skip to main content

Title: Effects of Improved 17 O Correction on Interlaboratory Agreement in Clumped Isotope Calibrations, Estimates of Mineral‐Specific Offsets, and Temperature Dependence of Acid Digestion Fractionation

The clumped isotopic composition of carbonate‐derived CO2(denoted Δ47) is a function of carbonate formation temperature and in natural samples can act as a recorder of paleoclimate, burial, or diagenetic conditions. The absolute abundance of heavy isotopes in the universal standards VPDB and VSMOW (defined by four parameters:R13VPDB,R17VSMOW,R18VSMOW, andλ) impact calculated Δ47values. Here, we investigate whether use of updated and more accurate values for these parameters can remove observed interlaboratory differences in the measured T‐Δ47relationship. Using the updated parameters, we reprocess 14 published calibration data sets measured in 11 different laboratories, representing many mineralogies, bulk compositions, sample types, reaction temperatures, and sample preparation and analysis methods. Exploiting this large composite data set (n= 1,253 sample replicates), we investigate the possibility for a “universal” clumped isotope calibration. We find that applying updated parameters improves the T‐Δ47relationship (reduces residuals) within most labs and improves overall agreement but does not eliminate all interlaboratory differences. We reaffirm earlier findings that different mineralogies do not require different calibration equations and that cleaning procedures, method of pressure baseline correction, and mass spectrometer type do not affect interlaboratory agreement. We also present new estimates of the temperature dependence of the acid digestion fractionation for Δ47(Δ*25‐X), based on more » combining reprocessed data from four studies, and new theoretical equilibrium values to be used in calculation of the empirical transfer function. Overall, we have ruled out a number of possible causes of interlaboratory disagreement in the T‐Δ47relationship, but many more remain to be investigated.

« less
 ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  more » ;  ;  ;  ;  ;  ;  ;  ;  ;  ;   « less
Publication Date:
Journal Name:
Geochemistry, Geophysics, Geosystems
Page Range or eLocation-ID:
p. 3495-3519
DOI PREFIX: 10.1029
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Increased use and improved methodology of carbonate clumped isotope thermometry has greatly enhanced our ability to interrogate a suite of Earth‐system processes. However, interlaboratory discrepancies in quantifying carbonate clumped isotope (Δ47) measurements persist, and their specific sources remain unclear. To address interlaboratory differences, we first provide consensus values from the clumped isotope community for four carbonate standards relative to heated and equilibrated gases with 1,819 individual analyses from 10 laboratories. Then we analyzed the four carbonate standards along with three additional standards, spanning a broad range of δ47and Δ47values, for a total of 5,329 analyses on 25 individual mass spectrometers from 22 different laboratories. Treating three of the materials as known standards and the other four as unknowns, we find that the use of carbonate reference materials is a robust method for standardization that yields interlaboratory discrepancies entirely consistent with intralaboratory analytical uncertainties. Carbonate reference materials, along with measurement and data processing practices described herein, provide the carbonate clumped isotope community with a robust approach to achieve interlaboratory agreement as we continue to use and improve this powerful geochemical tool. We propose that carbonate clumped isotope data normalized to the carbonate reference materials described in this publication should bemore »reported as Δ47(I‐CDES) values for Intercarb‐Carbon Dioxide Equilibrium Scale.

    « less
  2. The Cedar Mountain Formation is thought to span a significant portion of the lower Cretaceous and the base of the upper Cretaceous (Valanginian to Cenomanian). As such, the Cedar Mountain Formation is important for understanding the transition of terrestrial ecosystems from those characterized by pre-angiosperm ecosystems of the Jurassic to the angiosperm-dominated ecosystems that characterized the height of dinosaur diversity in the later part of the Cretaceous. Lacustrine strata offer unique opportunities to shed light on environmental and climate conditions of the past. This study presents results from a multi-proxy study of lacustrine strata in the Cedar Mountain Formation termed “Lake Carpenter.” The sequence of strata is about ~30 m thick and located near Arches National Park. The lower ~7 m is characterized by dark organic-rich mudstones, shales, and tan limestones and dolostone. The middle portion between about 7 and 25m consists of more massive carbonate-rich strata with abundant aquatic fossils including ostracodes, charophytes, and fish scales. The upper portion to about 30 m consists of green to tan mudstones with carbonate nodules and increases in siliciclastic content. Carbonate mineralogies include calcite, high-magnesium calcite, and dolomite (including dolomicrites) based on XRD analyses. To put the lacustrine sequence into stratigraphic context,more »bulk organic C isotope values were utilized to construct a chemostratigraphic record. The carbon isotope values range from -32.3‰ to -21.1‰ vs. VPDB. Zircons from four suspected volcanic ash layers were analyzed for U-Pb using LA-ICP-MS. One of these produced concordant Cretaceous dates. The youngest zircons from this sample was analyzed using CA-ID-TIMS and produced a date of 115.65 ± 0.18 Ma. Based on the chemostratigraphic record and the U-Pb date, the deposition of the lacustrine sequence occurs in the mid to late Aptian and spans a time that is thought to have coincided with a cold snap based on marine records. Carbonate analyses of the carbonates within the lacustrine sequence ranges from -9.2‰ to +5.4‰ vs. VPDB for carbon and -9.3 to -0.3‰ vs. VPDB for oxygen. Overall, carbonate isotope data is positively covariant and along with the minerology, seems to suggest that the lake was a closed-basin, alkaline lake and would have likely experience significant evaporation. To investigate paleotemperature, selected samples were analyzed for clumped isotope values (47) to determine temperature of formation. Preliminary temperature estimates of calcite formation range from 27°C to 41°C. Estimates for dolomite range from 19°C to 21°C. Lacustrine carbonate formation typically is biased toward spring and summer and as such some of these temperatures (particularly the values for dolomites) seem slightly lower than expected for a greenhouse climate but may be consistent with a “cold-snap” during the late Aptian. Palustrine carbonates from the type section of the Ruby Ranch Member range 19.8°C to 44.5°C (Suarez et al. 2021) and suggests the lacustrine strata records a similar range in temperatures during the Aptian Stage in this part of North America. REFERENCES CITED: Suarez, MB, Knight, J, Snell, KE, Ludvigson, GA, Kirkland, JI, Murphy, L 2020. Multiproxy paleoclimate estimates of the continental Cretaceous Ruby Ranch Member of the Cedar Mountain Formation. In: Bojar, A-V, Pelc., A, Lecuyer, C, editors. Stable Isotopes Studies of Water Cycle and Terrestrial Environments. Geol Soc, London, Spec Pub, 507: KEYWORDS: Early Cretaceous, lacustrine, stable isotopes, paleoclimate Presentation Mode: Invited Speaker« less
  3. Abstract

    Clumped isotope studies on CO2, Δ47, that is the excess in the isotopologue containing both13C and18O at mass 47, can be very useful since they can give temperature estimates independent of the bulk isotopic composition. The measurement itself can be affected by a number of items. Here we develop a data processing model to examine the effects different interferences might have on the final calculated value. It incorporates known issues, for example, pressure baseline,17O excess, and shifts in absolute ratios for primary reference materials and parameters used for17O correction. We also included linearity effects as well as differences in isotopologue absolute abundances at a givenm/z. What normally would be considered acceptable mass spectrometer45Rand46Rlinearity can skew Δ47results. That is 0.04‰/V and −0.04‰/V linearity on45Rand46Rrespectively would also cause an apparent shift in the parameters used for17O corrections. Measurements were made on CO2(g) equilibrated with water, and we were able to match up the effects seen with model results. Linearity and small differences in amplitude between sample and working reference gas affected Δ47determination, as did apparent shifts in isotopologue abundances under different conditions. This may (partially) account for discrepancies seen in Δ47‐temperature calibrations curves between laboratories. We also developed an easy waymore »to precisely calculate the δ13C and δ18O that works well in spreadsheets without the need for multiple iterations.

    « less
  4. Abstract

    Faunal analog reconstructions suggest that Last Interglacial (MIS 5e) sea surface temperatures were cooler around Bermuda and in the Caribbean than modern climate. Here we describe new and revised clumped isotope measurements ofCittarium picafossil shells supporting previous findings of cooler than modern temperatures in Bermuda during the Last Interglacial. We resolve temperature and δ18Owdifferences between two closely located and apparently coeval sites described in Winkelstern et al. (2017), reprocessing raw isotopic data with the updated Brand/IUPAC parameters. New subannual‐resolution clumped isotope data reveal large variations in δ18Owout of phase with seasonal temperature changes (i.e., lower δ18Owvalues in winter). Supported by modern δ18Owmeasurements identifying similar processes occurring today, we suggest past variations in coastal δ18Owwere driven by seasonally variable freshwater discharge from a subterranean aquifer beneath the island. Taken together, our results emphasize the importance of δ18Owin controlling carbonate δ18O, and suggest that typical assumptions of constant δ18Owshould be made cautiously in nearshore settings and can contribute to less accurate reconstructions of paleotemperature.

  5. Abstract

    Carbon, oxygen and clumped isotope (Δ47) values were measured from lacustrine and tufa (spring)‐mound carbonate deposits in the Lower Jurassic Navajo Sandstone of southern Utah and northern Arizona in order to understand the palaeohydrology. These carbonate deposits are enriched in both18O and13C across the basin from east to west; neither isotope is strongly sensitive to the carbonate facies. However,18O is enriched in lake carbonate deposits compared to the associated spring mounds. This is consistent with evaporation of the spring waters as they exited the mounds and were retained in interdune lakes. Clumped isotopes (Δ47) exhibit minor systematic differences between lake and tufa‐mound temperatures, suggesting that the rate of carbonate formation under ambient conditions was moderate. These clumped isotope values imply palaeotemperature elevated beyond reasonable surface temperatures (54 to 86°C), which indicates limited bond reordering at estimated burial depths ofca4 to 5 km, consistent with independent estimates of sediment thickness and burial depth gradients across the basin. Although clumped isotopes do not provide surface temperature information in this case, they still provide useful burial information and support interpretations of the evolution of groundwater locally. The findings of this study significantly extend the utility of combining stable isotope and clumped isotope methodsmore »into aeolian environments.

    « less