Growth pathways of calcium (Ca) phosphate minerals are still under debate, but non-classical growth pathways, which encompass any mode of growth involving attachment of primary particles instead of monomer ions, are currently thought to dominate over classical mechanisms under a wide range of growth conditions. Cation desolvation during ion-by-ion growth is associated with the preferential uptake of isotopically light Ca in Ca-bearing phases, so the Ca isotope composition of Ca-bearing minerals can help to elucidate the dominant growth mechanism. Here, we combine stable Ca isotope analysis with mineralogical characterization and nanoscale imaging of growth features to determine for the first time the rate-dependent Ca isotope fractionation during seeded growth of hydroxyapatite (HAP) involving an octacalcium phosphate (OCP) precursor. Our data reveal that growth rates are strongly attenuated by pH, and that Ca isotope fractionation between the solid and growth solution is independent of growth rate between 1.9 × 10−9 and 2.8 × 10−8 mol Ca m−2 s−1. Moreover, nanoscale images of surface topography reveal direct deposition of primary particles on the HAP seed surface following sustained growth, providing visual evidence of a non-classical growth pathway. Together, these findings support the hypothesis that hydroxyapatite growth is dominantly non-classical. The process of cluster nucleation from the bulk solution and attachment of these clusters to the seeded HAP apparently does not involve a significant kinetic isotope effect, which implies that abiogenically formed Ca-phosphates likely preserve the Ca isotope composition of the fluid from which the crystals originated.

We conducted hydroponic experiments growing soybean (Glycine max), rice (Oryza sativa), and wheat (Triticum aestivum) under K and Ca replete conditions to establish the degree of K isotopic fractionation by plants, and compare the isotopic fractionation of Ca and K. Each of the test plants displays fractionation relative to the growth solution favoring the light isotopes of K and Ca. The average δ41K values of the roots from the three plant species were similar, and have an overall average of -0.55 ± 0.24‰ 2s, while the overall average δ44Ca for roots is -0.67 ± 0.44. For leaves, the overall average of δ41K is -0.97 ± 0.4‰, compared to an overall average leaf δ44Ca of -0.83 ± 0.09‰. In the case of the soybean plants, the lightest K and Ca occurs in the stems with average δ41K of -1.31 ± 0.40‰ 2s and average δ44Ca of -1.20 ± 0.19 ‰ 2s. We present a simple box model involving the relative fluxes of K and its isotopic fractionation that reproduces our K isotopic observations and suggests a fractionation of ∼0.8‰ with K uptake from solution by roots. Directly comparing the per amu fractionation of K and Ca reveals an average factor of 2.05 ± 0.50 2s greater fractionation of K isotopes which may reflect their different roles and behaviors in plants.

Significant uranium (U) isotope fractionation has been observed during abiotic reduction of aqueous U, counter to the expectation that uranium isotopes are only fractionated by bioassociated enzymatic reduction. In our experiments, aqueous U is removed from solution by reductive precipitation onto the surfaces of synthetic iron monosulfide. The magnitude of uranium isotopic fractionation increases with decreasing aqueous U removal rate and with increasing amounts of neutrally charged aqueous Ca-U-CO₃ species. Our discovery means that abiotic U isotope fractionation likely occurs in any reducing environment with aqueous Ca ≥ 1 mM, and that the magnitude of isotopic fractionation changes in response to changes in aqueous major ion concentrations that affect U speciation. Our results have implications for the study of anoxia in the ancient oceans and other environments.

Variations in the Mg, Ca, Sr, and SO₄ concentrations of paleoseawater can affect the chemical exchange between seawater and oceanic basalt in hydrothermal systems at midocean ridges (MOR). We present a model for evaluating the nature and magnitude of these previously unappreciated effects, using available estimates of paleoseawater composition over Phanerozoic time as inputs and ⁸⁷Sr/⁸⁶Sr of ophiolite epidosites and epidote-quartz veins as constraints. The results suggest that modern hydrothermal fluids are not typical due to low Ca and Sr relative to Mg and SO₄ in modern seawater. At other times during the last 500 million years, particularly during the Cretaceous and Ordovician, hydrothermal fluids had more seawater-derived Sr and Ca, a prediction that is supported by Sr isotope data. The predicted ⁸⁷Sr/⁸⁶Sr of vent fluids varies cyclically in concert with ocean chemistry, with some values much higher than the modern value of ∼0.7037. The seawater chemistry effects can be expressed in terms of the transfer efficiency of basaltic Ca and Sr to seawater in hydrothermal systems, which varies by a factor of ∼1.6 over the Phanerozoic, with minima when seawater Mg and SO₄ are low. This effect provides a modest negative feedback on seawater composition and ⁸⁷Sr/⁸⁶Sr changes. For the mid-Cretaceous, the low ⁸⁷Sr/⁸⁶Sr of seawater requires either exceptionally large amounts of low-temperature exchange with oceanic crust or that the weathering flux of continentally derived Sr was especially small. The model also has implications for MOR hydrothermal systems in the Precambrian, when low-seawater SO₄ could help explain low seawater ⁸⁷Sr/⁸⁶Sr.

The end-Triassic mass extinction coincided with a negative δ13C excursion, consistent with release of 13C-depleted CO2 from the Central Atlantic Magmatic Province. However, the amount of carbon released and its effects on ocean chemistry are poorly constrained. The coupled nature of the carbon and calcium cycles allows calcium isotopes to be used for constraining carbon cycle dynamics and vice versa. We present a high-resolution calcium isotope (δ44/40Ca) record from 100 m of marine limestone spanning the Triassic/Jurassic boundary in two stratigraphic sections from northern Italy. Immediately above the extinction horizon and the associated negative excursion in δ13C, δ44/40Ca decreases by ∼0.8‰ in 20 m of section and then recovers to preexcursion values. Coupled numerical models of the geological carbon and calcium cycles demonstrate that this δ44/40Ca excursion is too large to be explained by changes to seawater δ44/40Ca alone, regardless of CO2 injection volume and duration. Less than 20% of the δ44/40Ca excursion can be attributed to acidification. The remaining 80% likely reflects a higher proportion of aragonite in the original sediment, based largely on high concentrations of Sr in the samples. Our study demonstrates that coupled models of the carbon and calcium cycles have the potential to help distinguish contributions of primary seawater isotopic changes from local or diagenetic effects on the δ44/40Ca of carbonate sediments. Differentiating between these effects is critical for constraining the impact of ocean acidification during the end-Triassic mass extinction, as well as for interpreting other environmental events in the geologic past.

We use uranium (U) isotope ratios to detect and quantify the extent of natural U reduction in groundwater across a roll front redox gradient. Our study was conducted at the Smith Ranch-Highland in situ recovery (ISR) U mine in eastern Wyoming, USA, where economic U deposits occur in the Paleocene Fort Union formation. To evaluate the fate of aqueous U in and adjacent to the ore body, we investigated the chemical composition and isotope ratios of groundwater samples from the roll-front type ore body and surrounding monitoring wells of a previously mined area. The (238)U/(235)U of groundwater varies by approximately 3‰ and is correlated with U concentrations. Fluid samples down-gradient of the ore zone are the most depleted in (238)U and have the lowest U concentrations. Activity ratios of (234)U/(238)U are ∼5.5 up-gradient of the ore zone, ∼1.0 in the ore zone, and between 2.3 and 3.7 in the down-gradient monitoring wells. High-precision measurements of (234)U/(238)U and (238)U/(235)U allow for development of a conceptual model that evaluates both the migration of U from the ore body and the extent of natural attenuation due to reduction. We find that the premining migration of U down-gradient of the delineated ore body is minimal along eight transects due to reduction in or adjacent to the ore body, whereas two other transects show little or no sign of reduction in the down-gradient region. These results suggest that characterization of U isotopic ratios at the mine planning stage, in conjunction with routine geochemical analyses, can be used to identify where more or less postmining remediation will be necessary.

One of the major ecological concerns associated with the in situ recovery (ISR) of uranium (U) is the environmental release of soluble, toxic selenium (Se) oxyanions generated by mining. Post-mining natural attenuation by the residual reductants in the ore body and reduced down-gradient sediments should mitigate the risk of Se contamination in groundwater. In this work, we investigate the Se concentrations and Se isotope systematics of groundwater and of U ore bearing sediments from an ISR site at Rosita, TX, USA. Our results show that selenate (Se(VI)) is the dominant Se species in Rosita groundwater, and while several up-gradient wells have elevated Se(VI), the majority of the ore zone and down-gradient wells have little or no Se oxyanions. In addition, the δ⁸²Se_VI of Rosita groundwater is generally elevated relative to the U ore up to +6.14‰, with the most enriched values observed in the ore-zone wells. Increasing δ⁸²Se with decreasing Se(VI) conforms to a Rayleigh type distillation model with an ε of -2.25‰ ± 0.61‰, suggesting natural Se(VI) reduction occurring along the hydraulic gradient at the Rosita ISR site. Furthermore, our results show that Se isotopes are excellent sensors for detecting and monitoring post-mining natural attenuation of Se oxyanions at ISR sites.

High Mg# andesites and dacites (Mg# = molar Mg/Mg + Fe) from western Aleutian seafloor volcanoes carry high concentrations of Sr (>1000 ppm) that is unradiogenic (87Sr/86Sr < 0.7029) compared to lavas from emergent volcanoes throughout the arc (200–800 ppm Sr, 87Sr/86Sr >0.7030). Data patterns in plots of 87Sr/86Sr vs Y/Sr and Nd/Sr imply the existence of an eclogite-melt source component – formed by partial melting of MORB eclogite in the subducting Pacific Plate – which is most clearly expressed in the compositions of western Aleutian andesites and dacites (Nd/Sr and Y/Sr < 0.02) and which dominates the source budget for Sr in volcanic rocks throughout the arc. When viewed in combination with inversely correlated εNd and 87Sr/86Sr, these patterns rule out aqueous fluids as an important source of Sr because mixtures of fluids from altered oceanic crust with depleted mantle and sediment produce compositions with 87Sr/86Sr higher than in common Aleutian rocks. The unradiogenic nature of Sr in the western Aleutian andesite–dacite end-member may be understood if H2O required to drive melting of the subducting oceanic crust is transported in fluids containing little Sr. Mass balance demonstrates that such fluids may be produced by dewatering of serpentinite in the mantle section of the subducting plate. If the eclogite-melt source component is present throughout the Aleutian arc, melting of the subducting plate must extend into minimally altered parts of the sheeted dike section or upper gabbros, at depths >2 km below the paleo-seafloor. Oxygen isotopes in western Aleutian seafloor lavas, which fall within a narrow range of MORB-like values (δ18O=5.1–5.7), are also consistent with this model. These results indicate that the subducting Pacific lithosphere beneath the Aleutian arc is significantly hotter than indicated my most thermal models.