Automated Extraction of a Five‐Year LA‐ICP‐MS Trace Element Data Set of Ten Common Glass and Carbonate Reference Materials: Long‐Term Data Quality,Optimisation and Laser Cell Homogeneity

LA‐ICP‐MS is increasingly applied to obtain quantitative multi‐element data with minimal sample preparation, usually achieved by calibration using reference materials (RMs). However, some ubiquitous RMs, for example the NIST SRM 61× series glasses, suffer from reported value uncertainties for certain elements. Moreover, no long‐term data set of analyses conducted over a range of ablation and tuning conditions exists. Thus, there has been little rigorous examination of the extent to which offsets between measured and reported values are the result of error in these values rather than analytically induced fractionation. We present new software (‘LA‐MINE’), capable of extracting LA‐ICP‐MS data with no user input, and apply this to our system, yielding over 5 years of data (~ 5700 analyses of ten glass and carbonate RMs). We examine the relative importance of systematic analytical bias and possible error in reported values through a mass‐specific breakdown of fourteen of the most commonly determined elements. Furthermore, these data, obtained under a wide range of different ablation conditions, enable specific recommendations of how data quality may be improved, for example the role of diatomic gas, the effect of differential inter‐glass fractionation factors and choice of transport tubing material. Finally, these data demonstrate that the two‐volume Laurin ablation cell is characterised by no discernible spatial heterogeneity in measured trace element ratios.     

Defining the Potential of Nanoscale Re‐Os Isotope Systematics Using Atom Probe Microscopy

Atom probe microscopy (APM) is a relatively new in situ tool for measuring isotope fractions from nanoscale volumes (< 0.01 μm³). We calculate the theoretical detectable difference of an isotope ratio measurement result from APM using counting statistics of a hypothetical data set to be ± 4δ or 0.4% (2s). However, challenges associated with APM measurements (e.g., peak ranging, hydride formation and isobaric interferences), result in larger uncertainties if not properly accounted for. We evaluate these factors for Re‐Os isotope ratio measurements by comparing APM and negative thermal ionisation mass spectrometry (N‐TIMS) measurement results of pure Os, pure Re, and two synthetic Re‐Os‐bearing alloys from Schwander et al. (2015, Meteoritics and Planetary Science, 50, 893) [the original metal alloy (HSE) and alloys produced by heating HSE within silicate liquid (SYN)]. From this, we propose a current best practice for APM Re‐Os isotope ratio measurements. Using this refined approach, mean APM and N‐TIMS ¹⁸⁷Os/¹⁸⁹Os measurement results agree within 0.05% and 2s (pure Os), 0.6–2% and 2s (SYN) and 5–10% (HSE). The good agreement of N‐TIMS and APM ¹⁸⁷Os/¹⁸⁹Os measurements confirms that APM can extract robust isotope ratios. Therefore, this approach permits nanoscale isotope measurements of Os‐bearing alloys using the Re‐Os geochronometer that could not be measured by conventional measurement principles.     

Ghaleh-khargushi rhyodacite and Gorid andesite from Iran: characterization,uses, and durability

Durability of building stones is an important issue in sustainable development. Crystallization of soluble salts is recognized as one of the most destructive weathering agents of building stones. For this reason, durability of Ghaleh-khargushi rhyodacite and Gorid andesite from Iran was investigated against sodium sulfate crystallization aging test. Petrographic and physico-mechanical properties and pore size distribution of these stones were examined before and after the aging test. The characteristics of the microcracks were quantified with fluorescence-impregnated thin sections. Durability and physico-mechanical characteristics of Ghaleh-khargushi rhyodacite are mainly influenced by preferentially oriented preexisting microcracks. Stress induced by salt crystallization led to the widening of preexisting microcracks in Ghaleh-khargushi rhyodacite, as confirmed by the pore size distributions before and after the aging test. The preexisting microcracks of Gorid andesite were attributed to the mechanical stress induced by contraction of lava during cooling. The number of transcrystalline microcracks was significantly increased after the aging test. The degree of plagioclase microcracking was proportional to its size. Durability of the studied stones depends on initial physico-mechanical properties, pore size distribution, and orientation of microcracks. Initial effective porosity is found to be a good indicator of the stones’ durability. Salt crystallization resulted in an increase in the effective porosity with a parallel decrease in the wave velocities. Surface microroughness parameters increased with the development of salt crystallization-induced microcracking. Gorid andesite showed higher quality and durability than Ghaleh-khargushi rhyodacite.     

Assessing shallow landslide hazards using the TRIGRS and SHALSTAB models,Serra do Mar,Brazil

The hillslopes of the Serra do Mar, a system of escarpments and mountains that extend more than 1500 km along the southern and southeastern Brazilian coast, are regularly affected by heavy rainfall that generates widespread mass movements, causing large numbers of casualties and economic losses. This paper evaluates the efficiency of susceptibility mapping for shallow translational landslides in one basin in the Serra do Mar, using the physically based landslide susceptibility models SHALSTAB and TRIGRS. Two groups of scenarios were simulated using different geotechnical and hydrological soil parameters, and for each group of scenarios (A and B), three subgroups were created using soil thickness values of 1, 2, and 3 m. Simulation results were compared to the locations of 356 landslide scars from the 1985 event. The susceptibility maps for scenarios A1, A2, and A3 were similar between the models regarding the spatial distribution of susceptibility classes. Changes in soil cohesion and specific weight parameters caused changes in the area of predicted instability in the B scenarios. Both models were effective in predicting areas susceptible to shallow landslides through comparison of areas predicted to be unstable and locations of mapped landslides. Such models can be used to reduce costs or to define potentially unstable areas in regions like the Serra do Mar where field data are costly and difficult to obtain.     

Effect of heat treatment on dynamic properties of selected rock types taken from the Salt Range in Pakistan

Temperature is one of the variables that influence the elasto-plastic behavior and integrity of rock outcrops. Fluctuations in temperature can trigger alteration of some of the mineral properties and impact the brittle-plastic transition. Initiation and propagation of thermally induced tension cracks tend to weaken most rock types. The principal goal of this study was to anticipate impacts of thermal stress-strain cycles on the dynamic response of representative rock units exposed in the Khewra Gorge of the Salt Range Punjab of Pakistan. Ten types of sedimentary rock units were sampled, including marl, dolomite, three types of limestone, and five different sandstones exhibiting varying characteristics in outcrop. Boulder specimens were collected from the field and transported to the laboratory to prepare 50 drill cores that could be subjected to thermal cycling between 50 and 200 °C in increments of 50 °C. Room temperature core samples were tested using an Erudite resonance frequency meter to measure their Q-factors and the resonance frequency (F_r) at an applied loading frequency of 7 KHz with 0.01 V output voltage. Results suggest that thermal cycling tends to reduce the dynamic Young’s modulus (E_d) and Q-factor. Other parameters, such as damping ratio (ξ), specific damping capacity (Ψ), and loss factor (?) appeared to increase with increasing temperature cycles, likely as a result of developing thermally induced tensile fractures. The resultant values of the null hypothesis (t-critical and t-stats) suggests that the null hypothesis can be discarded because there was no observable difference between the measured and expected values for the cores tested. The observations and data emanating from this study might be useful in designing low-level radioactive waste landfills, nuclear waste repositories, and deep underground excavations where the increased temperature could alter the mechanical behavior of the parent rock mass.     

The terrestrial fauna of the Late Triassic Pant-y-ffynnon Quarry fissures,South Wales,UK and a new species of Clevosaurus (Lepidosauria: Rhynchocephalia)

Pant-y-ffynnon Quarry in South Wales yielded a rich cache of fossils in the early 1950s, including articulated specimens of new species (the small sauropodomorph dinosaur Pantydraco caducus and the crocodylomorph Terrestrisuchus gracilis), but no substantial study of the wider fauna of the Pant-y-ffynnon fissure systems has been published. Here, our overview of existing specimens, a few described but mostly undescribed, as well as freshly processed material, provides a comprehensive picture of the Pant-y-ffynnon palaeo-island of the Late Triassic. This was an island with a relatively impoverished fauna dominated by small clevosaurs (rhynchocephalians), including a new species, Clevosaurus cambrica, described here from a partially articulated specimen and isolated bones. The new species has a dental morphology that is intermediate between the Late Triassic Clevosaurus hudsoni, from Cromhall Quarry to the east, and the younger C. convallis from Pant Quarry to the west, suggesting adaptive radiation of clevosaurs in the palaeo-archipelago. The larger reptiles on the palaeo-island do not exceed 1.5?m in length, including a small carnivorous crocodylomorph, Terrestrisuchus, and a possible example of insular dwarfism in the basal dinosaur Pantydraco.     

The stratigraphical signature of the Anthropocene in England and its wider context

The Anthropocene deposits of England, here regarded as those formed after ～1950 CE, are now extensive, take various forms, and may be characterized and recognized by a number of stratigraphic signals, such as artificial radionuclides, pesticide residues, microplastics, enhanced fly ash levels, concrete fragments and a novel variety of ‘technofossils’ and neobiotic species. They include the uppermost parts of both ‘natural’ deposits such as the sediment layers formed in lakes and estuaries, and more directly human-made or human-influenced ones such as landfill deposits and the ‘artificial ground’ beneath urban areas and around major constructions. ‘Negative deposits’ include the worked areas of quarries and regions such as the English Fenland, where thick peat deposits have ablated to leave a strongly modified underlying landscape, and extend beneath into the subterranean realm as mine workings, metro systems and boreholes. The production of these is still rapidly increasing and evolving in character, while the early signs of global change, such as warming, sea level rise, and modifications to biotic assemblages, are beginning to further modify the emerging geology of this new phase of Earth history.     

Origin of complex zoning in olivine from diverse,diamondiferous kimberlites and tectonic settings: Ekati (Canada), Alto Paranaiba (Brazil) and Kaalvallei (South Africa)

Olivine in kimberlites can provide unique insights into magma petrogenesis, because it is the most abundant xenocrystic phase and a stable magmatic product over most of the liquid line of descent. In this study we examined the petrography and chemistry of olivine in kimberlites from different tectonic settings, including the Slave craton, Canada (Ekati: Grizzly, Koala), the Brasilia mobile belt (Limpeza-18, Tres Ranchos-04), and the Kaapvaal craton, South Africa (Kaalvallei: Samada, New Robinson). Olivine cores display a wide range of compositions (e.g., Mg# = 78–95). The similarity in olivine composition, resorption of core zones and inclusions of mantle-derived phases, indicates that most olivine cores originated from the disaggregation of mantle peridotites, including kimberlite-metasomatised lithologies (i.e. sheared lherzolites and megacrysts). Olivine rims typically show a restricted range of Mg#, with decreasing Ni and increasing Mn and Ca contents, a characteristic of kimberlitic olivine worldwide. The rims host inclusions of groundmass minerals, which implies crystallisation just before and/or during emplacement. There is a direct correlation between olivine rim composition and groundmass mineralogy, whereby high Mg/Fe rims are associated with carbonate-rich kimberlites, and lower Mg/Fe rims are correlated with increased phlogopite and Fe-bearing oxide mineral abundances. There are no differences in olivine composition between explosive (Grizzly) and hypabyssal (Koala) kimberlites. Olivine in kimberlites also displays transitional zones and less common internal zones, between cores and rims. The diffuse transitional zones exhibit intermediate compositions between cores and rims, attributed to partial re-equilibration of xenocrystic cores with the ascending kimberlite melt. In contrast, internal zones form discrete layers with resorbed margins and restricted Mg# values, but variable Ni, Mn and Ca concentrations, which indicates a discrete crystallization event from precursor kimberlite melts at mantle depths. Overall, olivine exhibits broadly analogous zoning in kimberlites worldwide. Variable compositions for individual zones relate to different parental melt compositions rather than variations in tectonic setting or emplacement mechanism.

     

Application of Geochemistry and VNIR Spectroscopy in Mapping Heavy Metal Pollution of Stream Sediments in the Takab Mining Area, NW of Iran

This study considered the possibility of using visible and near infrared (VNIR) spectral absorption feature parameters (SAFPs) in predicting the concentration and mapping the distribution of heavy metals in sediments of the Takab area. In total, 60 sediment samples were collected along main streams draining from the mining districts and tailing sites, in order to measure the concentration of As, Co, V, Cu, Cr, Ni, Hg, Ti, Pb and Zn and the reflectance spectra (350–2500 nm). The quantitative relationship between SAFPs (Depth500nm, R610/500nm, R1344/778nm, Area500nm, Depth2200nm, Area2200nm, Asym2200nm) and geochemical data were assessed using stepwise multiple linear regression (SMLR) and enter multiple linear regression (EMLR) methods. The results showed a strong negative correlation between Ni and Cr with Area2200nm, a significant positive correlation between As and Asym2200nm, Ni and Co with Depth2200nm, as well as Co, V and total values with Depth500nm. The EMLR method eventuated in a significant prediction result for Ni, Cr, Co and As concentrations based on spectral parameters, whereas the prediction for Zn, V and total value was relatively weak. The spatial distribution pattern of geochemical data showed that mining activities, along with the natural weathering of base metal occurrences and rock units, has caused high concentrations of heavy metals in sediments of the Sarough River tributaries.     

Pattern,style and timing of British–Irish Ice Sheet advance and retreat over the last 45 000 years: evidence from NW Scotland and the adjacent continental shelf

Predicting the future response of ice sheets to climate warming and rising global sea level is important but difficult. This is especially so when fast-flowing glaciers or ice streams, buffered by ice shelves, are grounded on beds below sea level. What happens when these ice shelves are removed? And how do the ice stream and the surrounding ice sheet respond to the abruptly altered boundary conditions? To address these questions and others we present new geological, geomorphological, geophysical and geochronological data from the ice-stream-dominated NW sector of the last British–Irish Ice Sheet (BIIS). The study area covers around 45 000 km² of NW Scotland and the surrounding continental shelf. Alongside seabed geomorphological mapping and Quaternary sediment analysis, we use a suite of over 100 new absolute ages (including cosmogenic-nuclide exposure ages, optically stimulated luminescence ages and radiocarbon dates) collected from onshore and offshore, to build a sector-wide ice-sheet reconstruction combining all available evidence with Bayesian chronosequence modelling. Using this information we present a detailed assessment of ice-sheet advance/retreat history, and the glaciological connections between different areas of the NW BIIS sector, at different times during the last glacial cycle. The results show a highly dynamic, partly marine, partly terrestrial, ice-sheet sector undergoing large size variations in response to sub-millennial-scale climatic (Dansgaard–Oeschger) cycles over the last 45 000 years. Superimposed on these trends we identify internally driven instabilities, operating at higher frequency, conditioned by local topographic factors, tidewater dynamics and glaciological feedbacks during deglaciation. Specifically, our new evidence indicates extensive marine-terminating ice-sheet glaciation of the NW BIIS sector during Greenland Stadials 12 to 9 – prior to the main ‘Late Weichselian’ ice-sheet glaciation. After a period of restricted glaciation, in Greenland Interstadials 8 to 6, we find good evidence for rapid renewed ice-sheet build-up in NW Scotland, with the Minch ice-stream terminus reaching the continental shelf edge in Greenland Stadial 5, perhaps only briefly. Deglaciation of the NW sector took place in numerous stages. Several grounding-zone wedges and moraines on the mid- and inner continental shelf attest to significant stabilizations of the ice-sheet grounding line, or ice margin, during overall retreat in Greenland Stadials 3 and 2, and to the development of ice shelves. NW Lewis was the first substantial present-day land area to deglaciate, in the first half of Greenland Stadial 3 at a time of globally reduced sea-level c. 26 kabp , followed by Cape Wrath at c. 24 kabp. The topographic confinement of the Minch straits probably promoted ice-shelf development in early Greenland Stadial 2, providing the ice stream with additional support and buffering it somewhat from external drivers. However, c. 20–19 kabp , as the grounding-line migrated into shoreward deepening water, coinciding with a marked change in marine geology and bed strength, the ice stream became unstable. We find that, once underway, grounding-line retreat proceeded in an uninterrupted fashion with the rapid loss of fronting ice shelves – first in the west, then the east troughs – before eventual glacier stabilization at fjord mouths in NW Scotland by ~17 kabp. Around the same time, ~19–17 kabp , ice-sheet lobes readvanced into the East Minch – possibly a glaciological response to the marine-instability-triggered loss of adjacent ice stream (and/or ice shelf) support in the Minch trough. An independent ice cap on Lewis also experienced margin oscillations during mid-Greenland Stadial 2, with an ice-accumulation centre in West Lewis existing into the latter part of Heinrich Stadial 1. Final ice-sheet deglaciation of NW mainland Scotland was punctuated by at least one other coherent readvance at c. 15.5 kabp , before significant ice-mass losses thereafter. At the glacial termination, c. 14.5 kabp , glaciers fed outwash sediment to now-abandoned coastal deltas in NW mainland Scotland around the time of global Meltwater Pulse 1A. Overall, this work on the BIIS NW sector reconstructs a highly dynamic ice-sheet oscillating in extent and volume for much of the last 45 000 years. Periods of expansive ice-sheet glaciation dominated by ice-streaming were interspersed with periods of much more restricted ice-cap or tidewater/fjordic glaciation. Finally, this work indicates that the role of ice streams in ice-sheet evolution is complex but mechanistically important throughout the lifetime of an ice sheet – with ice streams contributing to the regulation of ice-sheet health but also to the acceleration of ice-sheet demise via marine ice-sheet instabilities.