Organic matter in a low productivity anoxic intraplatform basin in the Triassic Tethys

This paper presents isotopic, bulk geochemical and biomarker data measured on organic matter accumulated in a narrow extensional basin developed at the oceanward margin of the huge Triassic carbonate platform in the Alps–Appenines domain. The integration of isotope signatures, organic petrographical and biomarker evidence together with the composition of kerogen pyrolysates suggests immature organic matter predominantly of algal origin with a minor, but not negligible, higher plant derived and moderate bacterial contribution for the entire sequence. The mineral sources are dominated by platform-derived subtidal Dachstein limestone with a minor palaeosol input and a moderate contribution of autochtonous quartz. Nevertheless, parallel variations observed in the mineral content, as well as in the amount and the quality of the organic matter reflect variations in the palaeoenvironment. The increased humidity, existing in the period of the accumulation of the upper section of the sequence, led to the restriction of dolomitization. A slightly greater higher plant derived contribution, in this section, is evidenced by the composition of bitumen and the results on GC and GC/MS analyses on the non-aromatic hydrocarbon fraction of bitumen. Moreover, the climate-induced weathering enchanced the primary productivity and resulted in a pronounced increase in the TOC content. The average estimated value of the planktonic productivity is about three times higher for the calcite-rich sequence than the dolomite-rich one, being 44.2 and 15.3 tC_org/m²/Ma, respectively. The low to moderate planktonic productivity shows that anoxic conditions, observed for the entire succession, are a consequence of the stagnant water stratification rather than high planktonic productivity. Depth trends in the data measured on kerogens (HI, OI, δ¹³Corg values, composition of pyrolysate) together with the δ¹⁸O excursions and Δδ¹³C values appear to be controlled by sea-level fluctuations. Consistent with the high abundance of alkyltiophenes in kerogen pyrolysates, the high S_org/C ratios (ranging between 0.05 and 0.10) suggest the importance of natural sulfurization in the formation of the sulfur-rich type-II-S kerogen occurring in all of the samples.     

Interpretation of gamma-ray logs: The distribution of uranium in carbonate platform

High gamma-radioactivity in carbonates is usually ascribed to uranium of detrital minerals and organic matter, and to thorium and potassium of clays. The present study based on Urgonian marls and marly limestones (France) shows that some of the most radioactive values correspond instead to some ‘pure’ limestones. These peaks are generally associated with a sequence boundary or a maximum flooding surface. Low-level γ-spectrometry and ICP–MS analyses show that although high radioactivities are mostly associated with uranium, there is no obvious correlation between uranium enrichment and lithology. Also, correlation between high radioactivity and argillaceous beds might not be systematic. To cite this article: M.C. Raddadi et al., C. R. Geoscience 337 (2005).     

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.     

Soil paludification and Sphagnum bog initiation: the influence of indurated podzolic soil and fire

The initiation and growth of boreal peatlands developed on well‐drained, sandy landforms are closely associated with podzolic soil paludification processes. The origin of Sphagnum bogs extending on large deltaic plains was examined to test the hypothesis of the dual impact of indurated (ortstein) podzols and fire on forest soil paludification and concurrent peatland initiation and expansion. Mineral soil, basal organic matter and peat monoliths were sampled for soil and macrofossil analyses along an 800‐m toposequence starting from a mixed‐wood boreal forest to a Sphagnum bog (Lebel bog, eastern Quebec, Canada), and ending at a peat dome in the thickest section of the peatland. Mineral soils along the toposequence are ortstein humo‐ferric podzols distributed in the forest environment and beneath Sphagnum peat in the bog, except at the peat dome. Initial peatland growth occurred c. 6000 cal. a BP. Soil paludification coincided with the cessation of fire occurrence as recorded in the organic and mineral layers preceding Sphagnum expansion. Unlike most temperate and boreal raised bogs, the Sphagnum bog developed directly from a forest environment without passing through a transitional fen stage. Conifer forests regenerated successively after several fires between 4200 and 1600 cal. a BP before bog expansion. Pre‐bog forests were composed of fire‐prone black spruce (Picea mariana) and jack pine (Pinus banksiana) trees, and ericaceous species. Given the distribution and thickness of ortstein horizons progressively decreasing and disappearing towards the peatland dome, growth and expansion of the Sphagnum bog was not caused by soil induration processes, which could have potentially impeded vertical and horizontal drainage. The development of indurated podzols outside and several hundred metres inside the peatland preceded the initiation and expansion of the Sphagnum bog. Cessation of fire activity appears to be a key factor facilitating the lateral expansion of the Sphagnum bog under wet soil conditions.     

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.     

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.