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.
Carbonate concretions collected from the Dominican Republic present a valuable opportunity to evaluate the internal isotopic variations within concretions that have never been exposed to deep burial or structural deformation. Here, three concretions from the Neogene (Late Miocene–Early Pliocene) Cibao Basin are investigated, utilizing a multi‐isotope (δ13C, δ18O, δ34SCASand ∆47values) high‐resolution approach, to constrain the microenvironmental conditions associated with multiple stages of concretion growth. Isotopic variability and potential disequilibrium effects, which can influence geological interpretations utilizing concretions, are also considered. The petrographic characteristics and geochemical profiles indicate internal differences relating to concretion growth mechanisms and environmental changes, driven by sea‐level fluctuations. The δ34S values of carbonate‐associated sulphate indicate a closed system environment; however, the overall values are influenced by sulphide oxidation within the sediments, resulting in a complex signal. The ∆47‐derived temperatures of the concretions range between 29 to 55°C, indicating significantly warmer temperatures than are measured from the host sediments, which average 24°C. This indicates that carbonate concretion ∆47values are in disequilibrium with their environments of formation, likely related to ion diffusion in the pore fluids or isotopic fractionation associated with microbial processes. Here geochemical variations within concretions are utilized to assess the environmental conditions and microbial interactions after sediment deposition. However, for future studies, caution should be taken when using concretions for making environmental assessments as the signals can be influenced by a multitude of processes, even prior to diagenetic alteration.
more » « less- NSF-PAR ID:
- 10479358
- Publisher / Repository:
- Wiley-Blackwell
- Date Published:
- Journal Name:
- Sedimentology
- Volume:
- 70
- Issue:
- 5
- ISSN:
- 0037-0746
- Format(s):
- Medium: X Size: p. 1553-1579
- Size(s):
- ["p. 1553-1579"]
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
more » « less
Abstract Inorganic aragonite occurs in a wide spectrum of depositional environments and its precipitation is controlled by complex physio‐chemical factors. This study investigates diagenetic conditions that led to aragonite cement precipitation in Cenozoic glaciomarine deposits of McMurdo Sound, Antarctica. A total of 42 sandstones that host intergranular cement were collected from the
CIROS ‐1 core, located proximal to the terminus of Ferrar Glacier. Standard petrography, Raman spectroscopy and electron microprobe analysis reveal a prominent aragonite cement phase that occurs as a pore‐filling blocky fabric throughout the core. Oxygen isotope compositions (δ 18O = −30·0 to −8·6‰ Vienna Pee‐Dee Belemnite) and clumped isotope temperatures (TΔ47 = 13·1 to 31·5°C) determined from the aragonite cements provide precise constraints on isotopic compositions (δ 18Ow) of the parent fluid, which mostly range from −10·8 to −7·2‰ Vienna Standard Mean Ocean Water. The fluidδ 18Owvalues are consistent with those of pore water, previously identified as cryogenic brine in the nearbyAND ‐2A core. Petrographic and geochemical data suggest that aragonite cement in theCIROS ‐1 core precipitated from a similar brine. The brine likely formed and infiltrated sediments in flooded glacial valleys along the western margin of McMurdo Sound during the middle Miocene Climatic Transition, and subsequently flowed basinward in the subsurface. Consequently, the brine forms as a longstanding subsurface fluid that has saturated Cenozoic sediments below southern McMurdo Sound since at least the middle Miocene. Aragonite cementation in theCIROS ‐1 core is interpreted to reflect its proximal position to sites of brine formation and greater likelihood of experiencing brines with sustained high carbonate saturation states and Mg/Ca ratios. This unusual occurrence expands the range of known natural occurrences of aragonite cement. Given the potential for cryogenic brine formation in glaciomarine settings, blocky aragonite, as the end member of the spectrum of aragonite cement morphology, may be more widespread in glaciomarine sediments than currently thought. -
more » « less
Abstract Experiments have been conducted in which CO2gases with varying C and O isotopic compositions and with stochastic and nonstochastic Δ47values have been allowed to equilibrate with phosphoric acid of two concentrations in reaction vessels of varying dimensions at temperatures of 25 and 90 °C. Rates of13C18O and18O exchange between the CO2and the phosphoric acid varied as a function of the length of exposure, volume of reaction vessel, acid strength, and difference of the initial Δ47and δ18O values of the CO2from theoretical equilibrium values. The Δ47values were also altered by heated stainless steel surfaces such as those found within the Kiel device and other preparation systems. These results have been used to explain variations in the differences in the fractionation between 25 and 90 °C reported for calcite by different workers as well as differences in the slopes between temperature and Δ47values produced by reacting samples at different temperatures (25 and 90 °C).
-
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.
-
more » « less
Abstract Fast diffusing Li isotopes provide important insights into the “recent” transient events or processes for both modern and ancient times, but questions remain concerning the large Li isotopic variations of mantle peridotites, which greatly hampers their usage as a geochemical tracer. This study investigates in situ Li content and isotopic profiles of the constituent minerals of abyssal peridotites from the Gakkel Ridge and Southwest Indian Ridge. The complicated and large variations of Li isotopic profiles in Clinopyroxene (Cpx) and Orthopyroxene (Opx) indicate Li isotopic disequilibrium at millimeter scale. The negative correlations of a wide range of Li contents (0.5 to 6.5 ppm) and δ7Li values (−10 to +20‰) of olivine, Opx and Cpx grains/relicts, trace element zoning of Cpx, the occurrence of plagioclase, olivine serpentinization along cracks, together with numerical modeling demonstrate the observed Li characteristics to be a manifestation of high‐temperature mineral‐melt Li diffusion during melt impregnation overprinted by low‐temperature mineral‐fluid Li diffusion during dissolution and serpentinization. The preservation of the Li isotopic diffusion profiles requires rapid cooling of 0.3–5°C/year after final‐stage melt impregnation at the Moho boundary, which is consistent with the low temperature at very slow spreadin g ridges caused by conductive cooling. Compared with the well‐studied melt‐rock interaction process, our study indicates that low‐temperature fluid‐rock interaction can induce Li diffusion even in the visibly unaltered mineral relicts of partially altered rocks.
