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Antecedent hydrological conditions are recorded through the evolution of dissolved lithium isotope signatures (δ7 ${\delta }^{7}$Li) by juxtaposing two storm events in an upland watershed subject to a Mediterranean climate. Discharge and δ7 ${\delta }^{7}$Li are negatively correlated in both events, but mean δ7 ${\delta }^{7}$Li ratios and associated ranges of variation are distinct between them. We apply a previously developed reactive transport model (RTM) for the site to these event‐scale flow perturbations, but observed shifts in stream δ7 ${\delta }^{7}$Li are not reproduced. To reconcile the stability of the subsurface solute weathering profile with our observations of dynamic stream δ7 ${\delta }^{7}$Li signatures, we couple the RTM to a distribution of fluid transit times that evolve based on storm hydrographs. The approach guides appropriate flux‐weighting of fluid from the RTM over a range of flow path lengths, or equivalently fluid residence times. This flux‐weighted RTM approach accurately reproduces dynamic storm δ7 ${\delta }^{7}$Li‐discharge patterns distinguished by the antecedent conditions of the watershed. Plain Language Summary: Storm events often cause characteristic shifts in stream solute chemistry. Interpreting these signals offers insight into the water‐rock interactions occurring within watersheds. Here, we use lithium stable isotopes and reactive transport modeling to relate how long water spends in a catchment, or how deep water infiltrates through a catchment, to the extent of chemical weathering. We show that the first significant storm after a dry season exports more chemically evolved water, while a wet season storm releases less evolved, shallower, and younger water. Our results indicate that stream flow δ7 ${\delta }^{7}$Li in small watersheds offers a sensitive record of hydrological conditions prior to the storm, reflecting subtle shifts in the efficiency of the Critical Zone to generate, transport, and ultimately export solutes. Key Points: Stream lithium stable isotope ratios (δ7Li) recorded at high frequency over storm events are sensitive to antecedent conditionsA reactive transport model cannot produce observed shifts in stream chemistry through variations in flow rate aloneFlux‐weighting of model fluid outputs based on time‐varying fluid transit time distributions describes stream δ7Li over storm hydrographs [ABSTRACT FROM AUTHOR]

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. Using a lake sediment core taken from the European Alps and combining a source-sink approach with isotope geochemistry, it has been established that the effects of human activities have outweighed those of climate on erosion for more than 3800 years. [ABSTRACT FROM AUTHOR]

Gallium exhibits weak metallic properties owing to its proximity to non‐metals in the periodic table, yet is volatile in extra‐terrestrial bodies and fairly reactive in nature. It has been used extensively to elucidate the Solar System evolution, planet interior differentiation, and terrestrial processes. However, Ga speciation and transformation in various planetary compartments and the dynamics of its trans‐reservoir pathways remain to be fully resolved. Although recent studies and the development of modern analytical techniques for Ga isotopes have markedly improved our understanding of Ga geochemistry, a systematical summary of state‐of‐the‐art knowledge appears to be long overdue. Here we provide an overview of the geochemical properties of Ga in different reservoirs, including meteorites and Earth's interior and exterior compartments, and a timely review of Ga isotopic geochemistry. We also provide a first tentative estimate of total masses of Ga in different compartments and the trans‐reservoir Ga flux, based on the published data. This compilation reveals clearly the lack of geochemistry data of Ga in Earth's interior, the imbalance of oceanic Ga budget and the potential implications of Ga isotopes, stimulating future systematic studies of Ga and its isotopes in geosciences and related fields. [ABSTRACT FROM AUTHOR]

When rock is converted to weathering products, the involved processes can be fingerprinted using the stable isotope ratios of metals (for example Li, Mg, Ca, Fe, Sr) and metalloids (B, Si). Here we construct a framework for interpreting these "novel" stable isotope ratios quantitatively in the compartments of the weathering zone in a geomorphic context. The approach is applicable to any novel stable isotope system and is based on a simple steady-state mass balance model that represents the weathering zone from the scale of a soil column to that of entire continents. Our model is based on the assumption that the two main processes associated with isotope fractionation are formation of secondary precipitates such as clays, and uptake of nutrients by plants. The model results show that the isotope composition of a given element in the weathering zone compartments depends on (1) the ratio between the release flux to water through primary mineral dissolution and the erosion flux of isotopically fractionated solid material, consisting of secondary precipitates and organic matter; (2) the isotope fractionation factors associated with secondary mineral precipitation and uptake by plants. A relationship is established between isotope ratios, isotope fractionation factors, and indexes for chemical weathering [such as chemical depletion fractions (CDF) and elemental mass transfer coefficients (7)] derived from simple elemental concentration measurements. From this relationship, isotope fractionation factors can be calibrated from chemical and isotope data measured on field material. Furthermore, we show how the ratio of solid export to dissolved export of a given element from the weathering system can be estimated from the comparison of the isotope composition between bedrock, water, and sediment. This calculation can be applied to samples from soils, from rivers, and from the sedimentary record, and does not require knowing the isotope fractionation factors involved in the reactions. Finally, we apply the model to the oceanic Li isotope record reconstructed from marine carbonate sediments in order to discuss changes in global geomorphic regimes through the Cenozoic. [ABSTRACT FROM AUTHOR]

Abstract: The vertical variability in mineralogical, chemical and isotopic compositions observed in large river suspended sediments calls for a depth-integration of this variability to accurately determine riverine geochemical fluxes. In this paper, we present a method to determine depth-integrated chemical particulate fluxes of large rivers, based on river sampling along depth-profiles, and applied to the Amazon Basin lowland tributaries. The suspended particulate matter (SPM) concentration data from depth-profiles is modeled for a number of individual grain size fractions using the Rouse model, which allows to predict the grain size distribution of suspended sediment throughout the whole river cross-section. Then, using (1) the relationship between grain size distribution and the Al/Si ratio (2) relationships between the Al/Si ratio and the chemical concentrations, the chemical composition of river sediment is predicted throughout the river cross-section, and integrated to yield the depth-integrated chemical particulate flux for a number of chemical elements (e.g. Si, Al, Fe, Na, REEs,…). For elements such as Al, Fe, REEs, Th, the depth-integrated flux is around twice as high as the one calculated from river surface sample characteristics. For Na and Si, the depth-integrated flux is three times higher than the “surface” estimate, due to the enrichment of albite and quartz at the bottom of the river. Depth-integrated 87Sr/86Sr composition of suspended sediment, also predictable using this method, differs by more than 10−3 from the surface sample composition. Finally, potential implications of depth-integrated estimates of Amazon sediment chemistry are explored. Depth-integration of particulate 87Sr/86Sr isotopic ratios is necessary for a reliable use of Sr isotopes as a provenance tracer. The concept of steady-state weathering of a large river basin is revisited using depth-integrated sediment composition. This analysis shows that, in the Amazon Basin river, the previously observed discrepancy between (1) weathering intensities of channel surface sediment and (2) silicate-derived dissolved fluxes is only slightly accounted for by the vertical variability of suspended sediment weathering intensities. This observation confirms that most large rivers basins are not eroding at steady-state. [Copyright &y& Elsevier]

• Lake sediments record variation caused by climate change and human activities. • Humans significantly modified the pre-Alpine CZ in the Middle Ages. • Anthropogenic factors disrupt both soil development and sediment transport. • Soil formation and differentiation during transport shape lake sediment geochemistry. • It is important to distinguish clay-sized particles and clay minerals. Comprehending and predicting the way humans affect the Earth's Critical Zone remains a challenge. An understanding of the past changes resulting from human and non-human influences in the dynamics of the Critical Zone is crucial. Here, we use a retrospective approach to address this question based on a new lithium (Li) isotope record from the Late Glacial Period to the present from a pre-Alpine lake sediment sequence (Lake La Thuile, France). Coupled with the lake sediment archive, the investigation of present-day soils in the lake catchment suggests that lake sediments are not necessarily recording the erosoin of topsoil in the catchment. Our findings indicate that soil particles can be sorted during transportation to the lake, with finer particles being preferentially mobilized, highlighting the influence of fine particle transport on the Li isotope signature of soils and lake sediments. Characterized by low Li isotope signatures, changes in weathering signatures in lake sediments can be amplified by the combined effect of soil development and selective transport. In the La Thuile catchment, soil development was limited during the Late Glacial Period, whereas it became a dominant process during the Holocene climatic optimum together with enhanced selective transport of fine particles. Human activities since 3,000–4,000 yr cal BP induced a strong perturbation hindering both soil formation and selective transport by reinforcing erosion rates. After a period of topsoil destruction caused by intense deforestation and agriculture, lake Li isotopes record the evolution of soil profiles associated with changes in agricultural practices. [ABSTRACT FROM AUTHOR]