Stable Carbon and Nitrogen Isotope Variability of Bone Collagen to Determine the Number of Isotopically Distinct Specimens

Archaeological and palaeontological excavations frequently produce large quantities of highly fragmentary bone. These bones can help to answer questions regarding past environments and human and animal lifeways via a number of analytical techniques but this potential is limited by the inability to distinguish individual animals and generate sufficiently large samples. Using stable carbon and nitrogen isotope values of bone collagen (δ13C, δ15N), we present a metric to identify the number of isotopically distinct specimens (NIDS) from highly fragmented faunal assemblages. We quantified the amount of intra-individual isotopic variation by generating isotopic data from multiple elements from individual animals representing a wide variety of taxa as well as multiple samples from the same skeletal element. The mean intra-individual variation (inter-bone) was 0.52‰ (σ = 0.45) (Euclidean distance between two points in isotopic bivariate space), while the mean intra-bone variation was 0.63‰ (σ = 0.06). Using archaeological data consisting of large numbers of individual taxa from single sites, the mean inter-individual isotopic variation was 1.45‰ (σ = 1.15). We suggest the use of 1.50‰ in bivariate (δ13C, δ15N) space as a metric to distinguish NIDS. Blind tests of modelled archaeological datasets of different size and isotopic variability resulted in a rate of misclassification (two or more elements from the same individual being classified as coming from different individuals) of < 5%.

Molecular and Carbon Isotopic Variation during Canister Degassing of Terrestrial Shale: A Case Study from Xiahuayuan Formation in the Xuanhua Basin, North China

Molecular and carbon isotopic variation during degassing process have been observed in marine shale reservoirs, however, this behavior remains largely unexplored in terrestrial shale reservoirs. Here, we investigate the rock parameters of five terrestrial shale core samples from the Xiahuayuan Formation and the geochemical parameters of thirty natural gas samples collected during field canister degassing experiments. Based on these new data, the gas composition and carbon isotope variation during canister degassing are discussed and, further, the relationship between petrophysics and the carbon isotope variation is explored. The results show that methane content first increases and then decreases, the concentrations of carbon dioxide (CO2) and nitrogen gas (N2) peak in the early degassing stage, while heavier hydrocarbons gradually increase over time. Shale gas generated from humic source rocks contains more non-hydrocarbon and less heavy hydrocarbon components than that generated from sapropelic source rocks with similar maturity. Time-series sampling presents an upward increase in δ13C1 value during the degassing process with the largest variation up to 5.7‰, while the variation in δ13C3 and δ13C2 is insignificant compared to δ13C1. Moreover, we find that there is only a small variation in δ13C1 in shale samples with high permeability and relatively undeveloped micropores, which is similar to the limited δ13C1 variation in conventional natural gas. For our studied samples, the degree of carbon isotope variation is positively correlated with the TOC content, micropore volume, and micropore surface, suggesting that these three factors may play a significant role in carbon isotope shifts during shale gas degassing. We further propose that the strong 13C1 and C2+depletion of shale gas observed during the early degassing stage may have resulted from the desorption and diffusion effect, which may lead to deviation in the identification of natural gas origin. It is therefore shale gas of the late degassing stage that would be more suitable for study to reduce analytic deviations. In most samples investigated, significant isotopic variation occurred during the degassing stage at room temperature, indicating that the adsorbed gas had already been desorbed at this stage Our results therefore suggest that more parameters may need to be considered when evaluating the lost gas of shales.

Revealing capture sites and movements by strontium isotope analyses in bones of Caiman yacare in the Beni river floodplain, Bolivia

Studying the distribution of organisms and their movements is fundamental to understand population dynamics. Most studies indicated that crocodilians do not move around much but several studies demonstrated that some species showed movement patterns. Detection of these movements along the individual life is still a challenge. In this study we analyzed the variation of strontium isotopic ratio (87Sr/86Sr) in the femur bones of 70 Caiman yacare individuals caught in 16 sites located in five hydrological sectors of the Beni river floodplain in Bolivia. Our results demonstrated for the first time that such a methodology could yield indications about the capture sites and reconstruct individual life history. Analyses of the outer part of the femur of 70 individuals showed that capture sites could be differentiated between sectors and even between sites or groups of sites in each sector. Studies of complete 87Sr/86Sr profiles along the femur, representing entire life of the individual, were performed on 33 yacares. We found that most of the individuals did not show any significant isotopic variation throughout their lives. This absence of variation could result from a high fidelity to the birth site, and/or from an insignificant isotopic variation between the water bodies through which the animal has potentially moved. However, 24% of the analyzed individuals presented significant variations that can be considered as movements between different habitats. Based on the observed low proportion of moving yacares, we advocated that each water body should be considered an individual management unit.

Combining Models of Environment, Behavior, and Physiology to Predict Tissue Hydrogen and Oxygen Isotope Variance Among Individual Terrestrial Animals

Variations in stable hydrogen and oxygen isotope ratios in terrestrial animal tissues are used to reconstruct origin and movement. An underlying assumption of these applications is that tissues grown at the same site share a similar isotopic signal, representative of the location of their origin. However, large variations in tissue isotopic compositions often exist even among conspecific individuals within local populations, which complicates origin and migration inferences. Field-data and correlation analyses have provided hints about the underlying mechanisms of within-site among-individual isotopic variance, but a theory explaining the causes and magnitude of such variance has not been established. Here we develop a mechanistic modeling framework that provides explicit predictions of the magnitude, patterns, and drivers of isotopic variation among individuals living in a common but environmentally heterogeneous habitat. The model toolbox includes isoscape models of environmental isotopic variability, an agent-based model of behavior and movement, and a physiology-biochemistry model of isotopic incorporation into tissues. We compare model predictions against observed variation in hatch-year individuals of the songbird Spotted Towhee (Pipilo maculatus) in Red Butte Canyon, Utah, and evaluate the ability of the model to reproduce this variation under different sets of assumptions. Only models that account for environmental isotopic variability predict a similar magnitude of isotopic variation as observed. Within the modeling framework, behavioral rules and properties govern how animals nesting in different locations acquire resources from different habitats, and birds nesting in or near riparian habitat preferentially access isotopically lighter resources than those associated with the meadow and slope habitats, which results in more negative body water and tissue isotope values. Riparian nesters also have faster body water turnover and acquire more water from drinking (vs. from food), which exerts a secondary influence on their isotope ratios. Thus, the model predicts that local among-individual isotopic variance is linked first to isotopic heterogeneity in the local habitat, and second to how animals sample this habitat during foraging. Model predictions provide insight into the fundamental mechanisms of small-scale isotopic variance and can be used to predict the utility of isotope-based methods for specific groups or environments in ecological and forensic research.