Pyrite formation driven by MSW landfill leachate in the Madrid Basin, Spain

The role of municipal solid waste (MSW) landfill leachate on the genesis of minor amounts of pyrite associated with gypsum in an otherwise predominantly evaporitic sequence was studied in geological and geochemical terms. The potential association between landfill leachate and the conditions required for bacterial reduction of sulfate and fixation of H₂S as pyrite were examined. The lithological column was generally found to contain little or no Fe. The δ³⁴S values for sulfates were consistent with previously reported data; however, the measured δ¹⁸O values were slightly higher. Sulfides disseminated in the marl/lutite exhibited higher δ³⁴S values (≈−8‰) than gypsum-coating pyrite crystals (δ³⁴S < −30‰). Dissolution of gypsum to sulfate and the supply of metabolizable organic matter and Fe required for H₂S fixation as sulfides may have originated from landfill leachate. Intermittent availability of leachate, a result of the precipitation regime, can facilitate sulfur disproportionation and lead to fractionations as high as      

Spatial and temporal variation of the nekton and hyperbenthos from a temperate European estuary with regulated freshwater inflow

The aquatic macrofauna of the Guadalquivir estuary were sampled (1 mm mesh persiana net) at 5 sampling sites located along the entire (except the tidal freshwater region) estuarine gradient of salinity (outer 50 km). A total of 134 fish and macroinvertebrate species was collected but only 62 were considered common or regularly present in the estuary. Univariate measures of the community structure showed statistically significant differences among sampling sites: species richness, abundance, and biomass decreased in the upstream direction, being positively correlated with the salinity. Temporal differences of these three variables were also statistically significant. While a clear seasonal pattern (minimum densities in winter and maximum in spring-summer) was observed for abundance and biomass, no such pattern existed for the number of species. Mysids was the most dominant group throughout the estuary (96% to 99% of abundance; 49% to 85% of biomass), although fish biomass was also important at the outer estuary (36% to 38%). Multivariate analyses indicated highly significant spatial variation in the macrofaunal communities observed along the salinity gradient. These analyses suggest that the underlying structure was a continuum with more or less overlapping distributions of the species dependent on their ability to tolerate different physicochemical conditions. There were also significant temporal (intermonthly + interannual) variation of the estuarine community; the relative multivariate dispersion indicated that monthly variation was more considerable (relative multivariate dispersion >1) at the outer part of the estuary during the wet year (last 20 km) and was higher in the inner stations during the dry year (32 to 50 km from the river mouth). Since a clear negative exponential relationship was observed between the freshwater input (from a dam located 110 km upstream) and water salinity at all sampling stations, it is concluded that the human freshwater management is probably affecting the studied estuarine communities. While the higher seasonal (long-term) stability of the salinity gradient, due to the human control of the freshwater input, may facilitate the recruitment of marine species juveniles during the meteorologically unstable early-spring, the additional (short-term) salinity fluctuations during the warm period may negatively affect species that complete their lifecycle within the estuary.     

Pressure-Dependence of Rare Earth Element Distribution in Amphibolite- and Granulite- Grade Garnets. A LA-ICP-MS Study

Using an excimer (KrF) laser ablation ICP-MS system, we studied the distribution of REE in garnets from metapelites and metabasites from Ivrea-Verbano (Western Alps, Italy) and from the Peña Negra Anatectic Complex (Central Iberia), finding systematic variations that correlate well with the metamorphic grade. Chondrite-normalized REE patterns of garnets from amphibolite-grade metapelites have lower-than-chondrite levels from La to Sm, a very small or no Eu anomaly, and a steep rise in the abundance of heavy REE as the atomic number increases. Metapelitic garnets from the amphibolite-granulite transition have a marked Eu negative anomaly and are enriched in MREE such that Sm is 10-15 times chondrite and the pattern is almost flat from Dy to Yb-Lu. In garnets from granulite-grade metapelites, the intensity of the Eu anomaly and the relative concentration of Nd, Sm, Gd and Tb increase, with almost flat chondrite-normalized patterns from Sm to Lu. Garnets from mafic granulites are remarkably similar to those of metapelitic garnets equilibrated at the same pressure, except for the Eu anomaly. The apparent paradox of enhanced uptake of larger REE ions with increasing pressure is attributed to the 3M²⁺ 2REE³⁺+ vacancy substitution, which produces a net decrease in the dimensions of the unit-cell of garnet. Variations in REE patterns depend essentially on the pressure and have little dependence on either temperature, bulk-composition of garnet, or REE whole-rock composition, so they could represent a new approach for geobarometric studies. The best numerical parameter to express pressure-related variations of REE distribution in garnets is the Gd/Dy ratio which does not seem perceptibly affected by disequilibrium partitioning. The regression equation between GASP pressure and the average Gd/Dy^garnet is P = 3.6 + 5.6 Gd/Dy. This equation seems to be reliable for garnets: (1)equilibrated within a pressure range of 4-9 kbar, (2) coexisting with modal monazite; and (3) with unit-cell dimensions under 11.46 Å.     

The supergene origin of ruthenian hexaferrum in Ni‐laterites

For two decades, the nature of Fe‐rich, oxygen‐bearing, Ru–Os compounds found in the supergene environment has been debated. Ru–Os–Fe‐oxides and nano‐intergrowths of ruthenium with magnetite have been proposed. We applied FE‐SEM, EMPA, μ‐Raman spectroscopy and synchrotron tts‐μXRD to Ru–Os–Fe compounds recovered from Ni‐laterites from the Dominican Republic. The results demonstrate that a significant portion of Fe exists in a common structure with the Ru–Os alloy, that is, ruthenian hexaferrum. This mineral occurs both as nanoparticles and as micrometric patches within a matrix of Fe‐oxide(s). Our data suggest that supergene ruthenian hexaferrum with a (Ru_0.4(Os,Ir)_0.1Fe_0.5)_?1.0 stoichiometry represents the most advanced weathering product of primary laurite within Ni‐laterites from the Dominican Republic.     

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.     

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.     

Spatio‐temporal variability of the isotopic input signal in a partly forested catchment: Implications for hydrograph separation

The isotopic composition of precipitation (D and ¹⁸O) has been widely used as an input signal in water tracer studies. Whereas much recent effort has been put into developing methodologies to improve our understanding and modelling of hydrological processes (e.g., transit‐time distributions or young water fractions), less attention has been paid to the spatio‐temporal variability of the isotopic composition of precipitation, used as input signal in these studies. Here, we investigated the uncertainty in isotope‐based hydrograph separation due to the spatio‐temporal variability of the isotopic composition of precipitation. The study was carried out in a Mediterranean headwater catchment (0.56 km²). Rainfall and throughfall samples were collected at three locations across this relatively small catchment, and stream water samples were collected at the outlet. Results showed that throughout an event, the spatial variability of the input signal had a higher impact on hydrograph separation results than its temporal variability. However, differences in isotope‐based hydrograph separation determined preevent water due to the spatio‐temporal variability were different between events and ranged between 1 and 14%. Based on catchment‐scale isoscapes, the most representative sampling location could also be identified. This study confirms that even in small headwater catchments, spatio‐temporal variability can be significant. Therefore, it is important to characterize this variability and identify the best sampling strategy to reduce the uncertainty in our understanding of catchment hydrological processes.     

Modelling sediment deposition and phosphorus retention in a river floodplain

Phosphorus (P) is one of the major limiting nutrient in many freshwater ecosystems. During the last decade, attention has been focused on the fluxes of suspended sediment and particulate P through freshwater drainage systems because of severe eutrophication effects in aquatic ecosystems. Hence, the analysis and prediction of phosphorus and sediment dynamics constitute an important element for ecological conservation and restoration of freshwater ecosystems. In that sense, the development of a suitable prediction model is justified, and the present work is devoted to the validation and application of a predictive soluble reactive phosphorus (SRP) uptake and sedimentation models, to a real riparian system of the middle Ebro river floodplain. Both models are coupled to a fully distributed two‐dimensional shallow‐water flow numerical model. The SRP uptake model is validated using data from three field experiments. The model predictions show a good accuracy for SRP concentration, where the linear regressions between measured and calculated values of the three experiments were significant (r² ≥ 0.62; p ≤ 0.05), and a Nash–Sutcliffe coefficient (E) that ranged from 0.54 to 0.62. The sedimentation model is validated using field data collected during two real flooding events within the same river reach. The comparison between calculated and measured sediment depositions showed a significant linear regression (p ≤ 0.05; r² = 0.97) and an E that ranged from 0.63 to 0.78. Subsequently, the complete model that includes flow dynamics, solute transport, SRP uptake and sedimentation is used to simulate and analyse floodplain sediment deposition, river nutrient contribution and SRP uptake. According to this analysis, the main SRP uptake process appears to be the sediment sorption. The analysis also reveals the presence of a lateral gradient of hydrological connectivity that decreases with distance from the river and controls the river matter contribution to the floodplain. Copyright © 2014 John Wiley & Sons, Ltd.