Diagenetic paths in the margin of a Triassic Basin: NW zone of the Iberian Chain, Spain

Buntsandstein deposits generated in a slowly subsiding basin on the western margin of the Iberian Chain are represented by a stratigraphic succession of fluvial deposits less than 100 m thick (conglomerates, sandstones, and shales). Diagenetic processes in sandstones can be grouped as eodiagenetic, mesodiagenetic, and telodiagenetic. Eodiagenesis can be associated with Muschelkalk, Keuper, and probably early Jurassic times. Mesodiagenesis is probably related to Jurassic times. Diagenetic chemical reactions suggest a maximum burial less than 1.5 km and low temperatures (<120°C). Patterns of porosity reduction by compaction and cementation suggest four diagenetic stages: (1) Loss of primary porosity by early mechanical compaction; (2) early cementation (K-feldspar and dolomite); (3) dissolution of cements; and (4) framework collapse by re-compaction. These stages are manifested by the presence of two types of sandstone. Type I sandstones present high intergranular volume (mean, 30%). Type II sandstones are characterized by high compactional porosity loss and exhibit low values of intergranular volume (mean, 16.9%). Type II sandstones are associated with the dissolution of cement and later re-compaction of type I sandstones. An intermediate telodiagenetic phase is deduced and related to the sharp unconformity between Lower Cretaceous sediments and the underlying sediments. This suggests that a mechanically unstable framework collapsed during the Cretaceous, generating type II sandstones. The analyzed diagenetic paths have a wide applicability on similar marginal areas of rift basins.     

Nucleosynthetic zirconium isotope anomalies in acid leachates of carbonaceous chondrites

Stepwise dissolutions of the carbonaceous chondrites Orgueil (CI), Murchison (CM) and Allende (CV) reveal large nucleosynthetic anomalies for Zr isotopes that contrast with the uniform compositions found in bulk meteorites. Two complementary nucleosynthetic components are observed: one enriched and one depleted in s-process nuclides. The latter component, characterized by excess ⁹⁶Zr, is most distinctive in the acetic acid leachate (up to ε⁹⁶Zr ≈ 50). The excess decreases with increasing acid strength and the final leaching steps of the experiment are depleted in ⁹⁶Zr and thus enriched in s-process nuclides. Presolar silicon carbide grains are likely host phases for part of the anomalous Zr released during these later stages. However, by mass balance they cannot account for the ⁹⁶Zr excesses observed in the early leaching steps and this therefore hints at the presence of at least one additional carrier phase with significant amounts of anomalous Zr. The data provide evidence that average solar system material consists of a homogenized mixture of different nucleosynthetic components, which can be partly resolved by leaching experiments of carbonaceous chondrites.     

Long-term deforestation in NW Spain: linking the Holocene fire history to vegetation change and human activities

The Holocene fire regime is thought to have had a key role in deforestation and shrubland expansion in Galicia (NW Spain) but the contribution of past societies to vegetation burning remains poorly understood. This may be, in part, due to the fact that detailed fire records from areas in close proximity to archaeological sites are scarce. To fill this gap, we performed charcoal analysis in five colluvial soils from an archaeological area (Campo Lameiro) and compared the results to earlier studies from this area and palaeo-ecological literature from NW Spain. This analysis allowed for the reconstruction of the vegetation and fire dynamics in the area during the last ca 11 000 yrs. In the Early Holocene, Fabaceae and Betula sp. were dominant in the charcoal record. Quercus sp. started to replace these species around 10 000 cal BP, forming a deciduous forest that prevailed during the Holocene Thermal Maximum until ～5500 cal BP. Following that, several cycles of potentially fire-induced forest regression with subsequent incomplete recovery eventually led to the formation of an open landscape dominated by shrubs (Erica sp. and Fabaceae). Major episodes of forest regression were (1) ～5500–5000 cal BP, which marks the mid-Holocene cooling after the Holocene Thermal Maximum, but also the period during which agropastoral activities in NW Spain became widespread, and (2) ～2000–1500 cal BP, which corresponds roughly to the end of the Roman Warm Period and the transition from the Roman to the Germanic period. The low degree of chronological precision, which is inherent in fire history reconstructions from colluvial soils, made it impossible to distinguish climatic from human-induced fires. Nonetheless, the abundance of synanthropic pollen indicators (e.g. Plantago lanceolata and Urtica dioica) since at least ～6000 cal BP strongly suggests that humans used fire to generate and maintain pasture.     

Low-order stabilized finite element for the full Biot formulation in soil mechanics at finite strain

This article presents a novel finite element formulation for the Biot equation using low-order elements. Additionally, an extra degree of freedom is introduced to treat the volumetric locking steaming from the effective response of the medium; its balance equation is also stabilized. The accuracy of the proposed formulation is demonstrated by means of numerical analyses.     

Response of suspended sediment particle size distributions to changes in water chemistry at an Andean mountain stream confluence receiving arsenic rich acid drainage

Acid drainage is an important water quality issue in Andean watersheds, affecting the sustainability of urban, agricultural, and industrial activities. Mixing zones receiving acid drainage are critical sites where changes in pH and chemical environment promote the formation and dissolution of iron and aluminum oxy/hydroxides. These particles can significantly change the speciation of toxic metals and metalloids throughout drainage networks via sorption, desorption, and settling processes. However, little is known about the behavior of particle size distributions (PSDs) in streams affected by acid drainage and their relationship to metal speciation. This work studied: (a) the PSDs for a wide range of mixing ratios found at a fluvial confluence affected by acid drainage, and (b) the response of PSDs and arsenic speciation to environmental changes found when the particles approach complete mixing conditions. The confluence between the Azufre River (pH ~ 2, high concentration of dissolved metals) and Caracarani River (pH = 8.6, low concentration of dissolved metals) was used as a representative model for study. Field measurements show a bimodal PSD with modal diameters of ~50 and 300 μm. At shorter distances from the junction, the smaller modes with smaller particle volumes were dominant across the stream cross‐sections. A systematic shift towards larger particle sizes and larger particle volumes occurred downstream. The analysis of laboratory PSDs for Azufre/Caracarani mixing ratios between 0.01 and 0.5 (pH from 6.2 to 2.3) showed a bimodal trend with ~15 and 50 μm characteristic diameters; larger particles formed at pH>4. When particle suspensions were transferred in laboratory experiments from very low pH to full mixing conditions (pH ~ 2.8 and mixing ratio ~ 0.25) particle sizes varied, and the dissolved arsenic concentration decreased. The observed reaction kinetics were slow compared to the time scale of advective transport, creating opportunities for engineered controls for arsenic. This work contributes to a better understanding of the chemical‐hydrodynamic interactions in watersheds affected by mining, and identifying opportunities to improve water quality at points of use.     

A GLUE‐based uncertainty assessment framework for tritium‐inferred transit time estimations under baseflow conditions

The last decade has seen major technical and scientific improvements in the study of water transfer time through catchments. Nevertheless, it has been argued that most of these developments used conservative tracers that may disregard the oldest component of water transfer, which often has transit times greater than 5 years. Indeed, although the analytical reproducibility of tracers limits the detection of the older flow components associated with the most dampened seasonal fluctuations, this is very rarely taken into account in modelling applications. Tritium is the only environmental tracer at hand to investigate transfer times in the 5‐ to 50‐year range in surface waters, as dissolved gases are not suitable due to the degassing process. Water dating with tritium has often been difficult because of the complex history of its atmospheric concentration, but its current stabilization together with recent analytical improvements open promising perspectives. In this context, the innovative contribution of this study lies in the development of a generalized likelihood uncertainty estimation‐based approach for analysing the uncertainties associated with the modelling of transit time due to both parameter identification and tracer analytical precision issues. A coupled resampling procedure allows assessment of the statistical significance of the transfer time differences found in diverse waters. This approach was developed for tritium and the exponential‐piston model but can be implemented for virtually any tracer and model. Stream baseflow, spring and shallow aquifer waters from the Vallcebre research catchments, analysed for tritium in different years with different analytical precisions, were investigated by using this approach and taking into account other sources of uncertainty. The results showed three groups of waters of different mean transit times, with all the stream baseflow and spring waters older than the 5‐year threshold needing tritium. Low sensitivity of the results to the model structure was also demonstrated. Dual solutions were found for the waters sampled in 2013, but these results may be disambiguated when additional analyses will be made in a few years. Copyright © 2016 John Wiley & Sons, Ltd.     

Spatiotemporal variability in hydrochemistry of shallow groundwater in a small pre‐alpine catchment: The importance of landscape elements

Topography and landscape characteristics affect the storage and release of water and, thus, groundwater dynamics and chemistry. Quantification of catchment scale variability in groundwater chemistry and groundwater dynamics may therefore help to delineate different groundwater types and improve our understanding of which parts of the catchment contribute to streamflow. We sampled shallow groundwater from 34 to 47 wells and streamflow at seven locations in a 20‐ha steep mountainous catchment in the Swiss pre‐Alps, during nine baseflow snapshot campaigns. The spatial variability in electrical conductivity, stable water isotopic composition, and major and trace ion concentrations was large and for almost all parameters larger than the temporal variability. Concentrations of copper, zinc, and lead were highest at sites that were relatively dry, whereas concentrations of manganese and iron were highest at sites that had persistent shallow groundwater levels. The major cation and anion concentrations were only weakly correlated to individual topographic or hydrodynamic characteristics. However, we could distinguish four shallow groundwater types based on differences from the catchment average concentrations: riparian zone‐like groundwater, hillslopes and areas with small upslope contributing areas, deeper groundwater, and sites characterized by high magnesium and sulfate concentrations that likely reflect different bedrock material. Baseflow was not an equal mixture of the different groundwater types. For the majority of the campaigns, baseflow chemistry most strongly resembled riparian‐like groundwater for all but one subcatchment. However, the similarity to the hillslope‐type groundwater was larger shortly after snowmelt, reflecting differences in hydrologic connectivity. We expect that similar groundwater types can be found in other catchments with steep hillslopes and wet areas with shallow groundwater levels and recommend sampling of groundwater from all landscape elements to understand groundwater chemistry and groundwater contributions to streamflow.