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Carbonate archives record a brief snapshot of the ambient Earth’s surface conditions at their deposition. However, the geologically reasonable extraction and interpretation of geochemical proxy data from ancient, diagenetically altered rock archives is fraught with problems. Three issues stand out: the dichotomy between petrographic and geochemical alteration; the lack of quantitative age constraints for specific diagenetic phases resulting in a poorly constrained admixture of local, basin-wide and over-regional (far-field) features; and an often insufficient understanding of the temperatures and compositions of diagenetic fluids. Here, the archive of Devonian marine limestones exposed to multiple far-field diagenetic events is used as an example to explore the above-listed issues. Methods applied include petrography, micro XRF, fluid inclusion data, clumped isotopes, δ13C and δ18O isotopes, 87Sr/86Sr ratios and quartz trace element data. Devonian limestones studied here were overprinted by two cross-cutting regional fault zones (T ≈ 230 °C) by multiple events between the Variscan Orogeny and the late Paleogene. The following processes are recorded: (i) protolith deposition and partial dolomitisation during rapid burial in the Middle/Late Devonian (T ≈ 180 °C); (ii) deep burial to ca 6.5 km and tectonic/hydrothermal overprint during the Variscan Orogeny in the Carboniferous (T ≈ 90–230 °C); (iii) rapid uplift to 1–2 km burial depth at the end of the Variscan Orogeny and hypogene karstification (T ≈ 50 to 100 °C) initiated by regional geology in the Permian/Triassic; (iv) tectonic/hydrothermal overprint during the opening of the Proto-Atlantic Ocean between the Early Jurassic and the Early Cretaceous (T ≈ 50 to 130 °C); (v) tectonic/hydrothermal overprint including renewed hypogene karstification and hydrothermal calcite cement precipitation (T ≈ 50 to 180 °C) during Alpine Orogeny between the Late Cretaceous and late Paleogene. Despite this complex series of diagenetic events, the protolith limestones largely preserved their respective Middle/Late Devonian dissolved inorganic carbon (DIC) and 87Sr/86Sr signatures. This study documents that geochemical proxy data, placed into their petrographic, paleotemperature, and local to over-regional context, significantly increases the ability to extract quantitative information from ancient carbonate rock archives. Research shown here has wider relevance for carbonate archive research in general.
Highlights
• Constrictional structures range from dome-and-basin folds to coeval folds and boudins.
• Under bulk constriction, the competent layer rotates slower than a passive plane.
• Extension-parallel and –perpendicular folds grow simultaneously.
• Extension-perpendicular folds affect previous boudins.
Abstract
We conducted scaled analogue modelling to show the influence of varying single layer initial orientation on the geometry of folds and boudins in a bulk constrictional strain field. The initial angle between the plane of shortening and the competent layer (θZ(i)) was incrementally increased from 0° to 90° by multiples of 11.25°. While the amount of layer thickening decreased with increasing θZ(i), the deformation structures produced range from pure dome-and-basin folds to coeval folds and boudins. Based on the attitude of fold axes, there are extension-parallel (FEPR) and extension-perpendicular (FEPP) folds, with axes subparallel and subperpendicular to the principal stretching axis (X), respectively. Coeval growth of FEPR folds and boudins occurred when θZ(i) > ca. 25°. The FEPP folds can be subdivided into a first type which affect the entire layer (if θZ(i) ranges between 11.25 and 78.75°) and a second type, referred to as FBEPP folds, which are affecting pre-existing boudins if θZ(i) > 45°. The interlimb angle of all types of folds increases with increasing θZ(i). Folds and boudins similar to the ones produced in this study can be found in salt domes and in tectonites of subduction zones.
Non-matrix-matched calibration of laser ablation ICPMS (trace/major) element data is a common quantification strategy. However, LA sampling is associated with downhole elemental fractionation, potentially causing inaccuracies if the magnitude of fractionation between the sample and reference material (RM) differs. Here, we estimate fractionation factors (FFs) for different elements (El) in a range of RMs relative to NIST SRM610/612 (FFEl/Ca-NIST) and evaluate element-specific corrections for downhole fractionation using these measured FFEl/Ca-NIST. Significantly different mean El/Ca values were observed before and after correction, particularly for the alkali elements (all RMs), and B, Fe, and Zn (some RMs), notably improving accuracy, especially for the alkali elements. In cases where this methodology does not result in an accuracy improvement, this may help identify underlying issues in reported/reference values for RMs, given that this phenomenon should be accounted for. Overall, we recommend considering routine assessment of FFs and applying a FF correction to enhance data quality.
Rationale: Potassium (K) is a major component of several silicate minerals and seawater, and, therefore, constraining past changes in the potassium cycle is a promising way of tracing large-scale geological processes on Earth. However, [K] measurement using inductively coupled plasma mass spectrometry (ICP-MS) is challenging due to an ArH+ interference, which may be of a similar magnitude to the K+ ion beam in samples with <0.1% m/m [K].
Methods: In this work, we investigated the effect of the ArH+ interference on K/Ca data quality by comparing results from laser-ablation (LA)-ICP-MS measured in medium and high mass resolution modes and validating our LA results via solution ICP-optical emission spectroscopy (OES) and solution ICP-MS measurements. To do so, we used a wide range of geological reference materials, with a particular focus on marine carbonates, which are potential archives of past changes in the K cycle but are typically characterised by [K] < 200 μg/g. In addition, we examine the degree to which trace-element data quality is driven by downhole fractionation during LA-ICP-MS measurements.
Results: Our results show that medium mass resolution (MR) mode is sufficiently capable of minimising the effect of the ArH+ interference on K+. However, the rate of downhole fractionation for Na and K varies between different samples as a result of their differing bulk composition, resulting in matrix-specific inaccuracy. We show how this can be accounted for via downhole fractionation corrections, resulting in an accuracy of better than 1% and a long-term reproducibility (intermediate precision) of <6% (relative standard deviation) in JCp-1NP using LA-ICP-MS in MR mode.
Conclusion: Our [K] measurement protocol is demonstrably precise and accurate and applicable to a wide range of materials. The measurement of K/Ca in relatively low-[K] marine carbonates is presented here as a key example of a new application opened up by these advances.
Partial melting of crustal and mantle rocks under pressure from impedance spectroscopy measurements
(2004)
The purpose of this work is to achieve a better understanding of the physical properties of rocks during partial melting processes. The electrical conductivity of some crustal and upper mantle rocks was measured prior and above the melting under pressure. The variations of the electrical conductivity were compared with the distribution of melt in partially molten rock samples. The electrical conductivity was estimated from the impedance spectroscopy at temperatures between 800 and 1450˚C and at pressures between 0.3 and 2 GPa. These measurements were performed in a piston cylinder apparatus. At temperatures above the melting, samples were equilibrated during a long time and subsequently quenched. Thin sections were prepared and topology, volume fraction and chemical composition of melt was analyzed by using a microprobe. Above the solidus temperature, the electrical conductivity increases for about 1 to 2 orders of magnitude in comparison with non-melted rocks. The "melt effect" seems to reflect the formation of an interconnected network of melt. When a complete melt connectivity is established, the charge transport follows the network of the formed melt films at grain boundaries. Usually, it takes a long time in order to reach a steady state of the electrical resistance in partially molten rocks. Only when a steady state of the electrical resistance is achieved, the bulk conductivity of a sample can be measured properly. The time-independent electrical conductivity were found only after 200 h of annealing time at a desired temperature.
Usually, the measurements of a dihedral angle on grain-liquid interfaces in rocks show that the wetting of grain faces start to develop at temperatures slightly above the solidus temperature. The development of these faces should lead to a continuous melt network even at small melt fractions of few wt.%. This result is not confirmed by our electrical conductivity measurements. The complete interconnection of the melt phase, which was mark by an increase of the electrical conductivity, corresponds to a temperature significantly above the solidus temperature, for at least 30-50˚C. The development of these faces stimulate a significant increase of the electrical conductivity, and corresponds to the occurence of at least 5 wt.% of a melt fraction. This result could be explained by deviations from the textural equilibrium of a melt phase topology in partially molten samples due to heterogeneous grain size distribution, misorientation of grains and anisotropy of the superficial energy of adjacent grain boundaries.
Some mixing models that allow to calculate the electrical conductivity of a composite as a function of a melt fraction were examined and the results of these calculations are discussed.
The experimental results were compared to the conductivity data obtained from magnetotelluric and electromagnetic measurements in the Northern part of mid-Atlantic ridge where a series of magma chambers are presumably located. There is a good agreement between our conductivity values for a melt fraction of 10-13 the conductivity estimated in the Reykjanes ridge zone.
Highlights
• We find DBrfluid/melt = 1.19 to 3.92 for experimental Br degassing from basalt magma into aqueous fluids.
• D <1 under almost dry conditions propose only little Br degassing for dry intra-plate volcanism relative to volcanic arcs.
• An annual global Br flux of 23.5–72.9 × 109 g/y into the atmosphere was calculated.
Abstract
We present the first in-situ partitioning data for bromine between a natural basaltic melt and a coexisting fluid. For this study hydrothermal diamond anvil cell experiments at pressures up to 1.7 GPa were conducted. We combined laser heating to melt the basalt glass with external heating to lower the temperature gradient in the cell and to initiate circulation for the aqueous fluid. Bromine concentrations were measured in-situ with X-ray fluorescence in the basaltic melts, glasses, and in the fluid. From the results we calculated partition coefficients of DBrfluid/melt = 1.19 to 3.92 in the range of 0.4 to 1 GPa for aqueous fluids. Experiments with neon as the surrounding fluid (DBrfluid/melt = 0.38 ± 0.01 at 1.1 GPa) suggest that Br-release from a basalt into volatiles that have no bonding affinity with Br is weak. This should be the case for dry intra-plate volcanic eruptions. From the experimentally gained partition coefficients and from global Br concentration values in melt inclusions of arc magmas, we calculated an annual global Br flux of 23.5–72.9 × 109 g/y.
We present a new experimental dataset on the impact of the heavy halogens chlorine, bromine and iodine on the Raman water bands concerning pressure and their concentration at room temperature. These experiments were conducted at ambient temperature, with variations in halogen concentration and pressure ranging from 0 to 1.4 GPa.
The strength of the Raman water band shift change increases with the ionic size from chlorine, over bromine, to iodine. Our experiments further demonstrate that increased pressure diminishes the impact of the halogen shift change to a varying extent for each of the three halogens. This finding can have significant implications for the salinity calculation of fluid inclusions in minerals such as quartz or olivine. Particularly in the low salinity range, the concentration can be markedly underestimated if the pressure effect is neglected. For experiments in diamond anvil cells involving halogens dissolved in water, the change in Raman water band shifts can serve either as a new tool to monitor pressure, or to monitor the salinity.
Highlights
• We present the first results of a deep learning model based on a convolutional neural network for earthquake magnitude estimation, using HR-GNSS displacement time series.
• The influence of different dataset configurations, such as station numbers, epicentral distances, signal duration, and earthquake size, were analyzed to figure out how the model can be adapted to various scenarios.
• The model was tested using real data from different regions and magnitudes, resulting in the best cases with 0.09 ≤ RMS ≤ 0.33.
Abstract
High-rate Global Navigation Satellite System (HR-GNSS) data can be highly useful for earthquake analysis as it provides continuous high-frequency measurements of ground motion. This data can be used to analyze diverse parameters related to the seismic source and to assess the potential of an earthquake to prompt strong motions at certain distances and even generate tsunamis. In this work, we present the first results of a deep learning model based on a convolutional neural network for earthquake magnitude estimation, using HR-GNSS displacement time series. The influence of different dataset configurations, such as station numbers, epicentral distances, signal duration, and earthquake size, were analyzed to figure out how the model can be adapted to various scenarios. We explored the potential of the model for global application and compared its performance using both synthetic and real data from different seismogenic regions. The performance of our model at this stage was satisfactory in estimating earthquake magnitude from synthetic data with 0.07 ≤ RMS ≤ 0.11. Comparable results were observed in tests using synthetic data from a different region than the training data, with RMS ≤ 0.15. Furthermore, the model was tested using real data from different regions and magnitudes, resulting in the best cases with 0.09 ≤ RMS ≤ 0.33, provided that the data from a particular group of stations had similar epicentral distance constraints to those used during the model training. The robustness of the DL model can be improved to work independently from the window size of the time series and the number of stations, enabling faster estimation by the model using only near-field data. Overall, this study provides insights for the development of future DL approaches for earthquake magnitude estimation with HR-GNSS data, emphasizing the importance of proper handling and careful data selection for further model improvements.
PolarCAP – A deep learning approach for first motion polarity classification of earthquake waveforms
(2022)
Highlights
• We present PolarCAP, a deep learning model that can classify the polarity of a waveform with a 98% accuracy.
• The first-motion polarity of seismograms is a useful parameter, but its manual determination can be laborious and imprecise.
• We demonstrate that in several cases the model can assign trace polar-ity more accurately than a human analyst.
Abstract
The polarity of first P-wave arrivals plays a significant role in the effective determination of focal mechanisms specially for smaller earthquakes. Manual estimation of polarities is not only time-consuming but also prone to human errors. This warrants a need for an automated algorithm for first motion polarity determination. We present a deep learning model - PolarCAP that uses an autoencoder architecture to identify first-motion polarities of earth-quake waveforms. PolarCAP is trained in a supervised fashion using more than 130,000 labelled traces from the Italian seismic dataset (INSTANCE) and is cross-validated on 22,000 traces to choose the most optimal set of hyperparameters. We obtain an accuracy of 0.98 on a completely unseen test dataset of almost 33,000 traces. Furthermore, we check the model generalizability by testing it on the datasets provided by previous works and show that our model achieves a higher recall on both positive and negative polarities.
Highlights
• Germany plans more long-distances water transfers to secure drinking water supply.
• Long-distance water transfers can unfold lock-ins that limit adaptive water governance.
• Our interdisciplinary case study shows how lock-ins emerge over different spaces and times.
• Commercialisation of water but also local protests contributed to various lock-ins.
• We therefore call for context-specific assessments of potentials and risks of LDWT.
Abstract
Germany plans to expand water transfers over long distances in the light of numerous and pressing challenges for drinking water supply. Research on inter- and intrabasin water transfers warns, however, that major investments in large-scale infrastructure systems accompanied by institutional logics and political interests often lead to a so-called lock-in. As a consequence, long-distance water transfers can limit the potential for adaptive water governance in the involved supply areas over decades with negative impacts for people and the environment. By using a case study in Germany as an example, we researched when, where and how such lock-ins around long-distance water transfers emerge. In the infrastructural development of the Elbaue-Ostharz transfer system we found various lock-ins that overlap in space and time. Some are located at the centre others at the margins of the infrastructure and commercialization of the water sector as well as hydraulic and hygienic concerns interlock with local protests in a way that the expansion of the long-distance water transfer infrastructure is presented continuously as imperative. Our findings contribute to a relational understanding of lock-ins of long-distance water transfers as contingent and diverse processes. Given the widespread occurrence of lock-ins, we argue for a context-specific assessment of potentials and risks of long-distance water transfers in times of multiple crises.