Understanding how water and solutes enter and propagate through freshwater landscapes in the Anthropocene is critical to protecting and restoring aquatic ecosystems and ensuring human water security. However, high hydrochemical variability in headwater streams, where most carbon and nutrients enter river networks, has hindered effective modelling and management. We developed an analytical framework informed by landscape ecology and catchment hydrology to quantify spatiotemporal variability across scales, which we tested in 56 headwater catchments, sampled periodically over 12 years in western France. Unexpectedly, temporal variability in dissolved carbon, nutrients and major ions was preserved moving downstream and spatial patterns of water chemistry were stable on annual to decadal timescales, partly because of synchronous variation in solute concentrations. These findings suggest that while concentration and flux cannot be extrapolated among subcatchments, periodic sampling of headwaters provides valuable information about solute sources and subcatchment resilience to disturbance.

[1] To obtain better constraints on the control of seasonal hydrological variations on dissolved organic carbon (DOC) dynamics in headwater catchments, we combined hydrometric monitoring with high-frequency analyses of DOC concentration and DOC chemical composition (specific UV adsorption, 13 C) in soil and stream waters during one complete hydrological cycle in a small lowland catchment of western France. We observed a succession of four hydrological periods, each corresponding to specific DOC signatures. In particular, the rise of the upland water table at the end of the rewetting period yielded to a strong increase of the specific UV absorbance (from 2.5 to 4.0 L mg C À1 m À1 ) and of the 13 C values (from À29 to À27%) of the soil DOC. Another striking feature was the release of large amounts of DOC during reduction of soil Fe-oxyhydroxides at the end of the highflow period. Comparison of hydrometric data with DOC composition metrics showed that soils from the upland domains were rapidly DOC depleted after the rise of the water table in these domains, whereas wetland soils acted as quasi-infinite DOC sources. Results from this study showed that the composition and ultimate source of the DOC exported to the stream will depend on the period within the annual hydrological cycle. However, we found that the aromatic DOC component identified during the high-flow period will likely represent the dominant DOC component in stream waters on an annual basis, because most of the annual stream DOC flux is exported during such periods.Citation: Lambert, T., A.-C. Pierson-Wickmann, G. Gruau, A. Jaffrezic, P. Petitjean, J.-N Thibault, and L. Jeanneau (2013), Hydrologically driven seasonal changes in the sources and production mechanisms of dissolved organic carbon in a small lowland catchment, Water Resour. Res., 49,[5792][5793][5794][5795][5796][5797][5798][5799][5800][5801][5802][5803]

The oxygen content of Earth's atmosphere has varied greatly through time, progressing from exceptionally low levels before about 2.3 billion years ago, to much higher levels afterward. In the absence of better information, we usually view the progress in Earth's oxygenation as a series of steps followed by periods of relative stasis. In contrast to this view, and as reported here, a dynamic evolution of Earth's oxygenation is recorded in ancient sediments from the Republic of Gabon from between about 2,150 and 2,080 million years ago. The oldest sediments in this sequence were deposited in well-oxygenated deep waters whereas the youngest were deposited in euxinic waters, which were globally extensive. These fluctuations in oxygenation were likely driven by the comings and goings of the Lomagundi carbon isotope excursion, the longest-lived positive δ 13 C excursion in Earth history, generating a huge oxygen source to the atmosphere. As the Lomagundi event waned, the oxygen source became a net oxygen sink as Lomagundi organic matter became oxidized, driving oxygen to low levels; this state may have persisted for 200 million years.GOE | Paleoproterozoic | marine chemistry | Mo isotope | trace metal

The evidence for macroscopic life during the Palaeoproterozoic era (2.5-1.6 Gyr ago) is controversial. Except for the nearly 2-Gyr-old coil-shaped fossil Grypania spiralis, which may have been eukaryotic, evidence for morphological and taxonomic biodiversification of macroorganisms only occurs towards the beginning of the Mesoproterozoic era (1.6-1.0 Gyr). Here we report the discovery of centimetre-sized structures from the 2.1-Gyr-old black shales of the Palaeoproterozoic Francevillian B Formation in Gabon, which we interpret as highly organized and spatially discrete populations of colonial organisms. The structures are up to 12 cm in size and have characteristic shapes, with a simple but distinct ground pattern of flexible sheets and, usually, a permeating radial fabric. Geochemical analyses suggest that the sediments were deposited under an oxygenated water column. Carbon and sulphur isotopic data indicate that the structures were distinct biogenic objects, fossilized by pyritization early in the formation of the rock. The growth patterns deduced from the fossil morphologies suggest that the organisms showed cell-to-cell signalling and coordinated responses, as is commonly associated with multicellular organization. The Gabon fossils, occurring after the 2.45-2.32-Gyr increase in atmospheric oxygen concentration, may be seen as ancient representatives of multicellular life, which expanded so rapidly 1.5 Gyr later, in the Cambrian explosion.

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International audienceUsing groundwater age determination done through CFC analysis and geochemical data obtained from seven sites in Brittany (France), a hydrogeochemical model for hard-rock aquifers is presented. According to the geological structure, three zones can be defined: the weathered layer, about 30 m thick; the weathered-fissured layer (fractured rock with a high density of fissures induced by weathering), which represents a transition zone between the weathered zone and the lower fractured zone; and the unweathered part of the aquifer. (1) The weathered layer (alterites) is often considered as a porous medium and is the only part frequently used in hard-rock aquifers. Recent apparent ages (0­10 a) are observed in the groundwater fluctuation zone in a thin layer, which is from 1­2 m-thick in the lower parts and 10­15 m-thick in the upper parts of the catchments. Below this thin layer, the groundwater apparent age is high (between 10 and 25 a) and is unexpectedly homogeneous at the regional scale. This groundwater apparent age contrast, which also corresponds to a Cl- concentration contrast, is attributed to rapid lateral transfers in the fluctuation zone which limit water transfer to the underlying weathered zone. Groundwater chemistry is characterized by and Cl- concentrations related to land uses (high in agricultural areas, low in preserved ones). (2) At the interface between the weathered and the weathered-fissured layers a strong biogeochemical reactivity is observed. Autotrophic denitrification is enhanced by a higher availability of sulfides. (3) Under this interface, in the weathered-fissured layer and the underlying fractured deep part of the aquifer, groundwater apparent age is clearly correlated to depth. The vertical groundwater velocity is estimated to be 3 m/a, whatever be the site, which seems to indicate a regional topographic control on groundwater circulation in the deep part of the aquifer. In this deep part, groundwater chemistry is modified by water­rock interaction processes as indicated by Ca and Na concentrations, and a slight sea-water contribution (from 0.1% to 0.65%) in the sites close to the seacoast. One site inland shows a saline and old end-member. The global hydrogeochemical scheme is modified when the aquifer is pumped at a high rate in the fissured-weathered layer and/or the fractured layer. The increase in water velocity leads to a homogeneous groundwater apparent age, whatever be the depth in the weathered-fissured and fractured layers

Main finding Nanoplastics are able to sorb high amount of Pb(II) through sorption and intraparticle diffusion processes. They could be important vector of metallic pollutant in the environment. Highlights • Pb(II) binding experiments onto nanoplastics extracted from environmental micro-plastics were performed. • Pb(II) was largely bound onto nanoplastics by specific adsorption and intraparticle diffusion.

International audienceMonitoring the isotopic composition ( 13CDOC) of dissolved organic carbon (DOC) during flood events can be helpful for locating DOC sources in catchments and quantifying their relative contribution to stream DOC flux. Highresolution (< hourly basis) 13CDOC data were obtained during six successive storm events occurring during the highflow period in a small headwater catchment in western France. Intra-storm 13CDOC values exhibit a marked temporal variability, with some storms showing large variations (> 2 ‰), and others yielding a very restricted range of values (< 1 ‰). Comparison of these results with previously published data shows that the range of intra-storm 13CDOC values closely reflects the temporal and spatial variation in 13CDOC observed in the riparian soils of this catchment during the same period. Using 13CDOC data in conjunction with hydrometric monitoring and an end-member mixing approach (EMMA), we show that (i) > 80% of the stream DOC flux flows through the most superficial soil horizons of the riparian domain and (ii) the riparian soil DOC flux is comprised of DOC coming ultimately from both riparian and upland domains. Based on its 13C fingerprint, we find that the upland DOC contribution decreases from ca. 30% of the stream DOC flux at the beginning of the high-flow period to < 10% later in this period. Overall, upland domains contribute significantly to stream DOC export, but act as a sizelimited reservoir, whereas soils in the wetland domains act as a near-infinite reservoir. Through this study, we show that 13CDOC provides a powerful tool for tracing DOC sources and DOC transport mechanisms in headwater catchments, having a high-resolution assessment of temporal and spatial variability