The Hekla 1947 tephra in the north of Ireland: regional distribution,concentration and geochemistry

A cryptotephra layer from the eruption of Hekla in 1947 has recently been discovered in Irish peatlands. This tephra layer represents the most recent deposition of volcanic ash in the UK prior to the eruption of Eyjafjallajökull in 2010. Here we examine the concentration and geochemistry of the Hekla 1947 tephra in 14 peat profiles from across Northern Ireland. Electron probe microanalysis of individual tephra shards (n = 91) reveals that the tephra is of dacitic–andesitic geochemistry and is highly similar to the Hekla 1510 tephra, although spheroidal carbonaceous particle profiles can be used for successful discrimination of the two layers. The highest concentrations of Hekla 1947 are found in western sites, probably reflecting the pathway of the ash fall event due to the prevailing wind direction. Comparable tephra concentrations from two cores (1 km apart) from a single bog and from nearby sites may suggest that tephra shard concentrations in peat profiles reflect ash fallout densities across a specific region, rather than site‐specific factors associated with peatlands. This paper firmly establishes Hekla 1947 as a useful chronostratigraphic marker for the twentieth century, although within a restricted zone. Copyright © 2012 John Wiley & Sons, Ltd.     

A Holocene tephra record from the Lofoten Islands, Arctic Norway

Pilcher, J., Bradley, R. S., Francus, P. & Anderson, L. 2005 (May): A Holocene tephra record from the Lofoten Islands, Arctic Norway. Boreas , Vol. 34, pp. 136–156. Oslo. ISSN 0300–9483.
A tephrochronology has been established for a peat bog in the Lofoten Islands that provides a dating framework for future lake and bog studies of climate variation in this climatically sensitive area. Twenty-three tephra layers were identified, all apparently of Icelandic origin. These included the historically dated tephras of AD 1875 (Askja), AD 1362 (Öraefajökull), AD 1158 (Hekla), AD 1104 (Hekla) and the Landnam tephra identified at AD 875 in the GRIP ice core. Other layers, previously radiocarbon dated in Ireland and elsewhere, include the Hekla eruptions of c. 2310 BC and c. 5990 BC. The basal clays below the peat contain tephra of both the Askja eruption of c. 9500 BC (10 000 radiocarbon years BP) and the well-known Vedde Ash of c. 12 000 BP (10 030 80 BC in GRIP ice core).     

Germanium in Icelandic geothermal systems

Germanium concentrations in geothermal waters in Iceland lie mostly in the range 2–30 ppb. There is an overall positive relation between the germanium content of the water and its temperature. Most of the germanium occurs as Ge(OH)^?₅in solution but Ge(OH)₄ may also be present in significant amounts in saline waters when above 200°C. Evidence indicates that aqueous germanium concentrations are controlled by exchange reactions where it substitutes for silica in silicates and iron in sulphides. It is the rate of dissolution and the relative abundance of the alteration minerals which take up germanium to a variable extent that ultimately fix Ge(OH)₄ concentrations in the water. This, together with water pH, fixes total dissolved germanium. It is mostly the primary rock composition that dictates the relative abundance of the alteration minerals. Conductive cooling in upflow zones favours removal of germanium from solution. During the initial stages of boiling of rising hot water dissolution is enhanced but precipitation at later stages.Thermodynamic data of various aqueous germanium species and several minerals are summarized and dissociation constants and solubilities estimated at elevated temperatures using available predictive methods.     

Magnetic characterisation and correlation of a Younger Dryas tephra in North Atlantic marine sediments

A technique for identifying non‐visible basaltic tephra‐rich horizons of Younger Dryas (YD)/Greenland Stadial (GS) 1 age in northeast Atlantic sediments using rapid, non‐destructive magnetic measurements is presented. Three high‐resolution marine sediment cores have been studied in an E–W transect across the Hebridean margin: St Kilda Basin (MD95‐2007), Barra Fan (MD95‐2006) and Rockall Trough (MD04‐2822). Magnetic susceptibilities and remanent magnetisations were measured at contiguous 1 cm resolution on bulk sediments. In all three cores, an interval with higher proportions of hard magnetic minerals coincides with a clearly defined peak in basaltic tephra shard (>250 µm) counts, which can be constrained to the early part of the YD/GS1 based on faunal climate proxies. Electron microprobe analyses of the magnetically distinct basaltic tephra interval, in all three cores, displays the same major element geochemistry as published for the Vedde basaltic (I Tab. 1), i.e. sourced from the Icelandic volcano Katla. The identification of transitional alkalic basaltic tephras within marine sediments could potentially be facilitated by magnetic analysis as a useful chronostratigraphic screening tool. Copyright © 2009 John Wiley & Sons, Ltd.     

Use of magnetic signatures to correlate tephra layers in Holocene loessial soil profiles from a small region, SE Iceland

Rock magnetic measurements have been applied to two adjacent loessial soil sections from a small region, SE Iceland. The soils are composed of reworked locally derived sediment (including airfall tephra) and also contain several visible discrete airfall tephra layers. The main magnetic minerals in the airfall tephras are ferrimagnetic (e.g. magnetite) with paramagnetic minerals also present. The main magnetic grain sizes in the tephras are pseudo single domain. The results show that individual tephras do not have unique magnetic signatures that can be used for identification and correlation between sedimentary sequences. However, a correlation of tephra layers was achieved through the application of statistical techniques to a comprehensive dataset of magnetic parameters. Similarity coefficients and Euclidian distance measures were used to identify the best correlation between tephra layers in the two soil profiles. The technique works well providing some tephras present within both profiles have been formally identified (e.g. Oraefajokulla ad 1362) using electron microprobe analyses. Given this initial framework, the statistical analyses of the magnetic parameters can help in the identification and correlation of unknown tephras between two soil profiles.     

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.     

Mechanism of pyroxene and amphibole weathering—I. Experimental studies of iron-free minerals

The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca²⁺, Mg²⁺, and Si(OH)₄ and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M₂ structural sites. Loss mainly from M₂ sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca²⁺ and/or Mg²⁺ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on a_H⁺ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.     

Electron microprobe data for tephra attributed to Glacier Peak,Washington

Reference samples of three prominent pumice units of Glacier Peak tephra collected east of the volcano within a distance of 100 km are similar petrographically to units described by earlier workers. Glass shards isolated from these samples were analyzed by electron microprobe to determine the content of Ca, Fe, and K. Resulting data, plus those published for two other references samples, provide a basis for attributing certain outlying tephra layers from 14 locations in eastern Washington, Idaho, Wyoming, and Montana to eruptions of Glacier Peak. Ten of the samples have properties of both Glacier Peak tephra and Mount St. Helens set J tephra, but proportions of Ca:Fe:K in glass shards indicate that 9 of the 10 outlying samples came from Glacier Peak, whereas one is assigned to Mount St. Helens set J. The remaining six outlying samples, all from southeastern Washington, contain cummingtonite phenocrysts and are chemically similar to some parts of Mount St. Helens tephra sets that are older than 12,000 BP.     

Detection of Lateglacial distal tephra layers in the Netherlands

Three distal tephra layers or cryptotephras have been detected within a sedimentary sequence from the Netherlands that spans the last glacial-interglacial transition. Geochemical analyses identify one as the Vedde Ash, which represents the southernmost discovery of this mid-Younger Dryas tephra so far. This tephra was found as a distinct horizon in three different cores sampled within the basin. The remaining two tephras have not been geochemically 'fingerprinted', partly due to low concentrations and uneven distributions of shards within the sequences sampled. Nevertheless, there is the potential for tracing these tephra layers throughout the Netherlands and into other parts of continental Europe. Accordingly, the possibilities for precise correlation of Dutch palaeoenvironmental records with other continental, marine and ice-core records from the North Atlantic region are highlighted.     

Agronomic impact of tephra fallout from the 1995 and 1996 Ruapehu Volcano eruptions, New Zealand

 Eruptions from Ruapehu Volcano on 11 and 14 October 1995 and 17 June 1996 distributed at least 36×10⁶ m³ of sulphur(S)-rich tephra over the central and eastern North Island of New Zealand. The tephras added between 30–1500 kg ha^–1 S to at least 25 000 km² of land in primary production. Smaller but beneficial amounts of selenium (Se) and in some areas potassium and magnesium were also supplied. Addition of S to the soils in the form of sulphate and elemental S resulted in a drop in soil pH and an increase in pasture S contents within seven weeks of the eruptions. The soils affected by the tephra are naturally low in S and Se, but following the eruptions S was not required in fertilizer applications in many areas. The strongest and longest lasting effects of S and Se deposition were in high anion-retention soils particularly Hapludands (moist, moderately weathered soils, derived from volcanic ash). Soluble fluorine concentrations within the tephras were low compared to historic Icelandic and Chilean examples. However, pastoral livestock deaths were apparently caused by fluorosis in addition to starvation when tephra covered feed. The Ruapehu tephra contained very low concentrations of other soluble toxic elements. Received: 17 January 1997 · Accepted: 31 March 1997     

Chemical alteration of tephra in the depositional environment: theoretical stability modelling

The study of the chemical stability of vitreous material in aqueous media is well‐established. There has to date been little consideration of the implications of variations in the chemical durability of tephra in Quaternary tephrochronology. Chemical alteration can take the form of cationic leaching from the matrix, or complete destruction of the silica network, either of which could constrain the ability to chemically identify distal tephra. Here we apply established models of vitreous durability to the published chemical analyses of a large number of Icelandic tephras in order to predict their relative durabilities under equivalent conditions. This suggests that some important tephras have relatively poor chemical stability, and that rhyolitic tephras are, in general, more stable than basaltic. We conclude that tephras should be expected to show predictable differential chemical stability in the post‐depositional environment. Copyright © 2003 John Wiley & Sons, Ltd.     

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.     

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.     

Electron microprobe analysis of glass shards from tephra assigned to set W,Mount St. Helens,Washington

We have extended the fallout areas for each of two members of tephra-set W, erupted from Mount St. Helens about 1500 ad, by several hundred kilometers beyond the limits mapped in 1975. We traced one member (We) east into Idaho, and the other (Wn) northeast into British Columbia. After using stratigraphic and petrographic observations to assign more than 100 tephra samples to set W, we found 26 of these, selected for chemical analysis, to be closely similar in content of Ca, Fe, and K in glass shards. But improved homogeneity was evident when the 26 sampling localities for tephra W were segregated geographically, east vs. northeast of the volcano. When Ca:Fe:K proportions were plotted on a ternary diagram, there was no overlap of the plotting areas for these two groups of tephra W samples. Without such data, tephra layers We and Wn are currently separable only from stratigraphic and geographic information. Partial glass analysis is also an aid, along with stratigraphic position and petrographic characteristics, in distinguishing tephra W from associated tephra layers. These include tephra layers T and Yn from Mount St. Helens, as well as older tephra layers from Mount Mazama and Glacier Peak.     

Identification and significance of a late Pleistocene tephra in Canterbury district,South Island,New Zealand

A rhyolitic ash 4 to 8 cm thick is well preserved within a thick loess unit in a coastal section 2 km long near Teviotdale, Canterbury district, South Island, New Zealand. The ash (informally named Tiromoana ash) contains fresh glass shards which give a fission-track age of 20,300 ± 7100 yr B.P. The only possible source for such a tephra with this age range is from Taupo Volcanic Zone (TVZ), North Island, some 550 km north of Teviotdale. Within the time span ca. 15,000 to 42,000 yr B.P. five widespread and voluminous rhyolitic tephras (viz. Rerewhakaaitu Ash, Rotoehu Ash, Kawakawa Tephra, Omataroa Tephra, and Mangaone Tephra) were erupted from TVZ. On the basis of the fission-track age, ferromagnesian mineralogy, and electron-microprobe analyses of glass shards and titanomagnetites from Tiromoana ash and the five possible correlatives listed above, Tiromoana ash is correlated with Kawakawa Tephra (dated by ¹⁴C at ca. 20,000 yr B.P.). This is the only known occurrence to date of Kawakawa Tephra in the South Island. Its preservation is attributed to special site conditions (low precipitation and minimal sheet erosion) leeward of a prominent terrace. The identification of the ash at Teviotdale as Kawakawa Tephra supports recently revised age assignments for the upper loess sheet in Canterbury. Moreover, it implies that loess enclosing Kawakawa Tephra in nonglaciated districts of southern North Island and Taupo Volcanic Zone is a correlative.     

Strontium Isotopic Signatures of Streams from Taylor Valley, Antarctica, Revisited: The Role of Carbonate Mineral Dissolution

We have collected and analyzed a larger set of stream waters for major ions and strontium isotopes in Taylor Valley, McMurdo Dry Valleys, Antarctica. These new data substantiate the concept that the dissolution of carbonate minerals is a significant source of strontium, even in polar desert environments where liquid water is primarily limited to stream channels. In Taylor Valley, most of the carbonate minerals present are the result of secondary processes, such as mineral precipitation and/or eolian deposition, and not through primary geologic sources, such as bedrock or till sources. In Von Guerard Stream (Lake Fryxell basin) and Andersen Creek (Lake Hoare basin), water samples were collected during the austral summer to determine short-term ⁸⁷Sr/⁸⁶Sr patterns. The observed variability in both time and space may be dependent on the relative amounts of primary and secondary carbonates present in the streambeds and hyporheic zone as well as contingent on the relative proportions of carbonate and aluminosilicate weathering.     

The influence of amphibole fractionation on the evolution of calc-alkaline andesite and dacite tephra from the central Aleutians,Alaska

Petrologic studies of tephra from Kanaga, Adak, and Great Sitkin Islands indicate that amphibole fractionation and magma mixing are important processes controlling the composition of calc-alkaline andesite and dacite magmas in the central Aleutians. Amphibole is ubiquitous in tephra from Kanaga and Adak Islands, whereas it is present only in a basaltic-andesite pumice from Great Sitkin. Dacitic tephra from Great Sitkin do not contain amphibole. Hornblende dacite tephra contain HB+PLAG+OX±OPX±CPX phenocrysts with simple zoning patterns, suggesting that the dacites evolved in isolated magma chambers. Andesitic tephra from Adak contain two pyroxene and hornbelende populations, and reversely zoned plagioclase, indicating a more complex history involving mixing and fractional crystallization. Mass balance calculations suggest that the andesitic tephra may represent the complements of amphibole-bearing cumulate xenoliths, both formed during the evolution of high-Al basalts. The presence of amphibole in andesitic and dacitic tephra implies that Aleutian cale-alkaline magmas evolve in the mid to lower crust under hydrous (>4 wt.% H₂O) and oxidizing (Ni–NiO) conditions. Amphibole-bearing andesites and pyroxene-bearing dacites from Great Sitkin indicates fractionation at several levels within the arc crust. Despite its absence in many calc-alkaline andesite and dacite lavas, open system behavior involving amphibole fractionation can explain the trace element characteristies of lavas found on Adak Island. Neither open nor closed system fractionation involving a pyroxene-bearing assemblage is capable of explaining the trace element concentrations or ratios found in the Adak suite. We envision a scenario where amphibole was initially a liquidus phase in many calc-alkaline magmas, but was later replaced by pyroxenes as the magmas rose to shallow levels within the crust. The mineral assemblage in these evolved lavas reflects shallow level equilibration of the magma, whereas the trace element chemistry provides evidence for a earlier, amphibole-bearing, mineral assemblage.     

Marker tephra layers in the late quaternary deposits of the Sea of Okhotsk as evidence of catastrophic eruptions in the Nemo caldera complex (Onekotan Island, Kuril Islands)

On the basis of complex studies of tephra layers (morphology of volcanic glass particles, chemical composition of glass particles and minerals, and REE distribution), marker tephra layers (K2, K3) were distinguished in the stratigraphic columns in the area of the Sea of Okhotsk. The areas of distribution of tephra layers and their age datings were determined. Tephra layers are shown to be similar in their chemical composition. They are correlated with strong explosive eruptions in the Nemo caldera complex on Onekotan Island (northern part of the Kuril Islands) in the Late Pleistocene.     

The Lateglacial to early Holocene tephrochronological record from Lake Hämelsee,Germany: a key site within the European tephra framework

Here we present the results of a detailed cryptotephra investigation through the Lateglacial to early Holocene transition, from a new sediment core record obtained from Lake Hämelsee, Germany. Two tephra horizons, the Laacher See Tephra (Eifel Volcanic Field) and the Saksunarvatn Ash (Iceland), have been previously described in this partially varved sediment record, indicating the potential of the location as an important Lateglacial tephrochronological site in northwest Europe. We have identified three further tephra horizons, which we correlate to: the c. 12.1 ka BP Vedde Ash (Iceland), the c. 11 ka BP Ulmener Maar tephra (Eifel Volcanic Field) and the c. 10.8 ka BP Askja‐S tephra (Iceland). Three additional cryptotephra deposits have been found (locally named HÄM_T1616, HÄM_T1470 and HÄM_T1456‐1455), which cannot be correlated to any known eruption at present. Geochemical analysis of the deposits suggests that these cryptotephras most likely have an Icelandic origin. Our discoveries provide age constraints for the new sediment records from Lake Hämelsee and enable direct stratigraphical correlations to be made with other tephra‐bearing sites across Europe. The new tephrostratigraphical record, within a partially varved Lateglacial sediment record, highlights the importance of Lake Hämelsee as a key site within the European tephra lattice.     

Diffusion-controlled biotite breakdown reaction textures at the solid/liquid transition in the continental crust

Two-phase quartz intergrowths with garnet, cordierite and tourmaline occur commonly in prograde high-temperature migmatites, granulites, as well as in the last crystallization stages of biotite granites. Structural, microtextural and mineralogical data show that they result from the breakdown of biotite in the presence of a melt phase associated with incongruent dissolution of feldspars into the melt and silica release (giving quartz in silica saturated rocks). Biotite breakdown and growth of Al-rich ferromagnesian minerals, occurring at the solid–liquid transition in the crust (early melting or final crystallization), is kinetically controlled by Fe and Mg mass transport, the network-forming cations Si and Al being locally compensated for by feldspar dissolution/crystallization. This process leads to significant changes with respect to equilibrium dehydration-melting reactions wherein quartz is a reactant and K-feldspar a reaction product. Therefore, quartz inclusions commonly occurring in garnets from granulite-facies metapelites and metagraywackes are not simply grains passively included during garnet growth. They may also correspond to newly crystallized phases. Resorption of feldspar may lead to more alkaline melt and to crystalline residue richer in Al than expected under equilibrium conditions. Hence, excess alumina in granulite-facies rocks is not necessarily related to initial alumina-rich whole-rock compositions (as currently considered), but may be due, at least partly, to kinetics of melting.