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Human-induced environmental disturbances during the Holocene have provided support for the Early Anthropogenic Hypothesis (EAH), which proposes that with the advent of agro-pastoralism and associated deforestation, humans have modified CO2 and CH4 concentrations into the atmosphere. However, only limited evidence exists for human driven chemical alteration of the Earth’s Critical Zone (ECZ) in early antiquity. Here, we explore the impact of human activities on both erosion and chemical weathering patterns in the Nile basin during a time interval that includes the rise of the Aksumite Kingdom and Late Antique Egypt (${\sim }$3–${\sim }$1 ka BP). By coupling lithium and neodymium isotopes ($\delta ^7\mathrm{Li}$, $\varepsilon \mathrm{Nd}$) in clay-size fractions of two marine sediment cores from the Nile Deep Sea Fan (NDSF), we reconstruct the variability of sediment provenance and silicate weathering intensity in the Nile basin over the last 9000 years. Our high temporal resolution data show that for the last ${\sim }$3000 years, the Rosetta Nile Deep Sea Fan has been increasingly fed with clays delivered from the Ethiopian basaltic highlands ($\varepsilon \mathrm{Nd}= {\sim }{-}1$), despite the absence of hydrological intensification and major climatic drivers over that region. Concomitantly, the clay Li isotopic composition shifted towards lower ${\delta }^{7}\mathrm{Li}$ values (${\delta }^{7}\mathrm{Li} = 1$ to ${-}$2), yielding unprecedented negative values for at least the last 100,000 years. Combined with other archaeological, paleo-pedological and organic chemistry inferences, the Li–Nd isotope proxy records indicate a link between the intensification of continental weathering and intensified land-use and water management during the Pre-Aksumite (${\sim }$3 to ${\sim }$2 ka BP) and Aksumite (${\sim }$2 to ${\sim }$1 ka BP) periods. Therefore, our results provide direct support to the hypothesis of an early and large scale anthropogenic forcing on continental chemical weathering. A comparison with previously published records for Central Africa, Central Europe and China suggests that the impact of the intensification of early agriculture on the ECZ may have operated at a global scale starting around four thousand years ago.

Despite the crucial role of the Southern Hemisphere (SH) westerlies in modulating modern and past climate evolution, little is known about their behavior and possible forcing mechanisms during the early Cenozoic. We probe changes in the hydroclimate of southwest Australia during 62–51 Ma, based on sedimentary proxy records from the International Ocean Discovery Program Site U1514 in the Mentelle Basin. Our results reveal a transition from a less humid climate to wetter conditions at mid–high latitudes starting from the early Eocene, which suggests poleward migration of the SH westerlies. This long‐term trend is punctuated by short‐lived events of aridification during the Mid‐Paleocene Biotic Event and wetter intervals during the Paleocene‐Eocene Thermal Maximum, indicating additional short‐term meridional shifting of the westerlies. We propose that the evolution of SH westerlies was driven by the equator‐to‐pole temperature gradient regulated by global warming and ephemeral growth of the Antarctic ice sheet. Plain Language Summary: The Southern Hemisphere (SH) westerlies, which are the dominant atmospheric circulation patterns in the middle latitudes, play a key role in regulating global and regional climate. Currently, the knowledge of past changes in SH westerlies relies mainly on the late Quaternary. Its dynamics over longer timescales, especially under early Cenozoic greenhouse climate states, remain poorly understood. The Mentelle Basin off southwest Australia was located at a more southerly location than at the present day, and was potentially under the influence of SH westerlies. To examine the long‐term hydroclimate changes in southwest Australia during the mid‐late Paleocene to the early Eocene (62–51 Ma), we measured neodymium and hafnium isotopic compositions of fine‐grained detrital sediments from a borehole (IODP Site U1514) drilled in the Mentelle Basin, in addition to clay mineralogy, and elemental abundances. Our results suggest a gradual wetting of southwest Australia since the early Eocene, which we relate to the poleward migration of SH westerlies in response to a reduced latitudinal temperature gradient. An abrupt northward shift of SH westerlies was observed during the short‐lived Middle Paleocene Biotic Event (∼59 Ma), possibly driven by ephemeral growth of the Antarctica ice sheet. Key Points: We reconstruct the hydroclimate evolution of southwest Australia during 62–51 MaThe Southern Hemisphere (SH) westerlies remained relatively stable during the mid‐late Paleocene and shifted poleward since the early EoceneProcesses related to variations of pole‐equator temperature gradients drove meridional migration of the SH westerlies [ABSTRACT FROM AUTHOR]

Lake Van, the world's largest alkaline lake, hosts some of the largest microbialite towers worldwide, which are considered as modern analogues of ancient stromatolites. This study investigates the links between microbialite evolution, geology, climate and hydrology, and the role of biotic and abiotic processes in microbialite growth and morphology. For these objectives, the northern shelf of Lake Van was surveyed by sub‐bottom seismic profiling and diving, and two 9 m and 15 m high microbialite chimneys were sampled at 25 m water depth. Samples were analysed for stable oxygen and carbon isotopes, X‐ray diffractometry, scanning electron microscopy and U/Th age dating. Lake Van microbialites precipitate wherever focused Ca‐rich groundwater flows onto the lake floor to mix with alkaline lake water. Variable columnar, conical and branching morphologies of the microbialites indicate various processes of formation by groundwater channelling within the chimneys. Collectively, our data suggest that the microbialite chimneys have formed within the last millennium, most likely starting during the warm and humid Medieval Climate Anomaly (caad 800–1300), when lake level rose approximately to the present level due to enhanced Inputs of riverine Ca‐rich freshwater and groundwater. Our new scanning electron microscopy observations indicate that the internal structure of the microbialites below the outer cyanobacteria‐covered crust is constructed by calcified filaments, globular aggregates and nanocrystals of algal, cyanobacterial and heterobacterial origins and inorganically precipitated prismatic calcite crystals. These textural features, together with dive observations, clearly demonstrate the important role of inorganic carbonate precipitation at sites of groundwater discharge, followed by cyanobacteria and algal mucilage deposition and microbially meditated calcification in the photic zone in the rapid growth of the microbialite chimneys. Considering the close similarities of some textures with those of ancient stromatolites and meteorites, the results of this study provide new insights into the environmental conditions associated with stromatolite formation and extra‐terrestrial life evolution. [ABSTRACT FROM AUTHOR]

Understanding the interaction between molybdenum (Mo) and organic matter during microbial sulfate reduction is critical for the use of Mo to reconstruct marine redox conditions throughout Earth's history. However, little is known about Mo isotope fractionation and how it relates to organic matter remineralization during microbial sulfate reduction. Here, we report Mo abundances and isotopic (δ98Mo) compositions for bulk‐rock, non‐lithogenic and sequentially extracted fractions, including carbonate (carb), pyrite, and organic matter (OM), of seep carbonate rocks. Our data indicate that the difference between δ98Mocarb and δ98MoOM (Δ98Mocarb‐OM) displays significant variability in the studied samples, ranging between 0.72 and 1.01‰. Remarkably, the obtained Δ98Mocarb‐OM values indicate correlative trends with stable carbon isotope ratios and bulk abundances of (a) total organic carbon, (b) Mo, and (c) pyrite in seep carbonates, which we interpret as reflecting sustained adsorption of isotopically light Mo onto organic matter during enhanced sulfate reduction. On this basis, we put forward the concept that Δ98Mocarb‐OM of authigenic carbonate rocks can be used as a measure of the intensity of sulfate reduction and for reconstructing past interactions between Mo and organic matter in marine sediments. Plain Language Summary: Molybdenum (Mo) is a useful element for reconstructing marine redox conditions throughout the Earth's history. The sequestration of Mo through sulfate‐reducing bacterial activity acts as a significant pathway for Mo burial in the ocean. However, the impact of microbial sulfate reduction in Mo isotope fractionation remains unclear, preventing the understanding of the interaction between Mo and organic matter. We report Mo abundances and isotopic (δ98Mo) compositions for different phases extracted from seep carbonate rock fractions, including carbonate (carb), pyrite, and organic matter (OM). Our findings indicate that organic matter tends to preferentially adsorb isotopically light Mo. The observed δ98Mo difference between carbonate and organic matter fractions (Δ98Mocarb‐OM from 0.72 to 1.01‰) represents the first report of the extent of Mo isotope fractionation during Mo adsorption to organic matter in marine environments. We attribute greater Δ98Mocarb‐OM offsets to the preferential adsorption of isotopically light Mo onto organic matter during enhanced sulfate reduction, and in turn put forward the idea that such offsets can be possibly used in the sedimentary record to trace the intensity of sulfate reduction and to reconstruct the past interaction between Mo and organic matter in marine sediments. Key Points: Organic matter tends to adsorb isotopically light Mo, resulting in low δ98Mo values of organic matter in marine environmentsIsotopically light Mo is inferred to be preferentially adsorbed onto organic matter during enhanced sulfate reductionδ98Mo offset between carbonate and organic phases in authigenic carbonates is promising to trace the past intensity of sulfate reduction [ABSTRACT FROM AUTHOR]

Authigenic molybdenum (Moauth) in marine sediments holds great potential to archive the Mo isotopic composition of seawater and biogeochemical processes. However, the factors that control authigenic Mo isotope (δ98Moauth) distribution patterns remain poorly constrained. Here, we report Mo abundances and δ98Mo compositions for bulk‐rock (bulk) and sequentially extracted fractions—including total authigenic (auth; i.e., non‐lithogenic fraction), carbonate (carb), iron and manganese oxyhydroxides, pyrite (py), and organic fractions (OM)—of authigenic carbonates recovered from various hydrocarbon seep sites in the Gulf of Mexico and the South China Sea. Extracted pyrite fractions exhibit Mo contents varying from 0.1 to 23.4 μg/g and generally dominate the Mo budget of seep carbonate rocks. Our data indicate large ranges of δ98Mobulk and δ98Moauth values relative to NIST 3134 (0.25‰), varying from 1.02 to 1.98‰ (n = 4) and from 0.15 to 3.07‰ (n = 34), respectively. The difference in δ98Mo values between carbonate and pyrite fractions of seep carbonate rocks formed under sulfidic conditions increases with higher Moauth contents, suggesting a control of dissolved hydrogen sulfide concentrations on Mo isotope fractionation during carbonate precipitation. Compared with δ98Moauth and δ98Mopy, δ98Mocarb of seep carbonate rocks formed under sulfidic conditions shows a relatively narrow range with an average of 1.98 ± 0.31‰ (1 SD; n = 10), providing constraints on the δ98Mo composition of seawater in the course of Earth history. Overall, our findings show that the δ98Mo composition of sequentially extracted phases of carbonate‐rich sedimentary rocks can provide insights into seawater‐sediment interactions and biogeochemical pathways of Mo during early diagenesis. Plain Language Summary: Sulfate reduction has created widespread euxinic conditions in the water column of ancient oceans and prevalent sulfidic conditions in subseafloor pore‐water environments of the modern ocean. Ancient seawater δ98Mo compositions have been considered to reflect the overall extent of oxic versus euxinic conditions of the global ocean, highlighting the importance of a robust reconstruction of the marine Mo isotope inventory largely unaffected by diagenesis. Under sulfidic conditions, the seawater δ98Mo value can be archived by authigenic Mo in marine carbonate sediments formed during early diagenesis. However, the conditions of capturing the seawater δ98Mo signature remain poorly constrained. Using a sequentially chemical leaching procedure, we investigated Mo contents and isotopic compositions of different fractions of modern seafloor seep carbonate rocks. Our results show that a δ98Mo average value of 1.98 ± 0.31‰ (1 SD; n = 10) of the carbonate mineral phase results from small or no Mo isotope fractionation during near‐quantitative authigenic Mo sequestration under sulfidic conditions, potentially capturing seawater δ98Mo. Our study shows that δ98Mo of sequentially extracted phases of sedimentary carbonate rocks is a robust tool to constrain seawater and pore fluid properties. Key Points: δ98Mo of sequentially extracted phases of carbonates is useful to trace Mo isotope fractionation during early diagenesisDegree of Mo isotope fractionation during carbonate precipitation is controlled by hydrogen sulfide concentrationsAuthigenic Mo sequestration into the carbonate phase under sulfidic conditions generates small Mo isotope fractionation [ABSTRACT FROM AUTHOR]

The Niger River drains a large part of the West African Craton, where rocks ranging in age from Paleoarchean to recent offer an unexcelled opportunity to map the diverse time structures of sediment sources and provide essential information for provenance diagnoses. In this study, U‐Pb zircon dating is complemented with bulk‐sand geochemical (Zr, Hf, REE) and Nd‐Hf isotope data to pin‐point parent rocks of zircon grains and draw inferences on sediment generation across sub‐Saharan western Africa. In Upper Niger sand, zircon ages pass from exclusively Archean in Guinea headwaters to dominantly Paleoproterozoic in the Inner Delta in Mali, testifying to the progressive dilution by tributary sediment derived from the Birimian domain. Zircon ages abruptly change to dominantly Neoproterozoic downstream of the Inner Delta, becoming indistinguishable from those in Saharan eolian dunes across the Sahel. Most of the sediment generated in the headwaters is thus dumped in the marshlands and bedload is reconstituted downstream by recycling eolian sand. Zircon grains in the Lower Niger yielded virtually the same U‐Pb ages as in Benue sediment, indicating an overwhelming supply from the Benue tributary. In the Niger Delta, however, Archean zircons reappear, and both εNd and εHf values become notably more negative, indicating extensive reworking of sand deposited along the coastal plain at earlier times of wetter climate, when artificial barriers to the sediment flux did not exist in the upper to middle Niger River catchment. Plain Language Summary: Across sub‐Saharan western Africa, the Niger River drains rocks with ages spanning more than 3 billion years. In such a vast region, diverse techniques can be combined to identify processes of erosion and transport, starting from the analysis of sediments and the zircon grains they contain. The very old ages of zircons derived from Guinean headwaters (all older than 2650 million years) are gradually diluted by younger zircons generated in SW Mali (from 1900 to 2200 million years), whereas a sharp change to more recent zircon ages (from 500 to 700 million years) is documented downstream of the Inner Delta. Most sediment generated in the headwaters is thus dumped in these marshlands and subsequently replaced with sand eroded from eolian dunes along the southern edge of the Sahara Desert. Rigid segmentation of fluvial sediment transport has become the rule after the extensive construction of dams worldwide, but can also be caused by natural processes. Marshlands formed at the subequatorial edge of tropical deserts can represent very efficient natural barriers to sediment transport, preventing a large part of the detritus generated in the highlands from reaching the ocean, with consequent impact on both sediment budgets and sediment composition. Key Points: The Niger River offers an unexcelled opportunity to use detrital geochronology to map the diverse time structures of sediment sourcesSand generated in the headwaters is dumped in the Inner Delta as indicated by a significant change in the U‐Pb signature and εNd‐εHf valuesReworking of sand along the coastal plain testifies the absence of artificial or major natural barriers to the sediment flux in earlier times [ABSTRACT FROM AUTHOR]

Clay mineral authigenesis at continental margins plays an important role in global marine element cycles. However, despite being increasingly used as tracers for both modern and past oceanographic conditions, the behavior of the rare earth elements (REEs) and their isotopes during marine clay authigenesis still remains poorly known. In this study, we report on a detailed geochemical investigation of glauconite from the West African continental shelf, near the mouth of the Congo River. Elemental, neodymium, and hafnium isotope analyses were conducted on both acid leachate and separated clay-size fractions of glauconite pellets, in order to investigate the behavior of REE during the formation of authigenic clays. Our data indicate that kaolinite dissolution and subsequent Fe-bearing clay authigenesis act as a net source of REEs to seawater. We show that enhanced glauconitization, as inferred from increasing Fe and K contents, is accompanied by significant decoupling of the REE toward markedly LREE-enriched shale-normalized patterns in neoformed clay separates. Using both Nd and Hf isotopes and SEM observations, we rule out any seawater influence and argue that this shift primarily reflects the progressively overwhelming presence of insoluble nanocrystals of detrital LREE-rich phosphates, which are known to occur in close association with kaolinite in tropical soils. Due to their marked insolubility in surface environments, such nanocrystals can be preserved during kaolinite dissolution and subsequently incorporated into the aggregates of authigenic green clays forming the peloids. Most strikingly, we show that the combined influence of net REE loss (due to kaolinite dissolution) and decoupling (due to subsequent entrapment of inherited LREE-bearing accessory phases into neoformed clay minerals) is accompanied by preferential release of a dissolved REE fraction characterized by seawater-like distribution patterns. These findings reinforce the emerging view that clay mineral dissolution and authigenesis at continental margins possibly play a major role in marine REE cycling. [ABSTRACT FROM AUTHOR]

We measured the 14 C age of pre-bomb suspension-feeding bivalves of known age from coastal West Africa across a latitudinal transect extending from 33 ∘ N to 15 ∘ S. The specimens are from collections belonging to the Muséum National d'Histoire Naturelle (Paris, France). They were carefully chosen to ensure that the specimens were collected alive or that they died not long before collection. From the 14 C dating of the known-age bivalves, we calculated the marine reservoir age (as ΔR and R values) for each specimen. ΔR values were calculated relative to the Marine20 calibration curve, and the R values were calculated relative to Intcal20 or SHcal20 calibration curves. Except for five outliers, the ΔR and R values were generally homogenous with weighted mean values of - 72 ± 42 14 C years (1 SD, n=24) and 406 ± 56 14 C years (1 SD, n=24) respectively. These values are typical of low-latitude marine reservoir age values. Five suspension-feeding species living in five different ecological habitats were studied. For localities where several species were available, the results yielded similar results whatever the species considered, suggesting that, in these locations, the habitat has only a limited impact on marine reservoir age reconstruction. We show that our measured marine reservoir ages follow the declining trend of the global marine reservoir age starting ca. 1900 CE, suggesting that the marine reservoir age of coastal West Africa is driven, at least to the first order, by the atmospheric CO 2 14 C ageing due to fossil fuel burning rather than by local effects. Each outlier was discussed. Local upwelling conditions or sub-fossil specimens may explain the older 14 C age and thus the larger marine reservoir ages for these samples. Bucardium ringens might not be the best choice for marine reservoir age reconstructions. [ABSTRACT FROM AUTHOR]