The dynamics of chironomid assemblages and vegetation during the Late Quaternary at Laguna Facil, Chonos Archipelago, southern Chile

We compare high-resolution pollen and chironomid records from the last 15,000 yr in Laguna Facil, southern Chile. Major vegetation and chironomid changes are recorded between ca 14,900 and 14,700 cal. yr BP. During the Lateglacial, changes in the chironomid stratigraphy lag behind changes in the pollen stratigraphy suggesting that the chironomids are responding to changes in the tree canopy or in soil chemistry brought about by vegetational development. At about 7200 cal. yr BP there is a change in the chironomid stratigraphy in advance of changes in the vegetation. This suggests that the response is to regional climatic change. The relatively close correlation of the chironomid and pollen stratigraphies with changes in charcoal concentrations also implicates the importance of fire and/or vulcanism in influencing the dynamics of forest and limnological systems. There is no clear evidence of cooling during the Younger Dryas chronozone in Laguna Facil.     

The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from −0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ⁵⁶Fe values (relative to IRMM-14) ranging from −0.18(±0.02) to −2.290(±0.006) ‰, and corresponding δ⁵⁷Fe values of −0.247(±0.014) and −3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus’s theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.     

Gold partitioning in melt-vapor-brine systems

We used laser-ablation inductively coupled plasma mass spectrometry to measure the solubility of gold in synthetic sulfur-free vapor and brine fluid inclusions in a vapor + brine + haplogranite + magnetite + gold metal assemblage. Experiments were conducted at 800°C, oxygen fugacity buffered at Ni-NiO (NNO), and pressures ranging from 110 to 145 MPa. The wt% NaCl eq. of vapor increases from 2.3 to 19 and that of brine decreases from 57 to 35 with increasing pressure. The composition of the vapors and brines are dominated by NaCl + KCl + FeCl₂ + H₂O. Gold concentrations in vapor and brine decrease from 36 to 5 and 50 to 28 μg/g, respectively, and the calculated vapor:brine partition coefficients for gold decrease from 0.72 to 0.17 as pressure decreases from 145 to 110 MPa. These data are consistent with the thermodynamic boundary condition that the concentration of gold in the vapor and brine must approach a common value as the critical pressure is approached along the 800°C isotherm in the NaCl-KCl-FeCl₂-HCl-H₂O system.We use the equilibrium constant for gold dissolution as AuOH⁰, extrapolated from lower temperature and overlapping pressure range, to calculate expected concentrations of AuOH⁰ in our experimental vapors. These calculations suggest that a significant quantity of gold in our experimental vapors is present as a non-hydroxide species. Possible chloridogold(I) species are hypothesized based on the positively correlated gold and chloride concentrations in our experimental vapors. The absolute concentration of gold in our synthetic vapor, brine, and melt and calculated mass partition coefficients for gold between these physicochemically distinct magmatic phases suggests that gold solubility in aqueous fluids is a function of aqueous phase salinity, specifically total chloride concentration, at magmatic conditions. However, though we highlight here the effect of salinity, the combination of our data with data sets from lower temperatures evinces a significant decrease in gold solubility as temperature drops from 800°C to 600°C. This decrease in solubility has implications for gold deposition from ascending magmatic fluids.     

The influence of coupled physical swelling and chemical reactions on deformable geomaterials

Coupled thermo‐hydro‐mechanical‐chemical modelling has attracted attention in past decades due to many contemporary geotechnical engineering applications (e.g., waste disposal, carbon capture and storage). However, molecular‐scale interactions within geomaterials (e.g., swelling and dissolution/precipitation) have a significant influence on the mechanical behaviour, yet are rarely incorporated into existing Thermal‐Hydro‐Mechanical‐Chemical (THMC) frameworks. This paper presents a new coupled hydro‐mechanical‐chemical constitutive model to bridge molecular‐scale interactions with macro‐physical deformation by combining the swelling and dissolution/precipitation through an extension of the new mixture‐coupling theory. Entropy analysis of the geomaterial system provides dissipation energy, and Helmholtz free energy gives the relationship between solids and fluids. Numerical simulation is used to compare with the selected recognized models, which demonstrates that the swelling and dissolution/precipitation processes may have a significant influence on the mechanical deformation of the geomaterials.     

Segmentation and kinematics of the North America‐Caribbean plate boundary offshore Hispaniola

We explored the submarine portions of the Enriquillo–Plantain Garden Fault zone (EPGFZ) and the Septentrional–Oriente Fault zone (SOFZ) along the Northern Caribbean plate boundary using high‐resolution multibeam echo‐sounding and shallow seismic reflection. The bathymetric data shed light on poorly documented or previously unknown submarine fault zones running over 200 km between Haiti and Jamaica (EPGFZ) and 300 km between the Dominican Republic and Cuba (SOFZ). The primary plate‐boundary structures are a series of strike‐slip fault segments associated with pressure ridges, restraining bends, step overs and dogleg offsets indicating very active tectonics. Several distinct segments 50–100 km long cut across pre‐existing structures inherited from former tectonic regimes or bypass recent morphologies formed under the current strike‐slip regime. Along the most recent trace of the SOFZ, we measured a strike‐slip offset of 16.5 km, which indicates steady activity for the past ~1.8 Ma if its current GPS‐derived motion of 9.8 ± 2 mm a^?1 has remained stable during the entire Quaternary.     

Unraveling complex hydrogeological processes in Andean basins in south‐central Chile: An integrated assessment to understand hydrological dissimilarity

Groundwater storage, drainage, and interbasin water exchange are common hydrological processes but often difficult to quantify due to a lack of local observations. We present a study of three volcanic mountainous watersheds located in south‐central Chile (~36.9 ° S) in the Chillán volcanic complex (Chillán, Renegado, and Diguillín river basins). These are neighboring basins that are similar with respect to the metrics normally available for characterization everywhere (e.g., precipitation, temperature, and land cover). In a hydrological sense, similar (proportional) behavior would be expected if these catchments would be characterized with this general information. However, these watersheds show dissimilar behavior when analyzed in detail. The surface water balance does not fit for any of these watersheds individually; however, the water balance of the whole system can be explained by likely interbasin water exchanges. The Renegado river basin has an average annual runoff per unit of area on the order of 60–65% less than those of the Diguillín and Chillán rivers, which is contradictory to the hydrological similarity among the basins. To understand the main processes that control streamflow generation, two analyses were performed: (a) basin metrics (land cover, geologic, topographic, and climatological maps) and hydro‐meteorological data analyses and (b) a water balance model approach. The analyses contribute to a plausible explanation for the hydrogeological processes in the system. The soils, topography, and geology of the Chillán–Renegado–Diguillín system favor the infiltration and groundwater movements from the Renegado river basin, mainly to the neighboring Diguillín basin. The interbasin water exchanges affect hydrological similarity and explain the differences observed in the hydrological processes of these three apparently similar volcanic basins. The results highlight the complexity of hydrological processes in volcanic mountainous systems and suggest that a simple watershed classification approach based on widely available data is insufficient. Simple local analyses such as specific flow analysis with a review of the geology and morphology can contribute to a better understanding of the hydrology of volcanic mountainous areas.     

The Sima de los Huesos (Burgos,northern Spain): palaeoenvironment and habitats of Homo heidelbergensis during the Middle Pleistocene

Interpreting how environmental dynamics respond to global climate change and how this has affected human evolution and dispersal is an on-going topic of debate. During the early Middle Pleistocene (～0.6–0.4 Ma), as compared to earlier, environmental conditions were relatively more stable, with longer climatic cycles alternating between open and forested landscapes. During this interval, humans spread successfully providing an important number of fossil sites where fossils or tools are reported. The Atapuerca-Sima de los Huesos (Burgos, northern Spain) site (Atapuerca-SH) is one of the earliest localities with hominin evidence in the European Middle Pleistocene, with the most important accumulation of Homo heidelbergensis so far. We have analyzed the abundant faunal record from Sima de los Huesos, which is mainly comprised of carnivores, in order to approach an interpretation of the palaeoenvironmental circumstances where these hominids inhabited within the Sierra. Other sites from Sierra de Atapuerca referred to the same Faunal Unit (FU 6), are roughly contemporaneous, and include important ungulates, which are here analyzed with Atapuerca-SH. Additional information provided by isotopic analysis helps elucidate the ancient ecology of taxa present in Sima de los Huesos allowing for an accurate portrayal of the setting in which humans lived. The timing of the spread of Homo heidelbergensis is dominated by a relative climatic and environmental stability and points to a landscape dominated by savannah-like open woodland.     

Effect of rainfall uncertainty on the performance of physically based rainfall–runoff models

This paper analyses the effect of rain data uncertainty on the performance of two hydrological models with different spatial structures: a semidistributed and a fully distributed model. The study is performed on a small catchment of 19.6 km² located in the north‐west of Spain, where the arrival of low pressure fronts from the Atlantic Ocean causes highly variable rainfall events. The rainfall fields in this catchment during a series of storm events are estimated using rainfall point measurements. The uncertainty of the estimated fields is quantified using a conditional simulation technique. Discharge and rain data, including the uncertainty of the estimated rainfall fields, are then used to calibrate and validate both hydrological models following the generalized likelihood uncertainty estimation (GLUE) methodology. In the storm events analysed, the two models show similar performance. In all cases, results show that the calibrated distribution of the input parameters narrows when the rain uncertainty is included in the analysis. Otherwise, when rain uncertainty is not considered, the calibration of the input parameters must account for all uncertainty in the rainfall–runoff transformation process. Also, in both models, the uncertainty of the predicted discharges increase in similar magnitude when the uncertainty of rainfall input increase.