Interpreting the Ca isotope record of marine biogenic carbonates

An 18 million year record of the Ca isotopic composition (δ^44/42Ca) of planktonic foraminiferans from ODP site 925, in the Atlantic, on the Ceara Rise, provides the opportunity for critical analysis of Ca isotope-based reconstructions of the Ca cycle. δ^44/42Ca in this record averages +0.37 ± 0.05 (1σ SD) and ranges from +0.21‰ to +0.52‰. The record is a good match to previously published Neogene Ca isotope records based on foraminiferans, but is not similar to the record based on bulk carbonates, which has values that are as much as 0.25‰ lower. Bulk carbonate and planktonic foraminiferans from core tops differ slightly in their δ^44/42Ca (i.e., by 0.06 ± 0.06‰ (n = 5)), while the difference between bulk carbonate and foraminiferan values further back in time is markedly larger, leaving open the question of the cause of the difference. Modeling the global Ca cycle from downcore variations in δ^44/42Ca by assuming fixed values for the isotopic composition of weathering inputs (δ^44/42Ca_w) and for isotope fractionation associated with the production of carbonate sediments (Δ_sed) results in unrealistically large variations in the total mass of Ca²⁺ in the oceans over the Neogene. Alternatively, variations of ±0.05‰ in the Ca isotope composition of weathering inputs or in the extent of fractionation of Ca isotopes during calcareous sediment formation could entirely account for variations in the Ca isotopic composition of marine carbonates. Ca isotope fractionation during continental weathering, such as has been recently observed, could easily result in variations in δ^44/42Ca_w of a few tenths of permil. Likewise a difference in the fractionation factors associated with aragonite versus calcite formation could drive shifts in Δ_sed of tenths of permil with shifts in the relative output of calcite and aragonite from the ocean. Until better constraints on variations in δ^44/42Ca_w and Δ_sed have been established, modeling the Ca²⁺ content of seawater from Ca isotope curves should be approached cautiously.     

Calcium and magnesium isotope systematics in rivers draining the Himalaya-Tibetan-Plateau region: Lithological or fractionation control?

In rivers draining the Himalaya-Tibetan-Plateau region, the ²⁶Mg/²⁴Mg ratio has a range of 2‰ and the ⁴⁴Ca/⁴²Ca ratio has a range of 0.6‰. The average δ²⁶Mg values of tributaries from each of the main lithotectonic units (Tethyan Sedimentary Series (TSS), High Himalayan Crystalline Series (HHCS) and Lesser Himalayan Series (LHS)) are within 2 standard deviation analytical uncertainty (0.14‰). The consistency of average riverine δ²⁶Mg values is in contrast to the main rock types (limestone, dolostone and silicate) which range in their average δ²⁶Mg values by more than 2‰. Tributaries draining the dolostones of the LHS differ in their values compared to tributaries from the TSS and HHCS. The chemistry of these river waters is strongly influenced by dolostone (solute Mg/Ca close to unity) and both δ²⁶Mg (−1.31‰) and (0.64‰) values are within analytical uncertainty of the LHS dolostone. These are the most elevated values in rivers and rock reported so far demonstrating that both riverine and bedrock values may show greater variability than previously thought.Although rivers draining TSS limestone have the lowest values at −1.41 and 0.42‰, respectively, both are offset to higher values compared to bedrock TSS limestone. The average δ²⁶Mg value of rivers draining mainly silicate rock of the HHCS is −1.25‰, lower by 0.63‰ than the average silicate rock. These differences are consistent with a fractionation of δ²⁶Mg values during silicate weathering. Given that the proportion of Mg exported from the Himalaya as solute Mg is small, the difference in ²⁶Mg/²⁴Mg ratios between silicate rock and solute Mg reflects the ²⁶Mg/²⁴Mg isotopic fractionation factor () between silicate and dissolved Mg during incongruent silicate weathering. The value of of 0.99937 implies that in the TSS, solute Mg is primarily derived from silicate weathering, whereas the source of Ca is overwhelmingly derived from carbonate weathering. The average value in HHCS rivers is within uncertainty of silicate rock at 0.39‰. The widespread hot springs of the High Himalaya have an average δ²⁶Mg value of −0.46‰ and an average value of 0.5‰, distinct from riverine values for δ²⁶Mg but similar to riverine values. Although rivers draining each major rock type have and δ²⁶Mg values in part inherited from bedrock, there is no correlation with proxies for carbonate or silicate lithology such as Na/Ca ratios, suggesting that Ca and Mg are in part recycled. However, in spite of the vast contrast in vegetation density between the arid Tibetan Plateau and the tropical Lesser Himalaya, the isotopic fractionation factor for Ca and Mg between solute and rocks are not systematically different suggesting that vegetation may only recycle a small amount of Ca and Mg in these catchments.The discrepancy between solute and solid Ca and Mg isotope ratios in these rivers from diverse weathering environments highlight our lack of understanding concerning the origin and subsequent path of Ca and Mg, bound as minerals in rock, and released as cations in rivers. The fractionation of Ca and Mg isotope ratios may prove useful for tracing mechanisms of chemical alteration. Ca isotope ratios of solute riverine Ca show a greater variability than previously acknowledged. The variability of Ca isotope ratios in modern rivers will need to be better quantified and accounted for in future models of global Ca cycling, if past variations in oceanic Ca isotope ratios are to be of use in constraining the past carbon cycle.     

Non-biological fractionation of stable Ca isotopes in soils of the Atacama Desert, Chile

We measured Ca stable isotope ratios (δ^44/40Ca) in an ancient (2 My), hyperarid soil where the primary source of mobile Ca is atmospheric deposition. Most of the Ca in the upper meter of this soil (3.5 kmol m⁻²) is present as sulfates (2.5 kmol m⁻²), and to a lesser extent carbonates (0.4 kmol m⁻²). In aqueous extracts of variably hydrated calcium sulfate minerals, δ^44/40Ca_E values (vs. bulk Earth) increase with depth (1.4 m) from a minimum of −1.91‰ to a maximum of +0.59‰. The trend in carbonate-δ^44/40Ca in the top six horizons resembles that of sulfate-δ^44/40Ca, but with values 0.1-0.6‰ higher. The range of observed Ca isotope values in this soil is about half that of δ^44/40Ca values observed on Earth. Linear correlation among δ^44/40Ca, δ³⁴S and δ¹⁸O values indicates either (a) a simultaneous change in atmospheric input values for all three elements over time, or (b) isotopic fractionation of all three elements during downward transport. We present evidence that the latter is the primary cause of the isotopic variation that we observe. Sulfate-δ³⁴S values are positively correlated with sulfate-δ¹⁸O values (R² = 0.78) and negatively correlated with sulfate δ^44/40Ca_E values (R² = 0.70). If constant fractionation and conservation of mass with downward transport are assumed, these relationships indicate a δ^44/40Ca fractionation factor of −0.4‰ in CaSO₄. The overall depth trend in Ca isotopes is reproduced by a model of isotopic fractionation during downward Ca transport that considers small and infrequent but regularly recurring rainfall events. Near surface low Ca isotope values are reproduced by a Rayleigh model derived from measured Ca concentrations and the Ca fractionation factor predicted by the relationship with S isotopes. This indicates that the primary mechanism of stable isotope fractionation in CaSO₄ is incremental and effectively irreversible removal of an isotopically enriched dissolved phase by downward transport during small rainfall events.     

The impact of water-rock interaction and vegetation on calcium isotope fractionation in soil- and stream waters of a small, forested catchment (the Strengbach case)

This study aims to constrain the factors controlling the calcium isotopic compositions in surface waters, especially the respective role of vegetation and water-rock interactions on Ca isotope fractionation in a continental forested ecosystem. The approach is to follow changes in space and time of the isotopic composition and concentration of Ca along its pathway through the hydro-geochemical reservoirs from atmospheric deposits to the outlet of the watershed via throughfalls, percolating soil solutions and springs. The study is focused on the Strengbach catchment, a small forested watershed located in the northeast of France in the Vosges mountains. The δ^44/40Ca values of springs, brooks and stream waters from the catchment are comparable to those of continental rivers and fluctuate between 0.17 and 0.87‰. Soil solutions, however, are significantly depleted in lighter isotopes (δ^44/40Ca: 1.00-1.47‰), whereas vegetation is strongly enriched (δ^44/40Ca: −0.48‰ to +0.19‰). These results highlight that vegetation is a major factor controlling the calcium isotopic composition of soil solutions, with depletion in “light” calcium in the soil solutions from deeper parts of the soil compartments due to preferential ⁴⁰Ca uptake by the plants rootsystem. However, mass balance calculations require the contribution of an additional Ca flux into the soil solutions most probably associated with water-rock interactions. The stream waters are marked by a seasonal variation of their δ^44/40Ca, with low δ^44/40Ca in winter and high δ^44/40Ca in spring, summer and autumn. For some springs, nourishing the streamlet, a decrease of the δ^44/40Ca value is observed when the discharge of the spring increases, with, in addition, a clear covariation between the δ^44/40Ca and corresponding H₄SiO₄ concentrations: high δ^44/40Ca values and low H₄SiO₄ concentrations at high discharge; low δ^44/40Ca values and high H₄SiO₄ concentrations at low discharge. These data imply that during dry periods and low water flow rate the source waters carry a Ca isotopic signature from alteration of soil minerals, whereas during wet periods and high flow rates admixture of significant quantities of ⁴⁰Ca depleted waters (vegetation induced signal) from uppermost soil horizons controls the isotopic composition of the source waters. This study clearly emphasizes the potential of Ca isotopes as tracers of biogeochemical processes at the water-rock-vegetation interface in a small forested catchment.     

Large fractionation of calcium isotopes during cave-analogue calcium carbonate growth

We have measured δ^44/42Ca of laboratory-precipitated calcite grown in an experimental setup that closely replicates stalagmite formation. Calcium solutions were dripped onto two different substrates in tightly-controlled conditions and calcite precipitated due to rapid CO₂ degassing. With seeded glass slides as the substrate, we observe a Ca isotope ratio in the calcite which is ∼0.5‰ per amu lower than that in the growth solution. This fractionation is generally almost twice that observed in previously published calcite growth experiments and indicates a large kinetic effect on Ca isotopes in the stalagmite growth environment. The precipitate forming near the spot where the drip lands shows slightly greater solution-to-precipitate fractionation than calcite further from the drip reflecting a decrease in this kinetic fractionation as precipitation continues. We interpret these results in the context of the model of Fantle and DePaolo (2007) which involves surface entrapment of light Ca isotopes to decrease calcite δ^44/42Ca, and depletion of Ca from the solution in the direct vicinity of the growing calcite to increase calcite δ^44/42Ca. In the stalagmite setting, the second of these effects is minimized so that calcite Ca isotope ratios are unusually light. This interpretation suggests that stalagmite Ca isotope ratios should decrease with the saturation state of the drip water (i.e. with the growth rate of calcite). Ca isotopes might therefore allow reconstruction of surface entrapment of trace metals and isotopes more generally and might, for instance, allow an assessment of the appropriate relationship between oxygen isotope fractionation and temperature for periods of past growth in stalagmites.     

The major ion, δCa, δCa, and δMg geochemistry of granite weathering at pH = 1 and T = 25 °C: power-law processes and the relative reactivity of minerals

We dissolved Boulder Creek Granodiorite in a plug flow reactor for 5794 h at pH = 1 and T = 25 °C. The primary purpose of the experiment was to identify controls on dissolved δ^44/40Ca, δ^44/42Ca, and δ^26/24Mg values during granite weathering. Herein, we also examine the origin of Ca and Mg isotopic variability among minerals composing the Boulder Creek Granodiorite, and we constrain fundamental characteristics of granite weathering important for quantifying the elemental and isotopic geochemistry of the reactor output. Nine Ca-bearing minerals display an 8.80‰ range of δ^44/40Ca values and a 0.51‰ range of δ^44/42Ca values. Three Mg-bearing minerals display a 1.53‰ range of δ^26/24Mg values. These ranges expressed at the mineralogical scale are higher than the ranges thus far reported for bulk igneous rocks. Most of the δ^44/40Ca variability reflects ⁴⁰Ca enrichment in K-feldspar, and to a lesser extent, biotite, due to the radioactive decay of ⁴⁰K over the 1.7 Ga age of the rock, whereas the entire range of δ^44/42Ca values reflects mass-dependent isotope fractionation during igneous differentiation and crystallization. The range of δ^26/24Mg values may represent either fractionation during the chloritization of biotite or interaction of the Boulder Creek Granodiorite with Mg-rich metamorphic fluids having low δ^26/24Mg values.The elemental and isotopic composition of the reactor output varied substantially during the experiment. We synthesize the mineralogical and fluid data using coupled mass-conservation equations solved at non-steady-state. Model calculations reveal an intricate balance between increasing specific surface area and decreasing mineral concentrations. While surface area normalized dissolution rate constants were time-invariant, specific surface area increased as a power-law function of time through positive feedbacks between mechanical disaggregation, chemical dissolution, and mineral depletion. Variations in dissolved δ^44/40Ca, δ^44/42Ca, and δ^26/24Mg values reflect conservative mixing rather than fractionation. Apatite and calcite initially control δ^44/40Ca and δ^44/42Ca values, followed by biotite, titanite, epidote, hornblende, and plagioclase. The release of radiogenic ⁴⁰Ca clearly defines the period where biotite dissolution dominates. The brucite layer of chlorite initially controls δ^26/24Mg values, followed by biotite, the TOT layer of chlorite, and hornblende. Through direct isotopic tracking, these results demonstrate that trace minerals, such as apatite and calcite in the case of Ca and brucite in the case of Mg, dominate elemental release during the incipient stages of granite weathering. The results further show that biotite dissolution dominates the middle stages of granite weathering and that plagioclase dissolution only becomes important during relatively late stages. The Ca and Mg isotope variations associated with these stages are distinct and potentially resolvable in soil mineral weathering studies.     

Mg isotope constraints on soil pore-fluid chemistry: Evidence from Santa Cruz, California

Mg isotope ratios (²⁶Mg/²⁴Mg) are reported in soil pore-fluids, rain and seawater, grass and smectite from a 90 kyr old soil, developed on an uplifted marine terrace from Santa Cruz, California. Rain water has an invariant ²⁶Mg/²⁴Mg ratio (expressed as δ²⁶Mg) at −0.79 ± 0.05‰, identical to seawater δ²⁶Mg. Detrital smectite (from the base of the soil profile, and therefore unweathered) has a δ²⁶Mg value of 0.11‰, potentially enriched in ²⁶Mg by up to 0.3‰ compared to the bulk silicate Earth Mg isotope composition (although within the range of all terrestrial silicates). The soil pore-waters show a continuous profile with depth for δ²⁶Mg, ranging from −0.99‰ near the surface to −0.43‰ at the base of the profile. Shallow pore-waters (<1 m) have δ²⁶Mg values that are similar to, or slightly lower than the rain waters. This implies that the degree of biological cycling of Mg in the pore-waters is relatively small and is quantified as <32%, calculated using the average Mg isotope enrichment factor between grass and rain (δ²⁶Mg_grass-δ²⁶Mg_rain) of 0.21‰. The deep pore-waters (1-15 m deep) have δ²⁶Mg values that are intermediate between the smectite and rain, ranging from −0.76‰ to −0.43‰, and show a similar trend with depth compared to Sr isotope ratios. The similarity between Sr and Mg isotope ratios confirms that the Mg in the pore-waters can be explained by a mixture between rain and smectite derived Mg, despite the fact that Mg and Sr concentrations may be buffered by the exchangeable reservoir. However, whilst Sr isotope ratios in the pore-waters span almost the complete range between mineral and rain inputs, Mg isotopes compositions are much closer to the rain inputs. If Mg and Sr isotope ratios are controlled uniquely by a mixture, the data can be used to estimate the mineral weathering inputs to the pore-waters, by correcting for the rain inputs. This isotopic correction is compared to the commonly used chloride correction for precipitation inputs. A consistent interpretation is only possible if Mg isotope ratios are fractionated either by the precipitation of a secondary Mg bearing phase, not detected by conventional methods, or selective leaching of ²⁴Mg from smectite. There is therefore dual control on the Mg isotopic composition of the pore-waters, mixing of two inputs with distinct isotopic compositions, modified by fractionation. The data provide (1) further evidence for Mg isotope fractionation at the surface of the Earth and (2) the first field evidence of Mg isotope fractionation during uptake by natural plants. The coherent behaviour of Mg isotope ratios in soil environments is encouraging for the development of Mg isotope ratios as a quantitative tracer of both weathering inputs of Mg to waters, and the physicochemical processes that cycle Mg, a major cation linked to the carbon cycle, during continental weathering.     

Calcium isotopes in fossil bones and teeth — Diagenetic versus biogenic origin

We present the first systematic study of Ca isotopes (δ^44/40Ca) in Late Triassic to Late Cretaceous dinosaur bones and teeth (enamel and dentin) from sympatric herbivorous and carnivorous dinosaurs. The samples derive from five different localities, and data from embedding sediments are also presented. Additional δ^44/40Ca in skeletal tissues from modern reptiles and birds (avian dinosaurs) were measured for comparison in order to examine whether the original Ca isotopic composition in dinosaur skeletal apatite was preserved or might have changed during the diagenesis and fossilization process.δ^44/40Ca of fossil skeletal tissues range from −1.62‰ (Tyrannosaurus rex enamel) to +1.08‰ (Brachiosaurus brancai bone), while values in modern archosaur bones and teeth range from −1.63‰ (caiman enamel) to −0.37‰ (ostrich bone). The average δ^44/40Ca of the three types of fossil skeletal tissue analyzed - bone, dentin and enamel - show some systematic differences: while δ^44/40Ca in bone exhibits the highest values, while δ^44/40Ca in enamel has the lowest values, and dentin δ^44/40Ca falls in between. Values of δ^44/40Ca in the remains of herbivorous dinosaurs (0.1-1.1‰) are generally higher than those of bones of modern mammalian herbivores (−2.6‰ to −0.8‰) and from modern herbivorous archosaurs, which exhibit intermediate δ^44/40Ca (−0.8‰ to −0.4‰). These systematic isotopic shifts may reflect physiological differences between dinosaurs, mammals and reptiles representing different taxonomic groups of vertebrates.Systematic offsets in skeletal apatite δ^44/40Ca between herbivorous and carnivorous dinosaurs are not obvious, indicating a lack of a clear-cut Trophic Level Effect (TLE) shift between herbivores and carnivores in dinosaurs. This observation can be explained if the carnivorous dinosaurs in this study fed mainly on soft tissues from their prey and did not ingest hard (calcified) tissue to much extent. The most striking indication that the primary δ^44/40Ca is actually preserved in most of the fossil teeth is a difference in δ^44/40Ca of about 0.35 ± 0.10‰ (1SD) between dentin and enamel, based upon 11 of 16 analyzed dentin-enamel pairs. This difference is close to that found in modern reptiles (0.28 ± 0.05‰), and strongly suggests that this tell-tale signature is a primary feature of the fossilized dinosaur material as well. Furthermore, simple mass balance calculations show that changes of the original δ^44/40Ca in bones and teeth by diagenetically-formed calcium-bearing minerals are either small or would require implausible high original δ^44/40Ca values in the skeletal apatite.     

From biological to lithological control of the B geochemical cycle in a forest watershed (Strengbach, Vosges)

There is a fast growing interest in understanding the coupling between mineralogical and biological processes responsible for the migration of elements through continental ecosystems. This issue has fundamental impacts at the soil/plant scale because it can explain the tight links between soil and plant development and at the watershed scale because it gives a direct access to the water quality. In the present study, we performed an extended investigation of the bio-geochemical cycle of boron, which is an element known to be suitable for investigating water/rock interactions and vegetation cycling. New B data are provided along the hydro-bio-geochemical continuum in a forest ecosystem (Strengbach basin, Vosges, France), from rainwaters down to the outlet of the basin including systematic analyses of throughfalls, soil solutions, springs and brooks scattered in the watershed. At the watershed scale, we evidence a relationship between the B isotopic composition of river waters and the weathering regime outlining a predominant control of the parent rock mineralogy on the B geochemical behavior. At the soil/plant scale, it appears that the B geochemical cycle is controlled by the vegetation cycling, which is characterized by an uncommon, easy to distinguish, B isotopic composition (δ¹¹B ranging from about +30‰ to +45‰). Each year the amount of B being involved in the vegetation cycle is about four times greater than that of B being exported out of the watershed. At 10 cm depth in soil, where the plant roots are expected to be the most active, we observe a marked seasonal oscillation of the B isotopic values, which is interpreted as resulting from the vegetation activity. A mass balance calculation based on the assumption that that ¹⁰B is preferentially accumulated in the biomass tends to indicate that the soil/plant system does not behave at steady state with respect to B.Because of the very distinct B isotopic signature of vegetation and minerals in soil, box modeling allows to quantify the part of the B fluxes involved in the vegetation cycling and the mineral reactions, respectively. This calculation reveals a clear correlation between the amount of B derived from soil weathering and the amount of B absorbed by plant roots. This result clearly supports the idea that a coupling exists between mineral weathering and plant activity, for the study of which B isotopes appear particularly suitable.     

Stable silicon isotopes of groundwater, feldspars, and clay coatings in the Navajo Sandstone aquifer, Black Mesa, Arizona, USA

We present some of the first analyses of the stable isotopic composition of dissolved silicon (Si) in groundwater. The groundwater samples were from the Navajo Sandstone aquifer at Black Mesa, Arizona, USA, and the Si isotope composition of detrital feldspars and secondary clay coatings in the aquifer were also analyzed. Silicon isotope compositions were measured using high-resolution multi-collector inductively coupled mass spectrometry (HR-MC-ICP-MS) (Nu1700 & NuPlasma HR). The quartz dominated bulk rock and feldspar separates have similar δ³⁰Si of −0.09 ± 0.04‰ and −0.15 ± 0.04‰ (±95% SEM), respectively, and clay separates are isotopically lighter by up to 0.4‰ compared to the feldspars. From isotopic mass-balance considerations, co-existing aqueous fluids should have δ³⁰Si values heavier than the primary silicates. Positive δ³⁰Si values were only found in the shallow aquifer, where Si isotopes are most likely fractionated during the dissolution of feldspars and subsequent formation of clay minerals. However, δ³⁰Si decreases along the flow path from 0.56‰ to −1.42‰, representing the most negative dissolved Si isotope composition so far found for natural waters. We speculate that the enrichment in ²⁸Si is due to dissolution of partly secondary clay minerals and low-temperature silcretes in the Navajo Sandstone. The discovery of the large range and systematic shifts of δ³⁰Si values along a groundwater flow path illustrates the potential utility of stable Si isotopes for deciphering the Si cycling in sedimentary basins, tracing fluid flow, and evaluating global Si cycle.     

Lithium isotopic systematics of peridotite xenoliths from Hannuoba, North China Craton: Implications for melt-rock interaction in the considerably thinned lithospheric mantle

Li concentrations and isotopic compositions of coexisting minerals (ol, opx, and cpx) from peridotite xenoliths entrained in the Hannuoba Tertiary basalts, North China Craton, provide insight into Li isotopic fractionation between mantle minerals during melt-rock interaction in the considerably thinned lithospheric mantle. Bulk analyses of mineral separates show significant enrichment of Li in cpx (2.4-3.6 ppm) relative to olivine (1.2-1.8 ppm), indicating that these peridotites have been affected by mantle metasomatism with mafic silicate melts. Bulk olivine separates (δ⁷Li ∼ +3.3‰ to +6.4‰) are isotopically heavier than coexisting pyroxenes (δ⁷Li ∼ −3.3‰ to −8.2‰ in cpx, and −4.0‰ to −6.7‰ in opx). Such large variation suggests Li elemental and isotopic disequilibrium. This conclusion is supported by results from in situ SIMS analyses of mineral grains where significant Li elemental and isotopic zonations exist. The olivine and opx have lower Li concentrations and heavier Li isotopes in the rims than in the cores. This reverse correlation of δ⁷Li with Li concentrations indicates diffusive fractionation of Li isotopes. However, the zoning patterns in coexisting cpx show isotopically heavier rims with higher Li abundances. This positive correlation between δ⁷Li and Li concentrations suggests a melt mixing trend. We attribute Li concentration and isotope zonation in minerals to the effects of two-stage diffusive fractionation coupled with melt-rock interaction. The earliest melts may have been derived from the subducted oceanic slab with low δ⁷Li values produced by isotopic fractionation during the dehydration of the seawater-altered slab. Melts at later stages were derived from the asthenosphere and interacted with the peridotites, producing the Li elemental and isotopic zoning in mineral grains. These data thus provide evidence for multiple-stage peridotite-melt interaction in the lithospheric mantle beneath the northern North China Craton.     

Li isotope fractionation in peridotites and mafic melts

We have measured the Li isotope ratios of a range of co-existing phases from peridotites and mafic magmas to investigate high-temperature fractionations of ⁷Li/⁶Li. The Li isotopic compositions of seven mantle peridotites, reconstructed from analyses of mineral separates, show little variation (δ⁷Li 3.2-4.9‰) despite a wide range in fertility and radiogenic isotopic compositions. The most fertile samples yield a best estimate of δ⁷Li ∼ 3.5‰ for the upper mantle. Bulk analyses of olivine separates from the xenoliths are typically ∼1.5‰ isotopically lighter than co-existing orthopyroxenes, suggestive of a small, high-temperature equilibrium isotope fractionation. On the other hand, bulk analyses of olivine phenocrysts and their host melts are isotopically indistinguishable. Given these observations, equilibrium mantle melting should generate melts with δ⁷Li little different from their sources (<0.5‰ lighter). In contrast to olivine and orthopyroxene, that dominate peridotite Li budgets, bulk clinopyroxene analyses are highly variable (δ⁷Li = 6.6‰ to −8.1‰). Phlogopite separated from a modally metasomatised xenolith yielded an extreme δ⁷Li of −18.9‰. Such large Li isotope variability is indicative of isotopic disequilibrium. This inference is strongly reinforced by in situ, secondary ion mass-spectrometry analyses which show Li isotope zonation in peridotite minerals. The simplest zoning patterns show isotopically light rims. This style of zoning is also observed in the phenocrysts of holocrystalline Hawaiian lavas. More dramatically, a single orthopyroxene crystal from a San Carlos xenolith shows a W-shaped Li isotope profile with a 40‰ range in δ⁷Li, close to the isotope variability seen in all terrestrial whole rock analyses. We attribute Li isotope zonation in mineral phases to diffusive fractionation of Li isotopes, within mineral phases and along melt pathways that pervade xenoliths. Given the high diffusivity of Li, the Li isotope profiles we observe can persist, at most, only a few years at magmatic temperatures. Our results thus highlight the potential of Li isotopes as a high-resolution geospeedometer of the final phases of magmatic activity and cooling.     

Ca isotopes in carbonate sediment and pore fluid from ODP Site 807A: The Ca(aq)-calcite equilibrium fractionation factor and calcite recrystallization rates in Pleistocene sediments

The calcium isotopic compositions (δ⁴⁴Ca) of 30 high-purity nannofossil ooze and chalk and 7 pore fluid samples from ODP Site 807A (Ontong Java Plateau) are used in conjunction with numerical models to determine the equilibrium calcium isotope fractionation factor (α_s−f) between calcite and dissolved Ca²⁺ and the rates of post-depositional recrystallization in deep sea carbonate ooze. The value of α_s−f at equilibrium in the marine sedimentary section is 1.0000 ± 0.0001, which is significantly different from the value (0.9987 ± 0.0002) found in laboratory experiments of calcite precipitation and in the formation of biogenic calcite in the surface ocean. We hypothesize that this fractionation factor is relevant to calcite precipitation in any system at equilibrium and that this equilibrium fractionation factor has implications for the mechanisms responsible for Ca isotope fractionation during calcite precipitation. We describe a steady state model that offers a unified framework for explaining Ca isotope fractionation across the observed precipitation rate range of ∼14 orders of magnitude. The model attributes Ca isotope fractionation to the relative balance between the attachment and detachment fluxes at the calcite crystal surface. This model represents our hypothesis for the mechanism responsible for isotope fractionation during calcite precipitation. The Ca isotope data provide evidence that the bulk rate of calcite recrystallization in freshly-deposited carbonate ooze is 30-40%/Myr, and decreases with age to about 2%/Myr in 2-3 million year old sediment. The recrystallization rates determined from Ca isotopes for Pleistocene sediments are higher than those previously inferred from pore fluid Sr concentration and are consistent with rates derived for Late Pleistocene siliciclastic sediments using uranium isotopes. Combining our results for the equilibrium fractionation factor and recrystallization rates, we evaluate the effect of diagenesis on the Ca isotopic composition of marine carbonates at Site 807A. Since calcite precipitation rates in the sedimentary column are many orders of magnitude slower than laboratory experiments and the pore fluids are only slightly oversaturated with respect to calcite, the isotopic composition of diagenetic calcite is likely to reflect equilibrium precipitation. Accordingly, diagenesis produces a maximum shift in δ⁴⁴Ca of +0.15‰ for Site 807A sediments but will have a larger impact where sedimentation rates are low, seawater circulates through the sediment pile, or there are prolonged depositional hiatuses.     

Carbon, sulfur, and oxygen isotope evidence for a strong depth gradient and oceanic oxidation after the Ediacaran Hankalchough glaciation

In order to understand spatial variations of stable isotope geochemistry in the Quruqtagh basin (northwestern China) in the aftermath of an Ediacaran glaciation, we analyzed carbonate carbon isotopes (δ¹³C_carb), carbonate oxygen isotopes (δ¹⁸O_carb), carbonate associated sulfate sulfur (δ³⁴S_CAS) and oxygen isotopes (δ¹⁸O_CAS), and pyrite sulfur isotopes (δ³⁴S_py) of a cap dolostone atop the Ediacaran Hankalchough glacial diamictite at four sections. The four studied sections (YKG, MK, H and ZBS) represent an onshore-offshore transect in the Quruqtagh basin. Our data show a strong paleobathymetry-dependent isotopic gradient. From the onshore to offshore sections, δ¹³C_carb values decrease from −2‰ to −16‰ (VPDB), whereas δ¹⁸O_carb values increase from −4‰ to −1‰ (VPDB). Both δ³⁴S_CAS and δ³⁴S_py show stratigraphic variations in the two onshore sections (MK and YKG), but are more stable in the two offshore sections (H and ZBS). δ¹⁸O_CAS values of onshore samples are consistent with terrestrial oxidative weathering of pyrite. We propose that following the Hankalchough glaciation seawater in the Quruqtagh basin was characterized by a strong isotopic gradient. The isotopic data may be interpreted using a three-component mixing model that involves three reservoirs: deep-basin water, surface water, and terrestrial weathering input. In this model, the negative δ¹³C_carb values in the offshore sections are related to the upwelling of deep-basin water (where anaerobic oxidation of dissolved organic carbon resulted in ¹³C-depleted DIC), whereas sulfur isotope variations are strongly controlled by surface water sulfate and terrestrial weathering input derived from oxidative weathering of pyrite. The new data provide evidence for the oceanic oxidation following the Hankalchough glaciation.     

Characterization of calcium isotopes in natural and synthetic barite

The mineral barite (BaSO₄) accommodates calcium in its crystal lattice, providing an archive of Ca-isotopes in the highly stable sulfate mineral. Holocene marine (pelagic) barite samples from the major ocean basins are isotopically indistinguishable from each other (δ^44/40Ca = −2.01 ± 0.15‰) but are different from hydrothermal and cold seep barite samples (δ^44/40Ca = −4.13 to −2.72‰). Laboratory precipitated (synthetic) barite samples are more depleted in the heavy Ca-isotopes than pelagic marine barite and span a range of Ca-isotope compositions, Δ^44/40Ca = −3.42 to −2.40‰. Temperature, saturation state, , and aCa²⁺/aBa²⁺ each influence the fractionation of Ca-isotopes in synthetic barite; however, the fractionation in marine barite samples is not strongly related to any measured environmental parameter. First-principles lattice dynamical modeling predicts that at equilibrium Ca-substituted barite will have much lower ⁴⁴Ca/⁴⁰Ca than calcite, by −9‰ at 0 °C and −8‰ at 25 °C. Based on this model, none of the measured barite samples appear to be in isotopic equilibrium with their parent solutions, although as predicted they do record lower δ^44/40Ca values than seawater and calcite. Kinetic fractionation processes therefore most likely control the extent of isotopic fractionation exhibited in barite. Potential fractionation mechanisms include factors influencing Ca²⁺ substitution for Ba²⁺ in barite (e.g. ionic strength and trace element concentration of the solution, competing complexation reactions, precipitation or growth rate, temperature, pressure, and saturation state) as well as nucleation and crystal growth rates. These factors should be considered when investigating controls on isotopic fractionation of Ca²⁺ and other elements in inorganic and biogenic minerals.     

Model for kinetic effects on calcium isotope fractionation (δCa) in inorganic aragonite and cultured planktonic foraminifera

The calcium isotope ratios (δ⁴⁴Ca = [(⁴⁴Ca/⁴⁰Ca)_sample/(⁴⁴Ca/⁴⁰Ca)_standard −1] · 1000) of Orbulina universa and of inorganically precipitated aragonite are positively correlated to temperature. The slopes of 0.019 and 0.015‰ °C⁻¹, respectively, are a factor of 13 and 16 times smaller than the previously determined fractionation from a second foraminifera, Globigerinoides sacculifer, having a slope of about 0.24‰ °C⁻¹. The observation that δ⁴⁴Ca is positively correlated to temperature is opposite in sign to the oxygen isotopic fractionation (δ¹⁸O) in calcium carbonate (CaCO₃). These observations are explained by a model which considers that Ca²⁺-ions forming ionic bonds are affected by kinetic fractionation only, whereas covalently bound atoms like oxygen are affected by kinetic and equilibrium fractionation. From thermodynamic consideration of kinetic isotope fractionation, it can be shown that the slope of the enrichment factor α(T) is mass-dependent. However, for O. universa and the inorganic precipitates, the calculated mass of about 520 ± 60 and 640 ± 70 amu (atomic mass units) is not compatible with the expected ion mass for ⁴⁰Ca and ⁴⁴Ca. To reconcile this discrepancy, we propose that Ca diffusion and δ⁴⁴Ca isotope fractionation at liquid/solid transitions involves Ca²⁺-aquocomplexes (Ca[H₂O]_n²⁺ · mH₂O) rather than pure Ca²⁺-ion diffusion. From our measurements we calculate that such a hypothesized Ca²⁺-aquocomplex correlates to a hydration number of up to 25 water molecules (490 amu). For O. universa we propose that their biologically mediated Ca isotope fractionation resembles fractionation during inorganic precipitation of CaCO₃ in seawater. To explain the different Ca isotope fractionation in O. universa and in G. sacculifer, we suggest that the latter species actively dehydrates the Ca²⁺-aquocomplex before calcification takes place. The very different temperature response of Ca isotopes in the two species suggests that the use of δ⁴⁴Ca as a temperature proxy will require careful study of species effects.     

Iron isotope fractionation in oxic soils by mineral weathering and podzolization

Stable iron isotope ratios in three soils (two Podzols and one Cambisol) were measured by MC-ICPMS to investigate iron isotope fractionation during pedogenic iron transformation and translocation processes under oxic conditions. Podzolization is a soil forming process in which iron oxides are dissolved and iron is translocated and enriched in the subsoil under the influence of organic ligands. The Cambisol was studied for comparison, representing a soil formed by chemical weathering without significant translocation of iron. A three-step sequential extraction procedure was used to separate operationally-defined iron mineral pools (i.e., poorly-crystalline iron oxides, crystalline iron oxides, silicate-bound iron) from the soil samples. Iron isotope ratios of total soil digests were compared with those of the separated iron mineral pools. Mass balance calculations demonstrated excellent agreement between results of sequential extractions and total soil digestions. Systematic variations in the iron isotope signature were found in the Podzol profiles. An enrichment of light iron isotopes of about 0.6‰ in δ⁵⁷Fe was found in total soil digests of the illuvial Bh horizons which can be explained by preferential translocation of light iron isotopes. The separated iron mineral pools revealed a wide range of δ⁵⁷Fe values spanning more than 3‰ in the Podzol profiles. Strong enrichments of heavy iron isotopes in silicate-bound iron constituting the residue of weathering processes, indicated the preferential transformation of light iron isotopes during weathering. Iron isotope fractionation during podzolization is probably linked to the ligand-controlled iron translocation processes. Comparison of iron isotope data from eluvial and illuvial horizons of the Podzol profiles revealed that some iron must have been leached out of the profile. However, uncertainties in the initial iron content and iron isotopic composition of the parent materials prevented thorough mass balance calculations of iron fluxes within the profiles. In contrast to the Podzol profiles, the Cambisol profile displayed uniform δ⁵⁷Fe values across soil depth and showed only a small enrichment of light iron isotopes of about 0.4‰ in the poorly-crystalline iron oxide pool extracted by 0.5 M HCl. This work demonstrates that significant iron isotope fractionations can occur during pedogenesis in oxic environments under the influence of organic ligands. Our findings provide new insights into fractionation mechanisms of iron isotopes and will help in the development of stable iron isotopes as tracers for biogeochemical iron cycling in nature.     

Iron speciation and isotope fractionation during silicate weathering and soil formation in an alpine glacier forefield chronosequence

The chemical weathering of primary Fe-bearing minerals, such as biotite and chlorite, is a key step of soil formation and an important nutrient source for the establishment of plant and microbial life. The understanding of the relevant processes and the associated Fe isotope fractionation is therefore of major importance for the further development of stable Fe isotopes as a tracer of the biogeochemical Fe cycle in terrestrial environments. We investigated the Fe mineral transformations and associated Fe isotope fractionation in a soil chronosequence of the Swiss Alps covering 150 years of soil formation on granite. For this purpose, we combined for the first time stable Fe isotope analyses with synchrotron-based Fe-EXAFS spectroscopy, which allowed us to interpret changes in Fe isotopic composition of bulk soils, size fractions, and chemically separated Fe pools over time in terms of weathering processes. Bulk soils and rocks exhibited constant isotopic compositions along the chronosequence, whereas soil Fe pools in grain size fractions spanned a range of 0.4‰ in δ⁵⁶Fe. The clay fractions (<2 μm), in which newly formed Fe(III)-(hydr)oxides contributed up to 50% of the total Fe, were significantly enriched in light Fe isotopes, whereas the isotopic composition of silt and sand fractions, containing most of the soil Fe, remained in the range described by biotite/chlorite samples and bulk soils. Iron pools separated by a sequential extraction procedure covered a range of 0.8‰ in δ⁵⁶Fe. For all soils the lightest isotopic composition was observed in a 1 M NH₂OH-HCl-25% acetic acid extract, targeting poorly-crystalline Fe(III)-(hydr)oxides, compared with easily leachable Fe in primary phyllosilicates (0.5 M HCl extract) and Fe in residual silicates. The combination of the Fe isotope measurements with the speciation data obtained by Fe-EXAFS spectroscopy permitted to quantitatively relate the different isotope pools forming in the soils to the mineral weathering reactions which have taken place at the field site. A kinetic isotope effect during the Fe detachment from the phyllosilicates was identified as the dominant fractionation mechanism in young weathering environments, controlling not only the light isotope signature of secondary Fe(III)-(hydr)oxides but also significantly contributing to the isotope signature of plants. The present study further revealed that this kinetic fractionation effect can persist over considerable reaction advance during chemical weathering in field systems and is not only an initial transient phenomenon.     

Calcium isotope ratios in animal and human bone

Calcium isotopes in tissues are thought to be influenced by an individual’s diet, reflecting parameters such as trophic level and dairy consumption, but this has not been carefully assessed. We report the calcium isotope ratios (δ^44/42Ca) of modern and archaeological animal and human bone (n = 216). Modern sheep raised at the same location show 0.14 ± 0.08‰ higher δ^44/42Ca in females than in males, which we attribute to lactation by the ewes. In the archaeological bone samples the calcium isotope ratios of the herbivorous fauna vary by location. At a single site, the archaeological fauna do not show a trophic level effect. Humans have lower δ^44/42Ca than the mean site fauna by 0.22 ± 0.22‰, and the humans have a greater δ^44/42Ca range than the animals. No effect of sex or age on the calcium isotope ratios was found, and intra-individual skeletal δ^44/42Ca variability is negligible. We rule out dairy consumption as the main cause of the lower human δ^44/42Ca, based on results from sites pre-dating animal domestication and dairy availability, and suggest instead that individual physiology and calcium intake may be important in determining bone calcium isotope ratios.     

Stable isotope profiles (Ca,O, C) through modern brachiopod shells of T. septentrionalis and G. vitreus: Implications for calcium isotope paleo-ocean chemistry

Brachiopod shells are widely used as an archive to reconstruct elemental and isotopic composition of seawater. Studies, focused on oxygen and carbon isotopes over the last decades, are increasingly extending to the emerging calcium isotope system. To date, only little attention has been paid to test the reliability of fossil brachiopods on their modern counterparts.In this context, the present study investigates two modern brachiopods, Terebratulina septentrionalis (eastern Canada, 5–30 m depth, 7.1 °C seasonal temperature variation, two-layer shell) and Gryphus vitreus (northern Mediterranean, 200 m depth, constant all-year round temperature, three-layer shell). Both species were sampled along the ontogenetic growth direction and calcium, oxygen, and carbon isotopes as well as elemental concentration were measured. Calcium isotopes were analyzed on TIMS. The elemental composition was analyzed by LA-ICP-MS and ICP-AES.The results indicate an intra-specimen δ^44/40Ca variation ranging from 0.16 to 0.33‰, pointing to a fairly homogenous distribution of calcium isotopes in brachiopod shells. However, in the light of the suggested 0.7‰ increase in calcium isotopes over the Phanerozoic such intra-specimen variations constrain ocean reconstruction. δ^44/40Ca values of T. septentrionalis do not seem to be affected by growth rate. Calcium isotopic values of G. vitreus are heavy in the central part of the shell and trend towards lighter values in peripheral areas approaching the maximum isotopic composition of T. septentrionalis. The maximum inter-species δ^44/40Ca difference of 0.62‰ between T. septentrionalis and G. vitreus indicates that care should be taken when using different taxa, species with different strontium content or brachiopods with specialized shell structure, such as G. vitreus, for ocean water reconstruction in terms of Ca isotopic composition. T. septentrionalis may record Ca isotopic fractionation related to seasonal seawater temperature variations in its shell but this is difficult to resolve at the current analytical precision. Average δ¹⁸O-derived temperatures of the two investigated species are close to on-site measured temperatures.