Miocene and Pliocene Silicic Coromandel Volcanic Zone Tephras from ODP Site 1124-C: Petrogenetic Applications and Temporal Evolution

<p>The Coromandel Volcanic Zone (CVZ) was the longest-lived area of volcanism in New Zealand hosting the commencement of large explosive rhyolitic and ignimbrite forming eruptions. The NW trending Coromandel Peninsula is the subaerial remnant of the Miocene-Pliocene CVZ, which is regarded as a tectonic precursor to the Taupo Volcanic Zone (TVZ), currently the most dynamic and voluminous rhyolitic volcanic centre on Earth. This study presents new single glass shard major and trace element geochemical analyses for 72 high-silica volcanic tephra layers recovered from well-dated deep-sea sediments of the SW Pacific Ocean by the Ocean Drilling Program (ODP) Leg 181. ODP Site 1124, ~720 km south and east from the CVZ, penetrated sediments of the Rekohu Drift yielding an unprecedented record of major explosive volcanic eruptions owing to the favourable location and preservation characteristics at this site. This record extends onshore eruptive sequences of CVZ explosive volcanism that are obscured by poor exposure, alteration, and erosion and burial by younger volcanic deposits. Tephra layers recovered from Site 1124 are well-dated through a combination of biostratigraphic and palaeomagnetic methods allowing the temporal geochemical evolution of the CVZ to be reconstructed in relation to changes in the petrogenesis of CVZ arc magmas from ~ 10 to 2 Ma. This thesis establishes major and trace element geochemical "fingerprints" for all Site 1124-C tephras using well-established (wavelength dispersive electron probe microanalysis) and new (laser ablation inductively coupled plasma mass spectrometry) in situ single glass shard microanalytical techniques. Trace element analysis of Site 1124-C glass shards (as small as 20 um) demonstrate that trace element signatures offer a more specific, unequivocal characterisation for distinguishing (and potentially correlating) between tephras with nearly identical major element compositions. The Site 1124-C core contains 72 unaltered Miocene-Pliocene volcanic glass-shard-bearing laminae > 1 cm thick that correspond to 83 or 84 geochemical eruptive units. Revised eruptive frequencies based on the number of geochemical eruptive units identified represent at least one eruption every 99 kyr for the late Miocene and one per 74 kyr for the Pliocene. The frequency of tephra deposition throughout the history of the CVZ has not been constant, rather reflecting pulses of major explosive eruptions resulting in closely clustered groups of tephra separated by periods of reduced activity, relative volcanic quiescence or non-tephra deposition. As more regular activity became prevalent in the Pliocene, it was accompanied by more silicic magma compositions. Rhyolitic volcanic glass shards are characterised by predominantly calc-alkaline and minor high-K enriched major element compositions. Major element compositional variability of the tephras deposited between 10 Ma and 2 Ma reveals magma batches with pre-eruptive compositional gradients implying a broad control by fractional crystallisation. Trace element characterisation of glass shards reveals the role of magmatic processes that are not readily apparent in the relatively homogeneous major element compositions. Multi-element diagrams show prominent negative Sr and Ti anomalies against primitive mantle likely caused by various degrees of plagioclase and titanomagnetite fractional crystallisation in shallow magma chambers. Relative Nb depletion, characteristic of arc volcanism, is moderate in CVZ tephras. HFSEs (e.g. Nb, Zr, Ti) and HREEs (e.g. Yb, Lu) remain immobile during slab fluid flux suggesting they are derived from the mantle wedge. LILE (e.g. Rb, Cs, Ba, Sr) and LREE (e.g. La, Ce) enrichments are consistent with slab fluid contribution. B/La and Li/Y ratios can be used as a proxy for the flux of subducting material to the mantle wedge, they suggest there is a strong influence from this component in the generation of CVZ arc magmas, potentially inducing melting. CVZ tephra show long-term coherent variability in trace element geochemistry. Post ~ 4 Ma tephras display a more consistent, less variable, chemical fingerprint that persists up to and across the CVZ/TVZ transition at ~ 2 Ma. Initiation of TVZ volcanism may have occurred earlier than is presently considered, or CVZ to TVZ volcanism may have occurred without significant changes in magma generation processes.</p>

Miocene and Pliocene Silicic Coromandel Volcanic Zone Tephras from ODP Site 1124-C: Petrogenetic Applications and Temporal Evolution

<p>The Coromandel Volcanic Zone (CVZ) was the longest-lived area of volcanism in New Zealand hosting the commencement of large explosive rhyolitic and ignimbrite forming eruptions. The NW trending Coromandel Peninsula is the subaerial remnant of the Miocene-Pliocene CVZ, which is regarded as a tectonic precursor to the Taupo Volcanic Zone (TVZ), currently the most dynamic and voluminous rhyolitic volcanic centre on Earth. This study presents new single glass shard major and trace element geochemical analyses for 72 high-silica volcanic tephra layers recovered from well-dated deep-sea sediments of the SW Pacific Ocean by the Ocean Drilling Program (ODP) Leg 181. ODP Site 1124, ~720 km south and east from the CVZ, penetrated sediments of the Rekohu Drift yielding an unprecedented record of major explosive volcanic eruptions owing to the favourable location and preservation characteristics at this site. This record extends onshore eruptive sequences of CVZ explosive volcanism that are obscured by poor exposure, alteration, and erosion and burial by younger volcanic deposits. Tephra layers recovered from Site 1124 are well-dated through a combination of biostratigraphic and palaeomagnetic methods allowing the temporal geochemical evolution of the CVZ to be reconstructed in relation to changes in the petrogenesis of CVZ arc magmas from ~ 10 to 2 Ma. This thesis establishes major and trace element geochemical "fingerprints" for all Site 1124-C tephras using well-established (wavelength dispersive electron probe microanalysis) and new (laser ablation inductively coupled plasma mass spectrometry) in situ single glass shard microanalytical techniques. Trace element analysis of Site 1124-C glass shards (as small as 20 um) demonstrate that trace element signatures offer a more specific, unequivocal characterisation for distinguishing (and potentially correlating) between tephras with nearly identical major element compositions. The Site 1124-C core contains 72 unaltered Miocene-Pliocene volcanic glass-shard-bearing laminae > 1 cm thick that correspond to 83 or 84 geochemical eruptive units. Revised eruptive frequencies based on the number of geochemical eruptive units identified represent at least one eruption every 99 kyr for the late Miocene and one per 74 kyr for the Pliocene. The frequency of tephra deposition throughout the history of the CVZ has not been constant, rather reflecting pulses of major explosive eruptions resulting in closely clustered groups of tephra separated by periods of reduced activity, relative volcanic quiescence or non-tephra deposition. As more regular activity became prevalent in the Pliocene, it was accompanied by more silicic magma compositions. Rhyolitic volcanic glass shards are characterised by predominantly calc-alkaline and minor high-K enriched major element compositions. Major element compositional variability of the tephras deposited between 10 Ma and 2 Ma reveals magma batches with pre-eruptive compositional gradients implying a broad control by fractional crystallisation. Trace element characterisation of glass shards reveals the role of magmatic processes that are not readily apparent in the relatively homogeneous major element compositions. Multi-element diagrams show prominent negative Sr and Ti anomalies against primitive mantle likely caused by various degrees of plagioclase and titanomagnetite fractional crystallisation in shallow magma chambers. Relative Nb depletion, characteristic of arc volcanism, is moderate in CVZ tephras. HFSEs (e.g. Nb, Zr, Ti) and HREEs (e.g. Yb, Lu) remain immobile during slab fluid flux suggesting they are derived from the mantle wedge. LILE (e.g. Rb, Cs, Ba, Sr) and LREE (e.g. La, Ce) enrichments are consistent with slab fluid contribution. B/La and Li/Y ratios can be used as a proxy for the flux of subducting material to the mantle wedge, they suggest there is a strong influence from this component in the generation of CVZ arc magmas, potentially inducing melting. CVZ tephra show long-term coherent variability in trace element geochemistry. Post ~ 4 Ma tephras display a more consistent, less variable, chemical fingerprint that persists up to and across the CVZ/TVZ transition at ~ 2 Ma. Initiation of TVZ volcanism may have occurred earlier than is presently considered, or CVZ to TVZ volcanism may have occurred without significant changes in magma generation processes.</p>

Unraveling the Holocene Eruptive History of Flores Island (Azores) Through the Analysis of Lacustrine Sedimentary Records

Lacustrine sequences from active volcanic settings usually hold a rich and continuous record of tephra layers, providing a critical source of information to reconstruct a most complete eruptive history of a region. Lake sedimentary records on volcanic islands are particularly useful as the typical small size of these islands and their steep subaerial and submarine slopes lead to a lower preservation of potential erodible pyroclastic deposits. Here we explore the lacustrine sedimentary record of Lagoa da Lomba, a crater lake in the central upland area of Flores Island (Azores), to gain insight into the recent eruptive history of this island. The strategic location of Lagoa da Lomba, half distance between the two clusters of recent volcanic activity of the island, together with its long-lasting record, back to 23.52 cal kyr BP, makes this lake a privileged site to investigate the Holocene volcanic history of Flores. Based on a detailed stratigraphic characterization of sediments from a lake transect of three cores, supported by glass shard geochemistry and radiocarbon dating, we recognized four Holocene eruptive events taking place between 6.28 and 2.36 cal kyr BP, demonstrating that the Holocene volcanic activity at Flores Island may have lasted longer than previously reported. Glass shard geochemistry from the different tephra layers suggests three populations, basaltic to trachybasaltic in composition, where the last eruption is the least evolved endmember. Two of the four eruptive events correlate with subaerially-exposed pyroclastic sequences, in terms of stratigraphy and geochemistry. The most recent event recorded at Lagoa da Lomba was constrained to 3.66 – 2.36 cal kyr BP and linked to an eruption sourced from Lagoa Comprida Volcanic System. The second most recent eruptive event was sourced from Lagoa Funda Volcanic System and dated at 3.66 cal kyr BP. Our observations show that Flores experienced vigorous volcanic activity during the Late Holocene. Therefore, contrary to what is assumed, the possibility of future eruptions should be properly considered, and the volcanic hazard here should not be underestimated. Moreover, we highlight the importance of tephrostratigraphy in recent lake sediments to reconstruct past volcanic activity, especially at small volcanic islands, such as Flores, where exposure is poor due to erosion within the limited subaerial area and the dense vegetation.

TephraNZ: a major- and trace-element reference dataset for glass-shard analyses from prominent Quaternary rhyolitic tephras in New Zealand and implications for correlation

Although analyses of tephra-derived glass shards have been undertaken in New Zealand for nearly four decades (pioneered by Paul Froggatt), our study is the first to systematically develop a formal, comprehensive, open-access reference dataset of glass-shard compositions for New Zealand tephras. These data will provide an important reference tool for future studies to identify and correlate tephra deposits and for associated petrological and magma-related studies within New Zealand and beyond. Here we present the foundation dataset for TephraNZ, an open-access reference dataset for selected tephra deposits in New Zealand. Prominent, rhyolitic, tephra deposits from the Quaternary were identified, with sample collection targeting original type sites or reference locations where the tephra's identification is unequivocally known based on independent dating and/or mineralogical techniques. Glass shards were extracted from the tephra deposits, and major- and trace-element geochemical compositions were determined. We discuss in detail the data reduction process used to obtain the results and propose that future studies follow a similar protocol in order to gain comparable data. The dataset contains analyses of glass shards from 23 proximal and 27 distal tephra samples characterising 45 eruptive episodes ranging from Kaharoa (636 ± 12 cal yr BP) to the Hikuroa Pumice member (2.0 ± 0.6 Ma) from six or more caldera sources, most from the central Taupō Volcanic Zone. We report 1385 major-element analyses obtained by electron microprobe (EMPA), and 590 trace-element analyses obtained by laser ablation (LA)-ICP-MS, on individual glass shards. Using principal component analysis (PCA), Euclidean similarity coefficients, and geochemical investigation, we show that chemical compositions of glass shards from individual eruptions are commonly distinguished by major elements, especially CaO, TiO2, K2O, and FeOtt (Na2O+K2O and SiO2/K2O), but not always. For those tephras with similar glass major-element signatures, some can be distinguished using trace elements (e.g. HFSEs: Zr, Hf, Nb; LILE: Ba, Rb; REE: Eu, Tm, Dy, Y, Tb, Gd, Er, Ho, Yb, Sm) and trace-element ratios (e.g. LILE/HFSE: Ba/Th, Ba/Zr, Rb/Zr; HFSE/HREE: Zr/Y, Zr/Yb, Hf/Y; LREE/HREE: La/Yb, Ce/Yb). Geochemistry alone cannot be used to distinguish between glass shards from the following tephra groups: Taupō (Unit Y in the post-Ōruanui eruption sequence of Taupō volcano) and Waimihia (Unit S); Poronui (Unit C) and Karapiti (Unit B); Rotorua and Rerewhakaaitu; and Kawakawa/Ōruanui, and Okaia. Other characteristics, including stratigraphic relationships and age, can be used to separate and distinguish all of these otherwise-similar tephra deposits except Poronui and Karapiti. Bimodality caused by K2O variability is newly identified in Poihipi and Tahuna tephras. Using glass-shard compositions, tephra sourced from Taupō Volcanic Centre (TVC) and Mangakino Volcanic Centre (MgVC) can be separated using bivariate plots of SiO2/K2O vs. Na2O+K2O. Glass shards from tephras derived from Kapenga Volcanic Centre, Rotorua Volcanic Centre, and Whakamaru Volcanic Centre have similar major- and trace-element chemical compositions to those from the MgVC, but they can overlap with glass analyses from tephras from Taupō and Okataina volcanic centres. Specific trace elements and trace-element ratios have lower variability than the heterogeneous major-element and bimodal signatures, making them easier to fingerprint geochemically.

Rapid Tephra Identification in Geological Archives With Computed Tomography: Experimental Results and Natural Applications

Volcanic ash (tephra) horizons represent powerful chronological and stratigraphic markers: rapid and widespread deposition allows for correlation of geological records in time and space. Recent analytical advances enable identification of invisible ash (cryptotephra) up to thousands of kilometers from its volcanic source. This momentum has greatly expanded the reach and potential of tephrochronology: some deposits can now be traced across continents and oceans. However, the laborious laboratory procedures required to identify tephra horizons in geological archives hold back the pace of progress. By allowing the rapid visualization of ash at micrometer (µm) scales, computed tomography (CT) holds great promise to overcome these restrictions. In this study, we further demonstrate the potential of this tool for the tephra community with experimental results and applications on conventionally analyzed archives. A custom-made scanner helps us strike a balance between the convenience of whole-core medical scanners and the µm-resolution of micro-CT systems. Using basic image processing tools that can be readily mastered by tephrochronologists, we identified invisible horizons down to ∼500 shards in synthetic cores. In addition, procedures for the removal of image artifacts can be used to visualize other paleoenvironmental indicators such as bioturbation burrows, ice rafted debris or mineral dust. When applied on segments of manually counted natural archives, our approach captures cryptic glass shard maxima down to ∼300 shards/cm3. We also highlight the value of CT to help optimize sampling strategies by identifying micrometer-scale ash horizons that were not detected in shard count profiles. In conclusion, this work helps broaden the applicability of CT as a promising frontier in tephrochronology that can advance the field by optimizing the efficiency and accuracy of isochron detection.

TephraNZ: a major and trace element reference dataset for prominent Quaternary rhyolitic tephras in New Zealand and implications for correlation

Although analyses of tephra-derived glass shards have been undertaken in New Zealand for nearly four decades (pioneered by Paul Froggatt), our study is the first to systematically develop a formal, comprehensive, open access, reference dataset of glass-shard compositions for New Zealand tephras. These data will provide an important reference tool for future studies to identify and correlate tephra deposits and for associated petrological and magma-related studies within New Zealand and beyond. Here we present the foundation dataset for TephraNZ, an open access reference dataset for selected tephra deposits in New Zealand. Prominent, rhyolitic, tephra deposits from the Quaternary were identified, with sample collection targeting original type sites or reference locations where the tephra's identification is unequivocally known based on independent dating or mineralogical techniques. Glass shards were extracted from the tephra deposits and major and trace element geochemical compositions were determined. We discuss in detail the data reduction process used to obtain the results and propose that future studies follow a similar protocol in order to gain comparable data. The dataset contains analyses of twenty-three proximal and twenty-seven distal tephra samples characterising 45 eruptive episodes ranging from Kaharoa (636 &amp;pm; 12 cal. yrs BP) to the Hikuroa Pumice member (2.0 &amp;pm; 0.6 Ma) from six or more caldera sources, most from the central Taupō Volcanic Zone. We report 1385 major element analyses obtained by electron microprobe (EMPA), and 590 trace element analyses obtained by laser ablation (LA)-ICP-MS, on individual glass shards. Using PCA, Euclidean similarity coefficients, and geochemical investigation, we show that chemical compositions of glass shards from individual eruptions are commonly distinguished by major elements, especially CaO, TiO2, K2O, FeOt (Na2O+ K2O and SiO2/K2O), but not always. For those tephras with similar glass major-element signatures, some can be distinguished using trace elements (e.g. HFSEs: Zr, Hf, Nb; LILE: Ba, Rb; REE: Eu, Tm, Dy, Y, Tb, Gd, Er, Ho, Yb, Sm), and trace element ratios (e.g. LILE / HFSE: Ba / Th, Ba / Zr, Rb / Zr; HFSE / HREE: Zr / Y, Zr / Yb, Hf / Y; LREE / HREE: La / Yb, Ce / Yb). Geochemistry alone cannot be used to distinguish between glass shards from the following tephra groups: Taupō (Unit Y in the post-Ōruanui eruption sequence of Taupō volcano) and Waimihia (Unit S); Poronui (Unit C) and Karapiti (Unit B); Rotorua and Rerewhakaaitu; and Kawakawa/Ōruanui, Okaia, and Unit L (of the Mangaone subgroup eruption sequence). Other characteristics can be used to separate and distinguish all of these otherwise-similar eruptives except Poronui and Karapiti. Bimodality caused by K2O variability is newly identified in Poihipi and Tahuna tephras. Using glass shard compositions, tephra sourced from Taupō Volcanic Centre (TVC) and Mangakino Volcanic Centre (MgVC) can be separated using bivariate plots of SiO2/K2O vs. Na2O+K2O. Glass shards from tephras derived from Kapenga Volcanic Centre, Rotorua Volcanic Centre, and Whakamaru Volcanic Centre have similar major- and trace-element chemical compositions to those from the MgVC, but can overlap with glass analyses from tephras from Taupō and Okataina volcanic centres. Specific trace elements and trace element ratios have lower variability than the heterogeneous major element and bimodal signatures, making them easier to geochemically fingerprint.

Cryptotephra from Lipari Volcano in the eastern Gulf of Taranto (Italy) as a time marker for paleoclimatic studies

We present the first tephroanalysis based on geochemical fingerprinting of volcanic glass shards from eastern Apulian shelf sediments in the Gulf of Taranto (Italy). High sedimentation rates in the gulf are ideal for high-resolution paleoclimate studies, which rely on accurate age models. Cryptotephrostratigraphy is a novel tool for the age assessment of marine sediment cores in the absence of discrete tephra layers. High-resolution quantitative analysis of glass shard abundance in the uppermost 45 cm of a gravity core identified two cryptotephras. Microprobe analysis of glass shards supported by an accelerator mass spectrometry 14C–based age model identified the pronounced primary cryptotephra at 36 cm bsf (below sea floor) as the felsic AD 776 Monte Pilato Eruption on the island of Lipari, whereas the thinner, mafic tephra layer at 1.5 cm bsf is associated with the AD 1944 eruption of Somma-Vesuvius. Identifying these tephra layers provides an additional, 14C-independent, stratigraphic framework for further paleoclimatic studies allowing us to link Mediterranean climate and hydrology to orbital variation and large-scale atmospheric processes. Our results underline the importance of qualitative tephrostratigraphy in a highly geodynamic region, where solely quantitative approaches have demonstrated to bear a high potential for false correlations between tephra layers and eruptions.

Capability of U–Pb dating of zircons from Quaternary tephra: Jemez Mountains, NM, and La Sal Mountains, UT, USA

Two Quaternary tephras derived from the Jemez Mountains, New Mexico – the Guaje and Tsankawi tephras – are difficult to distinguish due to their similar glass-shard chemical composition. Differences in bulk chemical composition are small as well. Here we examine the feasibility to assign an age to a distal tephra layer in the La Sal Mountains, Utah, by U–Pb dating of zircons and to correlate it with one of the two Jemez eruptions. We also dated original Jemez tephras for comparison. Even though the tephras are very young, we obtained reasonable age determinations using the youngest cluster of zircon grains overlapping in age at 2σ. Thereafter, the Guaje tephra is 1.513 ± 0.021 Myr old. The La Sal Mountains tephra is correlated with the Tsankawi tephra. Three samples yielded a common age range of 1.31–1.40 Myr. All ages are in slight disagreement with published age determinations obtained by 40Ar ∕ 39Ar dating. These findings indicate that distal Jemez tephras can be distinguished by U–Pb dating. Furthermore, we encourage giving this method a try for age assignments even of Quaternary volcanic material.