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.     

Geochemical characterization of marker tephra layers from major Holocene eruptions,Kamchatka Peninsula,Russia

Kamchatka Peninsula is one of the most active volcanic regions in the world. Many Holocene explosive eruptions have resulted in widespread dispersal of tephra-fall deposits. The largest layers have been mapped and dated by the ¹⁴C method. The tephra provide valuable stratigraphic markers that constrain the age of many geological events (e.g. volcanic eruptions, palaeotsunamis, faulting, and so on). This is the first systematic attempt to use electron microprobe (EMP) analyses of glass to characterize individual tephra deposits in Kamchatka. Eighty-nine glass samples erupted from 11 volcanoes, representing 27 well-identified Holocene key-marker tephra layers, were analysed. The glass is rhyolitic in 21 tephra, dacitic in two, and multimodal in three. Two tephra are mixed with glass compositions ranging from andesite/dacite to rhyolite. Tephra from the 11 eruptive centres are distinguished by their glass K₂O, CaO, and FeO contents. In some cases, individual tephra from volcanoes with multiple eruptions cannot be differentiated. Trace element compositions of 64 representative bulk tephra samples erupted from 10 volcanoes were analysed by instrumental neutron activation analysis (INAA) as a pilot study to further refine the geochemical characteristics; tephra from these volcanoes can be characterized using Cr and Th contents and La/Yb ratios.

Unidentified tephra collected at the islands of Karaginsky (3), Bering (11), and Attu (5) as well as Uka Bay (1) were correlated to known eruptions. Glass compositions and trace element data from bulk tephra samples show that the Karaginsky Island and Uka Bay tephra were all erupted from the Shiveluch volcano. The 11 Bering Island tephra are correlated to Kamchatka eruptions. Five tephra from Attu Island in the Aleutians are tentatively correlated with eruptions from the Avachinsky and Shiveluch volcanoes.     

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.     

Biotite composition as a tool for the identification of Quaternary tephra beds

Stratigraphically important Quaternary rhyolitic tephra deposits that erupted from the Okataina and Taupo volcanic centers in New Zealand can be geochemically identified using the FeO and MgO contents of their biotite phenocrysts. The FeO/MgO ratio in biotite does not correlate with FeO/MgO in the coexisting glass phase so that tephra beds with similar glass compositions can be discriminated by their different biotite compositions. Some individual tephra deposits display sequential changes in biotite composition that allow separate phases of the eruption to be identified, greatly increasing the potential precision for correlation. In addition, devitrified lavas that are unsuitable for glass analysis can be correlated to coeval tephra deposits by their biotite compositions. Biotite is common in high-K₂O (>4 wt%) tephra beds and is widely dispersed in ash plumes because of its platy form, thus making it important in correlation studies.     

Glass geochemical compositions from widespread tephras erupted over the last 200 years from Mount St. Helens

Building reliable chronologies from lake sediments, peat and other paleoenvironmental archives can be challenging, especially for historical times where radiocarbon is unreliable. Nineteenth- and 20th-century eruptions from Mount St. Helens (MSH) provide important chronostratigraphic markers for regional paleoenvironmental studies within this time frame, but are constrained by poorly geochemically characterized tephra and/or limited published data. Here, we present glass geochemistry from the most significant eruptions from this time. This includes proximal, medial and distal deposits of the 18 May 1980 MSH eruption, layer T ( ad 1799/1800), a new tephra that we argue represents the ad 1842 eruption, and the 22 July 1980 eruption that had reported ashfall in Canada. Our results indicate that most tephras ejected during these eruptions, within a time frame of ~200 years, have distinct glass geochemical characteristics that can be used to identify distal deposits for tephrochronological studies. Layer T is on trend with analyses of the 1980 eruption but has a distinct dacitic glass population. The 1980 and ad 1842 eruptions are similar, both having rhyolitic glass compositions, but the ad 1842 event can be differentiated by a more constrained SiO₂ range in the main geochemical population, and the presence of a unique SiO₂ sub-population.     

Using cryptotephras to extend regional tephrochronologies: An example from southeast Alaska and implications for hazard assessment

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.     

Machine learning classifiers for attributing tephra to source volcanoes: an evaluation of methods for Alaska tephras

Glass composition-based correlations of volcanic ash (tephra) traditionally rely on extensive manual plotting. Many previous statistical methods for testing correlations are limited by using geochemical means, masking diagnostic variability. We suggest that machine learning classifiers can expedite correlation, quickly narrowing the list of likely candidates using well-trained models. Eruptives from Alaska's Aleutian Arc-Alaska Peninsula and Wrangell volcanic field were used as a test environment for 11 supervised classification algorithms, trained on nearly 2000 electron probe microanalysis measurements of glass major oxides, representing 10 volcanic sources. Artificial neural networks and random forests were consistently among the top-performing learners (accuracy and kappa > 0.96). Their combination as an average ensemble effectively improves their performance. Using this combined model on tephras from Eklutna Lake, south-central Alaska, showed that predictions match traditional methods and can speed correlation. Although classifiers are useful tools, they should aid expert analysis, not replace it. The Eklutna Lake tephras are mostly from Redoubt Volcano. Besides tephras from known Holocene-active sources, Holocene tephra geochemically consistent with Pleistocene Emmons Lake Volcanic Center (Dawson tephra), but from a yet unknown source, is evident. These tephras are mostly anchored by a highly resolved varved chronology and represent new important regional stratigraphic markers.     

A little goes a long way: discovery of a new mid-Holocene tephra in Sweden

This pilper reports the presence of a volcanic ash layer in western Sweden which is geochemically identiticd as the Kebister tephra. This tephrdpresenceof (dated c . 3600 ¹⁴C BP) was discovered at Kebister, Shetland and thc rcsults presented here indicate that the deposit may have a greater geographical distribution than previously thought. The geochemistry of the volcanic glass was analysed by using discrete grain electron probe microanalysis (EPMA). Thc SiO₂ content of the glass ranges from 66.19 to 71.96%, FeO content 2.73 to 6.07% and MgO content 0.15 to 0.57%_˜ The tephra can he distinguished from the more widespread Hekla 4 tephra ( c . 3800 ¹⁴C BP) on the basis of calcium and magnesium contents.     

Geochemistry of late quaternary sediments from Tecocomulco lake, central Mexico: Implication to chemical weathering and provenance

This paper presents the first detailed multi-element geochemical data from the late Quaternary sediments of the Tecocomulco lake basin (central Mexico) and rocks exposed in the basin catchments to understand the extents of chemical weathering and provenance of the siliciclastic fractions. Ternary diagrams of A-CN-K, A-C-N and A-CNK-FM and elemental ratios suggest that most of the lacustrine sediments were derived from mafic volcanic deposits comprising the Chichicuatla and the Apan-Peñon andesites and the Apan-Tezontepec basaltic-andesites. The felsic tephra layers have chemical compositions comparable to the Acoculco volcanic sequences. The calculated indices of chemical weathering such as chemical index of alteration (CIA), plagioclase index of alteration (PIA) and chemical index of weathering (CIW) indicate low to extreme chemical weathering for the lacustrine sediments and low chemical weathering for tephra layers. The varying degree of chemical weathering in lacustrine sediments is related to the fluctuating average annual precipitation during the late Quaternary. However, the low weathering of tephra layers are due to their higher rate of deposition. The dacite-rhyolitic tephra layers of ca. 31,000 ¹⁴C yr BP are relatively more weathered compared to the unweathered rhyolitic tephra of ca. 50,000 ¹⁴C yr BP. This could be due to the rapid deposition of ca. 200 cm of tephra layers during the ca. 50,000 ¹⁴C yr BP volcanic eruption that might have prevented the interaction between tephra layers and weathering agents.     

Automated statistical matching of multiple tephra records exemplified using five long maar sequences younger than 75 ka,Auckland, New Zealand

Detailed tephrochronologies are built to underpin probabilistic volcanic hazard forecasting, and to understand the dynamics and history of diverse geomorphic, climatic, soil-forming and environmental processes. Complicating factors include highly variable tephra distribution over time; difficulty in correlating tephras from site to site based on physical and chemical properties; and uncertain age determinations. Multiple sites permit construction of more accurate composite tephra records, but correctly merging individual site records by recognizing common events and site-specific gaps is complex. We present an automated procedure for matching tephra sequences between multiple deposition sites using stochastic local optimization techniques. If individual tephra age determinations are not significantly different between sites, they are matched and a more precise age is assigned. Known stratigraphy and mineralogical or geochemical compositions are used to constrain tephra matches. We apply this method to match tephra records from five long sediment cores (≤ 75 cal ka BP) in Auckland, New Zealand. Sediments at these sites preserve basaltic tephras from local eruptions of the Auckland Volcanic Field as well as distal rhyolitic and andesitic tephras from Okataina, Taupo, Egmont, Tongariro, and Tuhua (Mayor Island) volcanic centers. The new correlated record compiled is statistically more likely than previously published arrangements from this area.     

Towards a comprehensive distal andesitic tephrostratigraphic framework for New Zealand based on eruptions from Egmont volcano

The chronology and glass composition of 43 andesitic tephra layers in palaeolake sediments in northern New Zealand provide the basis for a fine‐resolution tephrostratigraphy of the interval 10–70 cal. ka. Their ages are constrained by 14 interbedded, (mostly) well‐dated rhyolitic tephra layers. The andesitic tephra have the potential to subdivide time intervals (1–5 kyr) bracketed by well known rhyolitic layers, including periods of rapid climate change such as the last glacial–interglacial transition and the Younger Dryas. The source of the distal andesitic tephra is identified as Egmont volcano (some 270 km S‐SW) on the basis of glass shard composition. The tephra contain high‐K₂O (3–6 wt%) andesitic‐dacitic (SiO₂ = 60–73 wt%) glass, with commonly heterogeneous shard populations (2–10 wt% SiO₂). Within stratigraphic intervals of < 10 kyr, individual tephra layers can be distinguished on the basis of their SiO₂ and K₂O contents, and variability in these contents can also be a distinguishing characteristic. The tephra record greatly extends the dated pyroclastic and geochemical record of Egmont volcano, and demonstrates that the volcano has frequently produced widely dispersed tephra over the last 70 kyr at a generally constant rate. Copyright © 2005 John Wiley & Sons, Ltd.     

Plio-Pleistocene microtephra in DSDP site 231, Gulf of Aden

We reconstruct a Plio-Pleistocene microscopic tephrostratigraphy for DSDP Site 231 in the Gulf of Aden. Systematic microtephrostratigraphy increases the potential for identifying tephra horizons for regional stratigraphic correlation and age control, as well as providing information about eruptive histories. Microtephra reveal three main pulses of volcanism c. 4.0–3.2 Ma, 2.4 Ma and 1.7–1.3 Ma, corresponding to peaks in volcanic activity recorded in the East African Rift System. Previous studies of DSDP Site 231 have reported six visible tephra horizons (up to 25 cm thick) with geochemical compositions matching East African tuffs. We find 68 additional microtephra horizons through microscopic examination of 1050 samples (each integrating c. 3 ka) in over 200 m of marine sediments. We report the major and minor element geochemical compositions of individual glass shards in six of these microtephra horizons and establish a robust correlation at 168.73 m to the Lokochot Tuff (3.58 Ma), which together with previously identified tephra, provides a tightly constrained chronostratigraphy for the mid Pliocene.     

Marine tephrochronology of the Mt. Edgecumbe Volcanic Field, Southeast Alaska, USA

The Mt. Edgecumbe Volcanic Field (MEVF), located on Kruzof Island near Sitka Sound in southeast Alaska, experienced a large multiple-stage eruption during the last glacial maximum (LGM)-Holocene transition that generated a regionally extensive series of compositionally similar rhyolite tephra horizons and a single well-dated dacite (MEd) tephra. Marine sediment cores collected from adjacent basins to the MEVF contain both tephra-fall and pyroclastic flow deposits that consist primarily of rhyolitic tephra and a minor dacitic tephra unit. The recovered dacite tephra correlates with the MEd tephra, whereas many of the rhyolitic tephras correlate with published MEVF rhyolites. Correlations were based on age constraints and major oxide compositions of glass shards. In addition to LGM-Holocene macroscopic tephra units, four marine cryptotephras were also identified. Three of these units appear to be derived from mid-Holocene MEVF activity, while the youngest cryptotephra corresponds well with the White River Ash eruption at ∼ 1147 cal yr BP. Furthermore, the sedimentology of the Sitka Sound marine core EW0408-40JC and high-resolution SWATH bathymetry both suggest that extensive pyroclastic flow deposits associated with the activity that generated the MEd tephra underlie Sitka Sound, and that any future MEVF activity may pose significant risk to local population centers.     

The Piànico tephra: an early Middle Pleistocene record of intraplate volcanism in the Mediterranean

ABSTRACT Distal tephra are a valuable record of the volcano-tectonic evolution of an area under study. Here, we document the case of the Early Middle Pleistocene rhyolitic tephra of Piànico, discovered in the Southern Italian Alps. The geochemical characteristics of Piànico are unique among the distal tephra outcropping in Italy and indicate an intraplate volcanism at the source. The alkali composition and trace elements show a striking resemblance with the rhyolitic complex of the Euganean Hills, located 170 km from Piànico. However, these rhyolites are much older (Oligocene). Alternatively, the source of this intraplate volcanic episode could be located in the southern Tyrrhenian Sea.     

Itrax μ-XRF core scanning for rapid tephrostratigraphic analysis: a case study from the Auckland Volcanic Field maar lakes

Itrax micro X-ray fluorescence (μ-XRF) core scanning is a non-destructive, rapid approach to measuring elemental concentrations and their variability in sediment cores. As such, it records elemental signatures of tephra layers, which serve as correlation tie points and chronological markers for these sedimentary archives of past climatic changes. The traditional tephra identification approach using electron microprobe-based geochemical fingerprinting of glass shards is a slow and invasive process, whilst μ-XRF scanning of rhyolite tephra in sediment cores from Auckland (New Zealand) could provide a faster, non-invasive approach to aid the recognition of tephra layers. This study highlights the potential and pitfalls in this novel approach: changes in most scanning parameters, and the use of two different Itrax core scanners, still led to similar chemical characterizations of the tephra layers. Changes in other scanning parameters have a biasing influence on the chemical characterization of the tephra, which would lead to misidentification of unknown layers. We demonstrate that μ-XRF core scanning provides a faster and non-invasive approach to correlation of sediment sequences using chemically distinct, visually pure tephra layers if a strict scanning protocol is followed. Nevertheless, an extensive database of μ-XRF-scanned rhyolite tephra is required for recognition of unknown tephra units using this approach.     

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.     

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.     

Cryptotephra detection using high-resolution trace-element analysis of Holocene marine sediments, southwest Japan

Detection techniques for invisible tephra, known as cryptotephra, have been exploited to construct precise and high-resolution correlations for a broad range of sedimentary sequences. We demonstrate that continuous trace-element profiles are an effective means for detecting probable positions of distal cryptotephra in Holocene hemipelagic sediments. Instrumental neutron activation analyses were performed on specimens of bulk sediments from five piston and gravity cores (water depths: 300-1500 m) taken from the southern Japan/East Sea. The down-core variations in the Ta/Sc ratio identify the positions of one to three alkaline cryptotephra in four of these cores. The Cr/Sc profiles show the position of one rhyolitic cryptotephra in three of the cores. The existence of tephra-derived components (glass ± crystals) was confirmed by microscopic observation, SEM-EPMA analysis and refractive index measurement on grains extracted from these layers. Based on microscopic observation and the stratigraphic correlations between cores, we identified eruption ages of the cryptotephras at 6.3, 7.5 and 9.3 ¹⁴C kyr BP, and two source volcanoes around 800 and 400 km from the study area.The tephra layers visible to the naked eye contained volcanic grains coarser than 200 μm, and the alkaline and rhyolitic tephra component comprised >20% and >33% of the sediment on weight basis, respectively. In contrast, the range of particle sizes of the cryptotephras detected in this study is finer than 125 μm, and almost all of the glass shards were finer than 40 μm. The alkaline and rhyolitic cryptotephras made up only 2-17% and 22-24%, respectively, of the sediment on weigh basis. The high sensitivity of this method stems from the significant difference in trace-element contents between the tephras and enclosing hemipelagic sediments in the core. Alkaline U-Oki tephra was enriched in Ta by one order of magnitude over that of the sediment, and depleted in Sc by one order. The rhyolitic tephra, K-Ah, was depleted by about one order in Cr relative to that of enclosing the sediment. The differences in chemical composition between within-plate alkaline tephras and hemipelagic sediments are usually so large that trace-element geochemical method is likely to be useful for alkaline cryptotephra detection in other areas with similar tectonic characteristics.     

A catalogue of major and trace element data for Icelandic Holocene silicic tephra layers

Tephra layers with Icelandic provenance have been identified across the North Atlantic region in terrestrial, lacustrine, marine and glacial environments. These tephra layers are used as marker horizons in tephrochronology including climate studies, archaeology and environmental change. The major element chemistries of 19 proximally deposited Holocene Icelandic silicic tephra layers confirm that individual volcanic systems have unique geochemical signatures and that eruptions from the same system can often be distinguished. In addition, glass trace element chemistry highlights subtle geochemical variations between tephra layers which appear to have identical major element chemistry and thus allows for the identification of some, if not all, tephra layers previously considered identical in composition. This paper catalogues the compositional variation between the widespread Holocene Icelandic silicic tephra deposits.