Non‐linear mixing effects on mass‐47 CO2 clumped isotope thermometry: Patterns and implications

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/110849/1/rcm7175.pd

Cooler winters as a possible cause of mass extinctions at the eocene/oligocene boundary

The Eocene/Oligocene boundary, at about 33.7 Myr ago, marks one of the largest extinctions of marine invertebrates in the Cenozoic period(1). For example, turnover of mollusc species in the US Gulf coastal plain was over 90% at this time(2,3). A temperature change across this boundary-from warm Eocene climates to cooler conditions in the Oligocene-has been suggested as a cause of this extinction event(4), but climate reconstructions have not provided support for this hypothesis. Here we report stable oxygen isotope measurements of aragonite in fish otoliths-ear stones-collected across the Eocene/Oligocene boundary. Palaeotemperatures reconstructed from mean otolith oxygen isotope values show little change through this interval, in agreement with previous studies(5,6). From incremental microsampling of otoliths, however, we can resolve the seasonal variation in temperature, recorded as the otoliths continue to accrete new material over the life of the fish. These seasonal data suggest that winters became about 4 degrees C colder across the Eocene/Oligocene boundary. We suggest that temperature variability, rather than change in mean annual temperature, helped to cause faunal turnover during this transition.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/62707/1/407887a0.pd

The role of early lithification in development of chalky porosity in calcitic micrites: Upper Cretaceous chalks, Egypt

Petrological and geochemical examination of Upper Cretaceous chalks from the Abu Roash area and Bahariya Oasis (Egypt) provide insights into factors which control porosity development in fine-grained calcitic carbonates.Petrological studies indicate that primary skeletal fabrics of coccoliths and foraminifera in micrites of Abu Roash are well preserved. In contrast, primary skeletal fabrics of the Bahariya Oasis chalks are pervasively altered. Geochemical analysis of these chalks reveals a striking contrast in composition. The high porosity chalks at Bahariya Oasis have depleted isotopic values ([delta]13C = -5.0[per mille sign], [delta]18O = -8.9[per mille sign] PDB) and low concentrations of trace elements (Sr and Na). In contrast, the low porosity chalks at Abu Roash are less depleted in terms of their isotopic values ([delta]13C = 1.0[per mille sign], [delta]18O = -4.0[per mille sign]) and possess elevated concentrations of Sr, Na, Fe and Zn. Importantly, fracture and collapse veins, present only at Abu Roash, are filled with calcite whose [delta]18O value is coincident with that of altered micrites at Bahariya Oasis. The lithic fragments cemented by this calcite, however, retain compositions identical to other lithified limestones at Abu Roash.Differences in fabric and chemistry of the pelagic marine micrites observed between Abu Roash and Bahariya Oasis reflect the degree of early lithification and compaction prior to exposure and meteoric diagenetic alteration associated with regional Late Cretaceous/pre-Eocene subaerial unconformity.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/31901/1/0000854.pd

Closed-system marine burial diagenesis: isotopic data from the Austin Chalk and its components

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/73692/1/j.1365-3091.1984.tb00892.x.pd

Sr/Mg ratios of modern marine calcite: Empirical indicators of ocean chemistry and precipitation rate

Holocene biotic and abiotic marine calcite have a similar range of Mg contents (0 to 22 and 4 to 21 mol% MgCO3, respectively), yet biotic calcite has Sr2+ concentrations that are consistently 1250 ppm higher than those of abiotic calcite. As in laboratory experiments, a positive linear relation is observed between DSr and calcite Mg content. This produces two distinct linear trends on a plot of Sr2+ vs. Mg2+ concentrations. Principal axes of variation for both trends have similar slopes, yet distinctly different Sr2+ concentration intercepts. (Biotic: y = 0.024x + 1298, r2 = 0.70; Abiotic: y = 0.027x + 47, r2 = 0.77). The similar slopes of these trends reflect the constancy of Mg/Ca and Sr/Ca ratios of modern seawater. Equations describing the dependence of DSr on calcite Mg content are derived from both trends (Biotic: DSr = 3.16 x 10t-6 (ppm Mg) + 0.169; Abiotic: DSr = 3.52 x 10-6 (ppm Mg) + 0.0062). Characterization of Sr-Mg trends for Holocene materials allows comparison with analogous trends from ancient samples to estimate relative changes in seawater Mg/Ca and Sr/Ca ratios.The relatively high Sr contents of biotic calcite result from rapid precipitation rates associated with shell accretion in marine organisms. Calcites precipitated from seawater in laboratory experiments have Dsr values that are similar to those of biotic marine calcite, suggesting that both precipitate at approximately the same rate. Our estimates of surface area-normalized precipitation rates in planktonic and benthonic foraminifera are comparable to those of seeded, pH-stat experiments. We conclude that the DSr values for biotic and experimental marine calcite are kinetically controlled, whereas the lower precipitation rates of abiotic marine calcite yield DSr values that approximate equilibrium conditions.Experimentally derived equations describing the relation between DSr and calcite precipitation rate indicate that the offset in Sr content between biotic and abiotic calcite is the result of abiotic precipitation rates that are two to five orders of magnitude lower than those of biotic precipitates. However, observations of naturally occurring marine cements suggest that the five-order-of-magnitude offset best represents natural system processes.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/30096/1/0000468.pd

Noble gases and stable isotopes in a shallow aquifer in southern Michigan: Implications for noble gas paleotemperature reconstructions for cool climates

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/95038/1/grl20200.pd

Noble gas composition in rainwater and associated weather patterns

This work represents the first comprehensive noble gas study in rainwater. It was carried out in southeast Michigan. Results show that all rainwater samples are in disequilibrium with surface conditions. Two noble gas patterns are identified. The first one, associated with low‐pressure systems, presence of fog and light rainfall, displays a relative Ar enrichment together with Ne, Kr, and Xe depletion. The second one, associated with the passage of frontal systems, displays a mass‐dependent depletion pattern. Precipitation is characterized by thunderstorms, heavy rainfall, and high cloud ceiling heights. A diffusion mass‐transfer model suggests that noble gas patterns originate from ice. Complete re‐equilibration with surface conditions should occur within hours. For the first time, this study establishes a direct correlation between the noble gas composition in rainwater and weather patterns and highlights their potential to identify timing and location of recharge in shallow aquifer systems where infiltration is rapid. Key Points Noble gases in rainwater are in disequilibrium with surface conditions Rainwater noble gas patterns are associated with weather conditions Ice is the starting point of rainwater formation in southeast MichiganPeer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/1/FigureS12.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/2/FigureS5.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/3/Supplementary_Text_3_revised2_Trackchanges.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/4/FigureS1.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/5/FigureS8.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/6/TableS2.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/7/Supplementary_all.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/8/SuppText_2.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/9/FigureS4.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/10/FigureS9.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/11/TableS3.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/12/FigureS7.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/13/TableS4.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/14/SuppText_1.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/15/FigureS10.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/16/Supplementary_Text_3_revised2_NOhighlight.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/17/FigureS3.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/18/grl50610.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/19/FigureS6.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/20/FigureS11.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/21/TableS1.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/22/SuppText_4.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/99103/23/FigureS2.pd

Diagenetic incorporation of Sr into aragonitic bivalve shells: implications for chronostratigraphic and palaeoenvironmental interpretations

Aragonite is easily altered during diagenesis, therefore presumed pristine when present. In effect, beyond polymorphic transformation to calcite, alteration paths of aragonite remain poorly understood despite heavy reliance on such material to produce palaeoenvironmental and chronostratigraphic interpretations. Previous work on core material from Southern McMurdo Sound, Antarctica, showed that unlike their calcitic counterparts, seemingly unaltered aragonite shell fragments invariably produced older than expected 87Sr/86Sr ages. In this study, we pursued additional analyses of these aragonite shells and of the porewater of the core to understand this discrepancy. Aragonite mineralogy was reconfirmed and elemental mapping of shell fragments revealed growth lines within the middle layer suggestive of good preservation. The outer layer, however, showed anomalously high Sr concentrations (average 4·5 ± 0·6 mole% SrCO3; ca 25 mmol mol−1 Sr/Ca) and was depleted in 18O and 13C compared to the middle layer, both features inconsistent with pristine material. The δ18O values and Sr concentrations of the porewater were used to model outer layer compositions reasonably well. Coincidentally, porewater Sr isotope composition was in general agreement with the age model of the core only at the aragonite‐bearing interval suggesting that Sr‐isotopic disequilibrium between porewater and the carbonates was the rule rather than the exception in the core. The Sr isotope compositions of the aragonite shells are most likely the result of early diagenesis as suggested by the inconsistent O and C isotope compositions between shell layers and the anomalously high Sr concentrations. We conclude that knowledge of Sr concentration and distribution in shells is critical to determine the viability of Sr stratigraphy and the scale at which it may be applied. Reliance on traditional indicators of lack of alteration, such as cathodoluminescence, Mn‐Fe concentration, and the presence of labile mineralogies to assert chronostratigraphic and palaeoenvironmental questions may produce erroneous conclusions due to obscurely altered material.Compositional map of Sr over BSE image and representative SEM detail overlay from a Miocene aragonitic Retrotape andrillorum bivalve, Southern McMurdo Sound, Antarctica. Signs of apparent good preservation, such as the presence of growth bands and the preservation of crystalline structure and mineralogy, appear in contrast to anomalously high Sr concentrations. Results suggest that relying solely on traditional methods to rule out diagenesis may in some cases lead to erroneous conclusions due to obscure alteration patterns.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/113152/1/dep23.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/113152/2/dep23-sup-0003-AppendixS3.pd

Paleoelevation estimates for the northern and central proto–Basin and Range from carbonate clumped isotope thermometry

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/99057/1/tect20016.pd

Composition of the early Oligocene ocean from coral stable isotope and elemental chemistry

A sectioned and polished specimen of the coral Archohelia vicksburgensis from the early Oligocene Byram Formation (∼30 Ma) near Vicksburg, Mississippi, reveals 12 prominent annual growth bands. Stable oxygen isotopic compositions of 77 growth-band-parallel microsamples of original aragonite exhibit well-constrained fluctuations that range between −2.0 and −4.8. Variation in Δ 18 O of coral carbonate reflects seasonal variation in temperature ranging from 12 to 24 °C about a mean of 18 °C. These values are consistent with those derived from a bivalve and a fish otolith from the same unit, each using independently derived palaeotemperature equations. Mg/Ca and Sr/Ca ratios were determined for 40 additional samples spanning five of the 12 annual bands. Palaeotemperatures calculated using elemental-ratio thermometers calibrated on modern corals are consistently lower; mean temperature from Mg/Ca ratios are 12.5 ± 1 °C while those from Sr/Ca are 5.8 ± 2.2 °C. Assuming that Δ 18 O-derived temperatures are correct, relationships between temperature and elemental ratio for corals growing in today's ocean can be used to estimate Oligocene palaeoseawater Mg/Ca and Sr/Ca ratios. Calculations indicate that early Oligocene seawater Mg/Ca was ∼81% (4.2 mol mol −1 ) and Sr/Ca ∼109% (9.9 mmol mol −1 ) of modern values. Oligocene seawater with this degree of Mg depletion and Sr enrichment is in good agreement with that expected during the Palaeogene transition from ‘calcite’ to ‘aragonite’ seas. Lower Oligocene Mg/Ca probably reflects a decrease toward the present day in sea-floor hydrothermal activity and concomitant decrease in scavenging of magnesium from seawater. Elevated Sr/Ca ratio may record lesser amounts of Oligocene aragonite precipitation and a correspondingly lower flux of strontium into the sedimentary carbonate reservoir than today.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/72914/1/j.1472-4677.2004.00025.x.pd