Source(s) and cycling of the nonhydrolyzable organic fraction of oceanic particles

A major fraction of particulate organic carbon (POC) in the deep ocean remains molecularly uncharacterized. In an effort to determine the chemical characteristics and source(s) of sinking POC, we studied a nonhydrolyzable fraction of sinking POC using ¹³C NMR (nuclear magnetic resonance) spectroscopy and analytical pyrolysis. ¹³C NMR spectra and products from analytical pyrolysis of the nonhydrolyzable fraction exhibit a strongly aliphatic character that is distinct from that of bulk POC. The aliphatic nature of this fraction is consistent with its low stable carbon isotope values. We hypothesize that the nonhydrolyzable fraction derives to a significant extent from a refractory component of organisms that selectively accumulates, resulting in its manifestation as a major part of POC sinking to the deep ocean and in underlying sediments.     

Elucidation of different forms of organic carbon in marine sediments from the Atlantic coast of Spain using thermal analysis coupled to isotope ratio and quadrupole mass spectrometry

Analysis of river, estuary and marine sediments from the Atlantic coast of Spain using thermogravimetry–differential scanning calorimetry–quadrupole mass spectrometry–isotope ratio mass spectrometry (TG–DSC–QMS–IRMS) was used to (a) distinguish bulk chemical hosts for C within a sediment and humic acid fraction, (b) track C pools with differing natural C isotope ratios and (c) observe variation with distance from the coast. This is the first application of such a novel method to the characterisation of organic matter from marine sediments and their corresponding humic acid fractions. Using thermal analysis, a labile, a recalcitrant and a refractory carbon pool can be distinguished. Extracted humic fractions are mainly of recalcitrant nature. The proportion of refractory carbon is greatest in marine sediments and humic acid fractions. Quadrupole mass spectrometry confirmed that the greatest proportion of m/z 44 (CO₂) and m/z 18 (H₂O) were detected at temperatures associated with recalcitrant carbon (510–540 °C). Isotope analysis detected progressive enrichment in δ¹³C for the sediment samples with an increase in marine influence. Isotopic heterogeneity in the refractory organic matter in marine sediments could be due to products of anthropogenic origin or natural combustion products. Isotope homogeneity of humic acids confirms the presence of terrigenous C in marine sediments, allowing the terrestrial input to be characterised.     

Comparative study of sampling methods and in situ and laboratory analysis for shallow-water submarine hydrothermal systems

A primary aim for sampling of submarine hydrothermal vents is to minimize inclusion of ambient seawater. Here, we compare the results of three different sampling methods (air displacement, two-valve bottle, and syringes) for shallow submarine systems. Mixing of hydrothermal fluid with seawater is unavoidable; however, calculations based on linear mixing models allow estimation of the hydrothermal fluid end-member composition. The results show that sampling with a two-valve bottle and syringes are the best options because they allow collection of samples with a large proportion of hydrothermal fluid. Additionally, we compare the results of in situ and laboratory analyses of the fluid samples, and demonstrate that determination of chemical composition in situ is the best option for some components, as re-equilibration affects some component concentrations (i.e. bicarbonate). Conversely, silica determination in situ usually underestimates the concentration in the fluid, as it does not account for polymeric silica. Other components can be measured either in the field or in the laboratory.     

The bimodal rift-related Juscelândia volcanosedimentary sequence in central Brazil: Mesoproterozoic extension and Neoproterozoic metamorphism

The Barro Alto Complex and Juscelândia volcanosedimentary sequence are exposed in the central part of the Neoproterozoic Brasília belt of central Brazil. The former is a large (approximately 150 km long), boomerang-shaped, mafic-ultramafic, layered complex formed by two different intrusions metamorphosed under granulite facies. These rocks are tectonically overlain by rocks of the Juscelândia volcanosedimentary sequence, represented mainly by biotite-gneiss and amphibolite, or amphibolite facies metamorphic equivalents of rhyolite and basalt, respectively. New SIMS U–Pb zircon data and Sm–Nd isochron data presented herein help clarify the igneous and metamorphic evolution of the Juscelândia volcanosedimentary sequence, as well as its relationship with the Barro Alto Complex. Zircon grains from two biotite gneisses were analyzed by SIMS (SHRIMP) and indicate Mesoproterozoic dates, approximately 1.28 Ga, interpreted as the time of bimodal volcanism in a tectonic setting transitional between a continental rift and an ocean basin. Metamorphism is constrained by Sm–Nd garnet-whole-rock isochrons for garnet amphibolite and pelitic schists of the Juscelândia sequence, as well as for clinopyroxene-garnet amphibolite and garnet granulite of the Barro Alto Complex, which give ages between 0.74 and 0.76 Ga, in agreement with SIMS dates for metamorphic zircon rims. These new data are significant, because they establish that a single metamorphic event affected both the Barro Alto Complex and the Juscelândia sequence. Based on these new data, we present a modified tectonic model for the Brasília belt.     

An Albian–Cenomanian unconformity in the northern Andes: Evidence and tectonic significance

The Villeta Group of Colombia and equivalent stratigraphic units of Venezuela and Ecuador comprise marine sequences ranging from Albian to Santonian in age. Deposition of the Villeta Group was presumed to take place entirely in quiet tectonic conditions in a passive margin setting that occupied NW South America. From a large database of 2D/3D seismic, well, surface geology, and biostratigraphic data, we present evidence for intra-Villeta (mostly late Albian–Cenomanian) deformation in parts of the Upper Magdalena Valley and Eastern Cordillera of Colombia, controlled by transpressional fault reactivation, produced by transpressional fault reactivation and thrusting that resulted in an angular unconformity. This event has been largely unnoticed in the literature, but previously scattered evidence supports our observations, suggesting regionally extensive tectonism. Published fission-track age determinations and other geologic evidence from Colombia and Venezuela suggest significant uplifts around 80–100 m.y., which may reflect changes in the subduction regime, with compressional deformation in certain regions and extensional deformation in others. A late Albian onset of compressional deformation along the Colombian and Peruvian segments of the Andes may be related to the opening of the South Atlantic Ocean at equatorial latitudes. Identification of tectonic activity with development of an unconformity in intra-Villeta times provides new insights into understanding the evolution of the Upper Magdalena Valley and adjacent areas of Colombia and western Venezuela and creates new possibilities for hydrocarbon exploration, with additional trapping phases, better reservoir preservation by early migration and secondary porosity, and ultimately facies changes with stratigraphic potential.     

Review: Microbial biocenoses in pristine aquifers and an assessment of investigative methods

The current knowledge of microbial biocenoses (communities) in pristine aquifers is presented in a review, which also discusses their relevance for questions of groundwater protection. Aquifers are heterogeneous on all scales and structured in a variety of habitats. The void spaces in many aquifers are small. The biocenoses are thus predominantly composed of microorganisms and, often, microinvertebrates. Larger voids and macroorganisms occur in karst cavities. Due to the absence of light, the biocenoses depend on chemical energy resources, which are, however, scarce in non-contaminated groundwater. The microorganisms thus show small cell sizes, low population densities and reduced activity; they developed specific strategies to survive oligotrophic conditions. The review also discusses the impact of contamination on the biocenoses, and the potential use of the biocenoses or specific organisms as indicators for groundwater quality, and the limits of this approach. Bacteria are either planktonic or attached to aquifer material, which requires both fluid and solid phase sampling. Most groundwater bacteria are viable but non-culturable. Consequently, cultivation techniques give an incomplete picture of the biocenoses, while methods from molecular microbiology provide genetic fingerprints of the entire community. Different analytical methods are available to count microorganisms, identify species, characterise microbial diversity, and measure activity.     

Effects of magnetic interactions in anisotropy of magnetic susceptibility: Models, experiments and implications for igneous rock fabrics quantification

Besides granites of the ilmenite series, in which the anisotropy of magnetic susceptibility (AMS) is mainly controlled by paramagnetic minerals, the AMS of igneous rocks is commonly interpreted as the result of the shape-preferred orientation of unequant ferromagnetic grains. In a few instances, the anisotropy due to the distribution of ferromagnetic grains, irrespective of their shape, has also been proposed as an important AMS source. Former analytical models that consider infinite geometry of identical and uniformly magnetized and coaxial particles confirm that shape fabric may be overcome by dipolar contributions if neighboring grains are close enough to each other to magnetically interact. On these bases we present and experimentally validate a two-grain macroscopic numerical model in which each grain carries its own magnetic anisotropy, volume, orientation and location in space. Compared with analytical predictions and available experiments, our results allow to list and quantify the factors that affect the effects of magnetic interactions. In particular, we discuss the effects of (i) the infinite geometry used in the analytical models, (ii) the intrinsic shape anisotropy of the grains, (iii) the relative orientation in space of the grains, and (iv) the spatial distribution of grains with a particular focus on the inter-grain distance distribution. Using documented case studies, these findings are summarized and discussed in the framework of the generalized total AMS tensor recently introduced by Cañon-Tapia (Cañon-Tapia, E., 2001. Factors affecting the relative importance of shape and distribution anisotropy in rocks: theory and experiments. Tectonophysics, 340, 117–131.). The most important result of our work is that analytical models far overestimate the role of magnetic interaction in rock fabric quantification. Considering natural rocks as an assemblage of interacting and non-interacting grains, and that the effects of interaction are reduced by (i) the finite geometry of the interacting clusters, (ii) the relative orientation between interacting grains, (iii) their heterogeneity in orientation, shape and bulk susceptibility, and (iv) their inter-distance distribution, we reconcile analytical models and experiments with real case studies that minimize the role of magnetic interaction onto the measured AMS. Limitations of our results are discussed and guidelines are provided for the use of AMS in geological interpretation of igneous rock fabrics where magnetic interactions are likely to occur.     

Modèles géostatistiques de concentrations ou de débits le long des cours d'eau

Estimating concentrations or flow rates along a stream network requires specific models. Two classes of models, recently proposed in the literature, are generalized, to the intrinsic case in particular. We present a global construction by ‘streams’, i.e. on the whole set of paths between sources and outlet. Combining stationary or intrinsic one-dimensional random functions leads to stationary or intrinsic models on segments, with discontinuities at the forks. A construction from outlet to sources, leads to stationary or intrinsic models on each stream, without any discontinuity at the forks. The linear variogram is found as a particular case. The extension to the linear model of coregionalization is immediate, allowing a multivariate modelling of concentrations. To cite this article: C. de Fouquet, C. Bernard-Michel, C. R. Geoscience 338 (2006).     

Study of geothermal water intrusion due to groundwater exploitation in the Puebla Valley aquifer system, Mexico

Significant intrusion of geothermal water into fresh groundwater takes place in the Puebla Valley aquifer system, Mexico. The decline in the potentiometric surface due to the overexploitation of the groundwater induces this intrusion. This hydrological system comprises three aquifers located in Plio-Quaternary volcanic sediments and Mesozoic calcareous rocks. The hydraulic balance of the aquifer shows that the annual output exceeds the natural inputs by 12 million m³. Between 1973 and 2002, a drop in the potentiometric surface, with an 80 m cone of depression, was identified in a 5-km-wide area located southwest of the city of Puebla. Chemical analyses performed on water samples since 1990 have shown an increase in total dissolved solids (TDS) of more than 500 mg/L, coinciding with the region showing a cone of depression in the potentiometric surface. A three-dimensional flow and transport model, based on the hydrogeological and geophysical studies, was computed by using the MODFLOW and MT3D software. This model reproduces the evolution of the aquifer system during the last 30 years and predicts for 2010 an additional drawdown in the potentiometric surface of 15 m, and an increase in the geothermal water intrusion.     

Monte Carlo simulation of mixing in Ca3Fe2Ge3O12–Ca4Ge4O12 garnets and implications for the thermodynamic stability of pyrope–majorite solid solution

Static lattice energy calculations, based on empirical pair potentials, were performed for a large set of structures differing in the arrangement of octahedral cations within the garnet 2 × 2 × 2 supercell. The compositions of these structures varied between Ca₃Fe₂Ge₃O₁₂ and Ca₄Ge₄O₁₂. The energies were cluster expanded using pair and quaternary terms. The derived ordering constants were used to constrain Monte Carlo simulations of temperature-dependent mixing properties in the ranges of 1,073–3,673 K and 0–10 GPa. The free energies of mixing were calculated using the method of thermodynamic integration. The calculations predict a wide miscibility gap between Fe-rich (cubic) and Fe-pure (tetragonal) garnets consistent with recent experimental observations of Iezzi et al. (Phys Chem Miner 32:197–207, 2005). It is shown that the miscibility gap arises due to a very strong cation ordering at the Fe-pure composition, driven by the charge difference between Ca²⁺ and Ge⁴⁺ cations. The structural and thermodynamic analogies between Ca–Ge and Mg–Si systems suggest that a similar miscibility gap should exist between pyrope and Mg–Si-majorite.