Exploring the importance of authigenic clay formation in the global Li cycle

Lithium isotopic (δ7Li) and elemental concentrations of pore fluids and carbonates from IODP Site U1338 Hole A (eastern equatorial Pacific Ocean) suggest that clay authigenesis (i.e., in situ precipitation) is a significant sink for Li in carbonate-rich sedimentary sections. Systematic variations in pore fluid δ7Li with depth in the section suggest that clay authigenesis can (i) strongly decrease pore fluid Li concentrations with depth and (ii) fractionate Li isotopically to a considerable degree (Δ ∼ 5–21‰ relative to seawater). We hypothesize that clay authigenesis in carbonate-rich sections occurs due to the presence of reactive biogenic silica, and reactive transport modeling supports the contention that the pore fluid δ7Li depth profile at Site U1338 is best explained by faster authigenesis at depth. The significance of clay authigenesis in carbonate-rich sediments is two-fold: if global in scale, (i) it can generate sizeable output fluxes in the global Li cycle, and (ii) the evolution of the sedimentary system over time can markedly impact the isotopic composition of the global Li output flux. We compile ODP and IODP pore fluid Li data from 267 sites; of these, 207 have Li pore fluid concentration gradients in the upper 50–100 meters that indicate the sites as diffusive sinks of Li. We then estimate that clay authigenesis in carbonate-rich sediments could reasonably generate a Li output flux on the order of ∼1.2·1010 moles/year, which is comparable to the gross input fluxes in the modern Li cycle. A series of reactive transport simulations illustrate how clay authigenesis might impact the isotopic composition of the output flux of Li from the global ocean. The suggestion is that applying a constant fractionation factor from the global ocean over time is likely incorrect, and that secular changes in the δ7Li of the output flux will be driven by rates of authigenesis, burial rates, and the depth extent of authigenesis in the sedimentary section. Utilizing a time-dependent, depositional diagenetic model, the δ7Li values of bulk carbonate are shown to be a consequence not of recrystallization alone, but recrystallization in the presence of clay authigenesis. Further, our model results are used to illustrate how carbonate δ7Li may be used to constrain the temporal evolution of clay authigenesis in the sedimentary section. Ultimately, this work suggests that the Li isotopic composition of bulk carbonates can be altered diagenetically. However, such alteration is not a detriment, but provides useful information on those diagenetic processes in the sedimentary column that impact the global Li cycle. Thus, Li isotopes in bulk carbonates have the potential to elucidate diagenetic controls on the global Li cycle over long time scales

The influence of river-derived particles on estuarine and marine elemental cycles: evidence from lithium isotopes

To examine the alteration of river-derived sediments through a large estuary and the implications for elemental cycling and global climate, this study analyses lithium (Li) isotopes and elemental concentrations (e.g., Li, Na, Mg, K, Ca, Fe and Al) of both the dissolved load and different phases of the sediment load (i.e., exchangeable, carbonate, oxide, clay and residue) in the Amazon estuary. The results show that river-derived sediments remove Li from the dissolved load, largely due to cation retention in secondary clays. By modelling the Li mass-balance and isotope fractionation, we estimate that the river-derived sediments gain 3–4 μg/g Li from the dissolved load in the Amazon estuary, with a Li isotope fractionation factor (αclay-solution) of approximately 0.975. Considering the whole Amazon estuary, the river-derived sediments remove around 3.6–4.8 × 109 g/yr of Li from the dissolved load. Specifically, around 1.0–1.7 × 108 g/yr of Li is removed from river water (∼1.8–3.0% of the dissolved Li discharge flux of the Amazon River) and around 3.5–4.7 × 109 g/yr of Li is removed from seawater, which represents a significant sink from the ocean. This estuarine Li sink is likely to be related to continental erosion rates; thus, continental weathering and erosion regimes could influence not only riverine Li input, but could also directly affect the Li sink, leading to a dual control on the Li budget and isotope composition in the ocean

Lithium isotopes in speleothems: temperature-controlled variation in silicate weathering during glacial cycles

Terrestrial chemical weathering of silicate minerals is a fundamental component of the global cycle of carbon and other elements. Past changes in temperature, rainfall, ice cover, sea-level and physical erosion are thought to affect weathering but the relative impact of these controls through time remains poorly constrained. This problem could be addressed if the nature of past weathering could be constrained at individual sites. In this study, we investigate the use of speleothems as local recorders of the silicate weathering proxy, Li isotopes. We analysed 7Li and [Li] in speleothems that formed during the past 200 ka in two well-studied Israeli caves (Soreq and Tzavoa), as well as in the overlying soils and rocks. Leaching and mass balance of these soils and rocks show that Li is dominantly sourced from weathering of the overlying aeolian silicate soils. Speleothem 7Li values are ubiquitously higher during glacials (~23‰) than during interglacials (~10‰), implying more congruent silicate weathering during interglacials (where “congruent” means a high ratio of primary mineral dissolution to secondary mineral formation). These records provide information on the processes controlling weathering in Israel. Consideration of possible processes causing this change of weathering congruency indicates a primary role for temperature, with higher temperatures causing more congruent weathering (lower 7Lispeleo). The strong relationship observed between speleothem d7Li and climate at these locations suggests that Li isotopes may be a powerful tool with which to understand the local controls on weathering at other sites, and could be used to assess the distribution of weathering changes accompanying climate change, such as that of Pleistocene glacial cycles

The boron and lithium isotopic composition of mid-ocean ridge basalts and the mantle

A global selection of 56 mid-ocean ridge basalt (MORB) glasses were analysed for Li and B abundances and isotopic compositions. Analytical accuracy and precision of analyses constitute an improvement over previously published MORB data and allow a more detailed discussion of the Li and B systematics of the crust-mantle system. Refined estimates for primitive mantle abundances ([Li]=1.39±0.10[Li]=1.39±0.10 μg/g and [B]=0.19±0.02[B]=0.19±0.02 μg/g) and depleted mantle abundances ([Li]=1.20±0.10[Li]=1.20±0.10 μg/g and [B]=0.077±0.010[B]=0.077±0.010 μg/g) are presented based on mass balance and on partial melting models that utilise observed element ratios in MORB. Assimilation of seawater (or brine) or seawater-altered material beneath the ridge, identified by high Cl/KCl/K, causes significant elevation of MORB δ11Bδ11B and variable elevation in δ7Liδ7Li. The B isotope ratio is, hence, identified as a reliable indicator of assimilation in MORB and values higher than −6‰ are strongly indicative of shallow contamination of the magma. The global set of samples investigated here were produced at various degrees of partial melting and include depleted and enriched MORB from slow and fast-spreading ridge segments with a range of radiogenic isotope signatures and trace element compositions. Uncontaminated (low-Cl/KCl/K) MORB show no significant boron isotope variation at the current level of analytical precision, and hence a homogenous B isotopic composition of δ11B=-7.1±0.9‰δ11B=-7.1±0.9‰ (mean of six ridge segments; 2SD). Boron isotope fractionation during mantle melting and basalt fractionation likely is small, and this δ11Bδ11B value reflects the B isotopic composition of the depleted mantle and the bulk silicate Earth, probably within ±0.4‰. Our sample set shows a mean δ7Li=+3.5±1.0‰δ7Li=+3.5±1.0‰ (mean of five ridge segments; 2SD), excluding high-Cl/KCl/K samples. A significant variation of 1.0–1.5‰ exists among various ridge segments and among samples within individual ridge segments, but this variation is unrelated to differentiation, assimilation or mantle source indicators, such as radiogenic isotopes or trace elements. It, therefore, seems likely that kinetic fractionation of Li isotopes during magma extraction, transport and storage may generate δ7Liδ7Li excursions in MORB. No mantle heterogeneities, such as those generated by deeply recycled subducted materials, are invoked in the interpretation of the Li and B isotope data presented here, in contrast to previous work on smaller data sets. Lithium and boron budgets for the silicate Earth are presented that are based on isotope and element mass balance. A refined estimate for the B isotopic composition of the bulk continental crust is given as δ11B=-9.1±2.4‰δ11B=-9.1±2.4‰. Mass balance allows the existence of recycled B reservoirs in the deep mantle, but these are not required. However, mass balance among the crust, sediments and seawater shows enrichment of 6Li6Li in the surface reservoirs, which requires the existence of 7Li7Li-enriched material in the mantle. This may have formed by the subduction of altered oceanic crust since the Archaean

Extreme magnesium isotope fractionation at outcrop scale records the mechanism and rate at which reaction fronts advance

Isotopic fractionation of cationic species during diffusive transport provides novel means of constraining the style and timing of metamorphic transformations. Here we document a major (~1‰) decrease in the Mg isotopic composition of the reaction front of an exhumed contact between rocks of subducted crust and serpentinite, in the Syros mélange zone. This isotopic perturbation extends over a notable length-scale (~1 m), implicating diffusion of Mg through an intergranular fluid network over a period of ~100 kyr. These novel observations confirm models of diffusion-controlled growth of reaction zones formed between rocks of contrasting compositions, such as found at the slab-mantle interface in subduction zones. The results also demonstrate that diffusive processes can result in exotic stable isotope compositions of major elements with implications for mantle xenoliths and complex intrusions

Osmium and lithium isotope evidence for weathering feedbacks linked to orbitally paced organic carbon burial and Silurian glaciations

The Ordovician (∼487 to 443 Ma) ended with the formation of extensive Southern Hemisphere ice sheets, known as the Hirnantian glaciation, and the second largest mass extinction in Earth History. It was followed by the Silurian (∼443 to 419 Ma), one of the most climatically unstable periods of the Phanerozoic as evidenced by several large scale (> 5‰) carbon isotope (δ13C) perturbations associated with further extinction events. Despite several decades of research, the cause of these environmental instabilities remains enigmatic. Here, we provide osmium (187Os/188Os) and lithium (δ7Li) isotope measurements of marine sedimentary rocks that cover four Silurian δ13C excursions. Osmium and Li isotope records resemble those previously recorded for the Hirnantian glaciation suggesting a similar causal mechanism. When combined with a new dynamic carbon-osmium-lithium biogeochemical model we suggest that astronomical forcing of the marine organic carbon cycle, as opposed to a decline in volcanic arc degassing or the rise of early land plants, resulted in drawdown of atmospheric CO2, triggering continental scale glaciation, intense global cooling and eustatic sea-level lows recognised in the geological record. Lower atmospheric pCO2 and temperatures during the Hirnantian and Silurian glaciations suppressed CO2 removal by silicate weathering, driving 187Os/188Os and δ7Li variability, supporting the existence of climate-regulating feedbacks

Temporal Evolution of Island Arc Magmatism and Its Influence on Long-Term Climate: Insights From the Izu Intra-Oceanic Arc

Continental arcs have an episodic magmatic activity over long-time periods, which is believed to modulate long-term climate. Island arcs have also the potential to release large amount of CO2 into the atmosphere, but whether they display an episodic magmatic history throughout their lifespan that contributes to the long-term (>10 Ma) climate changes remains an open question. To set additional constraints on the magmatic history of island arcs, here we examine fresh basalts and mineral-hosted melt inclusions from the Izu intra-oceanic arc, shortly after the eruption of boninites (∼45 Ma ago). Using chemical markers, we show that the long-term magmatic activity of the mature Izu arc has been relatively continuous over its lifespan, except during opening of the Shikoku back-arc Basin (∼23–20 Ma). Because slab dehydration and slab melting trigger decarbonation and carbonate dissolution of the subducted plate, we use slab-fluid markers (Ba/Th, Cs/Th, Cs/Ba, Rb/Th, Th/Nb) to examine the variations of slab-derived CO2 captured by the arc magmas. The long-term steadiness in the arc magmatic activity and in the slab-fluid contribution suggests that the CO2 outgassed during mature arc volcanism may have remained relatively homogeneous for the past 40 Ma in Izu. If worldwide mature island arcs also maintain a relatively steady-state magmatic activity over their lifespan, the long-term CO2 outgassed by these arc volcanoes may be rapidly balanced by chemical weathering and tectonic erosion, which rapidly draw down the atmospheric CO2 (within 200–300 kyr). This rapid negative feedback to long-term volcanic degassing permits to sustain a viable atmospheric CO2 for millions of years. The lack of co-variations between the markers of climate changes (δ13O, δ18C) and the long-term averages of the markers of slab fluids further implies that long-term volcanic degassing of CO2 from mature island arcs might play a minor role in the slide into icehouse climatic conditions. This long-term degassing stability may be, instead, a contributor to maintaining a broadly stable climate over long timescales

Lithium isotope evidence for enhanced weathering and erosion during the Paleocene-Eocene Thermal Maximum

The Paleocene-Eocene Thermal Maximum (PETM; ~55.9 Ma) was a geologically rapid warming period associated with carbon release, which caused a marked increase in the hydrological cycle. Here, we use lithium (Li) isotopes to assess the global change in weathering regime, a critical carbon drawdown mechanism, across the PETM. We find a negative Li isotope excursion of ~3‰ in both global seawater (marine carbonates) and in local weathering inputs (detrital shales). This is consistent with a very large delivery of clays to the oceans or a shift in the weathering regime toward higher physical erosion rates and sediment fluxes. Our seawater records are best explained by increases in global erosion rates of ~2× to 3× over 100 ka, combined with model-derived weathering increases of 50 to 60% compared to prewarming values. Such increases in weathering and erosion would have supported enhanced carbon burial, as both carbonate and organic carbon, thereby stabilizing climate

Precise magnesium isotope measurements in core top planktic and benthic foraminifera

This study presents a new methodology to obtain highly precise measurements (±0.1‰) of magnesium isotope ratios in very small samples of foraminiferal carbonate (40–50 μg). Here this technique is used to examine Mg isotopic variation among different species of core top foraminifera over a range of different ambient conditions. Despite the high degree of temperature control on the abundance of elemental Mg incorporated into foraminiferal tests, analyses of surface dwelling Globigerinoides ruber and G. sacculifer from five cores, with associated sea surface temperatures ranging from 20 to 31°C, show no significant temperature-dependent variations in their Mg isotope ratios. Analyses of different size fractions of G. sacculifer show an increase in Mg/Ca with test size but no variation of Mg isotope ratio. In all, nine planktic and benthic species were analyzed; all show identical Mg isotope ratios with a mean of δ26Mg = −4.72‰, apart from small differences in three species, namely O. universa, G. sacculifer (which are both ∼0.4‰ lighter than the average), and P. obliquiloculata (which is ∼0.4‰ heavier). These results highlight the constancy of foraminiferal Mg isotope ratios, despite changing environmental conditions which dominate Mg/Ca variation and arguably affect Ca isotope fractionation. This is an important observation which needs to be included in any model of foraminiferal calcification. The insusceptibility of δ26Mg values to external parameters makes Mg isotopes ideally suited to constraining past variations in the Mg isotope budget of the oceans and the information this carries about the history of oceanic dolomitization, continental weathering, and hydrothermal behavior

Lithium isotope evidence for enhanced weathering and erosion during the Paleocene-Eocene Thermal Maximum

The Paleocene-Eocene Thermal Maximum (PETM; ~55.9 Ma) was a geologically rapid warming period associated with carbon release, which caused a marked increase in the hydrological cycle. Here, we use lithium (Li) isotopes to assess the global change in weathering regime, a critical carbon drawdown mechanism, across the PETM. We find a negative Li isotope excursion of ~3‰ in both global seawater (marine carbonates) and in local weathering inputs (detrital shales). This is consistent with a very large delivery of clays to the oceans or a shift in the weathering regime toward higher physical erosion rates and sediment fluxes. Our seawater records are best explained by increases in global erosion rates of ~2× to 3× over 100 ka, combined with model-derived weathering increases of 50 to 60% compared to prewarming values. Such increases in weathering and erosion would have supported enhanced carbon burial, as both carbonate and organic carbon, thereby stabilizing climate