our understanding of sizes, recurrence intervals and geochemical make-up of the large explosive eruptions.
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Tephras, mainly from Iceland, are becoming increasingly important in interpreting leads and lags in the Holocene climate system across NW Europe. Here we demonstrate that Quantitative Phase Analysis of x-ray diffractograms of the <2 mm of marine sediment fraction (ie, sand, silt and clay) from Iceland and East Greenland can detect peaks in volcanic glass concentrations (weight%) even though discrete tephra layers are not visible; thus it provides a rapid overview of the probable location of volcanic glass within sediment sequences. Experiments in spiking samples from Baffin Bay and an artificial mixture of minerals with known weight% fractions of an Icelandic tephra (Hekla 4) demonstrate a significant correlation (r 2 =0.92 and 0.97) between known and estimated weight percentages, although the slope of the measured to observed weight% is around 0.65 and not 1.0 as expected. In core B997-321PC off North Iceland we identify tephras from point counting in the > 150 μm fraction and identify these same peaks in XRD scans two of these correlate geochemically and chronologically with Hekla 1104 and 3. At a distal site to the WNW of Iceland, on the East Greenland margin (core MD99-2317), the weight% of volcanic glass reaches values of 11% at about the time of the Saksunarvatn tephra. The XRD method identifies the presence of volcanic glass but not its elemental composition; hence it will assist in focusing attention on specific sections of sediment cores for subsequent geochemical fingerprinting of tephras.
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This paper presents a detailed record of volcanism extending back to ∼80 kyr BP for southern South America using the sediments of Laguna Potrok Aike (ICDP expedition 5022; Potrok Aike Maar Lake Sediment Archive Drilling Project - PASADO). Our analysis of tephra includes the morphology of glass, the mineral componentry, the abundance of glass-shards, lithics and minerals, and the composition of glass-shards in relation to the stratigraphy. Firstly, a reference database of glass compositions of known eruptions in the region was created to enable robust tephra correlations. This includes data published elsewhere, in addition to new glass-shard analyses of proximal tephra deposits from Hudson (eruption units H1 and H2), Aguilera (A1), Reclus (R1, R2-3), Mt Burney (MB1, MB2, MBx, MB1910) and historical Lautaro/Viedma deposits. The analysis of the ninety-four tephra layers observed in the Laguna Potrok Aike sedimentary sequence reveals that twenty-five tephra deposits in the record are the result of primary fallout and are sourced from at least three different volcanoes in the Austral Andean Volcanic Zone (Mt Burney, Reclus, Lautaro/Viedma) and one in the southernmost Southern Volcanic Zone (Hudson). One new correlation to the widespread H1 eruption from Hudson volcano at 8.7 (8.6–9.0) cal ka BP during the Quaternary is identified. The identification of sixty-five discrete deposits that were predominantly volcanic ashes (glass and minerals) with subtle characteristics of reworking (in addition to three likely reworked tephra, and one unknown layer) indicates that care must be taken in the analysis of both visible and invisible tephra layers to decipher their emplacement mechanisms.
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Maar
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Tephrochronology (the dating of sedimentary sequences using volcanic ash layers) is an important tool for the dating and correlation of sedimentary sequences containing archives and proxies of past environmental change. In addition, tephra layers provide valuable information on the frequency and nature of ash fallout from volcanic activity. Successful tephrochronology is usually reliant on the correct geochemical identification of the tephra which has, until now, been based primarily on the analysis of major element oxide composition of glass shards using electron probe microanalysis (EPMA). However, it is often impossible to differentiate key tephra layers using EPMA alone. For example, the Hekla AD 1947 and 1510 tephras (which are found as visible layers in Iceland and also as ‘crypto-tephra’ microscopic layers in NW Europe) are currently indistinguishable using EPMA. Therefore, other stratigraphic or chronological information is needed for their reliable identification. Raman spectroscopy is commonly used in chemistry, since vibrational information is specific to the chemical bonds and symmetry of molecules, and can provide a fingerprint by which these can be identified. Here, we demonstrate how Raman spectroscopy can be used for the successful discrimination of mineral species in tephra through the analysis of individual glass shards. In this study, we obtained spectra from minerals within the glass shards – we analysed the microlites and intratelluric mineral phases that can definitely be attributed to the tephra shards and the glass itself. Phenocrysts were not analysed as they could be sourced locally from near-site erosion. Raman spectroscopy can therefore be considered a valuable tool for both proximal and distal tephrochronology because of its non-destructive nature and can be used to discriminate Hekla 1510 from Hekla 1947.
Tephrochronology
Phenocryst
Volcanic glass
Volcanology
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A continuous ∼5280 calendar (cal.) yr long cryptotephrostratigraphic record of a peat core from northern New Zealand demonstrates that cryptotephra studies can enhance conventional tephra records by extending the known distribution of ash fall and enabling re-assessment of volcanic hazards. A systematic sampling strategy was used to locate peaks in glass-shard concentrations and to determine loci of individual geochemical populations, and a palynological method involving spiking samples with Lycopodium spores was adapted to facilitate accurate counting of glass-shard concentrations. Using glass shard major element compositions, and a core chronology based on eight AMS 14 C ages and two visible macroscopic tephra layers, Taupo Tephra (Unit Y) (1688-1748 cal. BP) and Tuhua Tephra (6800-7230 cal. BP) (2cr-age ranges), four cryptotephras were correlated with known eruptions: Whakaipo (Unit V) (2743-2782 cal. BP), Stent (Unit Q) (4240-4510 cal. BP), and Unit K (4970-5290 cal. BP), erupted from Taupo Volcanic Centre, and Whakatane Tephra (5470-5600 cal. BP) erupted from Okataina Volcanic Centre. Mixed glass populations were found in the core, most likely an artefact of post-depositional remobilization of shards vertically (both up and down) in the peat or on its surface by wind, or a result of closely spaced eruption events, or a combination of these. A secondary glass population identified within the macroscopic Taupo Tephra was tentatively attributed to either an earlier phase within that eruption or to mixing with a slightly older Taupo-derived eruptive or (less likely) a currently unknown Okataina-derived eruptive. These results indicate that, in the absence of continuous cryptotephrostratigraphic analysis, a peak in shard concentrations may not in itself be indicative of the ‘true’ stratigraphic (ie, isochronous) level of a tephra layer. For cryptotephra studies of peat cores, we recommend (1) using a detailed sampling strategy for the analysis of distal tephra-derived glass to detect and account for any mixed populations and possible vertical spread of glass shards through the peat, and (2) analysing more shards from larger samples to help ‘capture’ sparsely represented cryptic andesitic tephra deposits.
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Lapilli
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Cryptotephrochronology, the use of hidden, diminutive volcanic ash layers to date sediments, has rarely been applied outside western Europe but has the potential to improve the tephrochronology of other regions of the world. Here we present the first comprehensive cryptotephra study in Alaska. Cores were extracted from five peatland sites, with cryptotephras located by ashing and microscopy and their glass geochemistry examined using electron probe microanalysis. Glass geochemical data from nine tephras were compared between sites and with data from previous Alaskan tephra studies. One tephra present in all the cores is believed to represent a previously unidentified eruption of Mt. Churchill and is named here as the ‘Lena tephra’. A mid-Holocene tephra in one site is very similar to Aniakchak tephra and most likely represents a previously unidentified Aniakchak eruption, ca. 5300–5030 cal yr BP. Other tephras are from the late Holocene White River eruption, a mid-Holocene Mt. Churchill eruption, and possibly eruptions of Redoubt and Augustine volcanoes. These results show the potential of cryptotephras to expand the geographic limits of tephrochronology and demonstrate that Mt. Churchill has been more active in the Holocene than previously appreciated. This finding may necessitate reassessment of volcanic hazards in the region.
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Tephras preserved in lake sediments are commonly used to synchronize sedimentary archives of climate and environmental change and to correlate them with terrestrial environments.They also provide opportunities to reconstruct volcanic explosive activity, e.g., eruption frequency and tephra dispersal.Although sedimentary processes may affect the record of tephras in lakes, lake sediments are generally considered as one of the best archives of tephra stratigraphy.The 2011-2012 eruption of Cordón Caulle volcano (Chile, 40°S) offered an ideal opportunity to study the processes affecting tephra deposition in lakes.Although the prevailing westerlies transported the erupted pyroclastic material away from nearby Puyehue Lake, the tephra was identified within this relatively large lake with a thickness ranging from 1 to >10 cm.This is in contrast with smaller lakes, where tephra thickness was in agreement with ashfall distribution maps.Geomorphological observations and sedimentological analyses provide evidence that the tephra deposited in Puyehue Lake entirely consists of material reworked from the upper watershed, transported by rivers, and distributed by lake currents according to particle size and density.Our results have important implications for tephrochronology and volcanology.They suggest that (1) lakes do not act as passive tephra traps; (2) lakes with large watersheds record more eruptions than smaller lakes, which only register direct ashfalls, affecting conclusions regarding the recurrence of volcanic eruptions; and (3) using lakes with large watersheds for isopach mapping systematically leads to an overestimation of erupted tephra volumes.Smaller lakes with limited drainage basins are generally better suited for volcanological studies.
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Large volcanic eruptions from Iceland can produce significant volumes of glass-rich rhyolitic tephra, which are then deposited across NW Europe and the North Atlantic-Arctic region, forming time-parallel marker horizons useful to palaeoenvironmental studies. Here we investigate new ways of improving the tephrochronological record of Iceland using (thermo)luminescence analysis of rhyolitic volcanic glass shards that dominate airfall ash deposits of the Þórsmörk Ignimbrite (ÞIG), tephra from the Askja 1875 AD, Öræfi 1362 AD eruptions, and the Óþoli tephra from NW Iceland. Following screening experiments, which showed that pure volcanic glass samples retained age-related TL signals, we undertook glass-phase TL dating of the ÞIG and Óþoli tephra. Our TL age estimate of c. 40 ± 10 ka for the ÞIG supports the phenocryst-based radiometric age of c. 50 ka rather than older age estimates of c. 200 ka. Results from the Óþoli tephra were consistent with the fission track age established at c. 2 Ma age, but further investigations of high dose sensitivity changes and longer-term stability factors such as athermal fading are required for quantitative dating of volcanic glass deposits >100 ka. However, as thermoluminescence signals from purified glass fractions of Icelandic tephra can be obtained over 100–1,000,000-year time scales, luminescence characterisation of glass shards can be used alongside geochemical and morphological analysis to distinguish between distal tephras with similar geochemical signatures, and assist with tephrochronological investigations beyond the limits of radiocarbon dating.
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Thermoluminescence dating
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