Search

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. [ABSTRACT FROM AUTHOR]

The chemical composition of the wood reflects the composition of the soil over which the corresponding tree has developed. Multi-elemental and isotopic signatures, which are characteristic of the soil and underlying rock substrates, are potentially powerful tools for determining wood provenance. These tracers are of special interest for charred archaeological wood because they circumvent some limitations of dendrochronological provenancing linked to tree-ring loss. However, thermal degradation may introduce a significant bias in wood chemical and isotopic analyses. This experimental study focused on the effects of carbonization temperature on three geochemical wood markers: elemental signatures and isotopic signatures of strontium and neodymium (86Sr/87Sr and 143Nd/144Nd, respectively). Wood specimens from a variety of oak trees and stand locations were pyrolyzed at four temperatures (ranging from 200°C to 800°C) and analyzed using ICP-MS and μ -XRF (X-ray fluorescence) spectroscopy for elemental composition and with multiple collection ICP-MS (MC-ICP-MS) for strontium (Sr) and neodymium (Nd) isotope composition. The concentration of mineral nutrients generally increased with temperature, but the magnitude of the enrichment depended on the element, wood compartment (sapwood vs. heartwood), and geological substrate. The concentrations of rubidium, strontium, manganese, magnesium, potassium, and, to a lesser extent, calcium, were minimally affected by temperature, wood compartment, and substrate. The ratios between the concentrations of these elements, as well as the 86Sr/87Sr and 143Nd/144Nd isotope ratios, were stable over the entire temperature range. However, only 86Sr/87Sr and selected elemental ratios (calcium or magnesium normalized to manganese) were successful for site discrimination. Therefore, our multi-tracer approach provides promising new information to determine the provenance of charred archaeological wood. [ABSTRACT FROM AUTHOR]

We report Li isotope composition (δ 7 Li) of river-borne dissolved and solid material in the largest River system on Earth, the Amazon River basin, to characterize Li isotope fractionation at a continental scale. The δ 7 Li in the dissolved load (+1.2‰ to +32‰) is fractionated toward heavy values compared to the inferred bedrock (−1‰ to 5‰) and the suspended sediments (−6.8‰ to −0.5‰) as a result of the preferential incorporation of 6 Li into secondary minerals during weathering. Despite having very contrasted weathering and erosion regimes, both Andean headwaters and lowland rivers share similar ranges of dissolved δ 7 Li (+1.2‰ to +18‰). Correlations between dissolved δ 7 Li and Li/Na and Li/Mg ratios suggest that the proportion of Li incorporated in secondary minerals during weathering act as the main control on the δ 7 Li diss across the entire Amazon basin. A “batch” steady-state fractionation model for Andean and lowland rivers satisfactorily reproduces these variations, with a fractionation factor between weathering products and dissolved load ( α sec - dis ) of 0.983 ± 0.002. Two types of supply-limited weathering regimes can be identified for the lowlands: “clearwaters” with dominant incorporation of Li in secondary minerals, and “black waters” (e.g., Rio Negro) where dissolution of secondary minerals enhanced by organic matter produces low δ 7 Li. Apart from the black waters, the δ 7 Li of Andean and lowland rivers is negatively correlated to the denudation rates with the lowest δ 7 Li corresponding to the rivers having the highest denudation rates. In contrast, the main tributaries draining both the Andes and the lowlands have higher δ 7 Li compared to other rivers. We propose that part of the dissolved Li derived from weathering in the Andes is re-incorporated in sediments during transfer of water and sediments in floodplains and that this results in an increase of the dissolved δ 7 Li along the course of these rivers. Unlike other rivers, the dissolved δ 7 Li in the main tributaries is best described by a Rayleigh fractionation model with a fractionation factor α sec - dis of 0.991. Altogether, the control imposed by residence time in the weathering zone and floodplain processes results in (i) a non-linear correlation between dissolved δ 7 Li and the weathering intensity (defined as W/D) and (ii) a positive relationship between the dissolved Li flux and the denudation rate. These results have important implications for the understanding of past ocean δ 7 Li and its use as a paleo weathering proxy. [ABSTRACT FROM AUTHOR]

Mass-dependent isotope fractionation occurring during precipitation of solids in low-temperature environments often depends on precipitation rate. Using a series of precipitation experiments in which continuous precipitation and dissolution of Si solids is forced by daily cyclic freezing (solid formation) and thawing (solid re-dissolution), we show this dependence. We conducted six Si precipitation experiments for about 120 days with initial dissolved Si concentration of 1.6 mmol/l Si, at pH values between 4.5 and 7, with additions of 0.1–1 mM of dissolved aluminum (Al), and in the absence of Al. During all experiments increasing amounts of an X-ray amorphous silica-containing solid are formed. No Si isotope fractionation occurs during formation of almost pure Si solids, interpreted as an absence of Si isotope fractionation during polymerization of silicic acid. Si isotope fractionation occurs only in the high-Al concentration experiments, characterized by an enrichment of the light Si isotopes in the solids formed early. With ongoing duration of the experiments, a re-dissolution of these solids is indicated as the Si isotope value of the complementary solution shifts to lighter values and eventually reaches near-initial compositions. Hence, our high-Al experiments are characterized by a gradual shift from a regime that is dominated by unidirectional kinetic isotope fractionation with solids formed that are up to 5‰ lighter in their 30 Si/ 28 Si ratio than the corresponding solution, to one of steady-state between dissolution and precipitation with the 30 Si/ 28 Si ratio of the solid being almost identical to the solution (Δ solid ‐ solution ≈ 0). This suggests that the enrichment of light Si isotopes found in natural environments is caused exclusively by a unidirectional kinetic isotope effect during fast precipitation of solids, aided by co-precipitation with Al phases or other carrier phases (e.g. Fe(III)). By contrast, during slow precipitation, or in the absence of a carrier phase like Al, no Si isotope fractionation is expected and solids obtain the composition of the ambient fluid. [ABSTRACT FROM AUTHOR]

Many forest soils are acidic and have very low plant-available pools of magnesium. Past and present sylvicultural, nutritional and/or climatic pressures endured by forest ecosystems can result in net losses of nutrients and ecosystem function losses. Liming with a carbonate product is an alternative to counteract these degradations but the effects of liming on the biogeochemical cycling of nutrients over time and the dynamics of Mg released from liming products are still unclear. We studied the Mg isotopes composition in four paired-treatment experimental beech forest ecosystems in northern France. At the sites where dolomitic lime was applied, the variation in exchangeable and foliar δ26Mg demonstrated the direct contribution of dolomite-derived Mg to the replenishment of topsoil exchangeable pools and to tree nutrition improvement: dolomite-derived Mg was incorporated into the biological cycling which allows its retention on the mid to long term in the soil–plant system. At the sites limed with calcium carbonate, the changes in exchangeable and foliar Mg contents and δ26Mg observed on the long term suggest that the applied product contained a small amount of Mg and/or that Mg cycling changed after liming, to cope in particular with the low Mg availability. Lastly, our results highlight the high δ26Mg of the organic layer (humus): fractionation processes occurring within this layer (mineralization/ageing of organic matter, preferential retention of 26 Mg) could explain these singular signatures that could greatly influence the topsoil Mg exchangeable pools. [ABSTRACT FROM AUTHOR]

In this study, to better understand the factors controlling the concentration and isotope composition of lithium (Li) in the ocean, we investigated the behaviour of Li during interaction of kaolinite with artificial seawater. Dissolution of kaolinite in Li-free seawater at acidic conditions (exp. 1) results in a strong preferential release of light Li isotopes, with △7Li aq-kaol ∼ −19‰, likely reflecting both the preferential breaking of 6Li O bonds over 7Li O bonds and the release of Li from the isotopically lighter AlO 6 octahedral sites. Sorption experiments on kaolinite (exp. 2) revealed a partition coefficient between kaolinite and fluid of up to 28, and an isotopic fractionation of −24‰. Thermodynamic calculation indicates authigenic smectites formed from the dissolution of kaolinite in seawater at pH 8.4 (exp. 3). The formation of authigenic phase strongly removed Li from the solution (with a partition coefficient between the solid and the fluid equal to 89) and led to an increase of ca. 25‰ in seawater δ7Li. This fractionation can be described by a Rayleigh fractionation model at the early stage of the experiment during rapid clay precipitation, followed, at longer reaction time, by equilibrium isotope fractionation during the much slower removal of aqueous Li via co-precipitation and adsorption. Both processes are consistent with a fractionation factor between the solid and the aqueous solution of ∼−20‰. These experiments have implications for interpreting the Li isotopic composition of both continental and marine waters. For instance, the preferential release of 6Li observed during kaolinite far-from-equilibrium dissolution could explain the transient enrichments in 6Li observed in soil profiles. With regard to the evolution of seawater δ7Li over geological time scales, our experimental results suggest that detrital material discharged by rivers to the ocean and ensuing "reverse chemical weathering" have the potential to strongly impact the isotopic signature of the ocean through the neoformation of clay minerals. [ABSTRACT FROM AUTHOR]

Storms are responsible for up to ~50% of total annual rainfall on tropical islands and result in rapid increases in discharge from rivers. Storm events are, however, notoriously under-sampled and their effects on weathering rates and processes are poorly constrained. To address this, we have undertaken high-frequency sampling of Quiock Creek catchment, a Critical Zone Observatory located in Guadeloupe, over a period of 21 days, encompassing several storm events. Chemical and isotopic (Li and Mg) analyses of different critical zone reservoirs (throughfall, soil pore water, groundwater and river water) were used to assess the interactions between rock, water and secondary minerals. The Li concentrations and δ7Li values of these different reservoirs range from 14 to 95 nmol/kg and 1.8 to 16.8‰, respectively. After several rain events, the average δ7Li value (13.3‰) of soil solutions from the lower part of the soil profile (>~150 cm below the surface) was unchanged, whereas in the upper part of the profile δ7Li values increased by ~2–4‰ due to increased contribution from throughfall. By contrast, the δ26Mg value of soil waters in the upper part of the soil profile were not significantly affected by the rain events with an average value of −0.90‰. The δ26Mg values of the different fluid reservoirs were generally close to the value of throughfall (~−0.90‰), but higher δ26Mg values (up to −0.58‰) were measured in the deeper parts of the soil profile, whereas groundwaters that have a long residence time had lower δ26Mg values (down to −1.48‰). These higher and lower values are attributed to, respectively, adsorption/desorption of light Mg isotopes on/from the surface of clay minerals. The δ7Li value of the river waters was ~9.3‰, with a Li concentration of 60 μmol/kg, but during a storm these values decreased to, respectively, 7.8‰ and 40 μmol/kg. This change in δ7Li is consistent with an increased contribution of Li from the soil solution. Thus, even in highly weathered catchments, changes in hydrological conditions can have a significant impact on weathering processes and therefore the composition of river waters delivered to the ocean. • Series of rain events reduces the δ7Li value of river waters in a tropical catchment • Mg isotope composition of soil solutions is controlled by adsorption and desorption processes. • Storm events have little effect on δ26Mg values because most of the Mg in the studied catchment is supplied by throughfall. [ABSTRACT FROM AUTHOR]

In order to better understand how stable metal isotope signals in large rivers can be used to constrain present and past weathering, the seasonal riverine Mg Sr isotopic pattern in the middle Yellow River was systematically investigated based upon weekly collected samples for the whole year of 2013. The results demonstrate that Mg is mainly transported in the dissolved form (65%) in this river system and that 45% of the total dissolved Mg is transported during the monsoon seasons, with 2% exported over 4 days during a single storm event. Dissolved Mg in the middle Yellow River is dominantly derived from both silicate and carbonate (82–89%) in this semi-arid region, with limited evaporite contribution (∼7%). Lithological mixing is the first order control on riverine dissolved Mg and Sr isotopes, with a contribution from ∼40% carbonate dissolution and ∼ 60% from silicate dissolution in the dry seasons, and ∼ 50% carbonate and ∼ 50% silicate during the monsoon seasons according to δ26Mg signals. Furthermore, a significant role of prior calcite precipitation (PCP) can be quantified, which fractionates Mg isotopes by about 0.17‰ to 0.39‰ positively depending on the choice of elemental and isotope partition of Mg in secondary carbonates. Clay formation following the PCP further fractionates riverine Mg isotopes to the negative side. An ∼0.2‰ decrease of riverine Mg isotopes is attributable to (1) a single storm event causing carbonate dissolution and (2) delayed delivery of depleted waters to rivers (∼3 months after the storm event) because of subsurface hydrological circulation. Annually, the weighted average riverine δ26Mg (−1.05‰) in the middle Yellow River is identical to the global average (−1.09‰). Despite the significant impact of lithology on the riverine dissolved Mg isotope signature, the mixing proportions of different Mg sources remain virtually constant, even when there are huge contrast of temperature, hydrology, and precipitation seasonally along the year, providing a basis for dissolved δ26Mg response to climatic forcing on the continental scale. This means that significant changes in the sedimentary Mg isotope records would reflect extreme conditions in deep time. [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., (© 2024. The Author(s).)

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.