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.     

Determination of REE, Y, Nb, Zr, Hf, Ta, Th and U in Geological Reference Materials LSHC-1 and Amf-1 by Solution and Laser Ablation ICP-MS

This paper presents data on REE and Y, Nb, Zr, Hf, Ta, Th and U abundances for two candidate reference materials (RMs), spinel lherzolite LSHC-1 and amphibole Amf-1, being currently developed at the Institute of Geochemistry SB RAS, Irkutsk. To determine the contents of these elements inductively coupled plasma-mass spectrometry was applied with: (i) solution nebulisation (solution ICP-MS) and (ii) laser ablation (LA-ICP-MS) of fused glass disks. The precision of results obtained by both techniques was better than 6% RSD for most elements. Accuracy was assessed by using the geochemical RMs JB-2, JGb-1 (GSJ) and MAG-1 (USGS). The trace element results by solution ICP-MS for JGb-1 and JB-2 agree with reference values presented by Imai et al. (1995, this Journal) within 1–10%. Significant differences were found for Nb and Ta determinations. The accuracy of LA-ICP-MS results evaluated by RM MAG-1 was within 4%, except for Eu (about 10%). The analytical results obtained for LSHC-1 and Amf-1 by solution ICP-MS and LA-ICP-MS were in good agreement with each other and with INAA and XRF data presented for the certification of these RMs. They can be considered as the indicative values for assigning certified values to the above-mentioned RMs.     

Peralkaline magma evolution and the tephra record in the Ethiopian Rift

The 3.119 ± 0.010 Ma Chefe Donsa phreatomagmatic deposits on the shoulder of the Ethiopian Rift mark the northern termination of the Silti-Debre Zeyit Fault Zone, a linear zone of focused extension within the modern Ethiopian Rift. These peralkaline pumice fragments and glass shards span a wide range of glass compositions but have a restricted phenocryst assemblage dominated by unzoned sanidine. Glass shards found within the ash occupy a far more limited compositional range (75–76 wt% SiO₂) in comparison with the pumice (64–75 wt% SiO₂), which is rarely mingled. Thermodynamic modeling shows that liquids broadly similar to the least evolved glass composition can be achieved with 50–60 % fractionation of moderately crustally contaminated basalt. Inconsistencies between modeled solutions and the observed values of CaO and P₂O₅ highlight the important role of fluorine in stabilizing fluor-apatite and the limitations of current thermodynamic models largely resulting from the scarce experimental data available for the role of fluorine in igneous phase stability. On the basis of limited feldspar heterogeneity and crystal content of pumice at Chefe Donsa, and the difficulties of extracting small volumes of Si-rich melt in classical fractional crystallization models, we suggest a two-step polybaric process: (1) basaltic magma ponds at mid-upper-crustal depths and fractionates to form a crystal/magma mush. Once this mush has reached 50–60 % crystallinity, the interstitial liquid may be extracted from the rigid crystal framework. The trachytic magma extracted at this step is equivalent to the most primitive pumice analyzed at Chefe Donsa. (2) The extracted trachytic liquid will rise and continue to crystallize, generating a second mush zone from which rhyolite liquids may be extracted. Some of the compositional range observed in the Chefe Donsa deposits may result from the fresh intrusion of trachyte magma, which may also provide an eruption trigger. This model may have wider application in understanding the origin of the Daly Gap in Ethiopian magmas—intermediate liquids may not be extracted from crystal-liquid mushes due to insufficient crystallization to yield a rigid framework. The wide range of glass compositions characteristic of the proximal Chefe Donsa deposits is not recorded in temporally equivalent tephra deposits located in regional depocenters. Our results show that glass shards, which represent the material most likely transported to distal depocenters, occupy a limited compositional range at high SiO₂ values and overlap some distal tephra deposits. These results suggest that distal tephra deposits may not faithfully record the potentially wide range in magma compositions present in a magmatic system just prior to eruption and that robust distal–proximal tephra correlations must include a careful analysis of the full range of materials in the proximal deposit.     

Direct and indirect luminescence dating of tephra: A review

In Quaternary studies, tephras are widely used as marker horizons to correlate geological deposits. Therefore, accurate and precise dating is crucial. Among radiometric dating techniques, luminescence dating has the potential to date tephra directly using glass shards, volcanic minerals that formed during the eruption or mineral fragments that originate from the shattered country rock. Moreover, sediments that frame the tephra can be dated to attain an indirect age bracket. A review of numerous luminescence dating studies highlights the method's potential and challenges. While reliable direct dating of volcanic quartz and feldspar as a component in tephra is still methodically difficult mainly due to thermal and athermal signal instability, red thermoluminescence of volcanic quartz and the far-red emission of volcanic feldspar have been used successfully. Furthermore, the dating of xenolithic quartz within tephra shows great potential. Numerous studies date tephra successfully indirectly. Dating surrounding sediments is generally straightforward as long as samples are not taken too close to the tephra horizons. Here, issues arise from the occurrence of glass shards within the sediments or unreliable determination of dose rates. This includes relocation of radioelements, mixing of tephra into the sediment and disregarding different dose rates of adjacent material.     

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.     

The Development of Laser Ablation ICP-MS and Calibration Strategies: Examples from the Analysis of Trace Elements in Volcanic Glass Shards and Sulfide Minerals

This contribution presents a review of the recent developments in laser ablation inductively coupled plasma-mass spectrometry. We describe the important developments which have occurred in the laser systems used, leading to a spatial resolution of around 20 (im, and give an overview of the major instrument developments which have affected the geological applications of laser ablation ICP-MS. We describe the calibration of laser ablation for the analysis of trace elements in two different matrices: volcanic glass shards and sulfide minerals. We show how single glass shards can be analysed using the National Institute of Standards and Technology (NIST) glass certified reference materials for calibration and demonstrate the effect of using single spot analyses compared to rastering of the calibration sample. We show the importance of inter-shard variation and demonstrate that averaged single shard analyses produce data which compare well with bulk analyses. The calibration of the laser system for sulfide mineral analysis is discussed and two different strategies are proposed, one using spiked pressed powder pellets of sulfides and the other metal reference materials. We present conclusions and recommendations for the calibration of laser ablation ICP-MS instruments.     

Cryptotephras in the Lateglacial ICDP Dead Sea sediment record and their implications for chronology

Due to a lack of visible tephras in the Dead Sea record, this unique palaeoenvironmental archive is largely unconnected to the well-established Mediterranean tephrostratigraphy. Here we present first results of the ongoing search for cryptotephras in the International Continental Drilling Program (ICDP) sediment core from the deep Dead Sea basin. This study focusses on the Lateglacial (~15–11.4 cal. ka BP), when Lake Lisan – the precursor of the Dead Sea – shrank from its glacial highstand to the Holocene low levels. We developed a glass shard separation protocol and counting procedure that is adapted to the extreme salinity and sediment recycling of the Dead Sea. Cryptotephra is abundant in the Dead Sea record (up to ~100 shards cm^-3), but often glasses are physically and/or chemically altered. Six glass samples from five tephra horizons reveal a heterogeneous geochemical composition, with mainly rhyolitic and some trachytic glasses potentially sourced from Italian, Aegean and Anatolian volcanoes. Most shards likely originate from the eastern Anatolian volcanic province and can be correlated using major element analyses with tephra deposits from swarm eruptions of the Süphan Volcano ~13 ka BP and with ashes from Nemrut Volcano, presumably the Lake Van V-16 volcanic layer at ~13.8 ka BP. In addition to glasses that match the TM-10-1 from Lago Grande di Monticchio (15 820±790 cal. a BP) tentatively correlated with the St. Angelo Tuff of Ischia, we further identified a cryptotephra with glass analyses which are chemically identical with those of the PhT1 tephra in the Philippon peat record (13.9–10.5 ka BP), and also a compositional match for the glass analyses of the Santorini Cape Riva Tephra (Y-2 marine tephra, 22 024±642 cal. a BP). These first results demonstrate the great potential of cryptotephrochronology in the Dead Sea record for improving its chronology and connecting the Levantine region to the Mediterranean tephra framework.     

Effects of the peat acid digestion protocol on geochemically and morphologically diverse tephra deposits

Tephra shards for electron probe microanalysis are most efficiently extracted from peat using acid digestion, which removes organic material that hinders density separation methods. However, strong acids are known to alter glass chemical compositions, and several studies have examined how acid digestion affects rhyolitic volcanic glass. The focus on rhyolitic tephra in these studies leaves considerable uncertainty, as the dissolution rates of natural glasses (including tephra) are determined by the chemical composition and surface area/volume ratio, both of which vary in tephra deposits. Here, we use duplicate samples of basaltic, trachydacitic and rhyolitic tephra to examine physical and geochemical alteration following acid digestion. Scanning electron microscope imagery reveals no discernible degradation of glass surfaces, and electron probe microanalysis results from duplicate samples are statistically indistinguishable. These findings suggest the acid digestion protocol for organic peats does not significantly alter glass geochemistry regardless of shard morphologies or geochemical compositions.     

Determination of Trace Elements in Calcite Using Solution and Laser Ablation ICP-MS: Calibration to NIST SRM Glass and USGS MACS Carbonate, and Application to Real Landfill Calcite

We report new data on the trace element concentrations of Mg, Cr, Mn, Co, Ni, Cu, Zn, Sr, Cd, Ba, La, Ce, Nd, Pb and U in USGS carbonate reference materials (MACS-1 and MACS-2) and compare solution ICP-MS and LA-ICP-MS trace element determinations on landfill calcites using calibration to different reference materials (MACS-1 and MACS-2 carbonate and NIST SRM 612 glass). Very good agreement (differences below 10% relative) was found between laser ablation and solution ICP-MS data for MACS-1 with higher concentrations of trace elements (values between 100 and 150 μg g⁻¹), with the exception of Cu and Zn. Similarly good agreement was found for MACS-2 with lower trace element concentrations (units to tens of μg g⁻¹), with the exception of Cr, Co and Zn. The MACS-1 reference material for calibration of LA-ICP-MS was found to be extremely useful for in situ determination of trace elements in real-world carbonate samples (landfill calcites), especially those present in calcite in higher concentrations (Mn, Sr, Ba; < 5% RSD). Less accurate determinations were generally obtained for trace elements present at low concentrations (∼ units of μg g⁻¹). In addition, good agreement was observed between the instrument calibration to MACS and NIST SRM 612 glass for in situ measurements of trace elements in landfill calcites K-2, K-3 and K-4 (differences below 15% relative for most elements). Thus, the application of MACS carbonate reference materials is promising and points to the need for the development of new carbonate reference materials for laser ablation ICP-MS.     

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.     

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.     

Laser Ablation and Solution ICP-MS Determination of Rare Earth Elements in USGS BIR-1G, BHVO-2G and BCR-2G Glass Reference Materials

Data are reported for rare earth elements (REE) in three geological glass reference materials (BIR-1G, BHVO-2G and BCR-2G) using a UV (266 nm) laser ablation ICP-MS system and the classical (HF-HClO₄) acid decomposition method, followed by conventional nebulisation ICP-MS. External calibration of laser ablation analyses was performed using NIST SRM reference materials with internal standardisation using ²⁹Si and ⁴⁴Ca. Replicate analyses of reference basaltic glasses yielded an analytical precision of 1-5% (RSD) for all the elements by solution ICP-MS and 1-8% (RSD) by laser ablation ICP-MS. The relative differences between the REE concentrations measured by solution and laser ablation ICP-MS compared with the reference values were generally less than 11 % for most elements. The largest deviations occurred for La determined by solution ICP-MS in BIR-1G. The results of both solution and laser ablation ICP-MS agreed well, generally better than 7%, with the exception of La, Pr and Sm in BIR-1G. The measured REE laser ablation data for BIR-1G, BHVO-2G and BCR-2G agreed with the previously published data on these basaltic reference glasses, within a range of 0-10% for most elements. No significant influences were observed for the predicted spectral interferences on some REE isotopes in the analysis of basaltic glasses.     

Late Quaternary tephrostratigraphy,Ahklun Mountains,SW Alaska

Radiocarbon‐dated sediment cores from six lakes in the Ahklun Mountains, south‐western Alaska, were used to interpolate the ages of late Quaternary tephra beds ranging in age from 25.4 to 0.4 ka. The lakes are located downwind of the Aleutian Arc and Alaska Peninsula volcanoes in the northern Bristol Bay area between 159° and 161°W at around 60°N. Sedimentation‐rate age models for each lake were based on a published spline‐fit procedure that uses Monte Carlo simulation to determine age model uncertainty. In all, 62 ¹⁴C ages were used to construct the six age models, including 23 ages presented here for the first time. The age model from Lone Spruce Pond is based on 18 ages, and is currently the best‐resolved Holocene age model available from the region, with an average 2σ age uncertainty of about ± 109 years over the past 14.5 ka. The sedimentary sequence from Lone Spruce Pond contains seven tephra beds, more than previously found in any other lake in the area. Of the 26 radiocarbon‐dated tephra beds at the six lakes and from a soil pit, seven are correlated between two or more sites based on their ages. The major‐element geochemistry of glass shards from most of these tephra beds supports the age‐based correlations. The remaining tephra beds appear to be present at only one site based on their unique geochemistry or age. The 5.8 ka tephra is similar to the widespread Aniakchak tephra [3.7 ± 0.2 (1σ) ka], but can be distinguished conclusively based on its trace‐element geochemistry. The 3.1 and 0.4 ka tephras have glass major‐ and trace‐element geochemical compositions indistinguishable from prominent Aniakchak tephra, and might represent redeposited beds. Only two tephra beds are found in all lakes: the Aniakchak tephra (3.7 ± 0.2 ka) and Tephra B (6.1 ± 0.3 ka). The tephra beds can be used as chronostratigraphic markers for other sedimentary sequences in the region, including cores from Cascade and Sunday lakes, which were previously undated and were analyzed in this study to correlate with the new regional tephrostratigraphy. Copyright © 2012 John Wiley & Sons, Ltd.     

Methods for determination of the age of Pleistocene tephra,derived from eruption of Toba,in central India

Tephra, emplaced as a result of Pleistocene eruption of the Indonesian ‘supervolcano’ Toba, occurs at many localities in India. However, the ages of these deposits have hitherto been contentious; some workers have argued that these deposits mark the most recent eruption (eruption A, ca 75 ka), although at some sites they are stratigraphically associated with Acheulian (Lower Palaeolithic) artefacts. Careful examination of the geochemical composition of the tephras, which are composed predominantly of shards of rhyolitic glass, indicates that discrimination between the products of eruption A and eruption D (ca 790 ka) of Toba is difficult. Nonetheless, this comparison favours eruption D as the source of the tephra deposits at some sites in India, supporting the long-held view that the Lower Palaeolithic of India spans the late Early Pleistocene. In principle, these tephra deposits should be dateable using the K–Ar system; however, previous experience indicates contamination by a small proportion of ancient material, resulting in apparent ages that exceed the true ages of the tephras. We have established the optimum size-fraction in which the material from Toba is concentrated, 53–61 μm, and have considered possible origins for the observed contamination. We also demonstrate that Ar–Ar analysis of four out of five of our samples has yielded material with an apparent age similar to that expected for eruption D. These numerical ages, of 809 ± 51, 714 ± 62, 797 ± 45 and 827 ± 39 ka for the tephras at Morgaon, Bori, Gandhigram and Simbhora, provide a weighted mean age for this eruption of 799 ± 24 ka (plus-or-minus two standard deviations). However, these numerical ages are each derived from no more than 10–20% of the argon release in each sample, which is not ideal. Nonetheless, our results demonstrate that it is feasible, in principle, to date this difficult material using the Ar–Ar technique; future follow-up studies will therefore be able to refine our preparation and analysis procedures to better optimize the dating.     

湖光岩玛珥湖火山灰的成分及其来源

湖光岩玛珥湖沉积物中的火山灰保存了其原始形貌、原生的沉积和成分特征,是进行岩芯沉积物对比和定年的理想材料之一。除了对火山灰进行常规的定年外,通过精确测定火山灰中玻璃碎屑(玻屑)的成分,并与已知时代的火山喷发物成分对比确定火山灰的年龄已成为火山灰年代学研究的重要领域之一,因为它能够区分年龄差别在同位素定年误差之内的数层火山灰。本文利用电子探针分析了湖光岩玛珥湖岩芯火山灰中玻屑的成分,经与全球年龄已知火山喷发物的成分对比和分析,认为该火山灰的年龄为74000aB.P.,在此基础上,讨论了湖光岩玛珥湖岩芯74000aB.P.以来沉积速率的变化趋势。     

Late Quaternary tephra layers around Raoul and Macauley Islands,Kermadec Arc: implications for volcanic sources,explosive volcanism and tephrochronology

A suite of deep‐sea cores were collected along transects up to 100 km across the fore‐arc and back‐arc regions of the predominantly submarine Kermadec arc near Raoul and Macauley islands, southwest Pacific. The cores reveal a macroscopic tephra record extending back >50 ka. This is a significant addition to the dated record of volcanism, previously restricted to fragmented late Holocene records exposed on the two islands. The 27 macroscopic tephra layers display a wide compositional diversity in glass (～50–78 wt% SiO₂). Many tephra layers comprise silicic shards with a subordinate mafic shard population. This could arise from magma mingling and may reflect mafic triggering of the silicic eruptions. Broadly, the glass compositions can be distinguished on diverging high‐K and low‐K trends, most likely arising from different source volcanoes. This distinction is also reflected in the tephra records exposed on Raoul (low‐K) and Macauley (high‐K) islands, the likely source areas. Heterogeneous tephra comprising shards of both high‐ and low‐K affinity, silicic and mafic compositions, and more homogeneous tephra with subordinate outlier shard compositions, are best explained by post‐depositional mixing of separate eruption deposits or contemporaneous eruptions. Evidently, the slow sedimentation rates of the calcareous oozes (～10¹–10² mm ka^?1) were insufficient to adequately separate and preserve closely spaced eruption deposits. This exemplifies the difficulty in assessing eruption frequencies and magmatic trends, and erecting a tephrostratigraphy, using geochemical fingerprinting in such environments. Despite these difficulties, the ca. 5.7 ka Sandy Bay Tephra erupted from Macauley Island can be correlated over a distance of >100 km, extending east and west of the island, showing that the mostly submerged volcanoes are capable of wide tephra dispersal. Hence there is potential for developing chronostratigraphies for the southwest Pacific beyond the region covered by the extensive rhyolite marker beds from the Taupo Volcanic Zone. Copyright © 2011 John Wiley & Sons, Ltd.     

Application of Laser Ablation ICP-MS to U-Th-Pb Dating of Monazite

Recent advances in laser ablation ICP-MS techniques allow accurate U-Th-Pb age dating of monazites that are as young as several tens of million years to a precision better than 2%. Accuracy of the age determinations has been improved by true real-time mass bias correction via nebulisation of a solution containing enriched ²³³U and natural Tl isotopes. The Tl-U tracer solution eliminates possible effects of variable sample matrices on the precision and accuracy of measured isotopic ratios. Mass bias corrections based on measured ²⁰⁵Tl/²³³U ratios in the tracer solution allow direct measurement of ²³⁵U in monazite. Combined with high-sensitivity laser ablation ICP-MS measurements, direct measurement of ²³⁵U particularly improves the precision of U-Pb dating of young monazites. Correction for laser-induced Pb/U and Pb/Th elemental fractionation is based on a mathematical treatment of time resolved count-rate data that is independent of laser ablation characteristics, does not require external standardisation and allows variable laser pit size or raster patterns for each measurement. The new procedures make the LA ICP-MS technique more flexible for in situ U-Th-Pb analysis.     

Late Quaternary cryptotephra detection and correlation in loess in northeastern Japan using cummingtonite geochemistry

We detected late Pleistocene cummingtonite-bearing cryptotephras in loess deposits in NE Japan and correlated them with known tephras elsewhere by using major-element compositions of the cummingtonite. This is the first time cryptotephras have been identified by analysis of a crystal phase rather than glass shards. In central NE Japan, four cummingtonite-bearing tephras, the Ichihasama pumice, the Dokusawa tephra, the Naruko–Nisaka tephra, and the Adachi–Medeshima tephra, are present in late Pleistocene loess deposits. Because the cummingtonite chemistry of each tephra is different and characteristic, it is potentially a powerful tool for detecting and identifying cryptotephras. An unidentified cummingtonite-bearing cryptotephra previously reported to be present in the late Pleistocene loess deposits at Kesennuma (Pacific coast) did not correlate with any of the known cummingtonite-bearing tephras in central NE Japan, but instead with the Numazawa–Kanayama tephra (erupted from the Numazawa caldera, southern NE Japan), although Kesennuma is well beyond the previously reported area of the distribution of the Numazawa–Kanayama tephra. Three new cummingtonite-bearing cryptotephras in the mid and late Pleistocene loess deposits (estimated to be less than 82 ka, 100–200 ka, and ca. 250 ka) on the Isawa upland were also detected.     

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.     

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.