A statistical procedure for the analysis of seismotectonically induced hydrochemical signals: A case study from the Eastern Carpathians, Romania

Changes in the stress field of an aquifer system induced by seismotectonic activity may change the mixing ratio of groundwaters with different compositions in a well, leading to hydrochemical signals which in principle could be related to discrete earthquake events. Due to the complexity of the interactions and the multitude of involved factors the identification of such relationships is a difficult task. In this study we present an empiric statistical approach suitable to analyse if there is an interdependency between changes in the chemical composition of monitoring wells and the regional seismotectonic activity of a considered area. To allow a rigorous comparison with hydrochemistry the regional earthquake time series was aggregated into an univariate time series. This was realized by expressing each earthquake in form of a parameter “e”, taking into consideration both energetic (magnitude of a seismic event) and spatial parameters (position of epi/hypocentrum relative to the monitoring site). The earthquake and the hydrochemical time-series were synchronised aggregating the e-parameters into “earthquake activity” functions E, which takes into account the time of sampling relative to the earthquakes which occurred in the considered area. For the definition of the aggregation functions a variety of different “e” parameters were considered. The set of earthquake functions E was grouped by means of factor analysis to select a limited number of significant and representative earthquake functions E to be used further on in the relation analysis with the multivariate hydrochemical data set. From the hydrochemical data a restricted number of hydrochemical factors were extracted. Factor scores allow to represent and analyse the variation of the hydrochemical factors as a function of time. Finally, regression analysis was used to detect those hydrochemical factors which significantly correlate with the aggregated earthquake functions.This methodological approach was tested with a hydrochemical data set collected from a deep well monitored for two years in the seismically active Vrancea region, Romania. Three of the hydrochemical factors were found to correlate significantly with the considered earthquake activities. A screening with different time combinations revealed that correlations are strongest when the cumulative seismicity over several weeks was considered. The case study also showed that the character of the interdependency depends sometimes on the geometrical distribution of the earthquake foci. By using aggregated earthquake information it was possible to detect interrelationships which couldn't have been identified by analysing only relations between single geochemical signals and single earthquake events. Further on, the approach allows to determine the influence of different seismotectonic patterns on the hydrochemical composition of the sampled well. The method is suitable to be used as a decision instrument in assessing if a monitoring site is suitable or not to be included in a monitoring net within a complex earthquake prediction strategy.     

Tetrahedral Plots of the Phase Relations for Basalts

The phase relations of quaternary systems are generally represented by projections onto ternary compositional planes. Such projections often obscure relationships that would only be evident in a three-dimensional tetrahedral plot. The tetrahedral plot requires that compositions of the minerals and melts be transformed into Cartesian coordinates. It is shown here how this transformation is carried out. The application is demonstrated by tetrahedral plots of experimental melt compositions of partially molten lherzolite. Furthermore, the plot can be used to evaluate whether or not a particular basaltic composition represents a primary melt. The methods are applicable to any four-component system.     

Correlation between hydrogen isotope ratios of lipid biomarkers and sediment maturity

We investigated the influence of thermal maturity on the hydrogen isotope ratios of sedimentary hydrocarbons to prove that the isotope ratio of hydrocarbons mirrors paleoclimate signatures. δD values from n-alkanes and acyclic isoprenoids of two sediment sections (Kupferschiefer [KS], 258 Ma, and Posidonienschiefer [PS], 184 Ma) with different maturation history were investigated. Both covered thermal maturity from 0.48 to 1.3 R_c (vitrinite reflectance and reflectance calculated from MPI1). Sediment burial up to 4500 m caused thermal maturation of organic matter in the KS horizon from the Early Zechstein basin of Poland, whereas contact metamorphic thermal maturation originated in the Early Toarcian PS (Posidonienschiefer) of the North German Vlotho Massif. The δD values of the extracted n-alkanes positively correlate with thermal maturity in the KS (y = 56‰ × MPI1[x] − 160‰ [VSMOW]) and in the PS (y = 104‰ × MPI1[x] − 200‰ [VSMOW]). The δD values of isoprenoids (i.e., pristane, phytane) were even more enriched with increasing maturity (y = 179‰ × MPI1[x] − 341‰ [VSMOW] in the KS; y = 300‰ × MPI1[x] − 415‰ [VSMOW] in PS).These results explain why isotope ratios of n-alkanes and isoprenoids in mature sediments are generally enriched in D and do not have the expected isotopic difference between n-alkanes and isoprenoids of ∼190‰. Moreover, the correlation between sediment maturity parameters and δD values suggests that after correction the δD values of n-alkanes can be used to reconstruct climate and environment in the geological past.     

Spatially controlled Fe and Si isotope variations: an alternative view on the formation of the Torres del Paine pluton

We present new Fe and Si isotope ratio data for the Torres del Paine igneous complex in southern Chile. The multi-composition pluton consists of an approximately 1 km vertical exposure of homogenous granite overlying a contemporaneous 250-m-thick mafic gabbro suite. This first-of-its-kind spatially dependent Fe and Si isotope investigation of a convergent margin-related pluton aims to understand the nature of granite and silicic igneous rock formation. Results collected by MC-ICP-MS show a trend of increasing δ⁵⁶Fe and δ³⁰Si with increasing silica content as well as a systematic increase in δ⁵⁶Fe away from the mafic base of the pluton. The marginal Torres del Paine granites have heavier Fe isotope signatures (δ⁵⁶Fe = +0.25 ± 0.02 2se) compared to granites found in the interior pluton (δ⁵⁶Fe = +0.17 ± 0.02 2se). Cerro Toro country rock values are isotopically light in both Fe and Si isotopic systems (δ⁵⁶Fe = +0.05 ± 0.02 ‰; δ³⁰Si = ?0.38 ± 0.07 ‰). The variations in the Fe and Si isotopic data cannot be accounted for by local assimilation of the wall rocks, in situ fractional crystallization, late-stage fluid exsolution or some combination of these processes. Instead, we conclude that thermal diffusion or source magma variation is the most likely process producing Fe isotope ratio variations in the Torres del Paine pluton.     

Biogenic volatile compound emissions from a temperate forest,China: model simulation

Emissions of biogenic volatile organic compounds (BVOC) were measured using a relaxed eddy accumulation (REA) technique on an above-canopy tower in a temperate forest (Changbai Mountain, Jilin province, China) during the 2010 and 2011 summer seasons. Solar global radiation and photosynthetically active radiation (PAR) were also measured. Based on PAR energy dynamic balance, an empirical BVOC emission and PAR transfer model was developed that includes the processes of BVOC emissions and PAR transfer above the canopy level, including PAR absorption and consumption, and scattering by gases, liquids, and particles (GLPs). Simulated emissions of isoprene and monoterpenes were in agreement with observations. The averages of the relative estimator biases for the flux were 39.3 % for isoprene, and 27.1 % for monoterpenes in the 2010 and 2011 growing seasons, with NMSE (normalized mean square error) values of 0.133 and 0.101, respectively. The observed and simulated mean diurnal variations of isoprene and monoterpenes in the 2010 and 2011 growing seasons were evaluated for the validation of the empirical model. Under observed atmospheric conditions, the sensitivity analysis showed that emissions of isoprene and monoterpenes were more sensitive to changes in PAR than to water vapor content or to the magnitude of the scattering factor. The emissions of isoprene and monoterpenes in the 2010 and 2011 growing seasons (from June to September) were estimated using this empirical model along with hourly observational data, with mean hourly emissions of 1.71 and 1.55 mg m^?2 h^?1 for isoprene, and 0.48 and 0.47 mg m^?2 h^?1 for monoterpenes in 2010 and 2011, respectively. As formaldehyde (HCHO) is considered as the main oxidation product of isoprene and monoterpenes, it is necessary to investigate the link between HCHO and BVOC emissions. GOME-2 HCHO vertical column densities (VCDs) can be used to estimate BVOC emission fluxes in the Changbai Mountain temperate forest.     

Initiation of large-volume silicic centers in the Yellowstone hotspot track: insights from H<Subscript>2</Subscript>O- and F-rich quartz-hosted rhyolitic melt inclusions in the Arbon Valley Tuff of the Snake River Plain

During the onset of caldera cluster volcanism at a new location in the Snake River Plain (SRP), there is an increase in basalt fluxing into the crust and diverse silicic volcanic products are generated. The SRP contains abundant and compositionally diverse hot, dry, and often low-δ¹⁸O silicic volcanic rocks produced through time during the formation of individual caldera clusters, but more H₂O-rich eruptive products are rare. We report analyses of quartz-hosted melt inclusions from pumice clasts from the upper and lower Arbon Valley Tuff (AVT) to gain insight into the initiation of caldera cluster volcanism. The AVT, a voluminous, caldera-forming rhyolite, represents the commencement of volcanism (10.44 Ma) at the Picabo volcanic field of the Yellowstone hotspot track. This is a normal δ¹⁸O rhyolite consisting of early and late erupted members (lower and upper AVT, respectively) with extremely radiogenic Sr isotopes and unradiogenic Nd isotopes, requiring that ~50 % of the mass of these elements is derived from melts of Archean upper crust. Our data reveal distinctive features of the early erupted lower AVT melt including: variable F concentrations up to 1.4 wt%, homogenous and low Cl concentrations (~0.08 wt%), H₂O contents ranging from 2.3 to 6.4 wt%, CO₂ contents ranging from 79 to 410 ppm, and enrichment of incompatible elements compared to the late erupted AVT, subsequent Picabo rhyolites, SRP rhyolites, and melt inclusions from other metaluminous rhyolites (e.g., Bishop Tuff, Mesa Falls Tuff). We couple melt inclusion data with Ti measurements and cathodoluminescence (CL) imaging of the host quartz phenocrysts to elucidate the petrogenetic evolution of the AVT rhyolitic magma. We observe complex and multistage CL zoning patterns, the most critical being multiple truncations indicative of several dissolution–reprecipitation episodes with bright CL cores (higher Ti) and occasional bright CL rims (higher Ti). We interpret the high H₂O, F, F/Cl, and incompatible trace element concentrations in the context of a model involving melting of Archean crust and mixing of the crustal melt with basaltic differentiates, followed by multiple stages of fractional crystallization, remelting, and melt extraction. This multistage process, which we refer to as distillation, is further supported by the complex CL zoning patterns in quartz. We interpret new Δ¹⁸O(Qz-Mt) isotope measurements, demonstrating a 0.4 ‰ or ~180 °C temperature difference, and strong Sr isotopic and chemical differences between the upper and lower AVT to represent two separate eruptions. Similarities between the AVT and the first caldera-forming eruptions of other caldera clusters in the SRP (Yellowstone, Heise and Bruneau Jarbidge) suggest that the more evolved, lower-temperature, more H₂O-rich rhyolites of the SRP are important in the initiation of a caldera cluster during the onset of plume impingement.     

Long-term soil moisture dynamics derived from GNSS interferometric reflectometry: a case study for Sutherland,South Africa

Soil moisture is a geophysical key observable for predicting floods and droughts, modeling weather and climate and optimizing agricultural management. Currently available in situ observations are limited to small sampling volumes and restricted number of sites, whereas measurements from satellites lack spatial resolution. Global navigation satellite system (GNSS) receivers can be used to estimate soil moisture time series at an intermediate scale of about 1000 m². In this study, GNSS signal-to-noise ratio (SNR) data at the station Sutherland, South Africa, are used to estimate soil moisture variations during 2008–2014. The results capture the wetting and drying cycles in response to rainfall. The GNSS Volumetric Water Content (VWC) is highly correlated (r ² = 0.8) with in situ observations by time-domain reflectometry sensors and is accurate to 0.05 m³/m³. The soil moisture estimates derived from the SNR of the L1 and L2P signals compared to the L2C show small differences with a RMSE of 0.03 m³/m³. A reduction in the SNR sampling rate from 1 to 30 s has very little impact on the accuracy of the soil moisture estimates (RMSE of the VWC difference 1–30 s is 0.01 m³/m³). The results show that the existing data of the global tracking network with continuous observations of the L1 and L2P signals with a 30-s sampling rate over the last two decades can provide valuable complementary soil moisture observations worldwide.     

Recursive algorithm for fast GNSS orbit fitting

Gaussian elimination is an efficient and numerically stable algorithm for estimating parameters and their precision. However, before estimating the parameters, it is often prudent to perform statistical tests to achieve the best fitting model. We use Gaussian elimination to select the best fitting model among candidate models. A succinct relationship between the weighted sum of squared residuals and the previous one is revealed by a volume formula. For quick parameter estimation and determination of weighted sum of squared residuals, a recursive elimination algorithm is proposed in the context of Gaussian elimination. In order to improve the model selection efficiency, the parameter estimation and the determination of the weighted sum of squared residuals are carried out in parallel using the proposed recursive elimination algorithm in which the improvement at each recursive stage is judged by the Bayesian information criterion. Ultimately, the computational complexity and numerical stability of the recursive elimination proposed are briefly discussed, and a GNSS orbit interpolation example is used to verify the results. It shows that the proposed recursive elimination algorithm inherits the numerical stability of the Gaussian elimination, and this algorithm can be used to examine the gain from the newly introduced parameter, dynamically assess the fitting model, and fix the optimal model efficiently. The optimal fitting model with the lowest information is very close to the real situation verified by checkpoints.     

A new method for specular and diffuse pseudorange multipath error extraction using wavelet analysis

Multipath remains one of the major challenges in Global Navigation Satellite System (GNSS) positioning because it is considered the dominant source of ranging errors, which can be classified into specular and diffuse types. We present a new method using wavelets to extract the pseudorange multipath in the time domain and breaking it down into the two components. The main idea is an analysis-reconstruction approach based on application of both continuous wavelet transform (CWT) and discrete wavelet transform (DWT). The proposed procedure involves the use of L1 code-minus-carrier (CMC) observable where higher-frequency terms are isolated as residuals. CMC residuals are analyzed by applying the CWT, and we propose the scalogram as a technique for discerning time–frequency variations of the multipath signal. Unlike Fourier transform, the potential of the CWT scalogram for examining the non-stationary and multifrequency nature of the multipath is confirmed as it simultaneously allows fine detection and time localization of the most representative frequencies of the signal. This interpretation of the CWT scalogram is relevant when choosing the levels of reconstruction with DWT, allowing accurate time domain extraction of both the specular and diffuse multipath. The performance and robustness of the method and its boundary applicability are assessed. The experiment was carried out using a receiver of Campania GNSS Network. The results are given in which specular multipath error is achieved using DWT level 7 approximation component and diffuse multipath error is achieved using DWT level 6 denoised detail component.