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Cephalopod carbonate geochemistry underpins studies ranging from Phanerozoic, global-scale change to outcrop-scale paleoecological reconstructions. Interpreting these data hinges on assumed similarity to model organisms, such as Nautilus, and generalization from other molluscan biomineralization processes. Aquarium rearing and capture of wild Nautilus suggest shell carbonate precipitates quickly (35 μm/day) in oxygen isotope equilibrium with seawater. Other components of Nautilus shell chemistry are less well-studied but have potential to serve as proxies for paleobiology and paleoceanography. To calibrate the geochemical response of cephalopod δ15Norg, δ13Corg, δ13Ccarb, δ18Ocarb, and δ44/40Cacarb to modern anthropogenic environmental change, we analyzed modern, historical, and subfossil Nautilus macromphalus from New Caledonia. Samples span initial human habitation, colonialization, and industrial pCO2 increase. This sampling strategy is advantageous because it avoids the shock response that can affect geochemical change in aquarium experiments. Given the range of living depths and more complex ecology of Nautilus, however, some anthropogenic signals, such as ocean acidification, may not have propagated to their living depths. Our data suggest some environmental changes are more easily preserved than others given variability in cephalopod average living depth. Calculation of the percent respired carbon incorporated into the shell using δ13Corg, δ13Ccarb, and Suess-effect corrected δ13CDIC suggests an increase in the last 130 years that may have been caused by increasing carbon dioxide concentration or decreasing oxygen concentration at the depths these individuals inhabited. This pattern is consistent with increasing atmospheric CO2 and/or eutrophication offshore of New Caledonia. We find that δ44/40Ca remains stable across the last 130 years. The subfossil shell from a cenote may exhibit early δ44/40Ca diagenesis. Questions remain about the proportion of dietary vs ambient seawater calcium incorporation into the Nautilus shell. Values of δ15N do not indicate trophic level change in the last 130 years, and the subfossil shell may show diagenetic alteration of δ15N toward lower values. Future work using historical collections of Sepia and Spirula may provide additional calibration of fossil cephalopod geochemistry.

Carbon dioxide release during Deccan Traps volcanism and the Chicxulub impact likely contributed to the Cretaceous-Paleogene (K-Pg) mass extinction; however, the intensity and duration of CO2 input differed between the two events. Large and rapid addition of CO2 to seawater causes transient decreases in pH, [CO32–], and carbonate mineral saturation states. Compensating mechanisms, such as dissolution of seafloor sediment, reduced biomineralization, and silicate weathering, mitigate these effects by increasing the same parameters. The calcium isotope ratios (δ44/40Ca) of seawater and marine carbonates are hypothesized to respond to these perturbations through weathering/carbonate deposition flux imbalances and/or changes in fractionation between carbonate minerals and seawater. We used a high-precision thermal ionization mass spectrometry method to measure δ44/40Ca values of aragonitic bivalve and gastropod mollusk shells from the K-Pg interval of the López de Bertodano Formation on Seymour Island, Antarctica. Well-preserved shells spanning the late Maastrichtian (ca. 67 Ma) to early Danian (ca. 65.5 Ma) have δ44/40Ca values ranging from −1.89‰ to −1.57‰ (seawater [sw]). Shifts in δ44/40Ca inversely correlate with sedimentological indicators of saturation state. A negative excursion begins before and continues across the K-Pg boundary. According to a simple mass-balance model, neither input/output flux imbalances nor change in the globally integrated bulk carbonate fractionation factor can produce variations in seawater δ44/40Ca sufficient to explain the measured trends. The data are consistent with a dynamic molluscan Ca isotope fractionation factor sensitive to the carbonate geochemistry of seawater. The K-Pg extinction appears to have occurred during a period of carbonate saturation state variability caused by Deccan volcanism.

We report new whole rock U-Th and in-situ oxygen isotope compositions for partially melted (0–50 vol% melt), low-δ18O Pleistocene granitoid blocks ejected during the ∼7.7 ka caldera-forming eruption of Mt. Mazama (Crater Lake, Oregon). The blocks are interpreted to represent wall rocks of the climactic magma chamber that, prior to eruption, experienced variable amounts of exchange with meteoric hydrothermal fluids and subsequent partial melting. U-Th and oxygen isotope results allow us to examine the timescales of hydrothermal circulation and partial melting, and provide an “outside in” perspective on the buildup to the climactic eruption of Mt. Mazama. Oxygen isotope compositions measured in the cores and rims of individual quartz (n = 126) and plagioclase (n = 91) crystals, and for transects across ten quartz crystals, document zonation in quartz (Δ18OCore-Rim ≤ 0.1–5.5‰), but show homogeneity in plagioclase (Δ18OCore-Rim ≤ ±0.8‰). We propose that oxygen isotope zonation in quartz records hydrothermal exchange followed by high-temperature exchange in response to partial melting caused by injection of basaltic to andesitic recharge magma into the deeper portions of the chamber. Results of modeling of oxygen diffusion in quartz indicates that hydrothermal exchange in quartz occurred over a period of ∼1000–63,000 years. Models also suggest that the onset of melting of the granitoids occurred a minimum of ∼10–200 years prior to the Mazama climactic eruption, an inference which is broadly consistent with results for magnetite homogenization and for Zr diffusion in melt previously reported by others. Uranium-thorium isotope compositions of most granitoid blocks are in 238U excess, and are in agreement with a 238U enriched array previously measured for volcanic rocks at Mt. Mazama. Uranium excess in the granitoids is likely due to enrichment via hydrothermal circulation, given their low δ18O values. The sample with the highest U excess (≥5.8%) also has the most 18O isotope depletion (average δ18Oplag = −4.0‰). The granitoids are a probable assimilant and source of U excess in volcanic rocks from Mt. Mazama. Two granitoids have Th excess and low δ18O values, interpreted to record leaching of U during hydrothermal alteration. A U-Th isochron based on the U excess array of the granitoids and volcanic rocks indicates that hydrothermal circulation initiated ∼40–75 kyrs before the climactic eruption, potentially marking the initiation of a persistent upper-crustal magma chamber. The U-Th ages are consistent with the maximum timescales inferred for hydrothermal alteration based on oxygen isotope zoning in quartz.

Interaction of mantle melts with the continental crust can have significant effects on the composition of the resulting melts as well as on the crust itself, and tracing this interaction is key to our understanding of arc magmatism. Lava flows and pyroclastic deposits erupted from ∼50 to 7.7 ka at Mt. Mazama (Crater Lake, Oregon) were analyzed for their Re/Os and U–Th isotopic compositions. Mafic lavas from monogenetic vents around Mt. Mazama that erupted during the buildup to its climactic eruption have lower 187 Os/ 188 Os ratios (0.1394 to 0.1956) and high 230 Th excess (( 230 Th/ 238 U) 0 of 1.180 to 1.302), whereas dacites and rhyodacites tend to have higher 187 Os/ 188 Os ratios (0.2292 to 0.2788) and significant 238 U excess (( 230 Th/ 238 U) 0 of 0.975 to 0.989). The less radiogenic Os isotope compositions of the mafic lavas can be modeled by assimilation of young (∼2.5 to 7 Ma), mafic lower crust that was modified during regional extension, whereas the more radiogenic Os isotope compositions of the dacites and rhyodacites can be attributed to assimilation of older (∼10 to 16 Ma), mid to upper crust that acquired its composition during an earlier period of Cascade magmatism. Production of Th excesses in the lower crust requires very young garnet formation accompanying dehydration melting in the lower crust at less than a few 100 ka by heat from recent basaltic magma injection. The results from this study suggest that the combination of Os and Th isotopes may be used to provide insights into the timescales of evolution of the continental crust in arc settings, as well as the influence of the crust on erupted magmas, and suggest a link between the age and composition of the lower and upper crust to regional tectonic extension and/or earlier Cascade magmatism.

Uranium-series isotope ratios determined for 35 volcanic rocks and 4 glass separates erupted from ~36 to 4.8 ka at Mt. Mazama, Crater Lake, Oregon, identify both 230Th-excess and 238U-excess components. U–Th isotope compositions cover a wide range, exceeding those previously measured for the Cascade arc. Age-corrected (230Th/232Th) and (238U/232Th) activity ratios range from 1.113 to 1.464 and from 0.878 to 1.572 (44.4 % 230Th-excess to 8.8 % 238U-excess), respectively. The most distinctive aspect of the data set is the contrast in U–Th isotope ratios between low and high Sr (LSr, HSr) components that have been previously identified in products of the 7.7 ka caldera-forming climactic eruption and preclimactic rhyodacite lavas. The LSr component exclusively contains 238U-excess, but the HSr component, as well as more primitive lavas, are marked by 230Th-excess. 230Th-excesses such as those recorded at Mt. Mazama are commonly observed in the Cascades. Melting models suggest that high 230Th-excesses observed in the more primitive lavas evolved through mixing of a mantle melt with a partial melt of a mafic lower crustal composition that contained garnet in the residuum that was produced through dehydration melting of amphibolite that was initially garnet free. Dehydration melting in the lower crust offers a solution to the “hot-slab paradox” of the Cascades, where low volatile contents are predicted due to high slab temperatures, yet higher water contents than expected have been documented in erupted lavas. The 238U-excess observed at Mt. Mazama is rare in Cascade lavas, but occurs in more than half of the samples analyzed in this study. Traditionally, 238U-excess in arc magmas is interpreted to reflect slab fluid fluxing. Indeed, 238U-excess in arcs is common and likely masks 230Th-excess resulting from lower crustal interaction. Isotopic and trace element data, however, suggest a relatively minor role for slab fluid fluxing in the Cascades. We propose that 238U-excess reflects melting and assimilation of young, hydrothermally altered upper crust. The processes related to generating 238U-excess are likely important features at Mt. Mazama that accompanied development of a large-scale silicic magma chamber that led to the caldera-forming eruption.