More Like this

1. Comparison of δ ¹³ C analyses of individual foraminifer ( Orbulina universa ) shells by secondary ion mass spectrometry and gas source mass spectrometry

   https://doi.org/10.1002/rcm.9658  

   Wycech, Jody_B; Kelly, Daniel_Clay; Kozdon, Reinhard; Ishida, Akizumi; Kitajima, Kouki; Spero, Howard_J; Valley, John_W (November 2023, Rapid Communications in Mass Spectrometry)

   Abstract RationaleThe use of secondary ion mass spectrometry (SIMS) to perform micrometer‐scalein situcarbon isotope (δ¹³C) analyses of shells of marine microfossils called planktic foraminifers holds promise to explore calcification and ecological processes. The potential of this technique, however, cannot be realized without comparison to traditional whole‐shell δ¹³C values measured by gas source mass spectrometry (GSMS). MethodsPaired SIMS and GSMS δ¹³C values measured from final chamber fragments of the same shell of the planktic foraminiferOrbulina universaare compared. The SIMS–GSMS δ¹³C differences (Δ¹³C_SIMS‐GSMS) were determined via paired analysis of hydrogen peroxide‐cleaned fragments of modern cultured specimens and of fossil specimens from deep‐sea sediments that were either untreated, sonicated, and cleaned with hydrogen peroxide or vacuum roasted. After treatment, fragments were analyzed by a CAMECA IMS 1280 SIMS instrument and either a ThermoScientific MAT‐253 or a Fisons Optima isotope ratio mass spectrometer (GSMS). ResultsPaired analyses of cleaned fragments of cultured specimens (n = 7) yield no SIMS–GSMS δ¹³C difference. However, paired analyses of untreated (n = 18) and cleaned (n = 12) fragments of fossil shells yield average Δ¹³C_SIMS‐GSMSvalues of 0.8‰ and 0.6‰ (±0.2‰, 2 SE), respectively, while vacuum roasting of fossil shell fragments (n = 11) removes the SIMS–GSMS δ¹³C difference. ConclusionsThe noted Δ¹³C_SIMS‐GSMSvalues are most likely due to matrix effects causing sample–standard mismatch for SIMS analyses but may also be a combination of other factors such as SIMS measurement of chemically bound water. The volume of material analyzed via SIMS is ~10⁵times smaller than that analyzed by GSMS; hence, the extent to which these Δ¹³C_SIMS‐GSMSvalues represent differences in analyte or instrument factors remains unclear. 

   more » « less
2. Looking upstream with clumped and triple oxygen isotopes of estuarine oyster shells in the early Eocene of California, USA

   https://doi.org/10.1130/G49634.1  

   Kelson, Julia R.; Petersen, Sierra V.; Niemi, Nathan A.; Passey, Benjamin H.; Curley, Allison N. (April 2022, Geology)

   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
3. Triple oxygen isotope evidence for a hot Archean ocean

   https://doi.org/10.1130/G50230.1  

   McGunnigle, J.P.; Cano, E.J.; Sharp, Z.D.; Muehlenbachs, K.; Cole, D.; Hardman, M.F.; Stachel, T.; Pearson, D.G. (May 2022, Geology)

   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
4. Quantifying low fluence ion implants in diamond-like carbon film by secondary ion mass spectrometry by understanding matrix effects

   https://doi.org/10.1039/d0ja00375a  

   Jurewicz, Amy J.; Olinger, Chad T.; Burnett, Donald S.; Guan, Yunbin; Hervig, Richard; Rieck, Karen D.; Woolum, Dorothy S. (January 2021, Journal of Analytical Atomic Spectrometry)

   null (Ed.)

   Minor and trace elements in diamond-like carbon (DLC) are difficult to quantify using SIMS analysis because minor elemental and structural variations can result in major matrix effects even across individual, cm-sized samples. While this material is most commonly used for tribological coatings where minor element composition is not of critical importance, it is being increasingly used in electronic devices. However, it is a unique application that spurred this work: anhydrous, tetrahedrally-coordinated DLC (ta-C) was used as a solar wind (SW) collector material in the Genesis solar-wind sample return mission (NASA Discovery 5). So, for ∼15 years, we have been working on attaining accurate and precise measurement of minor and trace elements in the Genesis DLC using SIMS to achieve our mission goals. Specifically, we have learned to deal with relevant matrix effects in our samples, ion implants into ta-C. Our unknown element for quantification is SW Mg, a low-dose (1.67 × 10 12 at cm −2 ; ∼6 μg g −1 24 Mg), low-energy (∼24 keV average energy) implant; our standard is a high-dose (∼1 × 10 14 at cm −2 of both 25 Mg, 26 Mg) 75 keV laboratory implant for which the absolute 26 Mg/ 25 Mg ratio had been measured to account for variable instrumental mass fractionation. Analyses were performed using O 2 + primary ions having both a low impact energy and a current density of ∼2 × 10 14 ions per cm 2 . Although our unknown was solar wind, the method is applicable to many situations where minor elements in DLC need to be quantified. Recommendations are presented for modifying this data-reduction technique for other SIMS conditions. 

   more » « less
5. Orbital-pacing of South American Monsoon Strength and Regional Water Balance: New Evidence from Triple Oxygen Isotopes

   Katz, SA; Levin, N E; Rodbell, D T; Abbott, M B; Passey, B; Katz, S (December 2024, 2024 Fall Meeting, AGU)

   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