Laser ablation U/Pb age patterns of detrital zircons in the Schlieren Flysch (Central Switzerland): new evidence on the detrital sources

The palaeogeographic attribution of the Schlieren Flysch and its counterparts in the Gurnigel Nappe is still a matter of debate. These Late Alpine deep-sea trench deposits show a variable tectonic thrust relationship with other nappes inferring either an Ultrahelvetic or South Penninic origin of the elongated trench basin. An improved knowledge of the supplying source terranes of the Schlieren Flysch basin may add to the palaeogeographic ascription. Detrital zircons from seven representative samples have been dated by laser ablation ICP-MS analysis methods. The obtained age patterns are compared with standard provenance analysis methods including modal grain and heavy mineral statistics of the sandstones. The detrital zircons show two major populations of Pan-African (ca. 650-450Ma) and Variscan (ca. 360-320Ma) ages. A low abundance of Devonian detrital zircons separates the two main age populations. The Th/U signature of the zircons implies that igneous rocks of these two orogenic cycles directly, or indirectly (by multicyclic reworking of zircons) have strongly contributed to the clastic input. The earlier described bimodal turbiditic supply to the Schlieren Flysch basin is matched by the geochronologic data. With regard to the other petrographic signatures of the sandstones, it becomes evident that the granitic-rhyolitic source terrane derived (K-feldspar bearing) sandstones show a higher abundance of Pan-African zircons and a higher abundance of tourmaline in the heavy mineral fractions. In contrast, the exclusively plagioclase-bearing sandstones from the tonalitic-andesitic source contain a majority of Variscan zircons and higher contents of apatite. In addition, we observe a third minor population comprising Triassic-Early Jurassic detrital zircons. The correlation of the obtained detrital zircon ages with pre-Cretaceous igneous, metamorphic and geodynamic events, which affected the basement of the northern and southern margins of the Alpine Tethys reveals a major difference by the presence of Triassic magmatic products and volcaniclastics in South Alpine and Austroalpine units. The discovery of the minor Triassic-Early Jurassic population in both sandstone types of the Schlieren Flysch would argue for the derivation of the clastic material from the southern Alpine Tethys or Adriatic-Apulian margi

Size-related vaporisation and ionisation of laser-induced glass particles in the inductively coupled plasma

Ongoing discussions about the origin of elemental fractionation occurring during LA-ICP-MS analysis show that this problem is still far from being well understood. It is becoming accepted that all three possible sources (ablation, transport, excitation) contribute to elemental fractionation. However, experimental data about the vaporisation size limit of different particles in the ICP, as produced in laser ablation, have not been available until now. This information should allow one to determine the signal contributing mass within the ICP and would further clarify demands on suitable laser ablation systems and gas atmospheres in terms of their particle size distribution. The results presented here show a vaporisation size limit of laser induced particles, which was found at particle sizes between 90nm and 150nm using an Elan6000 ICP-MS. Due to the fact that the ICP-MS response was used as evaluation parameter, vaporisation and ionisation limits are not distinguishable. The upper limit was determined by successively removing the larger particles from the aerosol, which was created by ablation of a NIST610 glass standard at a wavelength of 266nm, using a recently developed particle separation device. Various particle fractions were separated from the aerosol entering the ICP. The decrease in signal intensity is not proportional to the decrease in volume, indicating that particles above 150nm in diameter are not completely ionised in the ICP. Due to the limited removal range of the particle separation device, which cannot remove particles smaller than 150nm, single hole ablations were used to determine the lower vaporisation limit. This is based on measurements showing that larger particles occur dominantly during the first 100laser pulses only. After this period, the ratio of ICP-MS counts and total particle volume was found to be constant while most of the particles are smaller than 90nm, indicating complete vaporisation and ionisation of these particles. To describe the influence of different plasma forward powers on the vaporisation limit, the range 1000-1600W was studied. Results indicate that optimum vaporisation and ionisation occurs at 1300W. However, an increase of the particle ionisation limit towards larger particles was not observed within the accuracy of this study using the full range of parameters available for optimisation on commonly used ICP-MS instrument

Rhyolite generation prior to a Yellowstone supereruption: insights from the Island Park-Mount Jackson rhyolite series

The Yellowstone volcanic field is one of the largest and best-studied centres of rhyolitic volcanism on Earth, yet it still contains little-studied periods of activity. Such an example is the Island Park–Mount Jackson series, which erupted between the Mesa Falls and Lava Creek caldera-forming events as a series of rhyolitic domes and lavas. Here we present the first detailed characterisation of these lavas and use our findings to provide a framework for rhyolite generation in Yellowstone between 1·3 and 0·6 Ma, as well as to assess whether magmatic evolution hints at a forthcoming super-eruption. These porphyritic (15–40% crystals) lavas contain mostly sanidine and quartz with lesser amounts of plagioclase (consistent with equilibrium magmatic modelling via rhyolite-MELTS) and a complex assemblage of mafic minerals. Mineral compositions vary significantly between crystals in each unit, with larger ranges than expected from a single homogeneous population in equilibrium with its host melt. Oxygen isotopes in quartz and sanidine indicate slight depletions (δ18Omagma of 5·0–6·1‰), suggesting some contribution by localised remelting of hydrothermally altered material in the area of the previous Mesa Falls Tuff-related caldera collapse. The preservation of variable O isotopic compositions in quartz requires crystal entrainment less than a few thousand years prior to eruption. Late entrainment of rhyolitic material is supported by the occurrence of subtly older sanidines dated by single-grain 40Ar/39Ar geochronology. The eruption ages of the lavas show discrete clusters illustrating that extended quiescence (>100 kyr) in magmatic activity may be a recurring feature in Yellowstone volcanism. Ubiquitous crystal aggregates, dominated by plagioclase, pyroxene and Fe–Ti oxides, are interpreted as cumulates co-erupted with their extracted liquid. Identical crystal aggregates are found in both normal-δ18O and low-δ18O rocks from Yellowstone, indicating that common petrogenetic processes characterise both volcanic suites, including the late-stage extraction of melt from an incrementally built upper crustal mush zone

Rapid magma generation or shared magmatic reservoir? Petrology and geochronology of the Rat Creek and Nelson Mountain Tuffs, CO, USA

This study was supported by the ETH Research Grant ETH-34 15-2 (JS).Large-volume silicic volcanism poses global hazards in the form of proximal pyroclastic density currents, distal ash fall and short-term climate perturbations, which altogether warrant the study of how silicic magma bodies evolve and assemble. The southern rocky mountain volcanic field (SRMVF) is home to some of the largest super-eruptions in the geological record, and has been studied to help address the debate over how quickly eruptible magma batches can be assembled–whether in decades to centuries, or more slowly over 100’s of kyr. The present study focuses on the San Luis caldera complex within the SRMVF, and discusses the paradigms of rapid magma generation vs. rapid magma assembly. The caldera complex consists of three overlapping calderas that overlie the sources of three large-volume mid-Cenozoic ignimbrites: first, the Rat Creek Tuff (RCT; zoned dacite-rhyolite, 150 km3), followed by the Cebolla Creek Tuff (mafic dacite, 250 km3) and finally, the Nelson Mountain Tuff (NMT; zoned dacite-rhyolite, 500 km3), which are all indistinguishable in age by 40Ar/39Ar dating. We argue for a shared magmatic history for the three units on the basis of (1) similar mineral trace element compositions in the first and last eruptions (plagioclase, sanidine, biotite, pyroxene, amphibole, titanite, and zircon), (2) overlapping zircon U-Pb ages in all three units, and (3) similar thermal rejuvenation signatures visible in biotite (low-Mn, high-Ba) and zircon (low-Hf, low-U) geochemistry within the RCT and NMT. It is postulated that the NMT was sourced from a pre-existing magma reservoir to the northeast, which is corroborated by the formation of the nearby Cochetopa Caldera during the eruption of the NMT. The inferred lateral magma transport has two important implications: (1) it demonstrates long-distance transport of highly viscosity magmas at volumes (100’s of km3) not previously recorded, and (2) the sourcing of magma from a nearby pre-existing magma reservoir greatly reduces the rate of magma generation necessary to explain the close coincidence of three overlapping, large-volume magma systems. Additionally, the concept of magmatic “flux” (km3 kyr−1) is discussed in this context, and it is argued that an area-normalized flux (km3 kyr–1 km−2) provides a more useful number for measuring magma production rates: it is expected that magmatic volumes will scale with footprint of the thermal anomaly, and not taking this into account may lead to errant volumetric flux (km3 kyr−1) estimates. Meanwhile, area-normalized flux estimates in a given area are similar between units, consistent with evolution in a relatively constant thermal regime. Such estimates also demonstrate similar fluxes for ∼cogenetic volcanic and plutonic units.Publisher PDFPeer reviewe

Chemical elements recorded by Quercus mongolica Fisch. ex Ledeb. Tree rings reveal trends of pollution history in Harbin, China

Rapid industrialization has led to a dramatic increase in air pollution. In China, the factors driving the abundance and composition of smog, particularly fine particulate matter, remain poorly understood, and short-term air pollution data are available from few air quality monitoring networks. Using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), chemical elements (Mg, Al, Si, S, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Tl, Pb, Bi) were analyzed in Quercus mongolica Fisch. ex Ledeb. tree rings from Harbin, China, in latewood at 5-year resolution over the period 1965–2020. The temporal trend of some elements was influenced by physiological factors, by environmental factors such as pollution, or influenced by both. Mg, K, Zn, Cu, Ni, Pb, As, Sr and Tl showed changes in pollution levels over time. The signal of K, Zn, Ni, Cu and Pb in trees from Harbin statistically did not differ from those at the control site after the 2000s. Our analysis confirmed the success of the undertaken emission reduction measures, which lead to an improvement in China’s urban air quality after 2010. However, As increased from 2000 to 2020 in Harbin which is consistent with rising As concentrations in China. Our study proved that dendrochemistry is a reliable tool to monitor the long-term history of pollution and to contribute to extending instrumental records of pollution back in time

Monitoring air pollution close to a cement plant and in a multi-source industrial area through tree-ring analysis

Thirty-two trace elements were examined in the tree rings of downy oak to evaluate the pollution levels close to a cement plant isolated in a rural context and an industrial area where multiple sources of air pollution are or were present. Tree cores were collected from trees growing 1 km from both the cement plant and the industrial area that are located 8 km from each other. The analysis of the trace elements was performed on annual tree rings from 1990 to 2016 using laser ablation inductively coupled plasma mass spectrometry. Trace elements Cs, Mg, Mn, S and Zn reflected the emission history of the cement plant. Their values have increased since early 2000s, when the cement plant started its activity. However, the lack of significant trends of pollutants in the tree rings from the industrial area and the possible effect of translocation and volatility of some elements left open questions. The very weak changes of the other trace elements in the period 1990–2016 suggest those elements do not mark any additional effect of the industrial activity on the background pollution. The results confirm that downy oak trees growing close to isolated industrial plants must be considered a pollution forest archive accessible through dendrochemistry

Controls on lithium concentration and diffusion in zircon

This study was supported by ETH Research Grants ETH-34 15-2 (JS), ETH-14 16-1 (FM) and by Swiss National Science Foundation research grant 200020-153112/1 (NK).Thermal annealing of zircons prior to uranium-lead dating by laser ablation inductively coupled plasma mass spectrometry is a commonly-implemented procedure which improves data accuracy and precision by partially repairing radiation damage from the decay of uranium and thorium. However, it also leads to significantly higher concentrations of lithium in the zircon lattice, which become positively correlated with trivalent yttrium and rare earth elements. Prior to such treatments, zircons typically contain lithium below detection limits (typically <0.55 μg g−1), unless correlated with lanthanum and aluminum (i.e., melt/mineral inclusion tracer elements). This suggests that lithium in zircon is primarily sequestered within inclusions, and is able to permeate the crystal lattice to couple with yttrium and rare earth elements during the thermal annealing procedure. This process occurs 2–3 orders of magnitude faster than diffusion experiments have previously determined, indicating that another diffusion mechanism may apply. A model is proposed, whereby: (i) charge compensation of stoichiometrically over-abundant trivalent cations under water-rich magmatic conditions is likely accomplished by hydrogen, given the incompatibility of lithium in zircon and the abundance of hydrogen. However, (ii) conditions that are high temperature and low pressure (characteristic of both thermal annealing and the syn-eruptive environment), drive silicate melt inclusions to exsolve water, generating a motive force for both hydrogen and lithium from inclusions to permeate the lattice in order to reestablish electrochemical equilibrium between the interior and exterior of the zircon. To test the pressure dependency of lithium migration in the zircon lattice, thermal annealing experiments were performed at 850 °C and 1 bar, 2 kbar and 6 kbar using zircons from the Fish Canyon Tuff. The experiments demonstrate that thermal annealing at 2 and 6 kbar inhibits lithium mobility, with zircons registering lithium concentrations below detection limits similar to controls. The experimental results suggest that lithium concentrations in zircon are vulnerable to rapid perturbation by decompression (concurrent with high temperatures), which further indicate that lithium-in-zircon diffusion data should be interpreted with caution.Publisher PDFPeer reviewe

Forming and preserving aragonite in shear zones: First report of blueschist facies metamorphism in the Jabal Akhdar Dome, Oman Mountains

We report the first occurrence of high-pressure metamorphic aragonite in Precambrian carbonates of the Jabal Akhdar Dome in the Oman Mountains (northern Oman). We propose a model for both its formation at blueschist facies conditions and its subsequent preservation to the surface within the tectonic framework of the Late Cretaceous obduction of the Semail Ophiolite. Aragonite formed at temperature ∼350 °C and pressure ≥0.9 GPa and is preserved within mylonitic shear zones and in stretched-fiber dilational veins where the necessary conditions for its formation and preservation, such as plastic strain accommodation, fluid-enhanced mineralogical reactions, and an anisotropic permeability structure, were preferentially met with respect to the surrounding rock. High-strain structural domains are ideal sites to look for and study prograde and retrograde high-pressure metamorphic histories in deeply subducted and exhumed terrains

Split-grain 40Ar/39Ar dating : integrating temporal and geochemical data from crystal cargoes

NERC is acknowledged for continued funding of AIF at SUERC, East Kilbride. This work was supported by an ETH research grant (ETH-05 13-2) and funds from Swiss National Science Foundation research grants (SNSF 200021-146268 and SNSF 200021-155923/1) and US National Science Grant 1425491.Large sanidine crystals from the Mesa Falls Tuff (MFT), Yellowstone volcanic field, have been split and individually dated via high-precision 40Ar/39Ar geochronology with the undated portions further analysed for major elements, trace elements, Pb and Sr isotopes in the sanidine and trace elements in the melt inclusions. This allows the geochemical and geochronological identity of an individual sanidine to be combined. Our MFT sanidines return a preferred eruption age of 1.3011 ± 0.0015/0.0016 Ma (2-sigma, n = 56, MSWD 0.8, analytical/full external) with a significant component of subtly older (up to ~ 2 Ma) crystals. Combined with recent results (Rivera et al., 2016, Journal of Petrology 57, 9, 1677–1704) our data define a global mean sanidine 40Ar/39Ar age for the MFT of 1.3022 ± 0.0006/0.0008 Ma (2 sigma, analytical/full external) relative to Alder Creek sanidine at 1.1891 Ma and total λ40Ar 5.5305e-10, which gives RACsMFT: 1.09542 ± 0.00050. The ability to couple geochemistry and geochronology from a single grain allows us, for the first time, to evaluate the origin of the subtly older sanidines present in the same pumices as juvenile sanidines. Melt inclusions from all Mesa Falls sanidines represent extremely fractionated melts with low Sr contents (max. 12 ppm, n = 39), and rare earth element patterns which require that they be formed from an A-type magma rather than the preceding subduction-related Eocene volcanism as previously suggested. 87Sr/86Sr from juvenile and subtly older sanidines shows the same range of 0.7073 to 0.7096, illustrating the susceptibility of such low-Sr melts to slight degrees of assimilation. Pb isotopic compositions are more restricted and identical between the juvenile and subtly older sanidines in the Mesa Falls Tuff (207Pb/206Pb 0.900–0.903, 208Pb/206Pb 2.217–2.226, n = 83) and these compositions rule out the underlying Huckleberry Ridge Tuff member B as a potential source for the subtly older sanidine. LA-ICPMS 206Pb/238U dating of Mesa Falls zircons supports no role for the Huckleberry Ridge Tuff. Rather, these subtly older sanidines are interpreted as containing excess mantle-derived Ar. The ability to couple the geochemical and geochronological records within individual sanidine crystals that we demonstrate here has potential to provide new insights for a variety of petrological studies such as diffusional modelling.PostprintPeer reviewe