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White mica and tourmaline are the dominant hydrothermal alteration minerals at the world-class Panasqueira W-Sn-Cu deposit in Portugal. Thus, understanding the controls on their chemical composition helps to constrain ore formation processes at this deposit and determine their usefulness as pathfinder minerals for mineralization in general. We combine whole-rock geochemistry of altered and unaltered metasedimentary host rocks with in situ LA-ICP-MS measurements of tourmaline and white mica from the alteration halo. Principal component analysis (PCA) is used to better identify geochemical patterns and trends of hydrothermal alteration in the datasets. The hydrothermally altered metasediments are enriched in As, Sn, Cs, Li, W, F, Cu, Rb, Zn, Tl, and Pb relative to unaltered samples. In situ mineral analyses show that most of these elements preferentially partition into white mica over tourmaline (Li, Rb, Cs, Tl, W, and Sn), whereas Zn is enriched in tourmaline. White mica has distinct compositions in different settings within the deposit (greisen, vein selvages, wall rock alteration zone, late fault zone), indicating a compositional evolution with time. In contrast, tourmaline from different settings overlaps in composition, which is ascribed to a stronger dependence on host rock composition and also to the effects of chemical zoning and microinclusions affecting the LA-ICP-MS analyses. Hence, in this deposit, white mica is the better recorder of the fluid composition. The calculated trace-element contents of the Panasqueira mineralizing fluid based on the mica data and estimates of mica-fluid partition coefficients are in good agreement with previous fluid-inclusion analyses. A compilation of mica and tourmaline trace-element compositions from Panasqueira and other W-Sn deposits shows that white mica has good potential as a pathfinder mineral, with characteristically high Li, Cs, Rb, Sn, and W contents. The trace-element contents of hydrothermal tourmaline are more variable. Nevertheless, the compiled data suggest that high Sn and Li contents are distinctive for tourmaline from W-Sn deposits.
The Devonian Las Chacras-Potrerillos batholith comprises six nested monzonitic to granitic intrusions with metaluminous to weakly peraluminous composition and a Sr-Nd isotopic signature indicating a dominantly juvenile mantle-derived source. The chemically most evolved units in the southern batholith contain a large number of intra-granitic, pod-shaped tourmaline-bearing pegmatites. This study uses in situ chemical and boron isotopic analyses of tourmaline from nine of these pegmatites to discuss their relationship to the respective host intrusions and the implications of their B-isotope composition for the source and evolution of the magmas. The tourmalines reveal a diversity in element composition (e.g., FeO, MgO, TiO2, CaO, MnO, F) which distinguishes individual pegmatites from one another. However, all have a narrow 5 11 B range of -13.7 to -10.5%0 (n = 100) which indicates a relatively uniform magmatic system and similar temperature conditions during tourmaline crystallization. The average delta(11) B value of -11.7%0 is typical for S-type granites and is within the range reported for peraluminous granites. pegmatites, and metamorphic units of the Ordovician basement into which the Las Chacras-Potrerillos batholith intruded. The B-isotope evidence argues for a crustal boron source like that of the Ordovician basement, in contrast to the metaluminous to weakly peraluminous composition and juvenile initial Sr and Nd isotope ratios of the Las Chacras-Potrerillos batholith magmas. We propose that the boron was not derived from the magma source region but was incorporated from dehydration melting of elastic metasedimentary rocks higher up in the crustal column.
Long- and short-term monitoring of a dam in response to seasonal changes and ground motion loading
(2021)
An experimental multi-parameter structural monitoring system has been installed on the Kurpsai dam, western Kyrgyz Republic. This system consists of equipment for seismic and strain measurements for making longer- (days, weeks, months) and shorter- (minutes, hours) term observations, dealing with, for example seasonal (longer) effects or the response of the dam to ground motion from noise or seismic events. Fibre-optic strain sensors allow the seasonal and daily opening and closing of the spaces between the dam's segments to be tracked. For the seismic data, both amplitude (in terms of using differences in amplitudes in the Fourier spectra for mapping the modes of vibration of the dam) and their time-frequency distribution for a set of small to moderate seismic events are investigated and the corresponding phase variabilities (in terms of lagged coherency) are evaluated. Even for moderate levels of seismic-induced ground motion, some influence on the structural response can be detected, which then sees the dam quickly return to its original state. A seasonal component was identified in the strain measurements, while levels of noise arising from the operation of the dam's generators and associated water flow have been provisionally identified.
Centroid moment tensor (CMT) parameters can be estimated from seismic waveforms. Since these data indirectly observe the deformation process, CMTs are inferred as solutions to inverse problems which are generally underdetermined and require significant assumptions, including assumptions about data noise. Broadly speaking, we consider noise to include both theory and measurement errors, where theory errors are due to assumptions in the inverse problem and measurement errors are caused by the measurement process. While data errors are routinely included in parameter estimation for full CMTs, less attention has been paid to theory errors related to velocity-model uncertainties and how these affect the resulting moment-tensor (MT) uncertainties. Therefore, rigorous uncertainty quantification for CMTs may require theory-error estimation which becomes a problem of specifying noise models. Various noise models have been proposed, and these rely on several assumptions. All approaches quantify theory errors by estimating the covariance matrix of data residuals. However, this estimation can be based on explicit modelling, empirical estimation and/or ignore or include covariances. We quantitatively compare several approaches by presenting parameter and uncertainty estimates in nonlinear full CMT estimation for several simulated data sets and regional field data of the M-1 4.4, 2015 June 13 Fox Creek, Canada, event. While our main focus is at regional distances, the tested approaches are general and implemented for arbitrary source model choice. These include known or unknown centroid locations, full MTs, deviatoric MTs and double-couple MTs. We demonstrate that velocity-model uncertainties can profoundly affect parameter estimation and that their inclusion leads to more realistic parameter uncertainty quantification. However, not all approaches perform equally well. Including theory errors by estimating non-stationary (non-Toeplitz) error covariance matrices via iterative schemes during Monte Carlo sampling performs best and is computationally most efficient. In general, including velocity-model uncertainties is most important in cases where velocity structure is poorly known.
Ice-rich permafrost has been subject to abrupt thaw and thermokarst formation in the past and is vulnerable to current global warming. The ice-rich permafrost domain includes Yedoma sediments that have never thawed since deposition during the late Pleistocene and Alas sediments that were formed by previous thermokarst processes during the Lateglacial and Holocene warming. Permafrost thaw unlocks organic carbon (OC) and minerals from these deposits and exposes OC to mineralization. A portion of the OC can be associated with iron (Fe), a redox-sensitive element acting as a trap for OC. Post-depositional thaw processes may have induced changes in redox conditions in these deposits and thereby affected Fe distribution and interactions between OC and Fe, with knock-on effects on the role that Fe plays in mediating present day OC mineralization. To test this hypothesis, we measured Fe concentrations and proportion of Fe oxides and Fe complexed with OC in unthawed Yedoma and previously thawed Alas deposits. Total Fe concentrations were determined on 1,292 sediment samples from the Yedoma domain using portable X-ray fluorescence; these concentrations were corrected for trueness using a calibration based on a subset of 144 samples measured by inductively coupled plasma optical emission spectrometry after alkaline fusion (R (2) = 0.95). The total Fe concentration is stable with depth in Yedoma deposits, but we observe a depletion or accumulation of total Fe in Alas deposits, which experienced previous thaw and/or flooding events. Selective Fe extractions targeting reactive forms of Fe on unthawed and previously thawed deposits highlight that about 25% of the total Fe is present as reactive species, either as crystalline or amorphous oxides, or complexed with OC, with no significant difference in proportions of reactive Fe between Yedoma and Alas deposits. These results suggest that redox driven processes during past thermokarst formation impact the present-day distribution of total Fe, and thereby the total amount of reactive Fe in Alas versus Yedoma deposits. This study highlights that ongoing thermokarst lake formation and drainage dynamics in the Arctic influences reactive Fe distribution and thereby interactions between Fe and OC, OC mineralization rates, and greenhouse gas emissions.
How biased are our models?
(2021)
Geophysical process simulations play a crucial role in the understanding of the subsurface. This understanding is required to provide, for instance, clean energy sources such as geothermal energy. However, the calibration and validation of the physical models heavily rely on state measurements such as temperature. In this work, we demonstrate that focusing analyses purely on measurements introduces a high bias. This is illustrated through global sensitivity studies. The extensive exploration of the parameter space becomes feasible through the construction of suitable surrogate models via the reduced basis method, where the bias is found to result from very unequal data distribution. We propose schemes to compensate for parts of this bias. However, the bias cannot be entirely compensated. Therefore, we demonstrate the consequences of this bias with the example of a model calibration.
Urban air pollution is a substantial threat to human health. Traffic emissions remain a large contributor to air pollution in urban areas. The mobility restrictions put in place in response to the COVID-19 pandemic provided a large-scale real-world experiment that allows for the evaluation of changes in traffic emissions and the corresponding changes in air quality. Here we use observational data, as well as modelling, to analyse changes in nitrogen dioxide, ozone, and particulate matter resulting from the COVID-19 restrictions at the height of the lockdown period in Spring of 2020. Accounting for the influence of meteorology on air quality, we found that reduction of ca. 30-50 % in traffic counts, dominated by changes in passenger cars, corresponded to reductions in median observed nitrogen dioxide concentrations of ca. 40 % (traffic and urban background locations) and a ca. 22 % increase in ozone (urban background locations) during weekdays. Lesser reductions in nitrogen dioxide concentrations were observed at urban background stations at weekends, and no change in ozone was observed. The modelled reductions in median nitrogen dioxide at urban background locations were smaller than the observed reductions and the change was not significant. The model results showed no significant change in ozone on weekdays or weekends. The lack of a simulated weekday/weekend effect is consistent with previous work suggesting that NOx emissions from traffic could be significantly underestimated in European cities by models. These results indicate the potential for improvements in air quality due to policies for reducing traffic, along with the scale of reductions that would be needed to result in meaningful changes in air quality if a transition to sustainable mobility is to be seriously considered. They also confirm once more the highly relevant role of traffic for air quality in urban areas.
In contrast to the common conception that the interfacial energy-level alignment is affixed once the interface is formed, we demonstrate that heterojunctions between organic semiconductors and metal-halide perovskites exhibit huge energy-level realignment during photoexcitation. Importantly, the photoinduced level shifts occur in the organic component, including the first molecular layer in direct contact with the perovskite. This is caused by charge-carrier accumulation within the organic semiconductor under illumination and the weak electronic coupling between the junction components.
This study is trying to understand the pre-eruptive magma storage and crystallization conditions of the Middle Miocene aged, silica-saturated trachytic rocks of the Afyon Volcanic Complex (AVC) in Western Anatolia, Turkey. Those rocks can be divided by their high K2O, K2O/Na2O ratio and Mg# into two groups, namely the intermediate-potassic (IPG) and the ultrapotassic (UPG). Here we are comparing calculated pressure (P) - temperature (T) conditions derived from geothermobarometric calculations of natural samples with results of high-pressure, high-temperature phase equilibria experiments. IPG samples are richer in silica (57-64 wt% SiO2), whereas UPG samples show intermediate SiO2 contents of 56-58 wt%. UPG are having high K2O contents ((>)9 wt %), K2O/Na2O ratios ((>)10 wt%) and Mg# values (75-77). IPG phenocrysts comprise plagioclase + biotite + amphibole + clinopyroxene +/- orthopyroxene +/- sanidine +/- phlogopite and oxides, while UPG mineralogical assemblage consists of amphibole + phlogopite + clinopyroxene + olivine + sanidine and oxides. IPG and UPG are enriched in Large-Ion Lithophile Elements (LILE), and both have negative anomalies in Nb, Sr, Zr and Ti elements. Additionally, IPG shows positive anomalies in Pb. Both IPG and UPG display enrichment in Light Rare Earth Elements (LREE), while IPG shows a more significant negative anomaly in Eu when compared to UPG. Plagioclase fractionation may play a role in magma generation. In IPG samples Ni and Cr values range between (3.3-18.8 ppm) and (2.6-27.8 ppm), respectively; whereas UPG samples have (119.1-120.7 ppm) Ni and (212.1-219.9 ppm) Cr. Dy/Yb ratios of IPG and UPG are higher than 2 and may indicate that garnet was present in the source. Geothermobarometric calculations for natural IPG clinopyroxene-melt pairs imply higher PT conditions (Dogan-Kulahci et al., 2015), while in this study high-pressure/high-temperature (HP/HT) phase equilibria experiments recreated the natural mineral assemblage at 2-4 kbar, 6-9 km and c. 900 degrees C. New plagioclase-melt calculations have confirmed lower mean magma storage temperatures, which are closer to the experimental results but still slightly elevated. Thus, trace element results of the natural rocks and experimental data may imply that a deep garnet-bearing magma source mixed with shallower magmas (IPG) was feeding the volcanic eruption.
We traced diatom composition and diversity through time using diatom-derived sedimentary ancient DNA (sedaDNA) from eastern continental slope sediments off Kamchatka (North Pacific) by applying a short, diatom-specific marker on 63 samples in a DNA metabarcoding approach. The sequences were assigned to diatoms that are common in the area and characteristic of cold water. SedaDNA allowed us to observe shifts of potential lineages from species of the genus Chaetoceros that can be related to different climatic phases, suggesting that pre-adapted ecotypes might have played a role in the long-term success of species in areas of changing environmental conditions. These sedaDNA results complement our understanding of the long-term history of diatom assemblages and their general relationship to environmental conditions of the past. Sea-ice diatoms (Pauliella taeniata [Grunow] Round & Basson, Attheya septentrionalis [ostrup] R. M. Crawford and Nitzschia frigida [Grunow]) detected during the late glacial and Younger Dryas are in agreement with previous sea-ice reconstructions. A positive correlation between pennate diatom richness and the sea-ice proxy IP25 suggests that sea ice fosters pennate diatom richness, whereas a negative correlation with June insolation and temperature points to unfavorable conditions during the Holocene. A sharp increase in proportions of freshwater diatoms at similar to 11.1 cal kyr BP implies the influence of terrestrial runoff and coincides with the loss of 42% of diatom sequence variants. We assume that reduced salinity at this time stabilized vertical stratification which limited the replenishment of nutrients in the euphotic zone.