Human-triggered magnification of erosion rates in European Alps since the Bronze Age.

A major feature of the Anthropocene is the drastic increase in global soil erosion. Soil erosion is threatening Earth habitability not only as soils are an essential component of the Earth system but also because societies depend on soils. However, proper quantification of the impact of human activities on erosion over thousands of years is still lacking. This is particularly crucial in mountainous areas, where the highest erosion rates are recorded. Here we use the Lake Bourget catchment, one of the largest in the European Alps, to estimate quantitatively the impact of human activities on erosion. Based on a multi-proxy, source-to-sink approach relying on isotopic geochemistry, we discriminate the effects of climate fluctuations from those of human activities on erosion over the last 10,000 years. We demonstrate that until 3800 years ago, climate is the only driver of erosion. From that time on, climate alone cannot explain the measured rates of erosion. Thanks to an unprecedented regional paleoenvironmental reconstruction, we highlight that the development of pastoralism at high altitudes from the Bronze Age onwards and the extension of agriculture starting in the Middle Ages were key factors in the drastic increase in erosion observed in the Alps.

Climate-driven fluxes of organic-bound uranium to an alpine lake over the Holocene.

Uranium (U) isotopic signatures and concentration in sediments are widely used as paleo-redox proxies, as the behavior of U is often controlled by bottom water oxygenation. Here, we investigated the processes controlling U accumulation in the sediments of Lake Nègre (Mediterranean Alps, South-East France) over the past 9200 years. Exceptionally high natural U concentrations (350-1250 µg·g-1) allowed the measurement of U along with other elements by high-resolution X-Ray Fluorescence core-scanning. Weathering and erosion proxies (Ti content, Zr/Al and K/Ti ratios) indicate that sedimentary inputs were controlled by Holocene climatic variations. After a period of low erosion during the Holocene Climatic Optimum, a major regime shift was recorded at 4.2 kyr BP when terrigenous fluxes consistently increased until present with high sensitivity to centennial-scale climatic events. Sedimentary organic matter (OM) inputs were dominated by terrigenous OM from the catchment soils until 2.4 kyr BP, as attested by carbon to nitrogen (C/N) and bromine to organic carbon (Br/TOC) ratios. From 2.4 kyr BP to present, lake primary production and soils equally contributed to sedimentary OM. Uranium fluxes to the sediments were well correlated to terrigenous OM fluxes from 7 kyr BP to present, showing that U supply to the lake was controlled by U scavenging in the soils of the watershed followed by transport of U bound to detrital organic particles. Higher U/OM ratios before 7 kyr BP likely reflect the development of the upstream wetland. The fluctuations of U sedimentary inputs appear to be independent of bottom water oxygenation, as estimated from constant Fe/Mn ratios and δ238U isotopic signatures, and rather controlled by the production, erosion and sedimentation of terrigenous OM. This finding confirms that the use of U (and potentially other metals with high affinity to OM) concentrations alone should be used with caution for paleo-redox reconstructions.

Diagenetic formation of uranium-silica polymers in lake sediments over 3,300 years.

The long-term fate of uranium-contaminated sediments, especially downstream former mining areas, is a widespread environmental challenge. Essential for their management is the proper understanding of uranium (U) immobilization mechanisms in reducing environments. In particular, the long-term behavior of noncrystalline U(IV) species and their possible evolution to more stable phases in subsurface conditions is poorly documented, which limits our ability to predict U long-term geochemical reactivity. Here, we report direct evidence for the evolution of U speciation over 3,300 y in naturally highly U-enriched sediments (350-760 µg ⋅ g-1 U) from Lake Nègre (Mercantour Massif, Mediterranean Alps, France) by combining U isotopic data (δ238U and (234U/238U)) with U L3 -edge X-ray absorption fine structure spectroscopy. Constant isotopic ratios over the entire sediment core indicate stable U sources and accumulation modes, allowing for determination of the impact of aging on U speciation. We demonstrate that, after sediment deposition, mononuclear U(IV) species associated with organic matter transformed into authigenic polymeric U(IV)-silica species that might have partially converted to a nanocrystalline coffinite (UIVSiO4·nH2O)-like phase. This diagenetic transformation occurred in less than 700 y and is consistent with the high silica availability of sediments in which diatoms are abundant. It also yields consistency with laboratory studies that proposed the formation of colloidal polynuclear U(IV)-silica species, as precursors for coffinite formation. However, the incomplete transformation observed here only slightly reduces the potential lability of U, which could have important implications to evaluate the long-term management of U-contaminated sediments and, by extension, of U-bearing wastes in silica-rich subsurface environments.

A frugal implementation of Surface Enhanced Raman Scattering for sensing Zn2+ in freshwaters - In depth investigation of the analytical performances.

Surface Enhanced Raman Scattering (SERS) has been widely praised for its extreme sensitivity but has not so far been put to use in routine analytical applications, with the accessible scale of measurements a limiting factor. We report here on a frugal implementation of SERS dedicated to the quantitative detection of Zn2+ in water, Zn being an element that can serve as an indicator of contamination by heavy metals in aquatic bodies. The method consists in randomly aggregating simple silver colloids in the analyte solution in the presence of a complexometric indicator of Zn2+, recording the SERS spectrum with a portable Raman spectrometer and analysing the data using multivariate calibration models. The frugality of the sensing procedure enables us to acquire a dataset much larger than conventionally done in the field of SERS, which in turn allows for an in-depth statistical analysis of the analytical performances that matter to end-users. In pure water, the proposed sensor is sensitive and accurate in the 160-2230 nM range, with a trueness of 96% and a precision of 4%. Although its limit of detection is one order of magnitude higher than those of golden standard techniques for quantifying metals, its sensitivity range matches Zn levels that are relevant to the health of aquatic bodies. Moreover, its frugality positions it as an interesting alternative to monitor water quality. Critically, the combination of the simple procedure for sample preparation, abundant SERS material and affordable portable instrument paves the way for a realistic deployment to the water site, with each Zn reading three to five times cheaper than through conventional techniques. It could therefore complement current monitoring methods in a bid to solve the pressing needs for large scale water quality data.

Research questions to facilitate the future development of European long-term ecosystem research infrastructures: A horizon scanning exercise.

Distributed environmental research infrastructures are important to support assessments of the effects of global change on landscapes, ecosystems and society. These infrastructures need to provide continuity to address long-term change, yet be flexible enough to respond to rapid societal and technological developments that modify research priorities. We used a horizon scanning exercise to identify and prioritize emerging research questions for the future development of ecosystem and socio-ecological research infrastructures in Europe. Twenty research questions covered topics related to (i) ecosystem structures and processes, (ii) the impacts of anthropogenic drivers on ecosystems, (iii) ecosystem services and socio-ecological systems and (iv), methods and research infrastructures. Several key priorities for the development of research infrastructures emerged. Addressing complex environmental issues requires the adoption of a whole-system approach, achieved through integration of biotic, abiotic and socio-economic measurements. Interoperability among different research infrastructures needs to be improved by developing standard measurements, harmonizing methods, and establishing capacities and tools for data integration, processing, storage and analysis. Future research infrastructures should support a range of methodological approaches including observation, experiments and modelling. They should also have flexibility to respond to new requirements, for example by adjusting the spatio-temporal design of measurements. When new methods are introduced, compatibility with important long-term data series must be ensured. Finally, indicators, tools, and transdisciplinary approaches to identify, quantify and value ecosystem services across spatial scales and domains need to be advanced.

Earthquake-induced structural deformations enhance long-term solute fluxes from active volcanic systems.

Evidence for relationships between seismotectonic activity and dissolved weathering fluxes remains limited. Motivated by the occurrence of new springs emerging after the 2016 Kumamoto earthquake and supported by historical groundwater data, this study focuses on the long-term effect of near-surface structural deformation on the contribution of deep, highly saline fluids to the solute fluxes from the Aso caldera, Kyushu, Japan. Available hydrologic and structural data suggest that concentrated, over-pressured groundwaters migrate to the surface when new hydraulic pathways open during seismic deformation. These new springs have a hydrochemical fingerprint (including δDH2O, δ18OH2O, δ7Li, δ11B, δ18OSO4, and δ34SSO4) indistinguishable from long-established confined groundwater that likely reflects a mixture of infiltrated meteoric water with high-sulfate hydrothermal fluids. A comparison of historical hydrochemistry data and patterns of past seismicity suggests that discharge of deep fluids is associated with similar deformation structures to those observed during the Kumamoto earthquake, and that seismic activity plays an important role over historic timescales in delivering the majority of the solutes to the caldera outlet, sustaining fluxes that are amongst the world's highest. This upwelling mechanism might be relevant for other systems too, and could contribute to the over-proportional share of active volcanic areas in global weathering fluxes.

Are boron isotopes a reliable tracer of anthropogenic inputs to rivers over time?

This study aims at determining how the boron signal of the Seine River evolved in terms of concentration and isotopic signatures over eighteen years (1994-95 and 2006-12) and if boron isotopes can reliably trace anthropogenic inputs over time. In the anthropised Seine River watershed, boron is widely released by human activities, and even if boron concentrations ([B]) are below the potability limit, our study confirms the potential of boron isotopes (δ11B) to trace urban anthropogenic contaminations. Between 1994 and 2012, [B] have decreased across the anthropised part of the Seine River basin (and by a factor of two in Paris) while δ11B has increased. This means either that urban inputs have been reduced or that the boron signature of urban inputs has changed over time. Both hypotheses are in agreement with the decrease of perborate consumption in Europe over 15years and are not mutually exclusive. Results of a thorough analysis of urban effluents from the sewage network of Paris conurbation that are in fine released to the Seine River suggest a shift of the urban δ11B from -10‰ in 1994 to 1.5±2.0‰ in 2012, in agreement with our second hypothesis. We attribute this change to the removal of perborates from detergents rather than to the modernisation of wastewater treatment network, because it does not significantly impact the wastewater boron signatures. Eighteen years after the first assessment and despite the decreased use of perborates, geochemical and isotopic mass budgets confirm, that boron in the Seine River basin is mainly released from urban activities (60-100%), especially in Paris and the downstream part of the basin. Contrastingly, in headwaters and/or tributaries with low urbanisation, the relative boron input to river from agricultural practices and rains increased, up to 10% and by 10 to 30%, respectively.

Transient signal isotope analysis: validation of the method for isotope signal synchronization with the determination of amplifier first-order time constants.

RATIONALE: During transient signal acquisition by Multi-Collection Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS), an isotope ratio increase or decrease (isotopic drift hereafter) is often observed which is related to the different time responses of the amplifiers involved in multi-collection. This isotopic drift affects the quality of the isotopic data and, in a recent study, a method of internal amplifier signal synchronization for isotope drift correction was proposed. In this work the determination of the amplifier time constants was investigated in order to validate the method of internal amplifier signal synchronization for isotope ratio drift correction. METHODS: Two different MC-ICPMS instruments, the Neptune and the Neptune Plus, were used, and both the lead transient signals and the signal decay curves of the amplifiers were investigated. RESULTS: Our results show that the first part of the amplifier signal decay curve is characterized by a pure exponential decay. This part of the signal decay was used for the effective calculation of the amplifier first-order time constants. The small differences between these time constants were compared with time lag values obtained from the method of isotope signal synchronization and were found to be in good agreement. CONCLUSIONS: This work proposes a way of determining amplifier first-order time constants. We show that isotopic drift is directly related to the amplifier first-order time constants and the method of internal amplifier signal synchronization for isotope ratio drift correction is validated.

Erosion of organic carbon in the Arctic as a geological carbon dioxide sink.

Soils of the northern high latitudes store carbon over millennial timescales (thousands of years) and contain approximately double the carbon stock of the atmosphere. Warming and associated permafrost thaw can expose soil organic carbon and result in mineralization and carbon dioxide (CO2) release. However, some of this soil organic carbon may be eroded and transferred to rivers. If it escapes degradation during river transport and is buried in marine sediments, then it can contribute to a longer-term (more than ten thousand years), geological CO2 sink. Despite this recognition, the erosional flux and fate of particulate organic carbon (POC) in large rivers at high latitudes remains poorly constrained. Here, we quantify the source of POC in the Mackenzie River, the main sediment supplier to the Arctic Ocean, and assess its flux and fate. We combine measurements of radiocarbon, stable carbon isotopes and element ratios to correct for rock-derived POC. Our samples reveal that the eroded biospheric POC has resided in the basin for millennia, with a mean radiocarbon age of 5,800 ± 800 years, much older than the POC in large tropical rivers. From the measured biospheric POC content and variability in annual sediment yield, we calculate a biospheric POC flux of 2.2(+1.3)(-0.9) teragrams of carbon per year from the Mackenzie River, which is three times the CO2 drawdown by silicate weathering in this basin. Offshore, we find evidence for efficient terrestrial organic carbon burial over the Holocene period, suggesting that erosion of organic carbon-rich, high-latitude soils may result in an important geological CO2 sink.

Chemical composition of suspended sediments in World Rivers: New insights from a new database.

The aim of this paper is to present a new database on the chemical composition of suspended matter in World Rivers, together with the associated elemental fluxes. There is a lack of any recent attempt in the literature to update the pioneering work of Martin and Meybeck [Martin, J.-M., Meybeck, M., 1979. Elemental mass balance of material carried by major world rivers. Mar. Chem. 7, 173-206.] and Martin and Whitfield [Martin, J.-M., Whitfield, M., 1983. The significance of the river input of chemical elements to the ocean. Trace metals in sea water Wong, Boyle, Bruland, Burton, Goldberg (Eds) Plenum Publishing Corporation.] regarding the worldwide average major and trace element chemistry of riverine particulate matter. Apart from compiling a new database on particulate matter, this paper also aims to give a "snap-shot" of elemental fluxes for each continent. This approach should allow us to obtain new insights on weathering conditions in different environments and assess the influence of human activities on natural geochemical cycles. Finally, this study demonstrates the large uncertainties currently associated with estimating the flux of sediments transported by rivers. By comparing the riverine suspended sediment fluxes of some metals (Cd, Zn, Ni, Cu, Cr and Pb) given in this study with estimates of the anthropogenic fluxes of these metals to the atmosphere, soils and waters (natural ecosystems) [Nriagu, J.O., 1988. A silent epidemic of environmental poisoning. Environ. Pollut. 50, 139-161.], we can see that riverine fluxes are similar to anthropogenic fluxes. This casts light on the effect of human activities on the cycles of trace elements at the Earth's surface.

Zinc isotopes in the Seine River waters, France: a probe of anthropogenic contamination.

The use of zinc (Zn) isotope ratios as a tracer of anthropogenic contamination has been assessed using an extensive collection of river water samples from the Seine River basin (France) collected between 2004 and 2007. The 66Zn/64Zn ratios (expressed as delta66Zn) of dissolved Zn have been measured by MC-ICP-MS after chemical separation of Zn using an improved technique adapted to large volumes of water. Significant isotopic variations (0.07-0.58 per thousand) occur along a transect from pristine areas of the Seine basin to the estuary and with time in Paris, and are coherent with the Zn enrichment factor. Dissolved Zn in the Seine River displays conservative behavior, making Zn isotopes a good tracer of the different sources of contamination. Dissolved Zn in the Seine River is essentially of anthropogenic origin (> 90%) compared to natural sources (< 7%). Roof leaching from Paris conurbation is a major source of Zn, characterized by low delta66Zn values that are distinct from other natural and anthropogenic sources of Zn. Our study highlights the absence of distinctive delta66Zn signatures of fertilizer, compost or rain in river waters of rural areas, and therefore suggests the strong retention of Zn in the soils of the Basin. Our study demonstrates that Zn isotope ratios will be a powerful new tool to trace pathways of anthropogenic Zn in the environment.

Boron isotopes in the Seine River, France: a probe of anthropogenic contamination.

Boron concentrations and isotopic compositions have been measured in the dissolved load of the Seine Basin rivers, France. Hydrology and chemistry of the Seine River and its tributaries are strongly influenced by human activities, as the anthropogenic pressure on the Seine catchment is one of the highest in Europe. The samples were collected between 1994 and 1996 during various stages of flow, complemented by a time-series of the Seine River in Paris for 1 yr. In particular, the decennial flood event of winter 1994 was sampled. Boron appears to be conservative in rivers and not influenced by adsorption onto suspended matter and/or consumption by microorganisms. Despite the complexity of the Seine River system, dissolved boron and its isotopes are found to be suitable tracers of contamination. The total dissolved boron of the Seine River at Paris is explained by the contribution from three distinct components: Urban effluents constitute 65% of the boron discharge measured in the Seine River whereas agriculture-affected waters contribute less than 10% with a more marked influence during high water discharges. Rainwater contribution is important (25% mean), reaching 30% of dissolved boron during high flood events.