A model for oxygen and sulfur isotope fractionation in sulfate during bacterial sulfate reduction processes

We present a model of bacterial sulfate reduction that includes equations describing the fractionation relationship between the sulfur and the oxygen isotope composition of residual sulfate (δ³⁴S_{SO4_residual}, δ¹⁸O_{SO4_residual}) and the amount of residual sulfate. The model is based exclusively on oxygen isotope exchange between cell-internal sulfur compounds and ambient water as the dominating mechanism controlling oxygen isotope fractionation processes. We show that our model explains δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} patterns observed from natural environments and from laboratory experiments, whereas other models, favoring kinetic isotope fractionation processes as dominant process, fail to explain many (but not all) observed δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} patterns. Moreover, we show that a “typical” δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} slope does not exist. We postulate that measurements of δ³⁴S_{SO4_residual} and δ¹⁸O_{SO4_residual} can be used as a tool to determine cell-specific sulfate reduction rates, oxygen isotope exchange rates, and equilibrium oxygen isotope exchange factors. Data from culture experiments are used to determine the range of sulfur isotope fractionation factors in which a simplified set of equations can be used. Numerical examples demonstrate the application of the equations. We postulate that, during denitrification, the oxygen isotope effects in residual nitrate are also the result of oxygen isotope exchange with ambient water. Consequently, the equations for the relationship between δ³⁴S_{SO4_residual}, δ¹⁸O_{SO4_residual}, and the amount of residual sulfate could be modified and used to calculate the fractionation-relationship between δ¹⁵N_{NO3_residual}, δ¹⁸O_{NO3_residual}, and the amount of residual nitrate during denitrification.     

Modeling the impact of microbial activity on redox dynamics in porous media

The present study investigates the interaction between microbial growth and activity and the redox dynamics in natural porous media. The impact the transport regime has on this interaction is also addressed. Expressions for microbial growth are incorporated into a geochemical reaction network linking redox reaction rates to the activity of the microorganisms. A flexible simulation environment, the Biogeochemical Reaction Network Simulator (BRNS) is used for this purpose. Two reactive transport applications relevant to fields of contaminant hydrology and early diagenesis are simulated with the BRNS. Model results are evaluated based on a comparison with comprehensive datasets on the biodegradation of lactate in a sand column experiment and on the distribution of redox-sensitive chemical species in marine sediments of the Skagerrak, Denmark. It is shown that, despite quite different transport regimes, the geomicrobiological model performs equally well in the reproduction of measured chemical species distribution for both applications. This result emphasizes the broad applicability of the proposed approach. Our simulations support that the competitive behavior between various microbial groups is a process controlling the development of redox stratified environments. Furthermore, it is also shown that the transport regime is a key controlling factor for the degree of spatial correlation between microbial biomass distributions and redox reaction rates. Although all our simulations yield a pronounced stratification of the redox processes in the system, the biomass distribution is related to the associated reaction rates only in case of the advection controlled column experiment. In the early diagenetic application, mixing due to bioturbation is the dominant transport process for particulate matter, hence leading to fairly homogeneous distribution of bacterial biomasses which are unrelated to the spatial distribution of redox reaction rates. This homogeneous biomass distribution combined with the 1G carbon degradation model approach might explain why the steady state concentration profiles in such systems can be reproduced by diagenetic models without explicit representation of microbial growth.     

A multiphase approach for evaluating the horizontal and rocking impedances of pile group foundations

This paper advocates the use of a multiphase model, already developed for static or quasi‐static geotechnical engineering problems, for simulating the behaviour of piled raft foundations subject to horizontal as well as rocking dynamic solicitations. It is shown that such a model, implemented in a FEM code, yields appropriate predictions for the foundation impedance characteristics, provided that shear and bending effects in the piles are taken into account, thus corroborating the findings of the asymptotic homogenization theory. Besides, it is notably pointed out that such a multiphase‐based computational tool makes it possible to assess the dynamic behaviour of pile groups in a much quicker way than when using direct numerical simulations, which may face oversized problems when large pile groups are concerned. Copyright © 2016 John Wiley & Sons, Ltd.     

Geochronology of granulites from the south Itabuna-Salvador-Curaçá Block,São Francisco Craton (Brazil): Nd isotopes and U–Pb zircon ages

This work provides five new U–Pb zircon dating and the corresponding Nd isotope data for felsic granulites from the south Itabuna-Salvador-Curaçá Block (ISCB), in the São Francisco Craton, Brazil. Three major sets of felsic granulites can be recognised. The oldest set is tonalitic in composition and of TTG affinity. It is Archaean in age with magmatic zircon cores dated at 2675 ± 11 Ma by LA-ICPMS and up to ca 2.7–2.9 Ga by SHRIMP on an other sample. It exhibits epsilon Nd values between ?8 and ?11 at 2.1 Ga. This Nd signature is similar to that of granulites found in the western Archaean Jequié Block. Cartographically, this set of Archaean terrains represents at least 50% of the granulites in the studied area. The second set corresponds to a Palaeoproterozoic calc-alkaline tonalitic suite with zircon ages from 2019 ± 19 Ma to 2191 ± 10 Ma and epsilon Nd values between ?3 and ?4 at 2.1 Ga, corresponding partially to a newly formed crust. The third set of granulites is also Palaeoproterozoic. It is shoshonitic to monzonitic in composition and synchronous with the high grade metamorphism dated by metamorphic zircons at 2086 ± 7 Ma (average of five samples). The Nd isotope signature for this alkaline set is similar to that of the Palaeoproterozoic calc-alkaline one. Nd isotopes appear to be a very efficient tool to distinguish Archaean from Palaeoproterozoic felsic protoliths in granulitic suites of the Itabuna-Salvador-Curaçá Block (ISCB). Finally, the southern part of the ISCB is composed of a mixture of Archaean and Palaeoproterozoic protoliths, in similar amounts, suggesting that it was probably an active margin between 2.1 and 2.2 Ga located on the eastern border of the Archaean Jequié Block. A major crustal thickening process occurred at ca 2.09 Ga in the ISCB and seems significantly younger towards the west, in the Jequié granulites, where an average of 2056 ± 9 Ma is determined for the high grade event.     

Crustal segments in the North Patagonian Massif,Patagonia: An integrated perspective based on Sm–Nd isotope systematics

New insights on the Paleozoic evolution of the continental crust in the North Patagonian Massif are presented based on the analysis of Sm–Nd systematics. New evidence is presented to constrain tectonic models for the origin of Patagonia and its relations with the South American crustal blocks. Geologic, isotopic and tectonic characterization of the North Patagonian Massif and comparison of the Nd parameters lead us to conclude that: (1) The North Patagonian Massif is a crustal block with bulk crustal average ages between 2.1 and 1.6 Ga T_DM (Nd) and (2) At least three metamorphic episodes could be identified in the Paleozoic rocks of the North Patagonian Massif. In the northeastern corner, Famatinian metamorphism is widely identified. However field and petrographic evidence indicate a Middle to Late Cambrian metamorphism pre-dating the emplacement of the ca. 475 Ma granitoids. In the southwestern area, are apparent 425–420 Ma (?) and 380–360 Ma metamorphic peaks. The latter episode might have resulted from the collision of the Antonia terrane; and (3) Early Paleozoic magmatism in the northeastern area is coeval with the Famatinian arc. Nd isotopic compositions reveal that Ordovician magmatism was associated with attenuated crust. On the southwestern border, the first magmatic recycling record is Devonian. Nd data shows a step by step melting of different levels of the continental crust in the Late Palaeozoic. Between 330 and 295 Ma magmatism was likely the product of a crustal source with an average 1.5 Ga T_DM (Nd). Widespread magmatism represented by the 295–260 Ma granitoids involved a lower crustal mafic source, and continued with massive shallower-acid plutono volcanic complexes which might have recycled an upper crustal segment of the Proterozoic continental basement, resulting in a more felsic crust until the Triassic. (4) Sm–Nd parameters and detrital zircon age patterns of Early Paleozoic (meta)-sedimentary rocks from the North Patagonian Massif and those from the neighboring blocks, suggest crustal continuity between Eastern Sierras Pampeanas, southern Arequipa-Antofalla and the northeastern sector of the North Patagonian Massif by the Early Paleozoic. This evidence suggests that, at least, this corner of the North Patagonian Massif is not allochthonous to Gondwana. A Late Paleozoic frontal collision with the southwestern margin of Gondwana can be reconcilied in a para-autochthonous model including a rifting event from a similar or neighbouring position to its post-collision location. Possible Proterozoic or Early Paleozoic connections of the NPM with the Kalahari craton or the western Antartic blocks should be investigated.     

Earth's rotation variations: a wavelet analysis

Historical to up‐to‐date data of the minute variations in the solid Earth's rotation are subjected to a comprehensive time‐frequency wavelet analysis. The length‐of‐day for the period 1962–2012 confirms the presence of a prominent, robust 6‐year periodicity and reveals an anomalously strong 18.6‐year tidal oscillation as well as a ~13‐year quasi‐periodic signal. The polar‐motion excitation for the period 1900–2012 validates the existence of the ~26‐year Markowitz wobble and shows an ~8‐year quasi‐periodic signal, but no appreciable 18.6‐year periodicity. Although it is known that exchanges of angular momentum with the geophysical fluids are responsible for the rotational variations of the solid Earth, the exact physical mechanisms involved on interannual‐to‐decadal timescales are still far from understood.