Significance Circulation of seawater through midocean ridges results in large-scale chemical transfer between the solid Earth and oceans. Driven by magmatic heat, seawater undergoes hydrothermal reactions that affect the concentrations of Mg, Ca, SO 4 , and Sr in the oceans over millions of years. Changes in the composition of seawater during the past 500 million years may have previously unrecognized effects on the composition of hydrothermal fluids flowing back into the oceans through time. This work presents a model suggesting that Ca, and Sr exchange in particular, may have been much different in the geologic past, which has important implications for the interpretation of Sr isotope records in paleoseawater and ancient oceanic crust.
The distribution of stable and radiogenic isotopes within and among phases provides a critical means of quantifying the origin, residence and cycling of materials through terrestrial reservoirs (Wahl and Urey 1935; Epstein and Mayeda 1953; Johnson et al. 2004; Eiler 2007; Porcelli and Baskaran 2011; Wiederhold 2015). While isotopic variability is globally observable, the mechanisms that govern both their range and distribution occur largely at atomic (e.g., radioactive decay), molecular (e.g., the influence of mass on the free energy of atomic bonds) and pore (e.g., diffusive transport to reactive surface) scales. In contrast, the vast majority of isotope ratio measurements are based on sample sizes that aggregate multiple pathways, species and compositions. Inferring process from such macro-scale observations therefore requires unraveling the relative contribution of a variety of potential mechanisms. In effect, the use of isotopes as proxies to infer a specific parameter, such as temperature (Urey 1947) or residence time (Kaufman and Libby 1954), carries the implicit requirement that one mechanism is the primary influence on the measured isotopic composition of the composite sample.
In the present chapter, we consider a wide variety of macro-scale observations of isotope partitioning across fluid–solid phase boundaries. For this purpose we define the continuum scale as a representation in which interfaces are averaged over elementary volumes, as opposed to the pore scale in which these interfaces are explicitly resolved. Throughout this review it will be demonstrated that observations of isotope partitioning across fluid–solid boundaries require some representation of the isotopic composition of the solid surface and surrounding fluid distinct from ‘bulk’ or ‘well mixed’ reservoirs. For example, this distinction is necessary in order to (1) quantify the partitioning of radioactive and radiogenic species, (2) describe transport limitations that may impact the macroscopic partitioning of isotope ratios, (3) explain …
A spatial survey of the chemical and isotopic composition of fluids from the Long Valley hydrothermal system was conducted. Starting at the presumed hydrothermal upwelling zone in the west moat of the caldera, samples were collected from the Casa Diablo geothermal field and a series of monitoring wells defining a nearly linear, ~;;14 km long, west-to-east trend along the proposed fluid flow path (Sorey et al., 1991). Samples were analyzed for the isotopes of water, Sr, Ca, and noble gases, the concentrations of major cations and anions and total CO2. Our data confirm earlier models in which the variations in water isotopes along the flow path reflect mixing of a single hydrothermal fluid with local groundwater. Variations in Sr data are poorly constrained and reflect fluid mixing, multiple fluid-pathways or water-rock exchange along the flow path as suggested by Goff et al. (1991). Correlated variations among total CO2, noble gases and the concentration and isotopic composition of Ca suggest progressive fluid degassing (loss of CO2, noble gases) driving calcite precipitation as the fluid flows west-to-east across the caldera. This is the first evidence that Ca isotopes may trace and provide definitive evidence of calcite precipitation along fluid flow paths in geothermal systems.
In-situ recovery (ISR) of uranium (U) from sandstone-type roll-front deposits is a technology that involves the injection of solutions that consist of ground water fortified with oxygen and carbonate to promote the oxidative dissolution of U, which is pumped to recovery facilities located at the surface that capture the dissolved U and recycle the treated water. The ISR process alters the geochemical conditions in the subsurface creating conditions that are more favorable to the migration of uranium and other metals associated with the uranium deposit. There is a lack of clear understanding of the impact of ISR mining on the aquifer and host rocks of the post-mined site and the fate of residual U and other metals within the mined ore zone. We performed detailed petrographic, mineralogical, and geochemical analyses of several samples taken from about 7 m of core of the formerly the ISR-mined Smith Ranch–Highland uranium deposit in Wyoming. We show that previously mined cores contain significant residual uranium (U) present as coatings on pyrite and carbonaceous fragments. Coffinite was identified in three samples. Core samples with higher organic (> 1 wt.%) and clay (> 6–17 wt.%) contents yielded higher 234U/238U activity ratios (1.0–1.48) than those with lower organic and clay fractions. The ISR mining was inefficient in mobilizing U from the carbonaceous materials, which retained considerable U concentrations (374–11,534 ppm). This is in contrast with the deeper part of the ore zone, which was highly depleted in U and had very low 234U/238U activity ratios. This probably is due to greater contact with the lixiviant (leaching solution) during ISR mining. EXAFS analyses performed on grains with the highest U and Fe concentrations reveal that Fe is present in a reduced form as pyrite and U occurs mostly as U(IV) complexed by organic matter or as U(IV) phases of carbonate complexes. Moreover, U–O distances of ~ 2.05 Å were noted, indicating the potential formation of other poorly defined U(IV/VI) species. We also noted a small contribution from UO at 1.79 Å, which indicates that U is partially oxidized. There is no apparent U–S or U–Fe interaction in any of the U spectra analyzed. However, SEM analysis of thin sections prepared from the same core material reveals surficial U associated with pyrite which is probably a minor fraction of the total U present as thin coatings on the surface of pyrite. Our data show the presence of different structurally variable uranium forms associated with the mined cores. U associated with carbonaceous materials is probably from the original U mobilization that accumulated in the organic matter-rich areas under reducing conditions during shallow burial diagenesis. U associated with pyrite represents a small fraction of the total U and was likely deposited as a result of chemical reduction by pyrite. Our data suggest that areas rich in carbonaceous materials had limited exposure to the lixiviant solution, continue to be reducing, and still hold significant U resources. Because of their limited access to fluid flow, these areas might not contribute significantly to post-mining U release or attenuation. Areas with pyrite that are accessible to fluids seem to be more reactive and could act as reductants and facilitate U reduction and accumulation, limiting its migration.
Abstract A negative δ C 13 excursion in carbonate sediments near the Guadalupian/Lopingian (Middle/Late Permian) boundary has been interpreted to have resulted from a large carbon cycle disturbance during the end-Guadalupian extinction event (ca. 260 Ma). However, the carbon isotope data alone are insufficient to uniquely determine the type and magnitude of perturbation to the global carbon cycle. Calcium isotopes can be used to further constrain the cause of a carbon isotope excursion because the carbon and calcium cycles are coupled via CaCO3 burial. In this study, we present coupled carbon and calcium isotope records from three Guadalupian–Lopingian (G/L) sections in China (Penglaitan and Chaotian) and Turkey (Koserelik Tepe). The δ C 13 and δ Ca 44 / 40 records differ among our studied sections and do not co-vary in the same manner. No section shows δ C 13 and δ Ca 44 / 40 changes consistent with massive, rapid volcanic CO2 emissions or methane clathrate destabilization. Additionally, many sections with large ( > 3 ‰ ) changes in δ C 13 exhibit δ O 18 evidence for diagenetic alteration. Only one section exhibits a large excursion in the δ Ca 44 / 40 of limestone but the absence of a similar excursion in the δ Ca 44 / 40 of conodont apatite suggests that the limestone excursion reflects a mineralogical control rather than a perturbation to the global calcium cycle. Hence, we interpret the large isotopic changes observed in some sections to have resulted from local burial conditions or diagenetic effects, rather than from a large carbon and calcium cycle disturbance. Perturbations to the global carbon and calcium cycles across the G/L transition were much less intense than the disturbances that occurred across the subsequent Permian–Triassic boundary. This finding is consistent with the much smaller magnitude of the end-Guadalupian extinction relative to the end-Permian.
