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The Paleocene‐Eocene thermal maximum (PETM, 56 Ma) is an ancient global warming event closely coupled to the release of massive amounts of d13C‐depleted carbon into the ocean‐atmosphere system, making it an informative analogue for future climate change. However, uncertainty still exists regarding tropical sea‐surface temperatures (SSTs) in open ocean settings during the PETM. Here, we present the first paired d13C:Mg/Ca record derived in situ from relatively well‐preserved subdomains inside individual planktic foraminifer shells taken from a PETM record recovered in the central Pacific Ocean at Ocean Drilling Program Site 865. The d13C signature of each individual shell was used to confirm calcification during the PETM, thereby reducing the unwanted effects of sediment mixing that secondarily smooth paleoclimate signals constructed with fossil planktic foraminifer shells. This method of “isotopic screening” reveals that shells calcified during the PETM have elevated Mg/Ca ratios reflecting exceptionally warm tropical SSTs (∼33–34°C). The increase in Mg/Ca ratios suggests ∼6°C of warming, which is more congruent with SST estimates derived from organic biomarkers in PETM records at other tropical sites. These extremely warm SSTs exceed the maximum temperature tolerances of modern planktic foraminifers. Important corollaries to the findings of this study are (a) the global signature of PETM warmth was uniformly distributed across different latitudes, (b) our Mg/Ca‐based SST record may not capture peak PETM warming at tropical Site 865 due to the thermally‐induced ecological exclusion of planktic foraminifers, and (c) the record of such transitory ecological exclusion has been obfuscated by post‐depositional sediment mixing at Site 865. 

The early Eocene Climatic Optimum (EECO; ~ 53.3 to 49.1 Ma) was a period of the warmest sustained temperatures of the Cenozoic caused by perturbations to the global carbon cycle. Deep sea sediment cores and the microfossils preserved within them are the primary sources of information for these changes in climate and global carbon cycling but are subject to diagenetic alteration after deposition. One of the great challenges in paleoclimate research is determining how to accurately interpreting the proxy record by identifying the amount of chemical alteration of the isotopic and elemental compositions locked within microfossils such as foraminifera. The planktic foraminifera record has been biased by digenesis, provoking questions about the strength of the latitudinal temperature gradient throughout the EECO, specifically with respect to mismatches between proxy data and climate model simulations that remain unresolved. To investigate this question, we selected three deep sea sites that span across the Pacific Ocean, ODP Sites 865, 1209 and DSDP Site 207. From these sediments we extracted carefully screened planktic foraminifera and conducted analysis by two independent approaches on splits of the same individual foraminiferal shells. We measured the δ18O composition by conventional analysis (gas source mass spectrometry), and Mg/Ca ratios on fragments of the same shells by LA-ICP-MS that allows for a careful diagenetic screening. We then independently estimate sea surface temperatures and compare records to quantify the extent of bias in the planktonic foraminifera record. This approach helps to reassess the latitudinal temperature gradients across the EECO. 

The use of secondary ion mass spectrometry (SIMS) to perform micrometer‐scalein situcarbon isotope (δ¹³C) analyses of shells of marine microfossils called planktic foraminifers holds promise to explore calcification and ecological processes. The potential of this technique, however, cannot be realized without comparison to traditional whole‐shell δ¹³C values measured by gas source mass spectrometry (GSMS).

Paired SIMS and GSMS δ¹³C values measured from final chamber fragments of the same shell of the planktic foraminiferOrbulina universaare compared. The SIMS–GSMS δ¹³C differences (Δ¹³C_SIMS‐GSMS) were determined via paired analysis of hydrogen peroxide‐cleaned fragments of modern cultured specimens and of fossil specimens from deep‐sea sediments that were either untreated, sonicated, and cleaned with hydrogen peroxide or vacuum roasted. After treatment, fragments were analyzed by a CAMECA IMS 1280 SIMS instrument and either a ThermoScientific MAT‐253 or a Fisons Optima isotope ratio mass spectrometer (GSMS).

Paired analyses of cleaned fragments of cultured specimens (n = 7) yield no SIMS–GSMS δ¹³C difference. However, paired analyses of untreated (n = 18) and cleaned (n = 12) fragments of fossil shells yield average Δ¹³C_SIMS‐GSMSvalues of 0.8‰ and 0.6‰ (±0.2‰, 2 SE), respectively, while vacuum roasting of fossil shell fragments (n = 11) removes the SIMS–GSMS δ¹³C difference.

The noted Δ¹³C_SIMS‐GSMSvalues are most likely due to matrix effects causing sample–standard mismatch for SIMS analyses but may also be a combination of other factors such as SIMS measurement of chemically bound water. The volume of material analyzed via SIMS is ~10⁵times smaller than that analyzed by GSMS; hence, the extent to which these Δ¹³C_SIMS‐GSMSvalues represent differences in analyte or instrument factors remains unclear.

 

The isotopic and chemical compositions of benthic foraminifera have been used for decades to deduce a broad variety of paleoclimate information. However, there has been little research as to what extent quantitative physical characteristics of benthic foraminifer shells such as their size and mass are related to the quality of their preservation. We used a large data set containing detailed information about individual shell weights, shell sizes, and preservational quality of fossil benthic foraminifera of the genus Cibicidoides from the Pacific ODP Site 846 and the Atlantic ODP Sites 929 and 1089, spanning the last deglaciation (~0-25 ka). We found that during both MIS 1 (~0-8 ka) and 2 (~18-25 ka), smaller and lighter Cibicidoides shells from Pacific Site 846 were typically better-preserved than shells from larger size fractions. Poorly-preserved shells from ODP Site 846 feature a higher mass/size ratio than their better-preserved counterparts that cannot be attributed to the filling of chambers by clay or other contaminant phases. Interestingly, opposite trends were observed at both Atlantic sites, where larger and heavier shells and shells exhibiting higher mass/size ratios are among the best-preserved. These findings point towards minute differences in the ontogenetic development of Cibicidoides shells from Atlantic and Pacific waters, allowing for a better presentation of certain size-ranges, and/or different mechanisms controlling preservation and diagenesis in Atlantic and Pacific deep waters. In addition to these mass/size metrics, we also examine the progression of diagenesis through internal wall structures via SEM images of shell cross sections, as well as the impact on trace metal concentrations measured via LA-ICPMS. 

Abstract The 119 Ma Dinkey Dome pluton in the central Sierra Nevada Batholith is a peraluminous granite and contains magmatic garnet and zircon that are complexly zoned with respect to oxygen isotope ratios. Intracrystalline SIMS analysis tests the relative importance of magmatic differentiation processes vs. partial melting of metasedimentary rocks. Whereas δ18O values of bulk zircon concentrates are uniform across the entire pluton (7.7‰ VSMOW), zircon crystals are zoned in δ18O by up to 1.8‰, and when compared to late garnet, show evidence of changing magma chemistry during multiple interactions of the magma with wall rock during crustal transit. The evolution from an early high-δ18O magma [δ18O(WR) = 9.8‰] toward lower values is shown by high-δ18O zircon cores (7.8‰) and lower δ 18O rims (6.8‰). Garnets from the northwest side of the pluton show a final increase in δ18O with rims reaching 8.1‰. In situ REE measurements show zircon is magmatic and grew before garnets. Additionally, δ18O in garnets from the western side of the pluton are consistently higher (avg = 7.3‰) relative to the west (avg = 5.9‰). These δ18O variations in zircon and garnet record different stages of assimilation and fractional crystallization whereby an initially high-δ18O magma partially melted low-δ18O wallrock and was subsequently contaminated near the current level of emplacement by higher δ18O melts. Collectively, the comparison of δ18O zoning in garnet and zircon shows how a peraluminous pluton can be constructed from multiple batches of variably contaminated melts, especially in early stages of arc magmatism where magmas encounter significant heterogeneity of wall-rock assemblages. Collectively, peraluminous magmas in the Sierran arc are limited to small <100 km2 plutons that are intimately associated with metasedimentary wall rocks and often surrounded by later and larger metaluminous tonalite and granodiorite plutons. The general associations suggest that early-stage arc magmas sample crustal heterogeneities in small melt batches, but that with progressive invigoration of the arc, such compositions are more effectively blended with mantle melts in source regions. Thus, peraluminous magmas provide important details of the nascent Sierran arc and pre-batholithic crustal structure. 

Geochemical records generated from the calcite tests of benthic foraminifera, especially those of the generaCibicidoidesandUvigerina, provide the basis for proxy reconstructions of past climate. However, the extent to which benthic foraminifera are affected by postdepositional alteration is poorly constrained. Furthermore, how diagenesis may alter the geochemical composition of benthic foraminiferal tests, and thereby biasing a variety of proxy‐based climate records, is also poorly constrained. We present the Foraminiferal Preservation Index (FPI) as a new metric to quantify preservation quality based on objective, well‐defined criteria. The FPI is used to identify and quantify trends in diagenesis temporally, from late Pliocene to modern coretop samples (3.3–0 Ma), as well as spatially in the deep ocean. The FPI identifies the chemical composition of deep‐ocean water masses to be the primary driver of diagenesis through time, while also serving as a supplementary method of identifying periods of changing water mass influence at a given site. Additionally, we present stable isotope data (δ¹⁸O, δ¹³C) generated from individualCibicidoidesspecimens of various preservation quality that demonstrate the likelihood of significant biasing in a variety of geochemical proxy records, especially those used to reconstruct past changes in ice volume and sea level. These single‐test data further demonstrate that when incorporating carefully selected tests of only the highest preservation quality, robust paleorecords can be generated.

 

Abstract Ammonites have disparate adult morphologies indicative of diverse ecological niches, but ammonite hatchlings are small (~1 mm diameter), which raises questions about the similarity of egg incubation and hatchling life mode in ammonites. Modern Nautilus is sometimes used as a model organism for understanding ammonites, but despite their outward similarities, the groups are only distantly related. Trends in ammonite diversity and extinction vulnerability in the fossil record contrast starkly with those of nautilids, and embryonic shells from Late Cretaceous ammonites are two orders of magnitude smaller than nautilid embryonic shells. To investigate possible environmental changes experienced by ammonite hatchlings, we used secondary ion mass spectrometry to analyze the oxygen and carbon isotope composition of the embryonic shells and early postembryonic whorls of five juveniles of Hoploscaphites comprimus obtained from a single concretion in the Fox Hills Formation of South Dakota. Co-occurring bivalves and diagenetic calcite were also analyzed to provide a benthic baseline for comparison. The oxygen isotope ratios of embryonic shells are more like those of benthic bivalves, suggesting that ammonite eggs were laid on the bottom. Ammonite shell immediately after hatching has more negative δ 18 O, suggesting movement to more shallow water that is potentially warmer and/or fresher. After approximately one whorl of postembryonic growth, the values of δ 18 O become more positive in three of the five individuals, suggesting that these animals transitioned to a more demersal mode of life. Two other individuals transition to even lower δ 18 O values that could suggest movement to nearshore brackish water. These data suggest that ammonites, like many modern coleoids, may have spawned at different times of the year. Because scaphites were one of the short-term Cretaceous–Paleogene extinction survivors, it is possible that this characteristic allowed them to develop a broader geographic range and, consequently, a greater resistance to extinction.