Fingerprinting the Late Pleistocene tephras of Ciomadul volcano,eastern–central Europe

Late Pleistocene tephras derived by large explosive volcanic eruptions are widespread in the Mediterranean and surrounding areas. They are important isochronous markers in stratigraphic sections and therefore it is important to constrain their sources. We report here tephrochronology results using multiple criteria to characterize the volcanic products of the Late Pleistocene Ciomadul volcano in eastern–central Europe. This dacitic volcano had an explosive eruption stage between 57 and 30 ka. The specific petrological character (ash texture, occurrence of plagioclase and amphibole phenocrysts and their compositions), the high-K calc-alkaline major element composition and particularly the distinct trace element characteristics provide a strong fingerprint of the Ciomadul volcano. This can be used for correlating tephra and cryptotephra occurrences within this timeframe. Remarkably, during this period several volcanic eruptions produced tephras with similar glass major element composition. However, they differ from Ciomadul tephras by glass trace element abundances, ratios of strongly incompatible trace elements and their mineral cargo that serve as discrimination tools. We used (U-Th)/He zircon dates combined with U-Th in situ rim dates along with luminescence and radiocarbon dating to constrain the age of the explosive eruptions of Ciomadul that yielded distal tephra layers but lack of identified proximal deposits.     

Major and trace element abundances in volcanic glass shards in visible tephras in SG93 and SG06 drillcore samples from Lake Suigetsu,central Japan,obtained using femtosecond LA–ICP–MS

The major and trace element concentrations of volcanic glass shards from visible tephra layers in the SG93 and SG06 cores from Lake Suigetsu, central Japan, were determined by femtosecond laser ablation–inductively coupled plasma–mass spectrometry. The glass-shard analyses, together with the petrographic properties of the tephra samples, allow the Suigetsu tephra layers to be broadly classified into tephras derived from calderas on Kyushu Island, and from Daisen and Sambe volcanoes in the Chugoku district of southwest Japan. The layers correlated with tephras from Kuju caldera and Daisen volcano, and with the younger Sambe tephras, have adakitic elemental features. A Suigetsu tephra sample correlated with the Sambe−Kisuki tephra based on petrographic properties has an elemental pattern similar to that of the Toya tephra from Hokkaido Island, northeast Japan. This match implies that tephras from northeast Japan, as well as Kyushu–Chugoku tephras, are possible correlatives of the Suigetsu tephra layers. Both petrographic properties and major–trace element data of volcanic glass shards are essential for robust tephra correlations, and hierarchical cluster analysis proved additionally useful in statistically evaluating relationships among the tephras.     

Tephrochronological dating of varved interglacial lake deposits from Piànico‐Sèllere (Southern Alps,Italy) to around 400 ka

The sediment record from the Piànico palaeolake in the southern Alps is continuously varved, spans more than 15 500 years, and represents a key archive for interglacial climate variability at seasonal resolution. The stratigraphic position of the Piànico Interglacial has been controversial in the past. The identification of two volcanic ash layers and their microscopic analysis provides distinct marker layers for tephrochronological dating of these interglacial deposits. In addition to micro‐facies analyses reconstructing depositional processes of both tephra layers within the lake environment, their mineralogical and geochemical composition has been determined through major‐element electron probe micro‐analysis on glass shards. Comparison with published tephra data traced the volcanic source regions of the Piànico tephras to the Campanian volcanic complex of Roccamonfina (Italy) and probably the Puy de Sancy volcano in the French Massif Central. Available dating of near‐vent deposits from the Roccamonfina volcano provides a robust tephrochronological anchor point at around 400 ka for the Piànico Interglacial. These deposits correlate with marine oxygen isotope stage (MIS) 11 and thus are younger than Early to Middle Pleistocene previously suggested by K/Ar dating and older than the last interglacial as inferred from macrofloral remains and the geological setting. Copyright © 2006 John Wiley & Sons, Ltd.     

New major element analyses of proximal tephras from the Azores and suggested correlations with cryptotephras in North-West Europe

The Azores Archipelago is one of the most active volcanic areas in the North Atlantic region. Approximately 30 eruptions have been reported over the last 600 years with some major VEI 5 (Volcanic Explosivity Index) eruptions further back in time. The geochemical composition of associated tephra-derived glass, however, is not well characterized. An Azorean origin of cryptotephras found in distal areas such as North Africa, the British Isles and Greenland has been suggested, but proximal data from the Azores are scarce and the correlations have only been tentative. These tephras have a traychtic composition, which excludes an Icelandic origin. In a previous study, we presented major element analyses of proximal tephra-derived glass from five Holocene eruptions on the Azores Islands. There is a striking geochemical similarity between tephras from volcanoes on São Miguel and Irish cryptotephras, and especially with eruptives from the Furnas volcano. Here we present new analyses of proximal tephras that confirm and strengthen a link between Furnas and cryptotephras found in south-west Ireland. We also suggest a correlation between a previously unsourced tephra found in a Swedish bog with an eruption of the Sete Cidades volcano c. 3880 a cal BP.     

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.     

Mineral composition of tephra layers in the Quaternary deposits of the Sea of Okhotsk:: Heavy minerals associations and their geochemistry

Heavy mineral associations from tephra layers in the Quaternary deposits of the Sea of Okhotsk and their chemical characteristics were studied by various techniques. It was shown that such investigations may have a bearing on the problems of tephrostratigraphic correlation. We assessed the possibility of application of the mineral composition of distal tephra for identification and, in particular, estimation of the relation of tephras to the explosive volcanism of back-arc and frontal zones of island arcs. The investigation of the compositions of minerals and use of mineral geothermometers and geobarometers (two-pyroxene, magnetite–ilmenite, and amphibole) provided evidence on the physicochemical parameters of melt crystallization during the explosive volcanic eruptions that produced the distal tephra layers. It was established that the pyroclastic material of some tephra layers was supplied during explosive eruptions not only from shallow magma chambers but also from deeper and higher temperature reservoirs. Together with the geochemical signatures of volcanic glasses, the obtained results on mineral associations and the geochemistry of mineral inclusions are applicable for the comparative analysis and correlation of tephras from marine and continental sequences, as well as for the identification of explosive volcanic products in adjacent land areas.     

First evidence of a distal early Holocene ash layer in Eastern Mediterranean deep-sea sediments derived from the Anatolian volcanic province

A hitherto unknown distal volcanic ash layer has been detected in a sediment core recovered from the southeastern Levantine Sea (Eastern Mediterranean Sea). Radiometric, stratigraphic and sedimentological data show that the tephra, here termed as S1 tephra, was deposited between 8970 and 8690 cal yr BP. The high-silica rhyolitic composition excludes an origin from any known eruptions of the Italian, Aegean or Arabian volcanic provinces but suggests a prevailing Central Anatolian provenance. We compare the S1 tephra with proximal to medial-distal tephra deposits from well-known Mediterranean ash layers and ash fall deposits from the Central Anatolian volcanic field using electron probe microanalyses on volcanic glass shards and morphological analyses on ash particles. We postulate a correlation with the Early Holocene ‘Dikkart?n’ dome eruption of Erciyes Da? volcano (Cappadocia, Turkey). So far, no tephra of the Central Anatolian volcanic province has been detected in marine sediment archives in the Eastern Mediterranean region. The occurrence of the S1 tephra in the south-eastern part of the Levantine Sea indicates a wide dispersal of pyroclastic material from Erciyes Da? more than 600 km to the south and is therefore an important tephrostratigraphical marker in sediments of the easternmost Mediterranean Sea and the adjacent hinterland.     

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.     

Middle to late Pleistocene record of explosive volcanic eruptions in marine sediments offshore Kamchatka (Meiji Rise,NW Pacific)

This paper presents the first detailed study of a late Pleistocene marine tephra sequence from the NW Pacific, downwind from the Kamchatka volcanic arc. Sediment core SO201-2-40, located on the Meiji Rise ~400 km offshore the peninsula, includes 25 tephras deposited within the last 215 ka. Volcanic glass from the tephras was characterized using single-shard electron microprobe analysis and laser ablation inductively coupled mass spectrometry. The age of tephras was derived from a new age model based on paleomagnetic and paleoclimate studies. Geochemical correlation of distal tephras to Kamchatkan pyroclastic deposits allowed the identification of tephras from the Karymsky, Gorely, Opala and Shiveluch eruptive centers. Three of these tephras were also correlated to other marine and terrestrial sites and hence are identified as the best markers for the north-west Pacific region. These are an early Holocene tephra from the Karymsky caldera (~8.7 ka) and two tephras falling into the Marine Isotope Stage (MIS) 6 glacial time: an MIS 6.4 tephra from Shiveluch (~141 ka) and the MIS 6.5 Rauchua tephra (~175 ka) from Karymsky. The data presented in this study can be used in paleovolcanological and paleoceanographic reconstructions.     

Characteristics of tephra in Holocene lake sediments on King George Island, West Antarctica: implications for deglaciation and paleoenvironment

Several reworked tephra layers in gravity-flow deposits are present in lacustrine core sediments collected from Hotel and Rudy Lakes on King George Island, South Shetland Islands, maritime sub-Antarctica. This study tests the values of tephra for establishing regional tephrochronologies for lakes in ice-covered landscapes in the vicinity of volcanoes. The tephra record is more abundant in a long Hotel Lake core (515 cm long). This study uses volcanic glass samples from five tephra layers of Hotel Lake and from one tephra layer of Rudy Lake. Morphologically, tephras are mixtures of basaltic and pumice shards, both having various degrees of vesicularity. Major element analyses of glass shards reveal that the majority of the glass fragments belong to basic glass (<60 wt% SiO₂), compositionally ranging from basalt to low-silica andesite and subalkaline series medium-K tholeiites, probably sourced from Deception Island located 130 km southwest of King George Island. Less than 20% of tephra belongs to silicic glass and occurs in three tephra horizons E of Hotel Lake. However, source volcano(es) for about 10% of basic tephra and silicic tephra are not readily identified from nearby volcanic centers. Except for the studied tephra in Rudy Lake, all tephra samples in Hotel Lake are not ashfall deposits but reworked and redeposited pyroclasts derived from retreating ice sheet, resulting in the occurrence of geochemically equivalent tephra samples in different tephra horizons. The dating of the studied tephra horizons represents the timing of deglaciation rather than that of volcanic eruptions. The result of this study implies that combined with sedimentological information more chemical criterion is necessary to study tephrochronology and regional correlation and to understand paleoenvironmental changes using tephra.     

Identification of Lower Pleistocene widespread tephras associated with large caldera-forming eruptions in the Tohoku area,north-east Japan

Tephra fingerprinting techniques contributing to volcanology and palaeoenvironmental studies have been developed using a combination of laser-ablation inductively coupled-plasma mass spectrometry (LA-ICP-MS) and scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS). In particular, femtosecond LA-ICP-MS can determine major- and trace element abundances in individual glass shards. On the basis of the major oxide and trace element composition of the glass shards, using those methods, we re-examined the identification of four lower Pleistocene tephras originating from north-east Japan. All trace element abundances exhibited the typical pattern of tephras from the Hokkaido–Tohoku area, and major element concentrations were distinct. As a result, we re-examined the correlation of the widespread Tmg-R4 tephra (2.0 Ma), and newly defined the widespread Kd44-Naka tephra (1.968–1.781 Ma), both originating from the Sengan geothermal region. Furthermore, we re-examined identifications of Sr-Asn-Kd8 (1.219 Ma) and Sr-Kc-U8 (0.922–0.910 Ma) in central Japan, both derived from the Aizu volcanic region. The extensive distributions of the former two tephras suggest the occurrence of two large caldera-forming eruptions (Volcanic Explosivity Index 7) during a short period. Also, the distributions and volumes of the latter two tephras are broader and larger than those previously assumed. The results provide insight into large volcanic eruption history and terrestrial and marine palaeoenvironmental history.     

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.     

Traces of volcanic ash from the Mediterranean,Iceland and North America in a Holocene record from south Wales,UK

A tephra record is presented for a sediment core from Llyn Llech Owain, south Wales, spanning the early- to mid-Holocene. Seven cryptotephra deposits are discovered with three thought to correlate with known eruptions and the remaining four considered to represent previously undocumented events. One deposit is suggested to correlate with the ~6.9 cal ka bp Lairg A tephra from Iceland, whereas more distant sources are proposed as the origin for two of the tephra deposits. A peak of colourless shards in early-Holocene sediments is thought to tentatively correlate with the ~9.6 cal ka bp Fondi di Baia tephra (Campi Flegrei) and a second cryptotephra is tentatively correlated with the ~3.6 cal ka bp Aniakchak (CFE) II tephra (Alaska). The Fondi di Baia tephra has never been recorded beyond proximal sites and its discovery in south Wales significantly extends the geographical distribution of ash from this eruption. The remaining four cryptotephra deposits are yet to be correlated with known eruptions, demonstrating that our current understanding of widespread tephra deposits is incomplete. This new tephra record highlights the potential for sites at more southerly and westerly locations in northwest Europe to act as repositories for ash from several volcanic regions.     

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.     

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.     

Tephrostratigraphy and glass compositions of post-15 kyr Campi Flegrei eruptions: implications for eruption history and chronostratigraphic markers

Volcanic ash (tephra) erupted from the frequently active Campi Flegrei volcano forms layers in many palaeoenvironmental archives across Italy and the Mediterranean. Proximal deposits of 50 of the post-15 ka eruptions have been thoroughly sampled and analysed to produce a complete database of glass compositions (>1900 analyses) to aid identification of these units. The deposits of individual eruptions are compositionally diverse and this variability is often greater than that observed between different units. Many of the tephra units do not have a unique glass chemistry, with compositionally similar tephra often erupted over long periods of time (1000s years). Thus, glass chemistry alone is not enough to robustly correlate most of the tephra from Campi Flegrei, especially in the last 10 kyrs. In order to reliably correlate the eruption units it is important to take into account the stratigraphy, chronology, magnitude, and dispersal of the eruptions, which has been collated to aid identification. An updated chronology is also presented, which was constrained using Bayesian analysis (OxCal) of published radiocarbon dates and ⁴⁰Ar/³⁹Ar ages. All the data presented can be employed to help correlate post-15 ka tephra units preserved in archaeological and Holocene palaeoenvironmental archives. The new database of proximal glass compositions has been used to correlate proximal volcanic deposits through to distal tephra layers in the Lago di Monticchio record (Wulf et al., 2004, Wulf et al., 2008) and these correlations provide information on eruption stratigraphy and the tempo of volcanism at Campi Flegrei.     

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.     

Tephrochronology of the Siple Dome ice core,West Antarctica: correlations and sources

A total of 24 tephra-bearing volcanic layers have been recognized between 550 and 987 m depth in the Siple Dome A (SDM-A) ice core, in addition to a number already recognized tephra in the upper 550 m (Dunbar et al., 2003, Kurbatov et al., 2006). The uniform composition and distinctive morphological of the particles composing these tephra layers suggest deposition as a result of explosive volcanic eruptions and that the layers therefore represent time-stratigraphic markers in the ice core. Despite the very fine grain size of these tephra (mostly less than 20 microns), robust geochemical compositions were determined by electron microprobe analysis. The source volcanoes for these tephra layers are largely found within the Antarctic plate. Statistical geochemical correlations tie nine of the tephra layers to known eruptions from Mt. Berlin, a West Antarctic volcano that has been very active for the past 100,000 years. Previous correlations were made to an eruption of Mt. Takahe, another West Antarctic volcano, and one to Mt. Hudson, located in South America (Kurbatov et al., 2006). The lowest tephra layer in the ice core, located at 986.21 m depth, is correlated to a source eruption with an age of 118.1 ± 1.3 ka, suggesting a chronological pinning point for the lower ice. An episode of anomalously high volcanic activity in the ice in the SDM-A core between 18 and 35 ka (Gow and Meese, 2007) appears to be related to eruptive activity of Mt. Berlin volcano. At least some of the tephra layers found in the SDM-A core appear to be the result of very explosive eruptions that spread ash across large parts of West Antarctica, off the West Antarctic coast, as well as also being recognized in East Antarctica (Basile et al., 2001, Narcisi et al., 2005, Narcisi et al., 2006). Some of these layers would be expected to should be found in other deep Antarctic ice cores, particularly ones drilled in West Antarctica, providing correlative markers between different cores. The analysis of the tephra layers in the Siple Dome core, along with other Antarctic cores, provides a timing framework for the relatively proximal Antarctic and South American volcanic eruptive events, allowing these to be distinguished from the tropical eruptions that may play a greater role in climate forcing.     

The application of ICP-MS methods to tephrochronological problems

The accurate recognition of tephra deposits is of great value to Earth scientists because they facilitate stratigraphic correlation. The most useful tephra deposits form from violent volcanic eruptions; they are isochronous and widespread. Most are dacitic and rhyolitic in composition, and can be difficult to identify unequivocally using major element chemistry alone. Distal tephras are typically thin and are prone to contamination and thus are awkward to analyse by bulk methods. Here, the authors review their previous work in the development of analytical techniques for the analysis of small volumes of glass separates from tephra deposits, both by solution nebulisation and by laser ablation (LA) inductively coupled plasma mass spectrometry (ICP-MS), placing particular emphasis on the precision and accuracy of the various methods. In solution nebulisation ICP-MS, accurate data can be obtained from samples as small as 0.025 g. LA-ICP-MS methods are described for the analysis of small bulk samples and single glass shards as small as 40 μm in diameter. Accurate and reproducible analyses can be achieved by ICP-MS by both solution and laser ablation methods on homogeneous materials. Solution analyses are normally accurate to ±5% and have typical precisions (1 σ) of around ±4% for abundant trace elements (e.g. Zr, Rb) but this can deteriorate to about ±20% for rare elements in small samples (e.g. HREE in a 25 mg sample). Laser ablation methods are slightly less accurate (typically ±5–10%) and precision decreases from about ±3% at concentrations of a few hundred ppm, to about ±10% at 1 ppm and about ±30% at 0.05 ppm. An apparent lack of precision in the bulk analysis of small volumes of glass shards by LA-ICP-MS often represents within sample heterogeneity (and not analytical error), inter-shard variation becoming abundantly clear in some tephra deposits when individual glass shards are analysed. Single grain analysis on shards as small as 40 μm can provide an accurate analysis of the pure glass phase, which may not be achieved in solution or bulk sample LA-ICP-MS methods. Analyses affected by micro-phenocryst phases, such as feldspar or zircon can be easily removed following careful inspection of the data. Single shard LA-ICP-MS also allows any compositional variation within the parental magma to be defined.     

Geochemical stability of fine-grained silicic Holocene tephra in Iceland and Scotland

This paper tests two assumptions fundamental to the use of fine-grained silicic tephras from Iceland for creating chronological frameworks in northwest Europe. It is shown firstly, that glass shards can retain their overall chemical integrity on at least a four millennial time-scale in contrasting depositional environments in Iceland and Scotland, and secondly, that an acid digestion process, the most practical method for extracting tephra from peat, does not significantly bias the results of major element analysis by electron microprobe. The implication is that there is great potential and an appropriate method for developing both the resolution and the spatial coverage of chronologies based on silicic Icelandic tephras in northwest Europe.