Polycyclic aromatic hydrocarbons in samples of Ryugu formed in the interstellar medium.

Polycyclic aromatic hydrocarbons (PAHs) contain ≲20% of the carbon in the interstellar medium. They are potentially produced in circumstellar environments (at temperatures ≳1000 kelvin), by reactions within cold (~10 kelvin) interstellar clouds, or by processing of carbon-rich dust grains. We report isotopic properties of PAHs extracted from samples of the asteroid Ryugu and the meteorite Murchison. The doubly-13C substituted compositions (Δ2×13C values) of the PAHs naphthalene, fluoranthene, and pyrene are 9 to 51‰ higher than values expected for a stochastic distribution of isotopes. The Δ2×13C values are higher than expected if the PAHs formed in a circumstellar environment, but consistent with formation in the interstellar medium. By contrast, the PAHs phenanthrene and anthracene in Ryugu samples have Δ2×13C values consistent with formation by higher-temperature reactions.

Position-specific carbon isotope analysis of serine by gas chromatography/Orbitrap mass spectrometry, and an application to plant metabolism.

RATIONALE: Position-specific 13 C/12 C 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 13 C/12 C 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 δ13 C values relative to a working standard. RESULTS: This methodology constrains position-specific δ13 C values for nanomole amounts of serine isolated from chemically complex mixtures. The δ13 C 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 δ13 C 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.

Decoding the dynamics of dental distributions: insights from shark demography and dispersal.

Shark teeth are one of the most abundant vertebrate fossils, and because tooth size generally correlates with body size, their accumulations document the size structure of populations. Understanding how ecological and environmental processes influence size structure, and how this extends to influence these dental distributions, may offer a window into the ecological and environmental dynamics of past and present shark populations. Here, we examine the dental distributions of sand tigers, including extant Carcharias taurus and extinct Striatolamia macrota, to reconstruct the size structure for a contemporary locality and four Eocene localities. We compare empirical distributions against expectations from a population simulation to gain insight into potential governing ecological processes. Specifically, we investigate the influence of dispersal flexibility to and from protected nurseries. We show that changing the flexibility of initial dispersal of juveniles from the nursery and annual migration of adults to the nursery explains a large amount of dental distribution variability. Our framework predicts dispersal strategies of an extant sand tiger population, and supports nurseries as important components of sand tiger life history in both extant and Eocene populations. These results suggest nursery protection may be vital for shark conservation with increasing anthropogenic impacts and climate change.

Early plant organics increased global terrestrial mud deposition through enhanced flocculation.

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.

The Joinpoint-Jump and Joinpoint-Comparability Ratio Model for Trend Analysis with Applications to Coding Changes in Health Statistics.

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.

Probing the Ecology and Climate of the Eocene Southern Ocean With Sand Tiger Sharks Striatolamia macrota.

Many explanations for Eocene climate change focus on the Southern Ocean-where tectonics influenced oceanic gateways, ocean circulation reduced heat transport, and greenhouse gas declines prompted glaciation. To date, few studies focus on marine vertebrates at high latitudes to discern paleoecological and paleoenvironmental impacts of this climate transition. The Tertiary Eocene La Meseta (TELM) Formation has a rich fossil assemblage to characterize these impacts; Striatolamia macrota, an extinct (†) sand tiger shark, is abundant throughout the La Meseta Formation. Body size is often tracked to characterize and integrate across multiple ecological dimensions. †S. macrota body size distributions indicate limited changes during TELMs 2-5 based on anterior tooth crown height (n = 450, mean = 19.6 ± 6.4 mm). Similarly, environmental conditions remained stable through this period based on δ18OPO4 values from tooth enameloid (n = 42; 21.5 ± 1.6‰), which corresponds to a mean temperature of 22.0 ± 4.0°C. Our preliminary ε Nd (n = 4) results indicate an early Drake Passage opening with Pacific inputs during TELM 2-3 (45-43 Ma) based on single unit variation with an overall radiogenic trend. Two possible hypotheses to explain these observations are (1) †S. macrota modified its migration behavior to ameliorate environmental changes related to the Drake Passage opening, or (2) the local climate change was small and gateway opening had little impact. While we cannot rule out an ecological explanation, a comparison with climate model results suggests that increased CO2 produces warm conditions that also parsimoniously explain the observations.