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1. Seasonal SIMS δ18O record in Astarte borealis from the Baltic Sea tracks a modern regime shift in the NAO

   https://doi.org/10.3389/fmars.2023.1293823  

   Hughes, Hunter P; Surge, Donna; Orland, Ian J; Zettler, Michael L; Moss, David K (December 2023, Frontiers in Marine Science)

   IntroductionAstarte borealisholds great potential as an archive of seasonal paleoclimate, especially due to its long lifespan (several decades to more than a century) and ubiquitous distribution across high northern latitudes. Furthermore, recent work demonstrates that the isotope geochemistry of the aragonite shell is a faithful proxy of environmental conditions. However, the exceedingly slow growth rates ofA. borealisin some locations (<0.2mm/year) make it difficult to achieve seasonal resolution using standard micromilling techniques for conventional stable isotope analysis. Moreover, oxygen isotope (δ¹⁸O) records from species inhabiting brackish environments are notoriously difficult to use as paleoclimate archives because of the simultaneous variation in temperature and δ¹⁸O_watervalues. MethodsHere we use secondary ion mass spectrometry (SIMS) to microsample anA. borealisspecimen from the southern Baltic Sea, yielding 451 SIMS δ¹⁸O_shellvalues at sub-monthly resolution. ResultsSIMS δ¹⁸O_shellvalues exhibit a quasi-sinusoidal pattern with 24 local maxima and minima coinciding with 24 annual growth increments between March 1977 and the month before specimen collection in May 2001. DiscussionAge-modeled SIMS δ¹⁸O_shellvalues correlate significantly with bothin situtemperature measured from shipborne CTD casts (r² = 0.52, p<0.001) and sea surface temperature from the ORAS5-SST global reanalysis product for the Baltic Sea region (r² = 0.42, p<0.001). We observe the strongest correlation between SIMS δ¹⁸O_shellvalues and salinity when both datasets are run through a 36-month LOWESS function (r² = 0.71, p < 0.001). Similarly, we find that LOWESS-smoothed SIMS δ¹⁸O_shellvalues exhibit a moderate correlation with the LOWESS-smoothed North Atlantic Oscillation (NAO) Index (r² = 0.46, p<0.001). Change point analysis supports that SIMS δ¹⁸O_shellvalues capture a well-documented regime shift in the NAO circa 1989. We hypothesize that the correlation between the SIMS δ¹⁸O_shelltime series and the NAO is enhanced by the latter’s influence on the regional covariance of water temperature and δ¹⁸O_watervalues on interannual and longer timescales in the Baltic Sea. These results showcase the potential for SIMS δ¹⁸O_shellvalues inA. borealisshells to provide robust paleoclimate information regarding hydroclimate variability from seasonal to decadal timescales. 

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2. A High‐Precision Analytical Technique for Dissolved N ₂ Isotopes in Aquatic Systems: Biogeochemical Applications and Determination of Solubility Equilibrium Isotope Effects

   https://doi.org/10.1002/rcm.10094  

   McPaul, Katelyn; Wankel, Scott D; Seltzer, Alan M (October 2025, Rapid Communications in Mass Spectrometry)

   ABSTRACT RationaleThe isotopic composition of dissolved dinitrogen gas (δ¹⁵N‐N₂) in water can offer a powerful constraint on the sources and pathways of nitrogen cycling in aquatic systems. However, because of the large presence of atmosphere‐derived dissolved N₂in these systems, high‐precision (on the order of 0.001‰) measurements of N₂isotopes paired with inert gas measurements are required to disentangle atmospheric and biogeochemical signals. Additionally, the solubility equilibrium isotope fractionation of N₂and its temperature and salinity dependence are underconstrained at this level of precision. MethodsWe introduce a new technique for sample collection, processing, and dynamic dual‐inlet mass spectrometry allowing for high‐precision measurement of δ¹⁵N‐N₂and δ(N₂/Ar) with simultaneous measurement of δ(⁴⁰Ar/³⁶Ar) and δ(Kr/N₂) in water. We evaluate the reproducibility of this technique and employ it to redetermine the solubility equilibrium isotope effects for dissolved N₂across a range of temperatures and salinities. ResultsOur technique achieves measurement reproducibility (1σ) for δ¹⁵N‐N₂(0.006‰) and δ(N₂/Ar) (0.41‰) suitable for tracing biogeochemical nitrogen cycling in aquatic environments. Through a series of air–water equilibration experiments, we find a N₂solubility equilibrium isotope effect (ε = α/1000 − 1, where α = (²⁹N₂/²⁸N₂)_dissolved/(²⁹N₂/²⁸N₂)_gas) in water of ε(‰) = 0.753 − 0.004•TwhereTis the temperature (°C), with uncertainties on the order of 0.001‰ over the temperature range of ~2°C–23°C and salinity range of ~0–30 psu. We find no apparent dependence of ε on salinity. ConclusionsOur new method allows for high‐precision measurements of the isotopic composition of dissolved N₂and Ar, and dissolved N₂/Ar and Kr/N₂ratios, within the same sample. Pairing measurements of N₂with inert gases facilitates the quantification of excess N₂from biogeochemical sources and its isotopic composition. This method allows for a wide range of applications in marine, coastal, and freshwater environments to characterize and quantitatively constrain potential nitrogen‐cycling sources and pathways and to differentiate between physical and biological isotope signals in these systems. 

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3. Shark teeth zinc isotope values document intrapopulation foraging differences related to ontogeny and sex

   https://doi.org/10.1038/s42003-023-05085-6  

   McCormack, Jeremy; Karnes, Molly; Haulsee, Danielle; Fox, Dewayne; Kim, Sora L. (December 2023, Communications Biology)

   Abstract Trophic ecology and resource use are challenging to discern in migratory marine species, including sharks. However, effective management and conservation strategies depend on understanding these life history details. Here we investigate whether dental enameloid zinc isotope (δ⁶⁶Zn_en) values can be used to infer intrapopulation differences in foraging ecology by comparing δ⁶⁶Zn_enwith same-tooth collagen carbon and nitrogen (δ¹³C_coll, δ¹⁵N_coll) values from critically endangered sand tiger sharks (Carcharias taurus) from Delaware Bay (USA). We document ontogeny and sex-related isotopic differences indicating distinct diet and habitat use at the time of tooth formation. Adult females have the most distinct isotopic niche, likely feeding on higher trophic level prey in a distinct habitat. This multi-proxy approach characterises an animal’s isotopic niche in greater detail than traditional isotope analysis alone and shows that δ⁶⁶Zn_enanalysis can highlight intrapopulation dietary variability thereby informing conservation management and, due to good δ⁶⁶Zn_enfossil tooth preservation, palaeoecological reconstructions. 

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4. Trophic Ecology of Threatened Sympatric Coastal Dolphins and Other Odontocetes in North‐Western Madagascar

   https://doi.org/10.1111/mms.70027  

   Caputo, Michelle; Kiszka, Jeremy J; Andrianarivelo, Norbert; Jonas, Ariana; Andrianantenaina, Boris; Paz, Valeria; Cerchio, Salvatore (May 2025, Marine Mammal Science)

   ABSTRACT Investigating the foraging ecology and trophic interactions of threatened marine predators is critical to assess how community changes due to anthropogenic activities will affect predator–prey relationships. Two species of threatened coastal dolphins, the Indian Ocean humpback dolphin (Sousa plumbea) and the Indo‐Pacific bottlenose dolphin (Tursiops aduncus), occur off Nosy Be, north‐western Madagascar, in a region where artisanal fisheries are ecologically and socioeconomically important. Here, we investigated the feeding ecology of these two coastal dolphins and their trophic interactions with four other odontocetes using bulk stable carbon and nitrogen isotope analysis (δ¹³C andδ¹⁵N). Humpback dolphins had significantly enrichedδ¹³C values, reflecting a preference for coastal/benthic prey. Bottlenose dolphins had a broader isotopic niche, suggesting a broader range of prey and foraging habitats. The overlap in isotopic niche of all six odontocete species was limited, indicating partitioning of resources and habitats. Bayesian mass‐balance isotopic mixing models revealed that humpback dolphins forage primarily on reef planktivores (38.9%) and inner reef mesopredators (20.5%), while bottlenose dolphins had a broader diet, including reef‐associated (15%–32%) and pelagic prey (12%–23%). Our study reveals that the reliance on inshore prey by humpback dolphins may place them in competition with coastal fisheries. 

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5. Controls on Stable Methane Isotope Values in Northern Peatlands and Potential Shifts in Values Under Permafrost Thaw Scenarios

   https://doi.org/10.1029/2023JG007837  

   Kuhn, McKenzie A; Varner, Ruth K; McCalley, Carmody K; Perryman, Clarice R; Aurela, Mika; Burke, Sophia A; Chanton, Jeffrey P; Crill, Patrick M; DelGreco, Jessica; Deng, Jia; et al (July 2024, Journal of Geophysical Research: Biogeosciences)

   Abstract Northern peatlands are a globally significant source of methane (CH₄), and emissions are projected to increase due to warming and permafrost loss. Understanding the microbial mechanisms behind patterns in CH₄production in peatlands will be key to predicting annual emissions changes, with stable carbon isotopes (δ¹³C‐CH₄) being a powerful tool for characterizing these drivers. Given that δ¹³C‐CH₄is used in top‐down atmospheric inversion models to partition sources, our ability to model CH₄production pathways and associated δ¹³C‐CH₄values is critical. We sought to characterize the role of environmental conditions, including hydrologic and vegetation patterns associated with permafrost thaw, on δ¹³C‐CH₄values from high‐latitude peatlands. We measured porewater and emitted CH₄stable isotopes, pH, and vegetation composition from five boreal‐Arctic peatlands. Porewater δ¹³C‐CH₄was strongly associated with peatland type, with δ¹³C enriched values obtained from more minerotrophic fens (−61.2 ± 9.1‰) compared to permafrost‐free bogs (−74.1 ± 9.4‰) and raised permafrost bogs (−81.6 ± 11.5‰). Variation in porewater δ¹³C‐CH₄was best explained by sedge cover, CH₄concentration, and the interactive effect of peatland type and pH (r² = 0.50,p < 0.001). Emitted δ¹³C‐CH₄varied greatly but was positively correlated with porewater δ¹³C‐CH₄. We calculated a mixed atmospheric δ¹³C‐CH₄value for northern peatlands of −65.3 ± 7‰ and show that this value is more sensitive to landscape drying than wetting under permafrost thaw scenarios. Our results suggest northern peatland δ¹³C‐CH₄values are likely to shift in the future which has important implications for source partitioning in atmospheric inversion models. 

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