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.
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:
- NSF-PAR ID:
- 10367882
- Author(s) / Creator(s):
- ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; more »
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Geochemistry, Geophysics, Geosystems
- Volume:
- 20
- Issue:
- 7
- ISSN:
- 1525-2027
- Page Range / eLocation ID:
- p. 3495-3519
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract -
Abstract Ancient greenhouse periods are useful analogs for predicting effects of anthropogenic climate change on regional and global temperature and precipitation patterns. A paucity of terrestrial data from polar regions during warm episodes challenges our understanding of polar climate responses to natural/anthropogenic change and therefore our ability to predict future changes in precipitation. Ellesmere and Axel Heiberg Islands in the Canadian Arctic preserve terrestrial deposits spanning the late Paleocene to middle Eocene (59–45 Ma). Here we expand on existing regional sedimentology and paleontology through the addition of stable (δ13C, δ18O) and clumped (Δ47) isotope analyses on palustrine carbonates. δ13C isotope values range from −4.6 to +12.3‰ (VPDB), and δ18O isotope values range from −23.1 to −15.2‰ (VPDB). Both carbon and oxygen isotope averages decrease with increasing diagenetic alteration. Unusually enriched carbon isotope (δ13C) values suggest that analyzed carbonates experienced repeated dissolution‐precipitation enrichment cycles, potentially caused by seasonal fluctuations in water availability resulting in summer carbonate dissolution followed by winter carbonate re‐precipitation. Stable isotopes suggest some degree of precipitation seasonality or reduction in winter water availability in the Canadian Arctic during the Paleogene. Clumped (Δ47) temperature estimates range from 52 to 121°C and indicate low temperature solid‐state reordering of micritic samples and diagenetic recrystallization in sparry samples. Average temperatures agree with vitrinite reflectance data for Eureka Sound Group and underlying sediments, highlighting structural complexity across the region. Broadly, combined stable and clumped isotope data from carbonates in complex systems are effective for describing both paleoclimatic and post‐burial conditions.
-
Abstract Lacustrine carbonates are a powerful archive of paleoenvironmental information but are susceptible to post‐depositional alteration. Microbial metabolisms can drive such alteration by changing carbonate saturation
in situ , thereby driving dissolution or precipitation. The net impact these microbial processes have on the primary δ18O, δ13C, and Δ47values of lacustrine carbonate is not fully known. We studied the evolution of microbial community structure and the porewater and sediment geochemistry in the upper ~30 cm of sediment from two shoreline sites at Green Lake, Fayetteville, NY over 2 years of seasonal sampling. We linked seasonal and depth‐based changes of porewater carbonate chemistry to microbial community composition, in situ carbon cycling (using δ13C values of carbonate, dissolved inorganic carbon (DIC), and organic matter), and dominant allochems and facies. We interpret that microbial processes are a dominant control on carbon cycling within the sediment, affecting porewater DIC, aqueous carbon chemistry, and carbonate carbon and clumped isotope geochemistry. Across all seasons and sites, microbial organic matter remineralization lowers the δ13C of the porewater DIC. Elevated carbonate saturation states in the sediment porewaters (Ω > 3) were attributed to microbes from groups capable of sulfate reduction, which were abundant in the sediment below 5 cm depth. The nearshore carbonate sediments at Green Lake are mainly composed of microbialite intraclasts/oncoids, charophytes, larger calcite crystals, and authigenic micrite—each with a different origin. Authigenic micrite is interpreted to have precipitated in situ from the supersaturated porewaters from microbial metabolism. The stable carbon isotope values (δ13Ccarb) and clumped isotope values (Δ47) of bulk carbonate sediments from the same depth horizons and site varied depending on both the sampling season and the specific location within a site, indicating localized (μm to mm) controls on carbon and clumped isotope values. Our results suggest that biological processes are a dominant control on carbon chemistry within the sedimentary subsurface of the shorelines of Green Lake, from actively forming microbialites to pore space organic matter remineralization and micrite authigenesis. A combination of biological activity, hydrologic balance, and allochem composition of the sediments set the stable carbon, oxygen, and clumped isotope signals preserved by the Green Lake carbonate sediments. -
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. -
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.