Sharks migrate annually over large distances and occupy a wide variety of habitats, complicating analysis of lifestyle and diet. A biogeochemical technique often used to reconstruct shark diet and environment preferences is stable isotope analysis, which is minimally invasive and integrates through time and space. There are previous studies that focus on isotopic analysis of shark soft tissues, but there are limited applications to shark teeth. However, shark teeth offer an advantage of multiple ecological snapshots and minimum invasiveness during removal because of their distinct conveyor belt tooth replacement system. In this study, we analyze δC and δN values of the organic matrix in leopard shark teeth (Triakis semifasciata) from a captive experiment and report discrimination factors as well as incorporation rates. We found differences in tooth discrimination factors for individuals fed different prey sources (mean ± SD; ΔC = 4.7‰ ± 0.5‰, ΔC = 3.1‰ ± 1.0‰, ΔN = 2.0‰ ± 0.7‰, ΔN = 2.8‰ ± 0.6‰). In addition, these values differed from previously published discrimination factors for plasma, red blood cells, and muscle of the same leopard sharks. Incorporation rates of shark teeth were similar for carbon and nitrogen (mean ± SE; λ = 0.021 ± 0.009, λ = 0.024 ± 0.007) and comparable to those of plasma. We emphasize the difference in biological parameters on the basis of tissue substrate and diet items to interpret stable isotope data and apply our results to stable isotope values from blue shark (Prionace glauca) teeth to illustrate the importance of biological parameters to interpret the complex ecology of a migratory shark.
An irreversible increase in alluvial mudrock occurred with the Ordovician-Silurian evolution of bryophytes, challenging a paradigm that deep-rooted plants were responsible for this landscape shift. We tested the idea that increased primary production and plant organics promoted aggregation of clay into flocs in rivers and facilitated mud deposition on floodplains. In experiments, we observed that clay readily flocculated for organic and clay concentrations common to modern rivers, yielding settling velocities three orders of magnitude larger than those without organics. Using a transport model, we found that flocculation substantially increased mud deposition, resulting in muddier floodplains. Thus, organic-induced flocculation may have been more critical than deep-rooted plants in the proliferation of muddy floodplains.
Analysis of trends in health data collected over time can be affected by instantaneous changes in coding that cause sudden increases/decreases, or “jumps,” in data. Despite these sudden changes, the underlying continuous trends can present valuable information related to the changing risk profile of the population, the introduction of screening, new diagnostic technologies, or other causes. The joinpoint model is a well-established methodology for modeling trends over time using connected linear segments, usually on a logarithmic scale. Joinpoint models that ignore data jumps due to coding changes may produce biased estimates of trends. In this article, we introduce methods to incorporate a sudden discontinuous jump in an otherwise continuous joinpoint model. The size of the jump is either estimated directly (the Joinpoint-Jump model) or estimated using supplementary data (the Joinpoint-Comparability Ratio model). Examples using ICD-9/ICD-10 cause of death coding changes, and coding changes in the staging of cancer illustrate the use of these models.
Rationale Position‐specific 13C/12C ratios within amino acids remain largely unexplored in environmental samples due to methodological limitations. We hypothesized that natural‐abundance isotope patterns in serine may serve as a proxy for plant metabolic fluxes including photorespiration. Here we describe an Orbitrap method optimized for the position‐specific carbon isotope analysis of serine to test our hypothesis and discuss the generalizability of this method to other amino acids. Methods Position‐specific carbon isotope ratios of serine were measured using a Thermo Scientific™ Q Exactive™ GC Orbitrap™. Amino acids were hydrolyzed from Arabidopsis biomass, purified from potential matrix interferences, and derivatized alongside standards. Derivatized serine (N,O‐bis(trifluoroacetyl)methyl ester) was isolated using gas chromatography, trapped in a reservoir, and purged into the electron ionization source over tens of minutes, producing fragment ions containing different combinations of atoms from the serine‐derivative molecule. The 13C/12C ratios of fragments with monoisotopic masses of 110.0217, 138.0166, and 165.0037 Da were monitored in the mass analyzer and used to calculate position‐specific δ13C values relative to a working standard. Results This methodology constrains position‐specific δ13C values for nanomole amounts of serine isolated from chemically complex mixtures. The δ13C values of fragment ions of serine were characterized with ≤1‰ precisions, leading to propagated standard errors of 0.7–5‰ for each carbon position. Position‐specific δ13C values differed by up to ca 28 ± 5‰ between serine molecules hydrolyzed from plants grown under contrasting pCO2, selected to promote different fluxes through photosynthesis and photorespiration. The method was validated using pure serine standards characterized offline. Conclusions This study presents the first Orbitrap‐based measurements of natural‐abundance, position‐specific carbon isotope variation in an amino acid isolated from a biological matrix. We present a method for the precise characterization of isotope ratios in serine and propose applications probing metabolism in plants. We discuss the potential for extending these approaches to other amino acids, paving the way for novel applications.
Evaluating the molecular distribution of organic compounds in pristine extraterrestrial materials is cornerstone to understanding the abiotic synthesis of organics and allows us to better understand the molecular diversity available during the formation of our solar system and before the origins of life on Earth. In this work, we identify multiple organic compounds in solvent extracts of asteroid Ryugu samples A0106 and C0107 and the Orgueil meteorite using two-dimensional gas chromatography and time-of-flight high resolution mass spectrometry (GC×GC–HRMS). Our analyses found similarities between the molecular distribution of organic compounds in Ryugu and the CI carbonaceous chondrite Orgueil. Specifically, several PAHs and organosulfides were found in Ryugu and Orgueil suggesting an interstellar and parent body origin for these compounds. We also evaluated the common relationship between Ryugu, Orgueil, and comets, such as Wild-2; however, until comprehensive compound-specific isotopic analyses for these organic species are undertaken, and until the effects of parent body processes and Earth’s weathering processes on meteoritic organics are better understood, their parent–daughter relationships will remain unanswered. Finally, the study of organic compounds in Ryugu samples and the curation practices for the future preservation of these unvaluable materials are also of special interest for future sample return missions, including NASA’s OSIRIS-REx asteroid sample return mission. Graphical Abstract
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