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.     

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.     

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.     

Precise and Accurate In Situ Determination of Lead Isotope Ratios in NIST,USGS, MPI‐DING and CGSG Glass Reference Materials using Femtosecond Laser Ablation MC‐ICP‐MS

Lead isotope ratio data were obtained with good precision and accuracy using a 266 nm femtosecond laser ablation (fLA) system connected to a multi‐collector ICP‐MS (MC‐ICP‐MS) and through careful control of analytical procedures. The mass fractionation coefficient induced by 266 nm femtosecond laser ablation was approximately 28% lower than that by 193 nm excimer laser ablation (eLA) with helium carrier gas. The exponential law correction method for Tl normalisation with optimum adjusted Tl ratio was utilised to obtain Pb isotopic data with good precision and accuracy. The Pb isotopic ratios of the glass reference materials NIST SRM 610, 612, 614; USGS BHVO‐2G, BCR‐2G, GSD‐1G, BIR‐1G; and MPI‐DING GOR132‐G, KL2‐G, T1‐G, StHs60/80‐G, ATHO‐G and ML3B‐G were determined using fLA‐MC‐ICP‐MS. The measured Pb isotopic ratios were in good agreement with the reference or published values within 2s measurement uncertainties. We also present the first high‐precision Pb isotopic data for GSE‐1G, GSC‐1G, GSA‐1G and CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5 glass reference materials obtained using the femtosecond laser ablation MC‐ICP‐MS analysis technique.     

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.     

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.     

High‐resolution study of Icelandic tephras in the Kangerlussuaq Trough,southeast Greenland,during the last deglaciation

Tephra abundance data and geochemistry in Late‐glacial and Holocene sediments on the East Greenland shelf are presented. Two well‐known tephras were identified from electron microprobe analysis of tephra shards picked from ash peaks in the cores. These are the Vedde Ash and Saksunarvatn Ash, which probably were deposited on the shelf after transport on drifting ice. The radiocarbon dates (marine reservoir corrected by −550 yr) that constrain the timing of deposition of the tephra layers compare well with the terrestrial and ice‐core ages of the tephras without requiring additional reservoir correction to align them with the known tephra ages. Several prominent tephra layers with a composition of Ash Zone 2 tephra punctuate the deglacial sediments. These tephra peaks coincide with significant light stable isotope events (signifying glacial meltwater) and fine‐grained sediments poor in ice‐rafted detritus. We interpret the Ash Zone 2 tephra peaks as sediment released from the Greenland Ice Sheet during strong melting pulses of the deglaciation. Copyright © 2002 John Wiley & Sons, Ltd.     

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.     

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.     

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.     

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.     

LA‐(MC)‐ICP‐MS Trends in 2006 and 2007 with Particular Emphasis on Measurement Uncertainties

Research in 2006 and 2007 dealing with laser ablation‐(multicollector)‐inductively coupled plasma‐mass spectrometry, LA‐(MC)‐ICP‐MS, involved studies concerned with optimising the technique itself, as well as applying the method to a variety of problems in the Earth sciences. The causes of elemental and isotopic fractionation produced during laser ablation continues to be of considerable interest, with evidence mounting that processes occurring both at the ablation site and in the argon plasma of the ICP are culpable. There is growing excitement in the use of femtosecond lasers for LA‐(MC)‐ICP‐MS, with the hope that they reduce or eliminate melting and non‐congruent volatilisation at the ablation site and thus approach stoichiometric sampling. Ablation chamber design emerged as a serious concern, particularly with respect to achieving the rapid washout needed for fine‐scale compositional mapping of geological objects. LA‐MC‐ICP‐MS provided data for a wide range of isotopic systems, especially hafnium, but also B, S, Mg, Cu, Fe, Sr, Nd, Pb and U. Measurement uncertainties in LA‐ICP‐MS were discussed by several researchers, and are critically reviewed here ‐ total uncertainties for trace element concentration measurements of silicates including errors on the calibration values of common reference materials are ～10% (95% confidence limits), though the precision of individual spot measurements (50 to 100 μm) is much better, ～1% RSD, using a 193 nm laser and a sector field‐ICP‐MS. LA‐ICP‐MS U‐Pb ages for zircon and other U‐rich accessory phases are claimed by most geoanalysts to have 2s uncertainties of ～0.7 and 1.3% respectively but the actual accuracy of the method is probably only as good as ～2% (2s), when uncertainties associated with laser‐induced Pb/U fractionation are included.     

Non‐Matrix‐Matched Calibration for the Multi‐Element Analysis of Geological and Environmental Samples Using 200 nm Femtosecond LA‐ICP‐MS: A Comparison with Nanosecond Lasers

LA‐ICP‐MS is one of the most promising techniques for in situ analysis of geological and environmental samples. However, there are some limitations with respect to measurement accuracy, in particular for volatile and siderophile/chalcophile elements, when using non‐matrix‐matched calibration. We therefore investigated matrix‐related effects with a new 200 nm femtosecond (fs) laser ablation system (NWRFemto200) using reference materials with different matrices and spot sizes from 10 to 55 μm. We also performed similar experiments with two nanosecond (ns) lasers, a 193 nm excimer (ESI NWR 193) and a 213 nm Nd:YAG (NWR UP‐213) laser. The ion intensity of the 200 nm fs laser ablation was much lower than that of the 213 nm Nd:YAG laser, because the ablation rate was a factor of about 30 lower. Our experiments did not show significant matrix dependency with the 200 nm fs laser. Therefore, a non‐matrix‐matched calibration for the multi‐element analysis of quite different matrices could be performed. This is demonstrated with analytical results from twenty‐two international synthetic silicate glass, geological glass, mineral, phosphate and carbonate reference materials. Calibration was performed with the certified NIST SRM 610 glass, exclusively. Within overall analytical uncertainties, the 200 nm fs LA‐ICP‐MS data agreed with available reference values.     

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.     

The Preparation and Preliminary Characterisation of Three Synthetic Andesite Reference Glass Materials (ARM‐1, ARM‐2, ARM‐3) for In Situ Microanalysis

Three synthetic reference glasses were prepared by directly fusing and stirring 3.8 kg of high‐purity oxide powders to provide reference materials for microanalytical work. These glasses have andesitic major compositions and are doped with fifty‐four trace elements in nearly identical abundance (500, 50, 5 µg g^?1) using oxide powders or element solutions, and are named ARM‐1, 2 and 3, respectively. We further document that sector‐field (SF) ICP‐MS (Element 2 or Element XR) is capable of sweeping seventy‐seven isotopes (from ⁷Li to ²³⁸U, a total of sixty‐eight elements) in 1 s and, thus, is able to quantify up to sixty‐eight elements by laser sampling. Micro‐ and bulk analyses indicate that the glasses are homogeneous with respect to major and trace elements. This paper provides preliminary data for the ARM glasses using a variety of analytical techniques (EPMA, XRF, ICP‐OES, ICP‐MS, LA‐Q‐ICP‐MS and LA‐SF‐ICP‐MS) performed in ten laboratories. Discrepancies in the data of V, Cr, Ni and Tl exist, mainly caused by analytical limitations. Preliminary reference and information values for fifty‐six elements were calculated with uncertainties [2 relative standard error (RSE)] estimated in the range of 1–20%.     

Evaluation of Major to Ultra Trace Element Bulk Rock Chemical Analysis of Nanoparticulate Pressed Powder Pellets by LA‐ICP‐MS

An efficient, clean procedure for the measurement of element mass fractions in bulk rock nanoparticulate pressed powder pellets (PPPs) by 193 nm laser ablation ICP‐MS is presented. Samples were pulverised by wet milling and pelletised with microcrystalline cellulose as a binder, allowing non‐cohesive materials such as quartz or ceramics to be processed. The LA‐ICP‐MS PPP analytical procedure was optimised and evaluated using six different geological reference materials (JP‐1, UB‐N, BCR‐2, GSP‐2, OKUM and MUH‐1), with rigorous procedural blank quantification employing synthetic quartz. Measurement trueness of the procedure was equivalent to that achieved by solution ICP‐MS and LA‐ICP‐MS analysis of glass. The measurement repeatability was as low as 0.5–2% (1s, n = 6) and, accordingly, PPP homogeneity could be demonstrated. Calibration based on the reference glasses NIST SRM 610, NIST SRM 612, BCR‐2G and GSD‐1G revealed matrix effects for glass and PPP measurement with NIST SRM 61×; using basalt glasses eliminated this problem. Most significantly, trace elements not commonly measured (flux elements Li, B; chalcophile elements As, Sb, Tl, In, Bi) could be quantified. The PPP‐LA‐ICP‐MS method overcomes common problems and limitations in analytical geochemistry and thus represents an efficient and accurate alternative for bulk rock analysis.     

U-Pb Age Determination for Seven Standard Zircons using Inductively Coupled Plasma–Mass Spectrometry Coupled with Frequency Quintupled Nd-YAG (λ = 213 nm) Laser Ablation System: Comparison with LA-ICP-MS Zircon Analyses with a NIST Glass Reference Material

This paper evaluates the analytical precision, accuracy and long‐term reliability of the U‐Pb age data obtained using inductively coupled plasma–mass spectrometry (ICP‐MS) with a frequency quintupled Nd‐YAG (λ = 213nm) laser ablation system. The U‐Pb age data for seven standard zircons of various ages, from 28 Ma to 2400 Ma (FCT, SL13, 91500, AS3, FC1, QGNG and PMA7) were obtained with an ablation pit size of 30 μm diameter. For ²⁰⁷Pb/²⁰⁶Pb ratio measurement, the mean isotopic ratio obtained on National Institute of Standards and Technology (NIST) SRM610 over 4 months was 0.9105 ± 0.0014 (n = 280, 95% confidence), which agrees well with the published value of 0.9096. The time‐profile of Pb/U ratios during single spot ablation showed no significant difference in shape from NIST SRM610 and 91500 zircon standards. These results encouraged the use of the glass standard as a calibration standard for the Pb/U ratio determination for zircons with shorter wavelength (λ = 213 nm) laser ablation. But ²⁰⁶Pb/²³⁸U and ²⁰⁷Pb/²³⁵U ages obtained by this method for seven zircon standards are systematically younger than the published U‐Pb ages obtained by both isotope dilution–thermal ionization mass spectrometry (ID‐TIMS) and sensitive high‐resolution ion‐microprobe (SHRIMP). Greater discrepancies (3–4% younger ages) were found for the ²⁰⁶Pb/²³⁸U ages for SL13, AS3 and 91500 zircons. The origin of the differences could be heterogeneity in Pb/U ratio on SRM610 between the different disks, but a matrix effect accuracy either in the ICP ion source or in the ablation‐transport processes of the sample aerosols cannot be neglected. When the ²⁰⁶Pb/²³⁸U (= 0.2302) newly defined in the present study is used, the measured ²⁰⁶Pb/²³⁸U and ²⁰⁷Pb/²³⁵U ages for the seven zircon standards are in good agreement with those from ID‐TIMS and SHRIMP within ±2%. This suggests that SRM610 glass standard is suitable for ICP‐MS with laser ablation sampling (LA‐ICP‐MS) zircon analysis, but it is necessary to determine the correction factor for ²⁰⁶Pb/²³⁸U by measuring several zircon standards in individual laboratories.     

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.     

Quaternary tephra marker beds and their potential for palaeoenvironmental reconstruction on Chatham Island,east of New Zealand,southwest Pacific Ocean

Tephras provide one of the most reliable methods of time control and synchronisation within Quaternary sequences. We report on the identification of two widespread rhyolitic tephras – the Kawakawa and Rangitawa tephras – preserved in extensive peat deposits on Chatham Island ～900 km east of New Zealand. The tephras, both products of supereruptions from the Taupo Volcanic Zone, occur as pale, fine‐ash dominated layers typically 10–150 mm thick. Mineralogically they are dominated by rhyolitic glass, together with subordinate amounts of quartz, feldspar, hypersthene, hornblende, Fe–Ti oxides and zircon. Phlogopite/biotite was identified additionally in Rangitawa Tephra. Ages for each tephra were obtained via mineralogical and major element glass composition‐based correlation with well‐dated equivalent deposits on mainland New Zealand, and we also obtained a new zircon fission‐track age for Rangitawa Tephra (350 ± 50 ka) on Chatham Island. Both tephras were erupted at critical times for palaeoenvironmental reconstructions in the New Zealand region: the Kawakawa at ca. 27 cal. ka, near the beginning of the ‘extended’ LGM early in marine isotope stage (MIS) 2; and the Rangitawa at ca. 350 ka near the end of MIS 10. The time constraints provided by the tephras demonstrate that Chatham Island peats contain long‐distance pollen derived from mainland New Zealand, which provides a reliable proxy for identifying glacial–interglacial climate conditions, in this case during the MIS 11–10 and MIS 2–1 cycles. The two tephras thus provide important chronostratigraphic tie‐points that facilitate correlation and synchronisation not only across the Quaternary deposits of the Chatham Islands group but also with climatically significant terrestrial and marine records in the wider New Zealand region. Copyright © 2010 John Wiley & Sons, Ltd.