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Paleosols (PSs) contain valuable information about the climatic conditions under which they formed and constitute an outstanding archive of past weathering processes. Nevertheless, paleosol dating over most of the Quaternary remains challenging. Volcanic environments are unique sites for such purposes, as precise radiometric age determination can be achieved on volcanic units ‘bracketing’ PSs. Here, we present a combined geochemical and geochronological study of PSs spanning the last Myr in the Central Azores archipelago (Pico, Faial and São Jorge Islands; central North Atlantic). Precise K-Ar dating of lava flows on groundmass separates (unspiked Cassignol-Gillot technique) yield ages with a typical uncertainty of a few kyr, allowing us to tightly constrain PS ages and weathering rates near key paleoclimatic transitions. PS geochemistry further allowed us to reconstruct weathering conditions and estimate Mean Annual Precipitation and Temperature (MAP & MAT) by two proxies previously validated for other volcanic terranes (CIA-K and Clayeyness).Four periods of PSs formation are constrained at 870-845 ka, ~725 ka, 320-280 ka and 130-45 ka. Most PSs formed just after interglacial peaks, with a few exceptions. Our MAP reconstructions are variable (600-1,500 mm/yr), but generally lower than current annual precipitations (~1,000 mm/yr). MAT estimates (14-28°C) are higher than present-day annual temperatures (~17.5°C). MAP & MAT variations are in general agreement with global climatic curves; the highest values (28°C, 1,500 mm/yr) are reached at ~855 ka, coinciding with an interglacial peak. The younger PSs (130-45 ka) indicate more stable MAP & MAT in the ranges 650-1,000 mm/yr and 15-20°C, respectively and seem to show a temperature decrease after the MIS5e interglacial stage.Most paleosols were formed in a few kyr under high MAT (>17°C) and moderate to high MAP (>700 mm/yr), supporting a major influence of temperature on weathering kinetics. Parental material texture also had an important role, as several PSs formed upon pyroclastic deposits over most of their depth, whereas those developed on lava flows were generally restricted to the highly fragmented upper brecciated parts. Minimum vertical soil formation rates are in the range of ~0.3-4.5 cm/kyr, with a mean of ~1.7 cm/kyr and an outlier around ~10 cm/kyr. Those generally high values can be explained by the highly vesicular parental material, and by an exceptionally feldspar-rich (easily weathered) parental rock for the outlier.As current precipitation and temperatures are higher than the threshold values of ~700 mm/yr and ~17°C under which most PSs formed, enhanced soil formation is expected for the near future, especially in the context of global warming and particularly in volcanic contexts. This may have important and fast impacts on local human activities, but also regarding CO2 consumption by rock weathering and geological hazards.

Relatively little is known about the deep water circulation and the role of deep weathering processes on the Critical Zone (CZ) evolution. In this study, major fractures from four deep boreholes and water collected from these fractures (20–60 m of depth) were studied to improve our understanding of the deep CZ in a granitic headwater watershed (Strengbach watershed, France). Geochemical analysis indicates that chemical composition of deep water (20–60 m) is clearly different than shallow subsurface waters (0–15 m), with higher mean concentrations and a stronger spatial variability across the watershed. Reactive-transport modeling performed with the 1D KIRMAT code (KInetic of Reaction and MAss Transport) highlights the role of minor mineral dissolution (i.e. dolomite) and of longer mean transit time (100–597 yr) along fractures for explaining these differences. The obtained results also shed light on the difference of hydrogeochemical functioning between shallow subsurface system (water sampled from springs and piezometers) and deep system (deep water from borehole fractures). The shallow subsurface system (0–15 m) is characterized by a spatially relatively homogeneous water flow, high mean pore velocities, and water–rock interactions in a porous regolith, while the deep water circulation (20–60 m) behaves much more as independent systems along fractures, with low mean pore velocities, and variable mineralogy and hydrodynamic conditions. A state of chemical equilibrium can also be reached along fractures in the deep CZ for some primary minerals (biotite and K-feldspar), a feature never observed so far in the simulations of shallow subsurface water chemical composition in the Strengbach watershed. Even if the deep water exhibits higher solute concentrations, significantly lower mean pore velocities inferred in the fractured zones imply that the deep water is responsible for a very small part of the total hydrologic and weathering fluxes in the watershed. The limited role of the deep weathering processes (20–60 m) compared to the shallow subsurface processes (0–15 m) suggests an up to bottom control of the CZ evolution at a millennial timescale. Our results also indicate that the majority of fresh water available for water supply at a human timescale originates from shallow subsurface waters, as the deep water circulation is too low for being critical at a timescale relevant for societal needs in this type of geological context.

International audience; A rare dataset of in-situ 10Be from high-resolution depth profiles, soils, rock outcrops and stream sediments is combined with geochemical analysis and modeling of regolith evolution to understand the variability of denudation rates in a mountain watershed (Strengbach critical zone observatory). High-resolution depth profiles are key to detect the presence of mobile regolith and to highlight how it affects the critical zone evolution. The modeling of regolith evolution and 10Be concentrations along depth profiles allow to estimate both the cosmic ray exposure age (19 kyr) and the mean denudation rate (22 mm.kyr-1) of the regolith without any steady-state assumption on 10Be concentrations. Comparison with maximum denudation rates inferred from topsoil samples collected from the surface of the depth profiles and calculated using the temporal steady-state assumption of 10Be concentrations highlight an overestimation of denudation by a factor of two. Maximum spatially-averaged denudation rates determined from stream sediment samples also likely overestimate denudation rates by a factor of two. These biases are significant for investigating the geomorphological evolution and we propose a method to correct denudation rates using the inherited 10Be concentrations and the cosmic ray exposure age deduced from the high-resolution depth profiles. A key result is also that a steady-state of 10Be concentrations and a steady-state of regolith thickness are two different equilibrium states that do not necessarily coincide. The comparison between locally corrected and spatially-averaged denudation rates indicates that the watershed geomorphology is not in a topographic steady-state but is modulated by regressive fluvial erosion. Nonetheless, our study demonstrates that even in a watershed where the steady-state assumption of 10Be concentrations is not verified, the spatial variations of in-situ 10Be concentrations in sediments still carry qualitatively relevant information on the geomorphological evolution of landscapes.

Since 60 years, a large amount of data has been acquired to survey river sediment quality, especially concerning regulatory trace metals such as Cd, Cr, Cu, Hg, Ni, Pb, and Zn. Large-scale syntheses are still rare and show some limits to assess the effectiveness of public regulations and the river systems' resilience. Based on a sediment contamination database comprising more than 12,000 samples, we propose a first attempt to decipher spatio-temporal trends of metal contamination along seven major rivers in Western Europe (Garonne-Lot, Loire, Meuse Rhine, Rhone, Scheldt and Seine Rivers). Facing heterogeneous sampling and analytical methods on different sediment matrices (bed and flood deposits – BFD, suspended particulate matter – SPM, dated sediment cores – DSC), this work investigates the effect of analytical protocols, spatial and temporal factors on metal concentration trends. At a large scale, an increase in metal concentrations (especially for Cd, Pb and Zn) is reported along most of the investigated rivers. It appears closely related to major urban-industrial hotspots (Paris-Rouen corridor on the Seine River, Bonn-Duisburg corridor on the Rhine River, etc.) and to the geology of each watershed, both influencing the regional sediment quality. Former mining and metallurgical districts, generally located in crystalline areas, also caused high metal concentrations on the long term (Upper Loire River, Middle Meuse River, Lot River). A global decrease of metal concentrations is observed in all river sections since the 1960s-1970s onwards, in response to European and national regulations, and to socio-economical changes affecting urban-industrial areas. The high influence of the location of the samples along the rivers and the decade of sampling is confirmed by a Factor Analysis of Mixed Data (FAMD). Secondary factors such as the influence of the sediment matrix type (BFD, SPM and DSC) and the different digestion procedures prior to elemental analysis also explained significant differences for Cr, Cd, Cu, Pb, or Zn, although this can also be locally balanced by the substratum (i.e. for alkaline rivers). This approach points out the limitations of the available data, particularly regarding the need of regional geological backgrounds and the more systematic acquisition of ancillary data such as grain-size and TOC. It also provides critical clues to intercompare metal sediment pollution in rivers at large spatial and temporal scales worldwide.

In recent decades, U- and Th- series nuclides have been successfully used to determine weathering rates in soils and regoliths. However, the redistribution of the nuclides within secondary minerals and/or organic matter may interfere with the recorded U- and Th-series weathering signals and can result in inaccurate and/or poorly constrained weathering rate determinations. In addition, the migration of radionuclides in the environment represents a major current issue. The objective of this study, therefore, was to evaluate the meaning of bulk soil data for weathering investigations and to assess the processes and timescales of U, Th and Ra redistribution in a forested-soil profile, both at the bulk soil scale level and for separated mineral fractions. This study was carried out at the INRAE-Andra experimental beech-forested site of Montiers (Meuse, France), which was developed on acidic detrital sediments inherited from tropical paleosoils erosion. U- and Th-series activity nuclides were measured in bulk soil samples and in separated Fe nodules and clay-size ( While bulk soil disequilibria suggested negligible to moderate mobility of the nuclides, an important transfer between mineral fractions was highlighted; this resulted in contrasting redistributions of U, Th and Ra within soil fractions. Fe-oxide nodules controlled the overall mobility of U on the bulk soil scale, while the fine Our results suggest that the fine

Based on Terrestrial Cosmogenic Nuclide (TCN) constraints from depth profiles of one granitic regolith from Wumingshan and five fluvial terraces from Xianshuihe and Zagunao rivers, we discuss the timing of the last deglaciation, the landscape-scale denudation and fluvial incision rates across the eastern Tibetan Plateau, in relation to previous work. We present a three-dimensional-graph visualization approach and corresponding constraints to better assess the feasibility and applicability of cosmogenic nuclides depth-profile dating. The exposure age (older than 19.4 ka) of the Wumingshan regolith corresponds to the retreat of the palaeo-Daocheng ice cap, which covered the Yidun terrane during the Last Glacial Maximum (LGM). Most basin-wide denudation rate data in the eastern Tibetan Plateau are lower than 130 mm/ka (47%, n = 90), which is consistent with the Wumingshan regolith denudation rate (lower than 52.8 mm/ka), and thus indicate that the landscape-scale denudation has been stabilized after the last deglaciation. Considering the reduction of integrated bulk density due to the accumulation of lower-density loess, we estimate mean exposure ages of Xianshuihe and Zagunao river terraces of 4.0 ± 0.7 ka, 5.9 ± 0.3 ka, 13.4 ± 2.0 ka, and 16.6 ± 1.4 ka. The observed increase in incision rate from 0.39 mm/yr over long timescale (∼600 ka) to 5.88 mm/yr over the last 15 ka at the Xianshuihe river site is probably due to the transition from glacial to interglacial climatic conditions. The fewer abandoned terraces along the Zagunao river after the Heinrich event 1 (H1) indicates that the climate change during the latest glacial-interglacial transition impacted less the landscape evolution in a relatively lower elevation area. Comparison with previously reported fluvial incision rates elsewhere across the eastern margin of the Tibetan Plateau indicates that incision rates are mainly influenced by abrupt climate change or intensified summer monsoon since the early Holocene, but probably controlled by regional tectonic uplift or fluvial headward retreat as the timescale increases. Overall, we propose a synthetic pattern of landscape evolution mainly dominated by long-term tectonic uplift together with fluvial headward erosion, episodically influenced by climatic change throughout the late Quaternary.

There are disparate views about the origin of global rift- or plume-related carbonatites. The Amba Dongar carbonatite complex, Gujarat, India, which intruded into the basalts of the Deccan Large Igneous Province (LIP), is a typical example. On the basis of new comprehensive major and trace element and Sr–Nd–Pb isotope data, we propose that low-degree primary carbonated melts from off-center of the Deccan–Réunion mantle plume migrate upwards and metasomatize part of the subcontinental lithospheric mantle (SCLM). Low-degree partial melting (∼2%) of this metasomatized SCLM source generates a parental carbonated silicate magma, which becomes contaminated with the local Archean basement during its ascent. Calcite globules in a nephelinite from Amba Dongar provide evidence that the carbonatites originated by liquid immiscibility from a parental carbonated silicate magma. Liquid immiscibility at crustal depths produces two chemically distinct, but isotopically similar magmas: the carbonatites (20% by volume) and nephelinites (80% by volume). Owing to their low heat capacity, the carbonatite melts solidified as thin carbonate veins at crustal depths. Secondary melting of these carbonate-rich veins during subsequent rifting generated the carbonatites and ferrocarbonatites now exposed at Amba Dongar. Carbonatites, if formed by liquid immiscibility from carbonated silicate magmas, can inherit a wide range of isotopic signatures that result from crustal contamination of their parental carbonated silicate magmas. In rift or plume-related settings, they can, therefore, display a much larger range of isotope signatures than their original asthenosphere or mantle plume source.

Mineral soil constituents play an important role in the storage/release of nutrients due to their ability to adsorb and desorb cations. Phyllosilicate minerals are particularly reactive due to their small size and high specific surface area (up to ∼800 m2·g−1). Previous work has highlighted the potential of Ca isotopes (δ44/40Ca) to identify secondary processes occurring within soils. Nevertheless, the mechanisms of isotopic fractionation (amplitude and nature) associated with Ca adsorption onto and desorption from different phyllosilicate minerals that are commonly found in soil remain poorly understood. This step is fundamental to improve our understanding of the Ca biogeochemical cycle at the water-soil-plant interface. Consequently, the study of the possible Ca isotopic fractionation during adsorption/desorption phenomena was approached experimentally using three “model” substrates representative of the phyllosilicate minerals frequently encountered within soils (KGa-2 kaolinite, Swy-2 montmorillonite and Tuftane muscovite). The experiments were carried out under abiotic conditions in “water-mineral” batch systems by precisely controlling the physico-chemical conditions: pH, solid/solution ratio, initial dissolved Ca concentration, particle size distribution, reaction time and other cations concentrations. Our results show no significant isotopic fractionation associated with Ca adsorption or desorption during KGa-2 and coarse size fraction of Tuftane muscovite (50–200 µm) experiments regardless of the physico-chemical parameters used. During Ca adsorption onto Swy-2 and fine size fraction of Tuftane muscovite (0.1–1 µm), light isotopes (e.g., 40Ca) are preferentially adsorbed to the clay mineral, and a positive apparent isotopic fractionation between 0.10‰ and 0.28‰ is measured in the supernatant recovered after adsorption experiments. Kinetic and thermodynamic isotopic fractionation are observed during the Swy-2 experiments while only a thermodynamic fractionation took place during the Tuftane muscovite (0.1–1 µm) experiments. The results obtained for the Ca desorption experiments performed with a chloride hexaamine cobalt solution suggest that Ca adsorption and the associated isotopic fractionation are fully reversible. Our results show that the Ca isotopic fractionation intensity during adsorption phenomena onto clay minerals is controlled by the layer charge and specific surface area of the considered phyllosilicate mineral, as well as the presence of an interlayer space open to cationic solute.

Several rivers of Chile from the latitude 30 degrees-38 degrees have been sampled during a stable anticyclonic period (October 2008). Firstly, our aim was to evaluate the dissolved chemical composition (major and trace elements) of poorly known central Chilean rivers. Secondly, we used a co-inertia analysis (see Doledec and Chessel in Freshw Biol 31:277-294, 1994) to explore the possible relationships between the concentrations of elements and the environmental parameters [surface of the basin (km(2))/mining activity (%)/average height (m)/watershed mean slope (%)/% of the surface covered by vegetation, sedimentary rocks, volcano-sedimentary rocks, volcanic rocks, granitoid rocks/erosion rate (mm/year)]. Globally, the major elements concentration could be explained by a strong control of mixed silicate and carbonate and evaporate lithology. The statistical treatment reveals that the highest metal and metalloids loads of Tinguiririca, Cachapoal, Aconcagua, Choapa, Illapel and Limari could be explained by the contribution of the mining activities in the uppermost part of these watersheds and/or by the higher geochemical background. Indeed, it remains difficult to decipher between a real mining impact and a higher geochemical background. Even if these rivers could be impacted by AMD process, the size of these watersheds is capable of diluting AMD waters by the alkaline character of tributaries that induce acid neutralization and decrease the level of metals and metalloids.

The determination of the mechanisms and extent of soil mineral weathering can be challenging, and the caveats reside in 1) difficulty identifying minerals that are actually involved in weathering reactions, 2) non-stoichiometric release of cations during weathering processes due to coupled dissolution, precipitation and transformation reactions and, 3) impact of vegetation activity on elemental cycles in upper soil horizons. To better characterize mechanisms controlling mineral weathering in soils and trace the evolution of B concentration and isotope ratios during chemical weathering, quantitative mineralogical analyses were coupled to B isotopes in a group of minerals (biotite, muscovite, K-feldspar and albite). Samples were selected along an Alocrisol (Alumic Cambisol, WRB FAO) soil profile from the bedrock (at 130 cm depth) up to 20 cm depth, developed on granitic bedrock in the Breuil-Chenue forest (France). The samples consist of residual primary minerals associated with weathering secondary phases (vermiculite, kaolinite…) in varying proportions. The B isotopic compositions of the most pristine minerals span a very narrow range of values (around −31‰), whereas all secondary phases point to a much heavier value (around −16‰), regardless of mineralogy. Our results also show a mineral-dependent evolution of B concentration or isotopic composition as weathering progresses: no variation is observed during dissolution of K-feldspars; B behaves like a very mobile element in micas (biotite and muscovite), whereas it concentrates in weathered products derived from albite. However, rates of B concentrations and changes in isotopic compositions appear to be much faster than those inferred from mineralogy or major element concentrations determined by XRD and bulk chemical analyses, respectively. These results indicate that B is involved in very early weathering reactions and raises the question of its actual location in the structure of the various soil minerals as well as its pathway to solution.

Understanding the variability of the chemical composition of surface waters is a major issue for the scientific community. To date, the study of concentration–discharge relations has been intensively used to assess the spatiotemporal variability of the water chemistry at watershed scales. However, the lack of independent estimations of the water transit times within catchments limits the ability to model and predict the water chemistry with only geochemical approaches. In this study, a dimensionally reduced hydrological model coupling surface flow with subsurface flow (i.e., the Normally Integrated Hydrological Model, NIHM) has been used to constrain the distribution of the flow lines in a headwater catchment (Strengbach watershed, France). Then, hydrogeochemical simulations with the code KIRMAT (i.e., KInectic Reaction and MAss Transport) are performed to calculate the evolution of the water chemistry along the flow lines. Concentrations of dissolved silica (H4SiO4) and in basic cations (Na+, K+, Mg2+, and Ca2+) in the spring and piezometer waters are correctly reproduced with a simple integration along the flow lines. The seasonal variability of hydraulic conductivities along the slopes is a key process to understand the dynamics of flow lines and the changes of water transit times in the watershed. The covariation between flow velocities and active lengths of flow lines under changing hydrological conditions reduces the variability of water transit times and explains why transit times span much narrower variation ranges than the water discharges in the Strengbach catchment. These findings demonstrate that the general chemostatic behavior of the water chemistry is a direct consequence of the strong hydrological control of the water transit times within the catchment. Our results also show that a better knowledge of the relations between concentration and mean transit time (C–MTT relations) is an interesting new step to understand the diversity of C–Q shapes for chemical elements. The good match between the measured and modeled concentrations while respecting the water–rock interaction times provided by the hydrological simulations also shows that it is possible to capture the chemical composition of waters using simply determined reactive surfaces and experimental kinetic constants. The results of our simulations also strengthen the idea that the low surfaces calculated from the geometrical shapes of primary minerals are a good estimate of the reactive surfaces within the environment.

The chemical weathering rate of silicates is a key parameter of several geochemical processes; however, the long-term field measurement of these rates remains challenging. Currently, there are several methods for quantifying field weathering rates, but each presents it's own unique set of difficulties. In this study uranium-series nuclides were used to investigate long-term biotite weathering in a soil profile. For this purpose, pseudomorph grains of biotites (including weathering products) were hand-picked from four horizons of a soil profile and from underlying granitic saprolite from the experimental Breuil-Chenue site (France). Unexpected behaviors of U and Th nuclides were recorded from these samples. An unambiguous leaching of 232Th occurs during the weathering of biotite, while reduced U release relative to Th was observed, implying an efficient redistribution of U between the primary mineral and weathering products within the pseudomorphs. The measured U-series activity ratios reflect a regular and self-consistent pattern evolution. However, the “U-series-derived-weathered-stage” is not always coherent with the weathering features of major elements and/or with the location of the samples within the soil profile. For instance, biotite from the saprolite displays U-series activity ratios typical of significantly weathered samples, while major elements present rather limited signs of weathering. These results suggest an incongruent leaching of U and Th isotopes and suggest that U- and Th-series nuclides probe some water-mineral interactions that occur before macroscopic mineral tansformation. Using an open-system leaching model, coupled (234U/238U), (234U/230Th), and (226Ra/230Th) disequilibria measured from the samples allow us to calculate a weathering duration range of 6–52 ky for most weathered samples of this soil profile. The biotite weathering rate deduced from these data ranges from 7.8 × 10−17 mol·m−2·s−1 to 6.5 × 10−16 mol·m−2·s−1, which is consistent with the range of field rates previously reported. This rate was compared to the weathering rate of biotites induced by the substitution of vegetation occuring 35 years ago in a nearby soil profile, which was about 2–3 orders of magnitude higher than the long-term rate reported above. This feature is perfectly consistent with the decrease in the weathering rate with time that was previously widely documented but that still remains debated. Our results allude to a valuable use of U-series isotopes for mineral-weathering field rate determination and report a decrease in silicate weathering rates over long- (10,000s of years) and short-term (10s of years) weathering events recorded from the same site. The results show that short term laboratory experiments can be representative of field processes, and suggest that some forms of mineral weathering reactivation, similar to that observed during laboratory experiments, may naturally occur in soils in response to high frequency perturbation processes such as land cover change.

The present study seeks to evaluate the application of the 238U-234U-230Th radioactive disequilibrium methodology for the determination of the regolith production rates in thick weathering profiles marked by long histories, encountered under various climate regimes, but still very little studied by these techniques. For this purpose, 238U-234U-230Th disequilibria have been analyzed in a ≈ 11 m-deep profile developed on a granitic bedrock in south China (Longnan, Jiangxi Province) under a subtropical climate. The results demonstrate that in such deep weathering profiles the determination of weathering rates from the analysis of U-series nuclides in bulk rock samples cannot be recovered by applying in one step to the entire alteration profile the modeling approach classically used to interpret the U-series nuclides, i.e. the “gain and loss” model. The modeling has to be made on subsections of relatively small size (10Be data from the same profile, when assuming non steady-state erosion of the upper part of the profile. Slow denudation rates similar to the U-series derived production rates of 2 m/Ma can thus be obtained with a minimum exposure time of 40 ky, and an inherited component of 20-25*104 at/g originating from the exhumed deeper part of the profile. Altogether the data demonstrate that the combined analysis of U-series and cosmogenic nuclides, which has the potential to become a relevant approach to constrain the dynamics of continental surfaces, requires (a) dense and deep sampling for both nuclides studies, and (b) also to consider more systematically the polyphased and variable history of erosion of the continental surface during the Quaternary. These results have implications for the interpretation of long-term accumulation of 10Be at depth and 10Be data variations in granitic alteration profiles.

Few studies using geochemistry of sediments from plains and delta of the Himalayan river system have reported contrasting results on the shift in erosion of different lithotectonic units, across the strike of Himalayan orogen, in response to changes in the intensity of Indian summer monsoon (ISM) and glacial cover during the late Quaternary. Here we present records of the 143Nd/144Nd (eNd) and 87Sr/86Sr ratios and δ13C of sediment organic matter (δ13CSOM) in bulk sediment samples from two ~45 m long alluvial cores, collected from a paleo-Sutlej channel (in Sirhind, Punjab) at an upstream connection of a large river (Ghaggar-Hakra) with present-day Sutlej River in NW India. The isotopic variations are compared with the available proxy records that document changes in the ISM and Himalayan glacial extent. Significant covariation in down-core profiles of eNd (−14.1 to −22.2) and 87Sr/86Sr (0.72251–0.79456) reveals changing contributions of sediment derived from the Higher and Lesser Himalaya end-member sources in the catchment. Higher eNd (and lower 87Sr/86Sr) during early marine isotope stage (MIS) 1 and late MIS3 reflects increased contribution from the Higher Himalaya as a result of receding glacial cover as well as intense ISM that penetrates into the interior of the Higher Himalaya during warm periods. The δ13CSOM varies from −28.5‰ to −21.3‰ and shows a 5–7‰ increase from colder MIS2 to warmer early MIS1, implying an increase in C4 plant abundance during the same period in response to intensification of the ISM in the post last glacial maximum period. These variations in sediment provenance and vegetation pattern thus highlight the pronounced influence of climate on distribution of erosion and vegetation types in the NW Himalaya.

In this study, we linked Ca speciation with isotope composition in plants. To do this, we performed leachate experiments to access the soluble Ca, structurally bound Ca and insoluble Ca (i.e., water and weak acid resistant) within beech tree organs (Fagus sylvatica L.). Ca isotopic measurements were combined with infrared spectroscopy and calcium oxalate biomineralization identification. The results from our study indicate that bark and leaves are the most enriched in monohydrated calcium oxalate crystals (whewellite), which are observable in parenchyma and sclerenchyma tissues, whereas roots and wood are enriched in structurally bound Ca. Our leaching experiments also show decreasing δ44/40Ca isotopic signatures in the order of soluble Ca > structurally bound Ca > insoluble Ca. This finding implies that because leaves degrade faster than wooden organs and because Ca linked to pectate decomposes faster than Ca linked to oxalate crystals, differential Ca isotopic signatures are expected to be observed during litter degradation. Fil: Schmitt, Anne Désirée. Université de Strasbourg; Francia Fil: Borrelli, Natalia Lorena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Marinas y Costeras. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Marinas y Costeras; Argentina Fil: Ertlen, Damien. Université de Strasbourg; Francia Fil: Gangloff, Sophie. Université de Strasbourg; Francia Fil: Chabaux, François. Université de Strasbourg; Francia Fil: Osterrieth, Margarita Luisa. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Geología de Costas y del Cuaternario. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Instituto de Geología de Costas y del Cuaternario; Argentina

This study presents the results of the coupled hydrogeochemical modeling of the geochemical compositions of spring and borehole waters from the Ringelbach catchment, which is located in the Vosges Mountains (France). This site has been equipped with 150-m-deep boreholes, facilitating the sampling of both rock and groundwater in the granitic bedrock. The data point to very contrasting chemical compositions between spring and borehole waters, which are discussed and explained in this study by the application of the coupled hydrogeochemical code KIRMAT. Using hydrological and geochemical data, simulations were performed through two different water pathways, which crossed different types of rocks within the Ringelbach massif: a subsurface and fast (>2.5 mH2O.yr−1) water flow, which is more or less parallel to the slope, for waters supplying the springs, and a rather vertical and slower flow (0.5–0.1 mH2O.yr−1) for the borehole waters. The KIRMAT simulations make it possible to account for not only the geochemical differences between the spring and borehole waters but also the geochemical variations observed in waters in both contexts. For borehole waters, the model confirms the importance of the dissolution of minor mineralogical phases that are present in the granite (here, carbonates/dolomites) on the chemical budget of waters. It also shows that the chemical differences between the waters collected in the two studied boreholes result from differences in the water flow in the granitic bedrock, i.e., the difference between water flow in a regular porous medium and water flow in a porous medium crossed by a fracture. This result likely highlights the role of geological inheritance on the hydrodynamical rock properties and the chemical compositions of waters circulating within the granitic bedrock. For spring waters, this model enabled us to constrain the nature of the rock in the pathway, which is neither saprolite nor fresh granite but is instead weathered granite with a weathering age of several tens of thousands of years. Spatial and seasonal variations in the chemical compositions of spring water can be explained as the result of the same circulation pattern for which the water-rock interaction time is determined by the length of the pathway and the water velocity. Especially in cases in which this interaction time is long enough, the precipitation of clay phases is enabled, which plays a major role in determining the chemical composition of the water. Despite the only one-dimensional approach and the uncertainties linked to the geochemical complexity and the associated kinetic data, the results obtained in this study demonstrate the effectiveness of using coupled hydrogeochemical modeling to better understand and quantify the weathering processes and the coupling that exists between water circulation dynamics and water-rock interactions at the catchment scale.

Calcium (Ca) is the fourth most abundant element in mineral nutrition and plays key physiological and structural roles in plant metabolism. At the soil-water-plant scale, stable Ca isotopes are a powerful tool for the identification of plant-mineral interactions and recycling via vegetation. Radiogenic Sr isotopes are often used as tracers of Ca sources and mixtures of different reservoirs. In this study, stable Ca and radiogenic Sr are combined and analysed in several organs from two beech trees that were collected in June and September in the Strengbach critical zone observatory (CZO) (NE France) and in corresponding soil solutions. At the beech-tree scale, this study confirms the field Ca adsorption (i.e., physico-chemical mechanism and not vital effects) on carboxyl acid groups of pectin in the apoplasm of small roots. The analysis of the xylem sap and corresponding organs shows that although the Strengbach CZO is nutrient-poor, Ca seems to be non-limiting for tree-growth. Different viscosities of xylem sap between the stemwood and branches or leaves can explain δ44/40Ca values in different tree-organs. The bark and phloem 40Ca-enrichments could be due to Ca-oxalate precipitation in the bark tissues and in the phloem. The results from this study regarding the combination of these two isotopic systems show that the isotopic signatures of the roots are dominated by Ca fractionation mechanisms and Sr, and thus Ca, source variations. In contrast, translocation mechanisms are only governed by Ca fractionation processes. This study showed that at the root-soil solution interface, litter degradation was not the main source of Ca and Sr and that the soil solutions are not the complement of uptake by roots for samples from the 2011/2013 period. The opposite is observed for older samples. These observations indicate the decreasing contribution of low radiogenic Sr fluxes, such as recycling, alimenting the soil solutions. Such reduced importance of nutrient uptake and biomass production by the trees could be because the Strengbach trees are ageing and probably weakened by repeated storm events and drought episodes.

International audience; In a Siberian river, the concentrations of chemical species vary with the hydrological regime. Dissolved Organic Matter (DOM) and aluminum ions show a parallel trend in the course of the hydrological year. However, the speciation of aluminum in this natural environment remains an open question. We propose here a combination of spectroscopic techniques to investigate the proximity between the aluminum atoms and DOM. First, one-dimensional (1D) solid-state Nuclear Magnetic Resonance (NMR), Electron Paramagnetic Resonance (EPR) and 1D and 2D solution NMR spectra were acquired, providing a clear overview of the DOM composition. Second, the sensitivity enhancement yielded by Dynamic Nuclear Polarization enabled the NMR detection of proximities between the 27Al and 13C nuclei. Hence, we show that 8.3 ± 1.3% of the carboxylate groups observed by NMR are connected to the Al3+ ions in the DOM sample. We here demonstrate for the first time how advanced solid-state NMR methods can provide key information about the localization of aluminum in such complex natural materials.

This study presents U-Th-Ra isotope data for soils, soil grain size fractions, soil solutions, throughfall, rainwater and tree samples from two experimental plots under spruce and beech trees, in the Strengbach catchment (France) that highlight the importance of the 238U-234U-230Th-226Ra nuclides and the (230Th/232Th) for the tracing of biogeochemical cycles in the plant-soil-water system of the critical zone (CZ). The results underscore the very contrasting impact of trees on the U-Th and Ra (Ba) budgets in forest ecosystems with Ra-Ba being strongly and U-Th very little cycled by vegetation, leading to high (226Ra/230Th) and (226Ra/238U) in trees. Thorium-Ra(Ba) fractionations in soil solutions and soils are therefore strongly influenced by tree uptake and litter decay but U-Th fractionations are little influenced. Compared to other classical isotope systems such as Sr or Nd that are routinely used in the study of the CZ and significantly affected by vegetation cycling, U-Th isotopes are probably among the few tracers to be specific tracers of water-rock interactions in the CZ. The Th activity ratios of soil minerals, especially of minor and secondary mineral phases, show a large range of variation, from 0.7 to 5 in the Strengabch case. These different characteristics give Th activity ratio an important role for tracing the sources of chemical fluxes in soils, soil solutions and vegetation that is currently under-exploited. The Strengbach study illustrates the utility of this approach and the methodology is further strengthened by the combination of U, Th activity ratios and Sr isotope ratios, which also provides additional constraints on the weathering processes affecting the Strengbach bedrocks and the nature of the reservoirs involved in the plant-soil-water transfers. The results emphasize that minor mineral phases such as zircon, sulfate and phosphate are important sources of the U-Th fluxes circulating in soil solutions and significantly control the U and Th budget of the Strengbach soil samples and their Th activity ratios. Furthermore, the comparison of the U-Th-Sr isotopic characteristics of soil solutions and soil grain size fractions allows the recognition of two stages of weathering of the bedrock i.e. 1- dissolution of the primary minerals and formation of the secondary ones in the deep soil horizons, and 2- dissolution of both primary and secondary minerals mainly from the finest soil grain size fractions in the nearest surface soil horizons. The latter might be related to recent modifications of the weathering processes in the catchment, stronger and older under the spruce than the beech plot. We propose that degree of weathering modification is related to the nature of tree cover because spruce plantations have caused an increase of soil acidity and hence of weathering intensity of some minerals and likely also of Ca leaching from the Ca-poor Strengbach soils over the past decades. The U-Th-Sr results of this study also point to the occurrence of isotopically different reservoirs of these elements for trees and gravity soil solutions collected by lysimetric plates. This further suggests that for the Strengbach watershed the gravity soil solutions cannot be the main tree nutrient reservoir.

The present study seeks to evaluate the application of the 238U-234U-230Th radioactive disequilibrium methodology for the determination of the regolith production rates in thick weathering profiles marked by long histories, encountered under various climate regimes, but still very little studied by these techniques. For this purpose, 238U-234U-230Th disequilibria have been analyzed in the top 11 m of a lateritic profile developed on a granitic bedrock in south China (Longnan, Jiangxi Province) under a subtropical climate. The results demonstrate that in such a weathering profile the determination of weathering rates from the analysis of U-series nuclides in bulk rock samples cannot be recovered by applying in one step to the entire alteration profile the modeling approach classically used to interpret the U-series nuclides, i.e. the “gain and loss” model. The modeling has to be made on subsections of relatively small size (

On Earth, the Critical Zone is the near-surface environment where interactions between the atmosphere, lithosphere, hydrosphere and biosphere take place. The development of the regolith mantle is controlled by the downwards propagation of the weathering front into the bedrock and denudation at the surface of the regolith by mass movements, water and wind erosion. When the removal of surface material is approximately balanced by the production of weatherable material at the bottom of the regolith profile, the soil system is assumed to be in steady-state. Although recent literature on chemical weathering often assumes that soils have a steady-state thickness, the concept has rarely been validated with empirical field data. In this study, we present and compare analytical data from two independent isotopic techniques: in-situ produced cosmogenic nuclides and U-series disequilibria to constrain soil development under semi-arid climatic conditions. Three soil profiles were sampled across the Betic Ranges, at the ridge crest of zero-order catchments with distinct topographic relief, hillslope gradient and 10Be-derived denudation rate. Soil production rates determined based on U-series isotopes (238U, 234U, 230Th and 226Ra) are of the same order of magnitude as 10Be-derived denudation rates, suggesting steady state soil thickness, in two out of three sampling sites. Our results show the potential of a combined U-series disequilibria and in-situ 10Be isotope approach to evaluate steady-state soil thickness. Our study also illustrates the frontiers in applying U-series disequilibria to track soil production in environments characterized by weak soil development.

Vegetal cover and the water cycle are closely linked. The climate controls the distribution and productivity of terrestrial vegetation, and the vegetal cover type is a key determinant for evapotranspiration and global runoff. In this study, a dynamic vegetation model (LPJ) has been coupled with a 3D hydrogeological model (MODFLOW) to estimate, for the first time, the impact of climate change on a small forested temperate watershed (Strengbach, Vosges, France). The model, calibrated with monthly hydrological and climate data, is able to globally reproduce the observed vegetal cover distribution and the water cycle over the 1987–2009 period. The discrepancies between calculated and observed intra-annual discharge variations highlight the importance of processes such as snow formation, snowmelt, and catchment recharge after drought periods, as well as the impact of evapotranspiration. Long-term simulations extending up to the year 2100 have been performed with climatic output from the Meteo-France climate model ARPEGE/Climate (IPCC, 2007 scenario A1B). With a predicted increase in temperature of 2.6 °C and a rise in atmospheric CO2 concentration of 80%, the mean annual precipitation decreases by 4.5% in the Strengbach watershed over the course of the century. The models cascade predicts a limited decrease of evapotranspiration (by 2.5%), an impact on discharge (11% decrease) at the watershed outlet over the 21st century, and a significant change in vegetation distribution starting in approximately 2085. The response of land plants to climate change in the future seems to only slightly affect the water resources in the Strengbach catchment. This study also highlights existing shortcomings and limitations of simulations for measuring the impacts of climate change.

U–Th–Ra disequilibria, cosmogenic in situ 10Be concentrations and major and trace element concentrations have been analyzed in a 2 m-deep weathering profile sampled at the summit of the granitic Strengbach catchment (France). The data have been used to independently estimate both the long-term regolith production and denudation rates and the weathering and erosion rates. Modeling of the 238U–234U–230Th–226Ra disequilibrium variations in the lower part of the profile yields a regolith production rate of 12 ± 4 mm/kyr (30 ± 10 T/km2/yr), while modeling of the high-resolution 10Be concentration profile leads to an exposure age of 19.7 ± 2.2 kyr , an inherited concentration of 15,000 ± 1,000 at/g in quartz and a mean denudation rate of 22 ± 10 mm/kyr (37 ± 15 T/km2/yr). The consistency between production and denudation rates suggests that, on a millennial timescale, the regolith mass balance at the summit of the catchment is close to a steady state, even if the watershed may have been impacted by Quaternary climatic changes and by recent anthropogenic perturbations (e.g., 20th century acid rain and recent afforestation efforts). The results also indicate that physical erosion is likely the dominant long-term process of regolith denudation in the catchment. Furthermore, the comparison of the long-term production and denudation rates and of weathering and erosion rates determined from the depth profile analyses with the current weathering and erosion rates estimated at the outlet of the watershed based on monitoring of the water chemistry and sediment fluxes suggests that physical erosion may have varied more than the chemical weathering flux during the last 150 kyr. Although very few other sites with U-series, in situ 10Be and stream monitoring data are available for comparison, the current data suggest that (1) the mass balance steady state of regolith might be commonly achieved in soil mantled landscapes, and (2) physical erosion has varied much more than chemical weathering in mid-mountain catchments over the last 10–150 kyr. These results highlight the importance of the combined analysis of U-series nuclides and in situ 10Be in the same weathering profile for the determination of key geomorphic parameters, which are important to constraining landscape stability and the responses of landscapes to natural or anthropogenic forcing.

The objectives of this study were to determine the processes and physico-chemical conditions that affect the composition of the soil solutions of a forest soil and to elucidate their impact on the transport of major and trace elements through the colloidal (0.2 μm to 5 kDa) and dissolved (

Revealing the potential of Ca isotopes in the research of travertine formation processes is the principal goal of this study. To achieve this, the hydrochemistry, travertine precipitation rates, and variations in Ca isotopic compositions (δ 44/40 Ca) of present-day endogenic (thermogenic) travertine in two different hydrodynamic systems (canal and pool) are studied at Baishuitai (Yunnan, SW China). In the canal, where the travertine precipitation is faster, δ 44/40 Ca values of both solution and travertine show a downstream increase, with Ca isotopic fractionation (Δ 44/40 Ca CaCO3-aq ) equal to ~− 1.6‰. Compared to the canal, Ca isotopic fractionation between travertine and aqueous Ca 2 + is smaller (Δ 44/40 Ca CaCO3-aq ≈ − 1.2‰) in the pools where travertine precipitation rates are lower. The spatial variations in δ 44/40 Ca values of solution and travertine are related to the amount of Ca removed from the solution when δ 44/40 Ca values of spring water remain stable. In addition, the results confirm the control of precipitation rates on Ca isotopic fractionation between calcite and parent aqueous Ca 2 + using natural samples. The observed negative correlation between Δ 44/40 Ca CaCO3-aq and travertine precipitation rates can be explained by the steady-state kinetic surface reaction model proposed by DePaolo (2011), with equilibrium and kinetic fractionation factors of α eq = 1.0000 ± 0.0001 and α f = 0.9983 ± 0.0002, respectively. An important consequence of this study is that Ca isotopes in travertine systems are good tools to have access to variations of δ 44/40 Ca aq , which are directly linked to the amount of precipitated Ca. This could then be useful for reconstructing past hydrodynamic conditions when applied to travertine core data.

A numerical coupling of a dynamic biogeochemical model (B-WITCH) and a model of forest balance water (BILJOU) was used to simulate the concentration of major species within soil profiles from two contrasted ecosystems: beech and spruce stands located in the Vosges Mountains and their evolution during decades. This coupled modelling allows an important vertical discretization of water and cation cycle and a direct comparison with the hydrological and geochemical data available over twenty-five years and on a seasonal basis. The processes controlling the past evolution of soil solution chemistry have been identified and tested. The biogeochemical cycles of cations estimated on the two sites shows that the biological fluxes control up to 70% (for Ca and Mg) and up to 95% (K) of the chemical composition of the soil solutions. The Ca and Mg concentrations decrease over the last decades, which can be explained by the evolution of atmospheric inputs and by the behavior of the exchange complex. This paper highlights the weak contribution of mineral dissolution and the key role of biological recycling and cation exchange processes in the soil solution signatures. The future sustainability of forest, in mountainous environment on base poor bedrock, depends strongly on the forest management and evolution of exchangeable pool nature.

[Departement_IRSTEA]Eaux; International audience; Estimating intermediate water residence times (a few years to a century) in shallow aquifers is critical to quantifying groundwater vulnerability to nutrient loading and estimating realistic recovery timelines. While intermediate groundwater residence times are currently determined with atmospheric tracers such as chlorofluorocarbons (CFCs), these analyses are costly and would benefit from other tracer approaches to compensate for the decreasing resolution of CFC methods in the 5–20 years range. In this context, we developed a framework to assess the capacity of dissolved silica (DSi) to inform residence times in shallow aquifers. We calibrated silicate weathering rates with CFCs from multiple wells in five crystalline aquifers in Brittany and in the Vosges Mountains (France). DSi and CFCs were complementary in determining apparent weathering reactions and residence time distributions (RTDs) in shallow aquifers. Silicate weathering rates were surprisingly similar among Brittany aquifers, varying from 0.20 to 0.23 mg L−1 yr−1 with a coefficient of variation of 7%, except for the aquifer where significant groundwater abstraction occurred, where we observed a weathering rate of 0.31 mg L−1 yr−1. The silicate weathering rate was lower for the aquifer in the Vosges Mountains (0.12 mg L−1 yr−1), potentially due to differences in climate and anthropogenic solute loading. Overall, these optimized silicate weathering rates are consistent with previously published studies with similar apparent ages range. The consistency in silicate weathering rates suggests that DSi could be a robust and cheap proxy of mean residence times for recent groundwater (5–100 years) at the regional scale. This methodology could allow quantification of seasonal groundwater contributions to streams, estimation of residence times in the unsaturated zone and improve assessment of aquifer vulnerability to anthropogenic pollution.

This study focuses on 20 years of hydrochemical monitoring of the small springs that emerge in the experimental granitic catchment of Strengbach (OHGE, France) and the simulation of these data using the KIRMAT code. The data indicate that the Strengbach springs display chemostatic behavior; that is, limited temporal variations were noted in the concentrations of dissolved silica (H4SiO4) and most of the basic cations during the studied period (1987–2010), resulting in relative stability of the global weathering fluxes exported by the springs. Only the Ca2+ concentrations reflect a significant decrease in all the Strengbach springs since 1987, and the variations differ from one spring to another. The modeling results show that the decrease in Ca2+ in the Strengbach springs is due to the response of the water-rock interactions within the bedrock to the variations in the chemical composition of the soil solutions, which were characterized by a significant increase in pH and a decrease in Ca2+ concentrations between 1987 and 2010. The decrease in Ca2+ concentrations seen in the Strengbach springs is controlled by changes in the apatite dissolution rate and the compositions of clay minerals induced by the soil solution changes. The differences observed between the Ca2+ trends of the springs are related to changes in the residence time of the water supplying the different springs. The weak impact of the soil solution modifications on the dissolution rates of other primary minerals and on the bulk precipitation rates of the clay minerals explains the relative stability over time of the concentrations of the other cations and dissolved silica in the water derived from the Strengbach springs. Further, the hydrochemical simulations suggest that the chemostatic behavior of the Strengbach springs cannot be explained by the mobilization of waters that are close to chemical equilibrium, but rather by a hydrological control of the spring water residence times. Finally, a comparison of current and long-term weathering rates determined from the spring water monitoring and a regolith profile shows that the modern chemical fluxes of Ca2+ are higher than the long-term ones, whereas the weathering fluxes of H4SiO4 and Na+ have likely been much more stable over time. All of these results indicate that the silicate weathering processes are characterized by weak spatial and temporal variability in the Strengbach catchment, while the chemical elements such as Ca2+, for which the budget in the spring waters is controlled by the dynamic behavior of clay minerals and minor minerals such as apatite, are significantly affected by Quaternary climatic variations and decennial environmental changes.

This study presents the results of a geochemical and isotope (U and Sr) study of soil solutions from two experimental sites in the Strengbach catchment, one under spruce trees and the other under beech trees. The soil solution data, combined with the data from soil and vegetation samples, indicate that the “dissolved” U (filtered to 0.45 μm) in the soil solutions is primarily of lithogenic origin, implying that the colloidal U is secondarily associated with organic matter or organo-metallic complexes present in the soil solutions. The uranium activity ratios and Sr isotope ratios of soil solutions are used to decipher the nature of the minerals that control the lithogenic contribution to the soil solutions. A comparison of soil solution data collected over the period 2004–2006 with those collected over the period 1993–2010 indicates a decrease in the Ca and K exported by the soil solutions between 1998 and 2004 at the spruce site and a significantly smaller decrease at the beech site. In addition, the Sr isotope ratios of the soil solutions vary significantly between these two periods at the spruce site but not or much less at the beech site. Such observations suggest that the forest ecosystem at the spruce site is in a transient state associated with recent changes in weathering reactions. The data also suggest that the comparison of U and Sr isotopes in soil solutions and plant samples could be a relevant method for determining whether a forest ecosystem is in a steady or transient state.

We developed a multicomponent, 1D advective transport model that describes the downgradient evolution of solute concentrations, 87 Sr/ 86 Sr ratios, and δ 11 B values in the Wyodak-Anderson Coal Bed (WACB) aquifer located in the Powder River Basin, Wyoming, USA. The purpose of the study was to evaluate the chemical vulnerability of groundwater to potential environmental change stemming from the extraction of coal bed methane and shale gas. Model calculations demonstrate that coupling between microbial activity and the dissolved carbonate system controls major ion transport in the WACB aquifer. The analysis of 87 Sr/ 86 Sr ratios further reveals the importance of ion-exchange reactions. Similarly, δ 11 B data emphasize the significance of pH-dependent surface reactions and demonstrate the vulnerability of the aquifer to the long-term acidification of recharge water.

Research activity associated with various observations at the Strengbach catchment in the Vosges Massif (880-1150 m) addresses many questions in the domains of hydrology and geochemistry. The catchment is the observation and experimental site of the Observatoire Hydro-Geochimique de l'Environnement appointed by the Centre National de la Recherche Scientifique. It also belongs to the research facilities that form the French Network of Critical Zone Observatories (OZCAR), which supports a network of critical zone observatories. The catchment is small (0.8 km(2)) with steep slopes (20-30%) on granitic bedrock that mainly allow for forestry (spruce and beech stands) as the main land cover. Meteorological, hydrological, and geochemical data have been monitored since 1986. The first studies conducted were dedicated to the elucidation of acid rain effects on forest ecosystems and particularly on forest decline. Multidisciplinary research studies conducted on the Strengbach catchment enable exploration of the following issues: (i) hydrological functioning at the scale of a small catchment and questions regarding the evolution and preservation of the water resources in mountainous environments (stock, recharge, infiltration, and water pathways), (ii) exchange processes observed at the soil-plant-atmosphere continuum and in particular weathering processes and the evolution of soil mineral fertility (Ca, Mg, K, P), (iii) processes responsible for the export of water and for associated fluxes (dissolved chemicals, suspended materials, bed loads) and their dynamic at the outlet, and (iv) responses of the ecosystems to environmental disturbances (acid rain, forest management, and climate change) and their current and future modeling.

The impact of mineralogical sorting on U-Th-Ra variations observed for the Ganga sediments in the Himalayan alluvial plain due to transport and deposition processes highlights the importance to better understand the U-series isotopic system in Himalayan minerals. For this purpose, U, Th, and Ra concentrations, along with 238U–234U–230Th–226Ra radioactive disequilibria, were measured in several pure mineral fractions, i.e. monazite, zircon, titanite, ilmenite, rutile, garnet, magnetite, quartz, biotite and muscovite, separated from one bank sediment of the Gandak River (Ganga Basin). The data, obtained through a double digestion protocol in high-pressure and high-temperature vessels, confirm that U and Th concentrations and isotopic ratios of the sediments are mainly influenced by a few minor mineral species that are very enriched in U and Th, namely, monazite, titanite and epidote, as well as major minerals with lower U and Th concentrations, such as quartz. More importantly, the data clearly indicate that, similarly to whole rock samples, the U-Th-Ra systematics of individual minerals have likely recorded complex U-Th-Ra fractionations. In particular, the 226Ra enrichment observed in the biotite and clay fractions likely results from the affinity of Ra for phyllosilicate minerals, while the 230Th and, to a lesser extent the 234U enrichment observed for the other minerals might result from a nuclide adsorption process on the Fe-oxide coatings present on the grains or directly on the mineral surface. The linear trend outlined by the minerals phases in the (226Ra/230Th) vs (230Th/234U) diagram suggests that 230Th is probably mobilized from zircons, the only fraction presenting (230Th/234U)

• U, 234 U, 230 Th and 226 Ra were determined in soils sampled on geological formations from the NE of the Basin of Paris.

The estimation of sediment transfer times remains a challenge to our understanding of sediment budgets and the relationships between erosion and climate. Uranium (U) and thorium (Th) isotope disequilibria offer a means of more robustly constraining sediment transfer times. Here, we present new uranium and thorium disequilibrium data for a series of nested moraines around Lago Buenos Aires in Argentine Patagonia. The glacial chronology for the area is constrained using in situ cosmogenic 10Be analysis of glacial outwash. Sediment transfer times within the periglacial domain were estimated by comparing the deposition ages of moraines to the theoretical age of sediment production, i.e., the comminution age inferred from U disequilibrium data and recoil loss factor estimates. Our data show first that the classical comminution age approach must include weathering processes accounted for by measuring Th disequilibrium. Second, our combined data suggest that the pre-deposition history of the moraine sediments is not negligible, as evidenced by the large disequilibrium of the youngest moraines despite the equilibrium of the corresponding glacial flour. Monte Carlo simulations suggest that weathering was more intense before the deposition of the moraines and that the transfer time of the fine sediments to the moraines was on the order of 100–200 kyr. Long transfer times could result from a combination of long sediment residence times in the proglacial lake (recurrence time of a glacial cycle) and the remobilization of sediments from moraines deposited during previous glacial cycles. 10Be data suggest that some glacial cycles are absent from the preserved moraine record (seemingly every second cycle), supporting a model of reworking moraines and/or fluctuations in the extent of glacial advances. The chronological pattern is consistent with the U–Th disequilibrium data and the 100–200 kyr transfer time. This long transfer time raises the question of the proportion of freshly eroded sediments that escape (or not) the proglacial environments during glacial periods.

International audience; Agricultural pollution is a matter of political and scientific concern throughout the world. Intensive agriculturecan cause nutrient contamination of groundwater and surface water. Nutrient pollution causes eutrophicationin freshwater and estuarine ecosystems. A secondary effect of agricultural intensification is river acidification.Oxidation of chemical fertilizers such as ammonium (NH4+) to nitrate (NO3-) produces H+ ions that causeleaching of cations from soil and deeper material to maintain charge balance. Monitoring of various rivers inBrittany (western France) revealed that agriculture intensification has led to increased cation export starting in the1980s. From the cation ratios, we deduced that cation increase comes approximately equally from dissolution ofcarbonate added to soil (liming practices) and silicate dissolution. Cation export represented about 30% of the soilcation exchange potential. If compensated by liming, it may constitute a non-negligible source to atmosphericCO2 (Aquilina et al., 2012).We further investigated the potential for silicate dissolution through the use of groundwater dating in various sitesof Brittany. Coupling chemical analyses to groundwater ages in a large range of aquifers and a large range ofdepths (down to 110m) allowed us to reconstruct a chronicle for the last 50 yrs of the cation concentrations ofgroundwater. It clearly shows a contemporaneous increase in sodium and nitrate and a decrease in calcium, withthe most dramatic changes occurring during the 70s and 80s.Using groundwater dating, we were also able to determine a silica production geochronometer. A tight and linearrelationship between silica concentration and groundwater age (Figure) was observed and allowed a productionrate in groundwater to be determined. Except for short residence-times (Kerrien), the silica production rate fordifferent granitic catchments was consistent, ranging from 0.3 to 0.4 mg.L-1.yr-1.To assess the role of anthropogenic activity in silica production rate, we compared production rates from Brittanywith catchments in the Vosges Mountains, a relatively pristine area. Dissolution rates were much higher in theBrittany catchments, indicating the effect of human activities on chemical weathering and cation export at thecatchment scale.Aquilina L. et al., 2012 - Long-term effects of high nitrogen loads on cation and carbon riverine export inagricultural catchments. Env. Sci & Technology 46-17, 9447-9455..

This chapter summarizes the methods, results, and conclusions of a 5-year research project (SoilTrEC: Soil Transformations in European Catchments) on experimentation, process modeling, and computational simulation of soil functions and soil threats across a network of European, Chinese, and United States Critical Zone Observatories (CZOs). The study focused on the soil functions of biomass production, carbon storage, water storage and transmission, water filtration, transformation of nutrients, and maintaining habitat and genetic diversity.The principal results demonstrate that soil functions can be quantified as biophysical flows and transformations of material and energy. The functions can be simulated with mathematical models of soil processes within the soil profile and at the critical zone interfaces with vegetation and atmosphere, surface waters and the below-ground vadose zone and groundwater. A new dynamic model for soil structure development, together with data sets from the CZOs, demonstrate both seasonal fluctuations in soil structure dynamics related to vegetation dynamics and soil carbon inputs, and long-term trends (decadal) in soil carbon storage and soil structure development.Cross-site comparison for 20 soil profiles at seven field sites with variation in soil type, lithology, land cover, land use, and climate demonstrate that sites can be classified, using model parameter values for soil aggregation processes together with climatic conditions and soil physical properties, along a trajectory of soil structure development from incipient soil formation through productive land use to overly intensive land use with soil degradation.A new modeling code, the Integrated Critical Zone model, was applied with parameter sets developed from the CZO site data to simulate the biophysical flows and transformations that quantify multiple soil functions. Process simulations coupled the new model for soil structure dynamics with existing modeling approaches for soil carbon dynamics, nutrient transformations, vegetation dynamics, hydrological flow and transport, and geochemical equilibria and mineral weathering reactions. Successful calibration, testing, and application of the model with data sets from horticulture plot manipulation experiments demonstrate the potential to apply modeling and simulation to the scoping and design of new practices and policy options to enhance soil functions and reduce soil threats worldwide.

Regoliths encompass different materials from the fresh bedrock to the top of the organic horizons. The occurrence and evolution of these materials are determined by deposition, erosion and weathering processes that are specific for each region. The origin and interaction of the regolith layers are still important issues in the study of critical zone functioning. Studies that attempt to understand the processes responsible for the structure and the evolution of regoliths often focus either on the soil or on the bedrock compartment, and often from a narrowly focused approach using just a single tool such as major element patterns or mineralogy. This limits the understanding of the complete regolith composition and evolution. The present study proposes the combination of mineralogy, major and trace element concentrations, and Sr-Nd-Pb-U isotopes as an extremely useful procedure for tracking the spatial and temporal origin of regolith materials and understanding their stratification. This multi-tracer approach was applied on a regolith profile from the south-western edge of the Rhenish Massif, which is characterised by the occurrence of slate bedrocks and overlying Pleistocene Periglacial Slope Deposits (PPSD). The data allowed the differentiation of three compartments within the regolith: 1) the organic compartment, where low (206)pb/(207)pb and Sr-87/Sr-86 isotopic ratios reflected the impact of atmosphere-derived components; 2) the PPSD compartment, whose upper horizons were characterised by the presence of atmosphere-derived particles rich in Cd, Sn, Sb, Hg and Pb and by relatively low Pb-206/Pb-207 and Sr-87/Sr-86 ratios, whereas the lower horizons showed Nb enrichments in their matrix and a mineralogical composition pointing to ancient volcanic events; and 3) the weathered slate compartment, whose weathering progression and genetic relationship with the PPSD were particularly well tracked with Sr-87/Sr-86 and Nd-143/Nd-144 isotope ratios, ((UU)-U-234-U-/238) activity ratios and positive Ce anomalies. The results prove the efficiency of radiogenic isotope measurements combined with the analysis of major and trace elements to complete regolith studies. Moreover, these isotopes and elements are shown to be potential geochemical tracers of exchange processes at the water-mineral interface. This approach allows for the first time the description of an evolution scheme of a complete slate regolith, which covers a large part of the Rhenish Massif.