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:
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 be reported as Δ47(I‐CDES) values for Intercarb‐Carbon Dioxide Equilibrium Scale.
more » « less- NSF-PAR ID:
- 10375746
- Author(s) / Creator(s):
- ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; more »
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Geochemistry, Geophysics, Geosystems
- Volume:
- 22
- Issue:
- 5
- ISSN:
- 1525-2027
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract R 13VPDB,R 17VSMOW,R 18VSMOW, 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 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. -
more » « less
Abstract Organic and inorganic stable isotopes of lacustrine carbonate sediments are commonly used in reconstructions of ancient terrestrial ecosystems and environments. Microbial activity and local hydrological inputs can alter porewater chemistry (e.g., pH, alkalinity) and isotopic composition (e.g., δ18Owater, δ13CDIC), which in turn has the potential to impact the stable isotopic compositions recorded and preserved in lithified carbonate. The fingerprint these syngenetic processes have on lacustrine carbonate facies is yet unknown, however, and thus, reconstructions based on stable isotopes may misinterpret diagenetic records as broader climate signals. Here, we characterize geochemical and stable isotopic variability of carbonate minerals, organic matter, and water within one modern lake that has known microbial influences (e.g., microbial mats and microbialite carbonate) and combine these data with the context provided by 16S rRNA amplicon sequencing community profiles. Specifically, we measure oxygen, carbon, and clumped isotopic compositions of carbonate sediments (δ18Ocarb, δ13Ccarb, ∆47), as well as carbon isotopic compositions of bulk organic matter (δ13Corg) and dissolved inorganic carbon (DIC; δ13CDIC) of lake and porewater in Great Salt Lake, Utah from five sites and three seasons. We find that facies equivalent to ooid grainstones provide time‐averaged records of lake chemistry that reflect minimal alteration by microbial activity, whereas microbialite, intraclasts, and carbonate mud show greater alteration by local microbial influence and hydrology. Further, we find at least one occurrence of ∆47isotopic disequilibrium likely driven by local microbial metabolism during authigenic carbonate precipitation. The remainder of the carbonate materials (primarily ooids, grain coatings, mud, and intraclasts) yield clumped isotope temperatures (T(∆47)), δ18Ocarb, and calculated δ18Owaterin isotopic equilibrium with ambient water and temperature at the time and site of carbonate precipitation. Our findings suggest that it is possible and necessary to leverage diverse carbonate facies across one sedimentary horizon to reconstruct regional hydroclimate and evaporation–precipitation balance, as well as identify microbially mediated carbonate formation.
-
more » « less
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 given
m /z . What normally would be considered acceptable mass spectrometer45R and46R linearity can skew Δ47results. That is 0.04‰/V and −0.04‰/V linearity on45R and46R respectively 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 way to precisely calculate the δ13C and δ18O that works well in spreadsheets without the need for multiple iterations. -
more » « less
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 of
ca 4 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 methods into aeolian environments. -
more » « less
Carbonate minerals contain stable isotopes of carbon and oxygen with different masses whose abundances and bond arrangement are governed by thermodynamics. The clumped isotopic value Δiis a measure of the temperature-dependent preference of heavy C and O isotopes to clump, or bond with or near each other, rather than with light isotopes in the carbonate phase. Carbonate clumped isotope thermometry uses Δivalues measured by mass spectrometry (Δ47, Δ48) or laser spectroscopy (Δ638) to reconstruct mineral growth temperature in surface and subsurface environments independent of parent water isotopic composition. Two decades of analytical and theoretical development have produced a mature temperature proxy that can estimate carbonate formation temperatures from 0.5 to 1,100°C, with up to 1–2°C external precision (2 standard error of the mean). Alteration of primary environmental temperatures by fluid-mediated and solid-state reactions and/or Δivalues that reflect nonequilibrium isotopic fractionations reveal diagenetic history and/or mineralization processes. Carbonate clumped isotope thermometry has contributed significantly to geological and biological sciences, and it is poised to advance understanding of Earth's climate system, crustal processes, and growth environments of carbonate minerals. ▪ Clumped heavy isotopes in carbonate minerals record robust temperatures and fluid compositions of ancient Earth surface and subsurface environments. ▪ Mature analytical methods enable carbonate clumped Δ47, Δ48, and Δ638measurements to address diverse questions in geological and biological sciences. ▪ These methods are poised to advance marine and terrestrial paleoenvironment and paleoclimate, tectonics, deformation, hydrothermal, and mineralization studies.
