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The Huanghe (Yellow River), one of the largest turbid river systems in the world, has long been recognized as a major contributor of suspended particulate matter (SPM) to the ocean. However, over the last few decades, the SPM export flux of the Huanghe has decreased over 90 % due to the high management, impacting the global export of particulate organic carbon (POC). To better constrain sources and modes of transport of POC beyond the previously investigated transportation of POC near the channel surface, SPM samples were for the first time collected over a whole channel cross-section in the lower Huanghe. Riverine SPM samples were analyzed for particle size and major element contents, as well as for POC content and dual carbon isotopes (13C and 14C). The results show clear vertical and lateral heterogeneity of SPM physical and chemical characteristics within the river cross-section, with for example finer SPM carrying more POC with higher 14C activity near the surface of the right bank. Notably, we discuss how bank erosion in the alluvial plain is likely to generate lateral heterogeneity in POC composition. The Huanghe POC is millennial-aged (4,020 ± 500 radiocarbon years), dominated by organic carbon (OC) from the biosphere, while the lithospheric fraction reaches up to ca. 33 %. The mobilization of aged and refractory OC, including radiocarbon-dead biospheric OC, from deeper soil horizons of the loess-paleosol sequence through erosion in the Chinese Loess Plateau is an important mechanism contributing to fluvial POC in the Huanghe drainage basin. Altogether, anthropogenic activities can drastically change the compositions and transport dynamics of fluvial POC, consequentially altering the feedback of the source-to-sink trajectory of a river system to regional and global carbon cycles.

The role of biological cycling on the chemistry of rivers remains poorly understood. in an attempt to close this knowledge gap, here we examine the difference between the elemental supply to catchments through rock degradation and the corresponding elemental riverine export, for two non-nutrient elements lithium (Li) and sodium (Na) and two nutrients-like elements potassium (K) and barium (Ba), in 20 of the largest world river catchments. Overall, the riverine export of K and Ba are lower than their estimated release by catchment scale rock degradation, while the two fluxes match for Li and Na. Barium isotope constraints lending support to this observation, we take this difference between these two element groups as a suggestion of the influence of biological uptake of rock-derived nutrients on river chemistry. Nevertheless, the magnitude of riverine K depletion cannot be reconciled with a pervasive growth of the biota on continents, nor with an "occult" export of organic material that would go unnoticed by common sampling protocols. One plausible explanation for this conundrum could lie in the complex partitioning of elements amongst soil, biota, and dead organic matter. As a consequence, our study emphasises the need for further work aiming at deciphering the cycle of rock-derived nutrients in the Critical Zone. ISSN:2410-339X ISSN:2410-3403

International audience; Stable Ti isotopes have been applied in the detrital sediment record to reconstruct the bulk composition of Earth's continental crust due to the relationship between magmatic differentiation and Ti isotopic compositions. However, no study has systematically evaluated the influence of provenance, physical, and chemical weathering on the composition of sediments relative to the protolith they originated from. To test the influence of these processes on Ti isotopic compositions we investigate the Ti isotope composition of 82 surface samples including loess, volcaniclastic rocks, river sediment, and two separate weathering profiles through igneous rocks, collected from a broad geographical area and a range of environmental conditions. Limited but significant Ti isotope fractionation exists in samples subjected to extreme chemical weathering processes, potentially as a result of elemental mobilization. For example, the δ49Ti isotopic composition of bauxites developed on Columbia River basalt varies by up to 0.1‰, becoming isotopically heavier with increasing weathering intensity. However, negligible variation in δ49Ti was found in a second profile of saprolites developed on weathered diabase. Titanium isotope variations in loess do not correlate with chemical weathering intensity or size sorting, but may instead be related to the provenance of the sediment. We find that the δ49Ti of Amazon River sediments is correlated with the Al/Zr ratio, indicating that δ49Ti is impacted by sediment sorting. At our study sites, the river averaged offset between the isotopic composition of the bedload and the suspended sediment fraction is 0.051‰, with the largest offset being + 0.116‰. Our data suggest that during chemical weathering, heavy Ti isotopes are preferentially incorporated into secondary minerals producing higher δ49Ti in intensely weathered soils. During fluvial transport, the Ti isotopic composition of fine-grained sediment is heavier than that of its coarser counterpart. Crustal protolith composition and sorting during transport and sedimentation have a stronger effect on the Ti isotopic composition than chemical weathering. Our results have implications for studies that utilize the Ti elemental concentration to calculate relative enrichment or depletion during chemical weathering and physical transport processes in the Critical Zone and for studies using Ti isotopes in terrigenous sediments to infer the composition of their provenance.

Poster presentation

Poster presentation

Barium and its isotopes are receiving growing interest in their capacity to record the variation of the oceanic biological pump through geological timescales. Nonetheless, only little is known about the continental sources and processes that can drive the Ba flux and isotope composition to the ocean. Whereas the role of processes such as secondary phase formation, sorption and biological uptake on Ba isotopes has been recently investigated, the potential of various rock sources in producing a range of Ba isotope compositions remains poorly known. In particular, black shales often exhibit enrichment in Ba that might potentially be associated with various Ba isotope signatures. In this study, we report the isotope composition of Ba in rivers with different relative contribution of black shale rocks in their catchments, located in the Mackenzie Basin (Northwest Canada). Both the dissolved and solid loads of the Mackenzie tributaries are enriched in heavy Ba isotopes with respect to the continental crust, which is consistent with an additional source to the weathering of igneous and siliciclastic rocks. Although the dissolved Ba abundance is partially driven by weathering processes, the river dissolved Ba isotope composition rather reflects a binary mixing between 1) a “classical” siliciclastic source (with a Ba isotope composition close to that of the upper continental crust δ138Ba ∼ 0.15 ± 0.05‰) and 2) an isotopically heavier source especially present in the Mackenzie Mountains (with a δ138Ba ∼ 0.40‰). The positive relationships between dissolved δ138Ba and radiogenic osmium isotope ratios, as well as with sulphuric acid production, indicate that the heavy Ba source is tightly linked to the weathering of black shale. Although the exact reason for such heavy Ba isotope signatures remains elusive, this study emphasises the potential of black shale weathering in shifting the Ba isotope composition of the dissolved flux to the ocean towards heavier values., Chemical Geology, 594, ISSN:0009-2541, ISSN:1872-6836

This study makes use of a highly instrumented active landslide observatory (9 years of data) in the French Alps, the Séchilienne slope. Using a combination of major element chemistry and isotopes ratios (87Sr / 86Sr, δ34S) measured in different water types of the stable and unstable part of the Séchilienne instability to assess the contribution of the different lithologies of the slope and the chemical weathering mechanisms. Chemical and isotopic ratios appear useful to characterize weathering processes and the origin of waters and their flowpaths through the massif. A mixing model allows us to allocate the different major elements to different sources and quantify the involvement sulfuric and carbonic acids as a source of protons. As a consequence of the model, we are able to show that the instability creates favorable and sustained conditions for the production of sulfuric acid by pyrite oxidation by supplying reactive surfaces. We clearly identify the contribution of gypsum dissolution to the sulfate budget in the landslide. We are also able to refine the pre-existing hydrogeological views on the local water circulation and water flow paths in the instability but showing the hydrological connectivity of the different zones. Overall, our results show that the Séchilienne landslide, despite its role in accelerating rock chemical and physical weathering, acts, at a geological time scale (i.e. at timescales longer that carbonate precipitation in the ocean) as a source of CO2 to the atmosphere. If generalizable to other instable zones in mountain ranges, this study illustrates the complex coupling between physical and chemical erosion and climate. The study also highlights the importance of deciphering between sulfite oxidation and gypsum dissolution as a source of sulfate ions to rivers, particularly in mountain ranges.

The Cambrian explosion, the rapid appearance of most animal phyla in the geological record, occurred concurrently with bottom seawater oxygenation. Whether this oxygenation event was triggered through enhanced nutrient supply and organic carbon burial forced by increased continental weathering, or by species engaging in ecosystem engineering, remains a fundamental yet unresolved question. Here we provide evidence for several simultaneous developments that took place over the Ediacaran–Cambrian transition: expansion of siliceous sponges, decrease of the dissolved organic carbon pool, enhanced organic carbon burial, increased phosphorus removal and seawater oxygenation. This evidence is based on silicon and carbon stable isotopes, Ge/Si ratios, REE-geochemistry and redox-sensitive elements in a chert-shale succession from the Yangtze Platform, China. According to this reconstruction, sponges have initiated seawater oxygenation by redistributing organic carbon oxidation through filtering suspended organic matter from seawater. The resulting increase in dissolved oxygen levels potentially triggered the diversification of eumetazoans., The Ediacaran–Cambrian oxygenation of seawater is thought to have been caused by lifeforms engaging in ecosystem engineering. Here, the authors show that siliceous sponges increased seawater dissolved oxygen concentrations by redistributing organic carbon oxidation through filtering suspended organic matter.

Large hydrological systems aggregate compositionally different waters derived from a variety of pathways. In the case of continental‐scale rivers, such aggregation occurs noticeably at confluences between tributaries. Here we explore how such aggregation can affect solute concentration‐discharge (C‐Q) relationships and thus obscure the message carried by these relationships in terms of weathering properties of the Critical Zone. We build up a simple model for tributary mixing to predict the behavior of C‐Q relationships during aggregation. We test a set of predictions made in the context of the largest world's river, the Amazon. In particular, we predict that the C‐Q relationships of the rivers draining heterogeneous catchments should be the most “dilutional” and should display the widest hysteresis loops. To check these predictions, we compute 10 day‐periodicity time series of Q and major solute (Si, Ca²⁺, Mg²⁺, K⁺, Na⁺, Cl‐, urn:x-wiley:00431397:media:wrcr22891:wrcr22891-math-0001) C and fluxes (F) for 13 gauging stations located throughout the Amazon basin. In agreement with the model predictions, C‐Q relationships of most solutes shift from a fairly “chemostatic” behavior (nearly constant C) at the Andean mountain front and in pure lowland areas, to more “dilutional” patterns (negative C‐Q relationship) toward the system mouth. More prominent C‐Q hysteresis loops are also observed at the most downstream stations. Altogether, this study suggests that mixing of water and solutes between different flowpaths exerts a strong control on C‐Q relationships of large‐scale hydrological systems. Por pares

Our understanding of hydrological and chemical processes at the catchment scale is limited by our capacity to record the full breadth of the information carried by river chemistry, both in terms of sampling frequency and precision. Here, we present a proof-of-concept study of a lab in the field called the River Lab (RL), based on the idea of permanently installing a suite of laboratory instruments in the field next to a river. Housed in a small shed, this set of instruments performs analyses at a frequency of one every 40 min for major dissolved species (Na+, K+, Mg2+, Ca2+, Cl−, SO42−, NO3−) through continuous sampling and filtration of the river water using automated ion chromatographs. The RL was deployed in the Orgeval Critical Zone Observatory, France for over a year of continuous analyses. Results show that the RL is able to capture long-term fine chemical variations with no drift and a precision significantly better than conventionally achieved in the laboratory (up to ±0.5 % for all major species for over a day and up to 1.7 % over 2 months). The RL is able to capture the abrupt changes in dissolved species concentrations during a typical 6-day rain event, as well as daily oscillations during a hydrological low-flow period of summer drought. Using the measured signals as a benchmark, we numerically assess the effects of a lower sampling frequency (typical of conventional field sampling campaigns) and of a lower precision (typically reached in the laboratory) on the hydrochemical signal. The high-resolution, high-precision measurements made possible by the RL open new perspectives for understanding critical zone hydro-bio-geochemical cycles. Finally, the RL also offers a solution for management agencies to monitor water quality in quasi-real time.

International audience; The isotopic composition of dissolved lithium (δ 7 Li) near the Congo River mouth varied from 14‰ to 22‰ in 2010 and was negatively correlated to discharge. From the relationship between dissolved δ 7 Li and strontium isotopes, we suggest that this large variation is due to mixing of waters from two contrasting continental weathering regimes. One end-member (high δ 7 Li ≈ 25‰) represents waters sourced from active lateritic soils covering the periphery of the basin (Li highly sequestered into secondary mineral products) and another representing blackwater rivers (low δ 7 Li ≈ 5.7‰) derived from the swampy central depression where high organic matter content in water leads to congruent dissolution of the Tertiary sedimentary bedrock. This suggests that the lithium isotopic signature of tropical low-relief surfaces is not unique and traces the long-term, large-scale vertical motions of the continental crust that control geomorphological settings. This evolution should be recorded in the oceanic secular δ 7 Li curve.

International audience; We explore the geochemistry and the isotopic composition of lithium (δ 7 Li) of rivers draining volcanic islands (Guadeloupe, Iceland, Java, Martinique and Sao Miguel) with a specific focus on continental hydrothermal activity. Our preliminary results reveal a global-scale trend between δ 7 Li and the elemental ratio Li/Na in rivers draining volcanic islands. We suggest that this trend results from a mixture between waters with low δ 7 Li and high Li/Na, inherited from high-temperature water rock interactions, and waters with low Li/Na and high δ 7 Li, in which Li is controlled by the neoformation of clays during low-temperature chemical weathering in basaltic soils. This latter process can be described by a simple isotope fractionation model, consistent with reported values for isotopic fractionation factors between secondary weathering products and water. These data highlight the important potential role of continental high-temperature weathering processes on the oceanic budget of lithium.

The general scope of the PhD research project falls within the framework of developing integrated catchment hydro-biogeochemical theories in the context of the Critical Zone (CZ). Significant advances in the understanding of water transit time theory, subsurface structure controls, and the quantification of catchment scale weathering rates have resulted in the convergence of classical biogeochemical and hydrological theories. This will potentially pave the way for a more mechanistic understanding of CZ because many challenges still exist. Perhaps the most difficult of all is a unifying hydro-biogeochemical theory that can compare catchments across gradients of climate, geology, and vegetation. Understanding the processes driving the evolution of chemical tracers as they move through space and time is of cardinal importance to validating mixing hypotheses and assisting in determining the residence time of water in CZ. The specific aim of the study is to investigate what physical and biogeochemical processes are driving variations in observable endmembers in stream discharge as a function of the hydrological state at headwater catchment scale. This requires looking beyond what can be observed in the stream and what is called ”unseen flowlines” in this thesis. The Weierbach Experimental Catchment (WEC) in Luxembourg provides a unique opportunity to study these processes, with an extensive biweekly groundwater chemistry dataset spanning over ten years. Additionally, WEC has been the subject of numerous published works in the domain of CZ science, adding to an already detailed hydrological and geochemical understanding of the system. Multivariate analysis techniques were used to identify the unseen flowlines in the catchment. Together with the excising hydrological perception model and a geochemical modelling approach, these flowlines were rigorously investigated to understand what processes drive their respective manifestations in the system. The existing perceptual model for WEC was updated by the new findings and tested on 27 flood events to assess if it could adequately explain the c − Q behaviour observed during these periods. The novelty of the study lies in the fact that it uses both data-driven modelling approaches and geochemical processbased modelling to look beyond what can be observed in the near-stream environment of headwaters.