The rapid resetting of the Ca isotopic signatures of calcite at ambient temperature during its congruent dissolution, precipitation, and at equilibrium

This study provides direct experimental evidence of the resetting of the calcium (Ca) isotope signatures of calcite in the presence of an aqueous fluid during its congruent dissolution, precipitation, and at equilibrium at ambient temperatures over week-long timescales. Batch reactor experiments were performed at 25 °C in aqueous NaCl solutions; air or CO2-gas mixtures were bubbled through this fluid to fix pH. During congruent calcite dissolution, the fluid became enriched in isotopically heavy Ca, and the Ca isotope composition continued to become heavier after the fluid attained bulk chemical equilibrium with the mineral; the δ44/42Ca composition of the fluid was up to 0.8‰ higher than the dissolving calcite at the end of the dissolution experiments. Calcite precipitation was provoked by increasing the reactor fluid pH after chemical equilibrium had been attained via dissolution. Rayleigh isotope fractionation effects were observed immediately after the pH was increased and rapid calcite precipitation occurred. However, isotopic exchange continued after the system chemically equilibrated, eradicating this Rayleigh signal. Taken together, these observations 1) confirm dynamic mineral-fluid equilibrium (i.e. dissolution and precipitation occur at equal, non-zero rates at equilibrium), and 2) indicate that isotopic compositions of calcite can readily equilibrate even when this mineral is in bulk chemical equilibrium with its coexisting fluid. This latter observation suggests the preservation of paleo-environmental isotopic signatures in calcite may require a combination of the isolation of the fluid-mineral system from external chemical input and/or the existence of a yet to be defined calcite dissolution/precipitation inhibition mechanism

Modern and Cenozoic records of seawater magnesium from foraminiferal Mg isotopes

Magnesium is an element critically involved in the carbon cycle, because weathering of Ca-Mg silicates removes atmospheric CO2 into rivers, and formation of Ca-Mg carbonates in the oceans removes carbon from the ocean-atmosphere system. Hence the Mg cycle holds the potential to provide valuable insights into Cenozoic climate-system history, and the shift during this time from a greenhouse to icehouse state. We present Mg isotope ratios for the past 40 Myr using planktic foraminifers as an archive. Modern foraminifera, which discriminate against elemental and isotopically heavy Mg during calcification, show no correlation between the Mg isotope composition (δ26Mg, relative to DSM-3) and temperature, Mg / Ca or other parameters such as carbonate saturation (ΔCO3). However, inter-species isotopic differences imply that only well-calibrated single species should be used for reconstruction of past seawater. Seawater δ26Mg inferred from the foraminiferal record decreased from ~0‰ at 15 Ma, to −0.83‰ at the present day, which coincides with increases in seawater lithium and oxygen isotope ratios. It strongly suggests that neither Mg concentrations nor isotope ratios are at steady state in modern oceans, given its ~10 Myr residence time. From these data, we have developed a dynamic box model to understand and constrain changes in Mg sources to the oceans (rivers) and Mg sinks (dolomitisation and hydrothermal alteration). Our estimates of seawater Mg concentrations through time are similar to those independently determined by pore waters and fluid inclusions. Modelling suggests that dolomite formation and the riverine Mg flux are the primary controls on the δ26Mg of seawater, while hydrothermal Mg removal and the δ26Mg of rivers are more minor controls. Using Mg riverine flux and isotope ratios inferred from the 87Sr / 86Sr record, the modelled Mg removal by dolomite formation shows minima in the Oligocene and at the present day (with decreasing trends from 15 Ma), both coinciding with rapid decreases in global temperatures

Deep fluid release in warm subduction zones from a breached slab seal

Petrological models and seismic data from subduction zones with geotherms of 7 K km−1 or higher suggest that slabs in these systems dehydrate effectively in the forearc. A large fluid flux is nevertheless released from these slabs at and beyond subarc depth, suggesting that large amounts of H2O can remain slab-bound to much greater depth than expected. We propose that this is due to a transient sealing effect exerted by the subducting lower crust. To test this concept, the petrological and geochemical evolution of such gabbroic crust is investigated through a textural, petrological and Li-chronometric analysis of eclogitized gabbros from an exhumed ultrahigh-pressure terrane. The samples record pristine transitions from dry, rigid gabbro to hydrated eclogite and eclogite mylonite, which occurred when these rocks resided at 90-110 km depth. The observations characterize step-by-step the deformation and overstepped mineral reactions that following the influx of external fluids along a developing network of permeable shear zones. Lithium chronometry indicates that the gabbroic rocks were breached and permeated within a few weeks at a very specific depth within the 90-110 km interval—depths where, in warm subduction zones, large fluid-filled channel system emanate from the slab. The data support a model in which fluids produced in the deserpentinizing slab mantle are trapped at high pore pressure beneath the slab Moho and are ultimately released at subarc depth where the lower crust fails and develops highly permeable fluid vents. The subducting lower crust thus may play an important role in regulating H2O and element budgets, and controlling slab rheology in warm subduction zones

On the use of Li isotopes as a proxy for water–rock interaction in fractured crystalline rocks: a case study from the Gotthard rail base tunnel

We present Li isotope measurements of groundwater samples collected during drilling of the 57 km long Gotthard rail base tunnel in Switzerland, to explore the use of Li isotope measurements for tracking water–rock interactions in fractured crystalline rocks at temperatures of up to 43 °C. The 17 groundwater samples originate from water-conducting fractures within two specific crystalline rock units, which are characterized by a similar rock mineralogy, but significantly different fluid composition. In particular, the aqueous Li concentrations observed in samples from the two units vary from 1–4 mg/L to 0.01–0.02 mg/L. Whereas δ7Li values from the unit with high Li concentrations are basically constant (δ7Li = 8.5–9.1‰), prominent variations are recorded for the samples from the unit with low Li concentrations (δ7Li = 10–41‰). This observation demonstrates that Li isotope fractionation can be highly sensitive to aqueous Li concentrations. Moreover, δ7Li values from the unit with low Li concentrations correlate well with reaction progress parameters such as pH and [Li]/[Na] ratios, suggesting that δ7Li values are mainly controlled by the residence time of the fracture groundwater. Consequently, 1D reactive transport modeling was performed to simulate mineral reactions and associated Li isotope fractionation along a water-conducting fracture system using the code TOUGHREACT. Modeling results confirm the residence time hypothesis and demonstrate that the absence of δ7Li variation at high Li concentrations can be well explained by limitation of the amount of Li that is incorporated into secondary minerals. Modeling results also suggest that Li uptake by kaolinite forms the key process to cause Li isotope fractionation in the investigated alkaline system (pH >9), and that under slow flow conditions (<10 m/year), this process is associated with a very large Li isotope fractionation factor (ε ≈ −50‰). Moreover, our simulations demonstrate that for simple and well-defined systems with known residence times and low Li concentrations, δ7Li values may help to quantify mineral reaction rates if more thermodynamic data about the temperature-dependent incorporation of Li in secondary minerals as well as corresponding fractionation factors become available in the future. In conclusion, δ7Li values may be a powerful tool to track water–rock interaction in fractured crystalline rocks at temperature higher than those at the Earth’s surface, although their use is restricted to low Li concentrations and well defined flow systems

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 Li isotope response to mountain uplift

Silicate weathering is a key process by which CO2 is removed from the atmosphere. It has been proposed that mountain uplift caused an increase in silicate weathering, and led to the long-term Cenozoic cooling trend, although this hypothesis remains controversial. Lithium isotopes are a tracer of silicate weathering processes, which may allow this hypothesis to be tested. Recent studies have demonstrated that the Li isotope ratio in seawater increased during the period of Himalayan uplift (~45 Ma), but the relationship between uplift and the Li isotope ratio of river waters has not been tested. Here we examine Li isotope ratios in rivers draining catchments with variable uplift rates from South Island, New Zealand. A negative trend between δ7Li and uplift shows that areas of rapid uplift have low δ7Li, whereas flatter floodplain areas have high δ7Li. Combined with U activity ratios, the data suggest that primary silicates are transported to floodplains, where δ7Li and (234U/238U) are driven to high values due to preferential uptake of 6Li by secondary minerals, and long fluid-mineral contact times that enrich waters in 234U. In contrast, in mountainous areas, fresh primary mineral surfaces are continuously provided, driving δ7Li and (234U/238U) low. This is the opposite trend to that expected if the increase in Cenozoic δ7Li in the oceans is driven directly by mountain uplift. These data suggests that, rather than weathering of mountain belts, the increase in seawater δ7Li reflects the formation of floodplains and the increased formation of secondary minerals

Controls on the Mg Cycle in the Tropics: Insights from a Case Study at the Luquillo Critical Zone Observatory

AbstractTo better constrain the mechanisms controlling short-term Mg dynamics in the tropics, we sampled critical zone compartments of a catchment covered by thick, highly weathered regolith. Our Mg and δ26Mg data indicate that rain is a main source of Mg throughout the regolith, and we do not observe Mg isotope offsets in vegetation/surficial pore water. In addition to rain and weathering inputs, a heavy isotope excursion at ∼1 m depth indicates a fractionation process, likely sorption-desorption or clay dissolution. Stream water δ26Mg reflects inputs from rain and a heavy source, likely differential weathering along deep bedrock fractures

Links between deformation, chemical enrichments and Li-isotope compositions in the lithospheric mantle of the central Siberian craton

We report the concentrations ([Li]) and isotopic compositions of Li in mineral separates and bulk rocks obtained by MC-ICPMS for 14 previously studied garnet and spinel peridotite xenoliths from the Udachnaya kimberlite in the central Siberian craton as well as major and trace element compositions for a new suite of 13 deformed garnet peridotites. The deformed Udachnaya peridotites occur at > 5 GPa; they are metasomatized residues of melt extraction, which as a group experienced greater modal and chemical enrichments than coarse peridotites. We identify two sub-groups of the deformed peridotites: (a) mainly cryptically metasomatized (similar to coarse peridotites) with relatively low modal cpx (< 6%) and garnet (< 7%), low Ca and high Mg#, sinusoidal REE patterns in garnet, and chemically unequilibrated garnet and cpx; (b) modally metasomatized with more cpx and garnet, higher Ca, Fe and Ti, and equilibrated garnet and cpx. The chemical enrichments are not proportional to deformation degrees. The deformation in the lower lithosphere is caused by a combination of localized stress, heating and fluid ingress from the pathways of ascending proto-kimberlite melts, with metasomatic media evolving due to reactions with wall rocks. Mg-rich olivine in spinel and coarse garnet Udachnaya peridotites has 1.2–1.9 ppm Li and δ7Li of 1.2–5.0‰, i.e. close to olivine in equilibrated fertile to depleted off-craton mantle peridotites from literature data, whereas olivine from the deformed peridotites has higher [Li] (2.4–7.5 ppm) and a broader range of δ7Li (1.8–11.6‰), which we attribute to pre-eruption metasomatism. [Li] in opx is higher than in coexisting olivine while Δ7LiOl-Opx (δ7LiOl − δ7LiOpx) ranges from − 6.6 to 7.8‰, indicating disequilibrium inter-mineral [Li] and Li-isotope partitioning. We relate these Li systematics to interaction of lithospheric peridotites with fluids or melts that are either precursors of kimberlite magmatism or products of their fractionation and/or reaction with host mantle. The melts rich in Na and carbonates infiltrated, heated and weakened wall-rock peridotites to facilitate their deformation as well as produce high [Li] and variable, but mainly high, δ7Li in olivine. The carbonate-rich melts preferentially reacted with the opx without achieving inter-mineral equilibrium because opx is consumed by such melts, and because of small volumes and uneven distribution of the metasomatic media, as well as short time spans between the melt infiltration and the capture of the wall-rock fragments by incoming portions of ascending kimberlite magma as xenoliths. Trapped interstitial liquid solidified as cryptic components responsible for high [Li] and the lack of δ7Li balance between olivine and opx, and bulk rocks. Unaltered δ26Mg values (0.20–0.26‰) measured in several olivine separates show no effects of the metasomatism on Mg-isotopes, apparently due to high Mg in the peridotites

Continental weathering and terrestrial (Oxyhydr)oxide export: comparing glacial and non-glacial catchments in Iceland

Glaciers enhance terrestrial erosion and sediment export to the ocean. Glaciers can also impact mineral specific weathering rates relative to analogous non-glacial terrains. In tandem these processes affect continent sediment export to the oceans over glacial-interglacial cycles. This study summarizes field data from glacial and non-glacial Icelandic river catchments to quantify the impact of weathering regime on iron and aluminium (oxyhydr)oxide mineral formation and flux rates. Aluminium and iron (oxyhydr)oxides are strong indicators of organic carbon preservation in soils and marine sediments. Tracing changes in (oxyhydr)oxide formation and deposition therefore provides a means of evaluating potential changes in organic carbon sequestration rates over glacial-interglacial cycles. Overall, there are several measurable chemical differences between the studied glacial and non-glacial catchments which reflect the key role of soil formation on terrestrial weathering. One of the noted chemical differences is that weathering in non-glacial catchments is characterized by higher apparent rates of iron and aluminium (oxyhydr)oxide formation relative to glacial catchments. However, the offset in (oxyhydr)oxide formation does not appear to be transferred into river sediment compositions, and physical weathering appears to be the dominant control of river sediment composition and export. Glacial rivers export far more total sediment to nearshore marine environments than analogous non-glacial rivers suggesting glacial weathering enhances carbon burial by increasing nearshore marine (oxyhydr)oxide accumulation

Assessing bulk carbonates as archives for seawater Li isotope ratios

Silicate weathering is a primary control on the carbon cycle and therefore long-term climate. Tracing silicate weathering in the geological record has been a challenge for decades, with a number of proxies proposed and their limits determined. Recently lithium isotopes in marine carbonates have emerged as a potential tracer. Bulk carbonates are increasingly being used as a Li isotope archive, though with limited tests thus far of the robustness of this approach in the modern ocean. As the bulk composition of marine pelagic carbonates has changed through time and geographically, assessing the fidelity of bulk carbonate as proxy carrier is fundamental. To address the impact of compositional variability in bulk carbonate on Li isotopes, we examine 27 Bahamian aragonitic bulk carbonates and 16 Atlantic largely calcitic core-top sediment samples. Two core-tops only have trace (<10 %) carbonate, and are analysed to test whether carbonates in such sections are still a viable archive. We selectively extract the exchangeable and carbonate fractions from the core-top samples. The exchangeable fraction contains ∼2 % of the total Li and has a fairly constant offset from seawater of 16.5 ± 0.8‰. When leaching silicate-containing carbonates, acetic acid buffered with sodium acetate appears a more robust method of solely attacking carbonates compared to dilute HCl, which may also liberate some silicate-bound Li. Carbonates from samples that do not contain aragonite have the isotopic fractionation of seawater of Δ7Liseawater-calcite = 6.1 ± 1.3‰ (2sd), which is not affected by latitude or the water depth the sample was deposited at. The pure aragonite bulk carbonates from the Bahamas have a fractionation of Δ7Liseawater-aragonite = 9.6 ± 0.6‰. A sediment sample from the Galician coast that mostly consists of quartz is highly offset from seawater by ∼20‰ and also has relatively high Li/Ca ratios. These high values are not due to leaching of silicate material directly (Al/Ca ratios are low). We interpret this addition via cation exchange of Li from silicate during recrystallisation. Overall bulk carbonates from the open ocean are a reliable archive of seawater δ7Li, but care must be taken with carbonate mineralogy and low-carbonate samples. Overall, therefore, any examination of the palaeo-seawater δ7Li record must be reproduced in different global settings (e.g. multiple global cores) before it can be considered robust