skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Looking upstream with clumped and triple oxygen isotopes of estuarine oyster shells in the early Eocene of California, USA
The δ18O of carbonate minerals that formed at Earth’s surface is widely used to investigate paleoclimates and paleo-elevations. However, a multitude of hydrologic processes can affect δ18O values, including mixing, evaporation, distillation of parent waters, and carbonate growth temperatures. We combined traditional carbon and oxygen isotope analyses with clumped (Δ47) and triple oxygen isotopes (Δ′17O) analyses in oyster shells (Acutostrea idriaensis) of the Goler Formation in southern California (USA) to obtain insights into surface temperatures and δ18O values of meteoric waters during the early Eocene hothouse climate. The Δ47-derived temperatures ranged from 9 °C to 20 °C. We found a correlation between the δ18O of growth water (δ18Ogw) (calculated using Δ47 temperatures and δ18O of carbonate) and the δ13C values of shells. The Δ′17O values of shell growth waters (0.006‰–0.013‰ relative to Vienna standard mean ocean water–standard light Antarctic precipitation [VSMOW-SLAP]) calculated from Δ′17O of carbonate (–0.087‰ to –0.078‰ VSMOW-SLAP) were lower than typical meteoric waters. These isotopic compositions are consistent with oyster habitation in an estuary. We present a new triple oxygen isotope mixing model to estimate the δ18O value of freshwater supplying the estuary (δ18Ofw). The reconstructed δ18Ofw of –11.3‰ to –14.7‰ (VSMOW) is significantly lower than the δ18Ogw of –4.4‰ to –9.9‰ that would have been calculated using “only” Δ47 and δ18O values of carbonate. This δ18Ofw estimate supports paleogeographic reconstructions of a Paleogene river fed by high-elevation catchments of the paleo–southern Sierra Nevada. Our study highlights the potential for paired Δ47 and Δ′17O analyses to improve reconstructions of meteoric water δ18O, with implications for understanding ancient climates and elevations.  more » « less
Award ID(s):
1854873
PAR ID:
10331714
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
Geology
ISSN:
0091-7613
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. none (Ed.)
    Abstract The South American monsoon is central to the continent’s water and energy cycles, however, the relationships between the monsoon, regional water balance, and global climate change is poorly understood. Sediment records at Lake Junín (11°S, 76°W) provide an opportunity to explore these connections over the last 650 ka. Here, we focus on two interglacials, the Holocene (11.7–0 ka) and MIS 15 (621–563 ka), when sediment proxies suggest rapid regional hydroclimate fluctuations occurred. Clumped isotope distributions of lake carbonates reveal that interglacial water temperatures were similar to present, though analytical limitations preclude detecting the small temperature differences expected in the tropics (<2 °C). Combining the reconstructed water temperatures with carbonate oxygen (δ18O) and triple oxygen (Δ′17O) isotope values, we reconstruct precipitation δ18O values and lake water Δ′17O values. Precipitation δ18O values, a proxy of monsoon strength, range from -18.6 to -12.3 ‰ with lower values reflecting a stronger monsoon. Lake water Δ′17O values are -14 to 43 per meg and indicate the extent of lake water evaporation; lower values reflect a higher proportion of evaporation to inputs (i.e., more negative P-E). The precipitation δ18O and lake water Δ′17O values from both interglacials vary with the pacing of local summertime insolation, which follows an orbital pacing. These data document the close connection between Andean water balance, the South American monsoon, and global climate. Further, we analyze the relationship between precipitation δ18O and insolation, and we find that the relationship is consistent among interglacials, suggesting a similar response of the monsoon to orbital forcings over time. In contrast, while lake water Δ′17O and insolation are also correlated during both interglacials, water balance was overall more positive during MIS 15 than the Holocene. This suggests that either other global forcings or local basin dynamics can also contribute to water balance at Lake Junín. Together, these data provide new evidence of the connections between global climate, monsoon strength, and regional water balance. 
    more » « less
  2. Triple oxygen isotope (δ17O and δ18O) values of high- and low-temperature altered oceanic crust and products of basalt alteration experiments were measured to better constrain ocean isotope compositions in deep time. The data define an array of δ18O and Δ′17O (Δ′17O=δ′17O – λRL × δ′18O + γ) values from mantle values toward 1‰ and –0.01‰, respectively, with a λ of ~0.523. The altered oceanic crust data were used to construct a model for estimating δ18O-Δ′17O values of the ancient oceans if the continental weathering flux (FCW) and/or hydrothermal oceanic crust alteration flux (FHT) changed through time. A maximum lowering of 7‰ and 4‰, respectively, is achieved in the most extreme cases. The δ18O value of the ocean cannot be raised by more than 1.1‰. Eclogites from the Roberts Victor kimberlite (South Africa), with a protolith age of 3.1 Ga, have δ18O-Δ′17O values that precisely overlap with those of the modern altered oceanic crust, suggesting that the Archean oceans had similar isotope values as today. Published triple isotope data for Archean cherts show that all samples have been altered to some degree and suggest an Archean ocean surface temperature of ~70–100 °C. An ocean as light as –2‰ is still consistent with our eclogite data and reduce our temperature estimates by 10 °C. 
    more » « less
  3. Fossiliferous carbonate concretions are commonly found in sediments deposited in the Late Cretaceous Western Interior Seaway. Although concretions are diagenetic features, well-preserved fossils from within them have been instrumental in reconstructing the temperature and δ18O value of Western Interior Seaway seawater, which is essential for accurate reconstruction of Late Cretaceous climate. Here, we constrain formation conditions of Late Campanian and early Maastrichtian carbonate concretions by combining triple oxygen isotope measurements with carbonate clumped isotope paleothermometry on different carbonate phases within the concretions. We measured both fossil skeletal aragonite and sparry calcite infill from cracks and within macrofossil voids to evaluate differences between “primary” and “altered” geochemical signals. Based on the two temperature-sensitive isotope systems of the primary fossil shell aragonite, the temperature of the Western Interior Seaway was between 20 °C and 40 °C and was likely thermally stratified during the Campanian. The reconstructed δ18Oseawater values of ∼−1‰ for Campanian Western Interior Seaway waters are similar to those expected for the open ocean during greenhouse climates, while the Maastrichtian Western Interior Seaway may have been more restricted, with a δ18Oseawater value of ∼2‰, which reflects more evaporative conditions. We reconstructed the diagenetic history of the sparry infill and altered fossils using a fluid-rock mixing model. Alteration temperature, alteration fluid δ18O value, and the initial formation temperature were calculated by applying the fluid-rock mixing model to a particle swarm optimization algorithm. We found a different range of initial formation temperatures between the Campanian (25−38 °C) and Maastrichtian (9−28 °C). We also found that alteration in the presence of light meteoric fluids (δ18O ≈ −10‰) is required to explain both the sparry infill and the altered fossil isotopic values. Based on our results, both lithification and alteration of the carbonates occurred soon after burial, and light meteoric fluids support prior findings that high-topographic relief existed on the western margin of the Western Interior Seaway during the Late Cretaceous. As one of the first studies to apply these techniques in concert and across multiple mineralogical phases within samples, our results provide important constraints on paleoenvironmental conditions in an enigmatic ocean system and will improve interpretations of the overall health of ecosystems leading into the end-Cretaceous mass extinction. 
    more » « less
  4. null (Ed.)
    The Plio-Pleistocene El Laco iron oxide-apatite (IOA) orebodies in northern Chile are some of the most enigmatic mineral deposits on Earth, interpreted to have formed as lava flows or by hydrothermal replacement, two radically different processes. Field observations provide some support for both processes, but ultimately fail to explain all observations. Previously proposed genetic models based on observations and study of outcrop samples include (1) magnetite crystallization from an erupting immiscible Fe- and P-rich (Si-poor) melt and (2) metasomatic replacement of andesitic lava flows by a hypogene hydrothermal fluid. A more recent investigation of outcrop and drill core samples at El Laco generated data that were used to develop a new genetic model that invokes shallow emplacement and surface venting of a magnetite-bearing magmatic-hydrothermal fluid suspension. This fluid, with rheological properties similar to basaltic lava, would have been mobilized by decompression- induced collapse of the volcanic edifice. In this study, we report oxygen, including 17O, hydrogen, and iron stable isotope ratios in magnetite and bulk iron oxide (magnetite with minor secondary hematite and minor goethite) from five of seven orebodies around the El Laco volcano, excluding San Vicente Bajo and the minor Laquito deposits. Calculated values of δ18O, Δ17O, δD, and δ56Fe fingerprint the source of the ore-forming fluid(s): Δ17Osample = δ17Osample – δ18Osample * 0.5305. Magnetite and bulk iron oxide (magnetite variably altered to goethite and hematite) from Laco Sur, Cristales Grandes, and San Vicente Alto yield δ18O values that range from 4.3 to 4.5‰ (n = 5), 3.0 to 3.9‰ (n = 5), and –8.5 to –0.5‰ (n = 5), respectively. Magnetite samples from Rodados Negros are the least altered samples and were also analyzed for 17O as well as conventional 16O and 18O, yielding calculated δ18O values that range from 2.6 to 3.8‰ (n = 9) and Δ17O values that range from –0.13 to –0.07‰ (n = 5). Bulk iron oxide from Laco Norte yielded δ18O values that range from –10.2 to +4.5‰ (avg = 0.8‰, n = 18). The δ2H values of magnetite and bulk iron oxide from all five orebodies range from –192.8 to –79.9‰ (n = 28); hydrogen is present in fluid inclusions in magnetite and iron oxide, and in minor goethite. Values of δ56Fe for magnetite and bulk iron oxide from all five orebodies range from 0.04 to 0.70‰ (avg = 0.29‰, σ = 0.15‰, n = 26). The iron and oxygen isotope data are consistent with a silicate magma source for iron and oxygen in magnetite from all sampled El Laco orebodies. Oxygen (δ18O Δ +4.4 to –10.2‰) and hydrogen (δ 2H ≃ –79.9 to –192.8‰) stable isotope data for bulk iron oxide samples that contain minor goethite from Laco Norte and San Vicente Alto reveal that magnetite has been variably altered to meteoric values, consistent with goethite in equilibrium with local δ18O and δ2H meteoric values of ≃ –15.4 and –211‰, respectively. The H2O contents of iron oxide samples from Laco Norte and San Vicente Alto systematically increase with increasing abundance of goethite and decreasing values of δ18O and δ2H. The values of δ2H (≃ –88 to –140‰) and δ18O (3.0–4.5‰) for magnetite samples from Cristales Grandes, Laco Sur, and Rodados Negros are consistent with growth of magnetite from a degassing silicate melt and/or a boiling magmatic-hydrothermal fluid; the latter is also consistent with δ18O values for quartz, and salinities and homogenization temperatures for fluid inclusions trapped in apatite and clinopyroxene coeval with magnetite. The sum of the data unequivocally fingerprint a silicate magma as the source of the ore fluids responsible for mineralization at El Laco and are consistent with a model that explains mineralization as the synergistic result of common magmatic and magmatic-hydrothermal processes during the evolution of a caldera-related explosive volcanic system. 
    more » « less
  5. The three-isotope system of oxygen (16O, 17O, 18O) is a powerful tool to study environmental oxidation chemistry and cycling of oxygen-bearing species (e.g., sulfates, nitrates, carbonates, etc.). Despite its evident utility, little work has focused onextending the triple oxygen isotope (Δ’17O) tool to oxygen contained in organic matter (OM). This is largely due to methodological challenges with isolating OM-bound oxygen and preparing it for isotopic analysis. Herein, we report on a newly developed method for high-precision Δ’17O measurements of OM (Δ’17O precision of 0.020‰) and apply this technique to investigate partial photochemical oxidation of Suwannee River natural OM in air-equilibrated aquatic samples. Through this, we reveal that the oxygen isotope evolution of the Suwannee OM supports a model whereby OM partial photo-oxidation proceeds via one or more reactive oxygen intermediates. Our measurements further highlight the potential of triple oxygen isotope analyses on OM-bound oxygen to fingerprint OM oxidation pathways, redox chemistry, and source and synthesis reactions. 
    more » « less