On the Use of Hydrological Models and Satellite Data to Study the Water Budget of River Basins Affected by Human Activities: Examples from the Garonne Basin of France

Natural and anthropogenic forcing factors and their changes significantly impact water resources in many river basins around the world. Information on such changes can be derived from fine scale in situ and satellite observations, used in combination with hydrological models. The latter need to account for hydrological changes caused by human activities to correctly estimate the actual water resource. In this study, we consider the catchment area of the Garonne river (in France) to investigate the capabilities of space-based observations and up-to-date hydrological modeling in estimating water resources of a river basin modified by human activities and a changing climate. Using the ISBA–MODCOU and SWAT hydrological models, we find that the water resources of the Garonne basin display a negative climate trend since 1960. The snow component of the two models is validated using the moderate-resolution imaging spectroradiometer snow cover extent climatology. Crop sowing dates based on remote sensing studies are also considered in the validation procedure. Use of this dataset improves the simulated evapotranspiration and river discharge amounts when compared to conventional data. Finally, we investigate the benefit of using the MAELIA multi-agent model that accounts for a realistic agricultural and management scenario. Among other results, we find that changes in crop systems have significant impacts on water uptake for agriculture. This work constitutes a basis for the construction of a future modeling framework of the sociological and hydrological system of the Garonne river region.     

A high-resolution analyser for the measurement of ammonium in oligotrophic seawater

In this work, we describe a high-resolution fluorometric shipboard analyser and an improved method to determine NH₄⁺ in oligotrophic seawater. The limit of detection is <5 nM, calculated with 95% confidence level using the weighted regression line applied to the standard addition method using real samples prepared with low nutrient seawater from the Atlantic. The results are summarised and cross-compared with spiked artificial seawater (ASW) and spiked Milli-Q water samples. The analyser has a precision of ±1–4% with a high performance over a wide range from 5 nM to 25 μM. The methodology of NH₄⁺ analysis is based on the fluorescent product formed between o-pthaldialdehyde and NH₄⁺ in the presence of sulfite. Due to the high resolution of the developed system, we were able to study in depth the sensitivity of the method to salinity, amines, amino acids and potential interferences from particles/algae. The method was found to be sensitive to salinity variations, reducing the signal by up to 85% at 5 nM; this effect decreased at higher concentrations of ammonium. It was noted that the interference from amines at low concentrations was negligible; however, at either high amino acid or high amine concentrations, the signal was depressed. To test for the effect of particles on the system, the system was tested with samples containing phytoplankton (Dunaliella primolecta) cells at different concentrations prepared with ASW to simulate the effect of a phytoplankton bloom. This experiment assessed the potential impact of both particles and other potential fluorescence interferences from cells and/or ammonium leaching from cells. This experiment showed that a phytoplankton bloom could potentially have an impact of up to 12% on the signal of interest. Thus, we propose that this method is suitable for oligotrophic environments rather than coastal and eutrophic environments. The reagent was found to be stable for 17 days and standards of 1 μM were stable for 6 days under laboratory conditions. The developed analyser was successfully demonstrated in the North Atlantic Ocean, in an area of oligotrophic, low NH₄⁺ oceanic waters.     

River flux uncertainties predicted by hydrological variability and riverine material behaviour

Data on riverine fluxes are essential for calculating element cycles (carbon, nutrients, pollutants) and erosion rates from regional to global scales. At most water‐quality stations throughout the world, riverine fluxes are calculated from continuous flow data (q) and discrete concentration data (C), the latter being the main cause of sometimes large uncertainties. This article offers a comprehensive approach for predicting the magnitude of these uncertainties for water‐quality stations in medium to large basins (drainage basin area > 1000 km²) based on the commonly used discharge‐weighted method. Uncertainty levels – biases and imprecisions – for sampling intervals of 3 to 60 days are correlated first through a nomograph with a flux variability indicator, the quantity of riverine material discharged in 2% of time (M_2%). In turn, M_2% is estimated from the combination of a hydrological reactivity index, W_2% (the cumulative flow volume discharged during the upper 2% of highest daily flow) and the truncated b_50sup exponent, quantifying the concentration versus discharge relationship for the upper half of flow values (C = a q ^b50sup, for q > q₅₀, where q₅₀ is the median flow): M_2% = W_2% + 27.6b_50sup. W_2% can be calculated from continuous flow measurements, and the b_50sup indicator can be calculated from infrequent sampling, which makes it possible to predict a priori the level of uncertainty at any station, for any type of riverine material either concentrated (b_50sup > 0) or diluted (b_50sup > 0) with flow. A large data base of daily surveys, 125 station variables of suspended particulate matter (SPM), total dissolved solids (TDS) and dissolved and particulate nutrients, was used to determine uncertainties from simulated discrete surveys and to establish relationships between indicators. Results show, for example, that for the same relatively reactive basin (W_2% > 25%), calculated fluxes from monthly sampling would yield uncertainties approaching ±100% for SPM (b_50sup > 1.4) fluxes and ±10% for TDS (b_50sup = ?0.2). The application to the nitrate survey of the river Seine shows significant trends for the 1972–2009 records. Copyright © 2012 John Wiley & Sons, Ltd.     

Insights into cation exchange selectivity of a natural clinoptilolite by means of dielectric relaxation spectroscopy

Purified natural clinoptilolite from the Tasajeras deposit, Cuba, and some of its metal exchanged forms are studied, at the dehydrated state, by means of dielectric relaxation spectroscopy (DRS) using two different modus operandi: complex impedance spectroscopy and dielectric dynamic thermal analysis. Data analysis yields the determination of the extra-framework cation (EFC) population into the various possible crystallographic sites of the zeolitic framework as well as of the activation energy characterizing the localized hopping mechanism of EFC. First, it is shown that the DRS responses obtained here match well with the previous reported data, which were previously localized EFCs in positions close to M1 and M2 sites when the clinoptilolite is modified to almost homoionic form. From this outcome, it can be concluded that all EFCs are in the same crystallographic situation regarding solvation or, in other terms, that no steric effect can be taken into account to explain cationic selectivity. Second, based on the assumption that the activation energy for EFC hopping is directly connected to the EFC/framework interaction and on simple thermodynamics consideration, we show this interaction does not govern the EFC exchange reaction. So, it is emphasized that EFC/H₂O interaction is the key factor for cation exchange selectivity.     

Emplacement of Semail–Emirates ophiolite at ridge–trench collision

The Oman‐Emirates is the largest and best‐exposed ophiolite; consequently, it has attracted significant interest among scientists, together with serious conflicts. Most geologists regard this ophiolite as having formed in an intra‐oceanic subduction zone before being accreted to the Arabian continent. Here, we propose an alternative scenario, supported by detailed field observations and integrated geophysics. The smaller Emirates part of the ophiolite was forced into a nearby continent, in the pre‐collision stage of Tethyan closure. The contraction led to the exhumation of the mantle floor of segmented basins accreted in a rifted system similar to the present‐day Gulf of California. The implied high temperature–high pressure metamorphism and the range of geochemical signatures were introduced during the process of rifting, whereas the larger Oman ophiolite was emplaced by obduction onto and along the subducting continental shore. This Ridge–Trench–Transform system might call for a new process to obduct over continents in particular Tethyan ophiolites.     

Thermal and mechanical behaviour of the orogenic middle crust during the syn‐ to late‐orogenic evolution of the Variscan root zone,Bohemian Massif

We combine structural observations, petrological data and ⁴⁰Ar–³⁹Ar ages for a stack of amphibolite facies metasedimentary units that rims high‐P (HP) granulite facies felsic bodies exposed in the southern Bohemian Massif. The partly migmatitic Varied and Monotonous units, and the underlying Kaplice unit, show a continuity of structures that are also observed in the adjacent Blanský les HP granulite body. They all exhibit an earlier NE?SW striking and steeply NW‐dipping foliation (S3), which is transposed into a moderately NW‐dipping foliation (S4). In both the Varied and Monotonous units, the S3 and S4 foliations are characterized by a Sil–Bt–Pl–Kfs–Qtz–Ilm±Grt assemblage, with occurrences of post‐D4 andalusite, cordierite and muscovite. In the Monotonous unit, minute inclusions of garnet, kyanite, sillimanite and biotite are additionally found in plagioclase from a probable leucosome parallel to S3. The Kaplice unit shows rare staurolite and kyanite relicts, a Sil–Ms–Bt–Pl–Qtz±Grt assemblage associated with S3, retrogressed garnet?staurolite aggregates during the development of S4, and post‐D4 andalusite, cordierite and secondary muscovite. Mineral equilibria modelling for representative samples indicates that the Varied unit records conditions higher than ~7 kbar at 725 °C during the transition from S3 to S4, followed by a P?T decrease from ~5.5 kbar/750 °C to ~4.5 kbar/700 °C. The Monotonous unit shows evidence of partial melting in the S3 fabric at P?T above ~8 kbar at 740–830 °C and a subsequent P?T decrease to 4.5–5 kbar/700 °C. The Kaplice unit preserves an initial medium‐P prograde path associated with the development of S3 reaching peak P?T of ~6.5 kbar/640 °C. The subsequent retrograde path records 4.5 kbar/660 °C during the development of S4. ⁴⁰Ar–³⁹Ar geochronology shows that amphibole and biotite ages cluster at c. 340 Ma close to the HP granulite, whereas adjacent metasedimentary rocks preserve c. 340 Ma amphibole ages, but biotite and muscovite ages range between c. 318 and c. 300 Ma. The P?T conditions associated with S3 imply an overturned section of the orogenic middle crust. The shared structural evolution indicates that all mid‐crustal units are involved in the large‐scale folding cored by HP granulites. The retrograde P–T paths associated with S4 are interpreted as a result of a ductile thinning of the orogenic crust at a mid‐crustal level. The ⁴⁰Ar–³⁹Ar ages overlap with U–Pb zircon ages in and around the HP granulite bodies, suggesting a short duration for the ductile thinning event. The post‐ductile thinning late‐orogenic emplacement of the South Bohemian plutonic complex is responsible for a re‐heating of the stacked units, reopening of argon system in mica and a tilting of the S4 foliation to its present‐day orientation.     

Sulphur solubility in andesitic to basaltic melts: implications for Hekla volcano

The solubility of sulphur in sulphide-saturated, H₂O-bearing basaltic–andesitic and basaltic melts from Hekla volcano (Iceland) has been determined experimentally at 1,050°C, 300 and 200 MPa, and redox conditions with oxygen fugacity (logfO₂) between QFM−1.2 and QFM+1.1 (QFM is a quartz–fayalite–magnetite oxygen buffer) in the systems containing various amounts of S and H₂O. The S content of the H₂O-rich glasses saturated with pyrrhotite decreases from 2,500 ppm in basalt to 1,500 ppm in basaltic andesite at the investigated conditions. Furthermore, the reduction of water content in the melt at pyrrhotite saturation and fixed T, P and redox conditions leads to a decrease in S concentration from 2,500 to 1,400 ppm for basaltic experiments (for H₂O decrease from 7.8 to 1.4 wt%) and from 1,500 to 900 ppm (for H₂O decrease from 6.7 to 1.7 wt%) for basaltic andesitic experiments. Our experimental data, combined with silicate melt inclusion investigations and the available models on sulphide saturation in mafic magmas, indicate that the parental basaltic melts of Hekla were not saturated with respect to sulphide. During magmatic differentiation, the S content in the residual melts increased and might have reached sulphide saturation with 2,500 ppm dissolved S. With further magma crystallization, the S concentration in the melt was controlled by the sulphide saturation of the magma, decreasing from ~2,500 to 900 ppm S.     

Interaction between tectonic and erosion processes on the morphogenesis of an Alpine valley: geological and geophysical investigations in the lower Romanche valley (Belledonne massif, western Alps)

In the Belledonne massif, the steep Paleozoic Belledonne Middle Fault (BMF) separates micaschists, displaying numerous landslides, from amphibolites. The massif is incised by the lower Romanche river valley. When crossing the BMF, the valley widens into a lozenge-shaped basin recently interpreted as an active pull-apart type structure associated with a major N110 striking Quaternary fault. Multidisciplinary investigations were carried out in the basin to check if this model has implications on the seismic and landslide hazard assessment. This study demonstrated the existence of a N80 sinistral strike slip Séchilienne Fault Zone (SFZ). This fault zone is suspected to offset the BMF by 375 m across the basin. Geophysical experiments revealed that the bedrock depth increases strongly in the basin, up to 350 m. Our study invalidates the active pull-apart origin of the basin and suggests it results from Quaternary glacial and fluvial erosion processes, magnified by the intersection of two inherited structures, the BMF and the SFZ.