Strontium, oxygen, and carbon isotope variation in modern human dental enamel.

OBJECTIVES: Isotopic analyses using human dental enamel provide information on the mobility and diet of individuals in forensic and archeological studies. Thus far, no study has systematically examined intraindividual coupled strontium (Sr), oxygen (O), and carbon (C) isotope variation in human enamel or the effect that caries have on the isotopic integrity of the enamel. The inadequate quantification of isotopic variation affects interpretations and may constrain sample selection of elements affected by caries. This study aims to quantify the intraindividual isotopic variation and provides recommendations for enamel sampling methods. MATERIAL AND METHODS: This study presents the first systematic results on intraindividual variation in Sr-O-C isotope composition and Sr concentration in modern human dental enamel of third molars (affected and unaffected by caries). A multiloci sampling approach (n = 6-20) was used to analyze surface and inner enamel, employing thermal ionization mass spectrometry (TIMS) and isotope ratio mass spectrometry (IRMS). Third molars were analyzed from 47 individuals from the Netherlands, Iceland, the United States, the Caribbean, Colombia, Somalia, and South Africa. RESULTS: Intradental isotopic variation in modern Dutch dental elements was recorded for Sr, O, and C and exceeded the variation introduced by the analytical error. Single loci and bulk sampling approaches of third molars established that a single analysis is only representative of the bulk Sr isotope composition in 60% of the elements analyzed. Dental elements affected by caries showed twice the variation seen in unaffected dental elements. Caries did not consistently incorporate the isotopic composition of the geographical environment in which they developed. DISCUSSION: The isotopic variability recorded in unaffected inner enamel indicates that variations greater than 0.000200 for 87 Sr/86 Sr and larger than 2‰ for δ18 O and δ13 C are required to demonstrate changes in modern Dutch human diet or geographic location.

Collagen proteins exchange oxygen with demineralisation and gelatinisation reagents and also with atmospheric moisture.

RATIONALE: The oxygen (O) isotope composition of collagen proteins is a potential indicator of adult residential location, useful for provenancing in ecology, archaeology and forensics. In acidic solution, proteins can exchange O from carboxylic acid moieties with reagent O. This study investigated whether this exchange occurs during demineralisation and gelatinisation preparation of bone/ivory collagen. METHODS: EDTA and HCl demineralisation or gelatinisation reagents were made up in waters with different δ18 O values, and were used to extract collagen from four skeletal tissue samples. Aliquots of extracted collagen were exposed to two different atmospheric waters, at 120°C and ambient temperature, and subsequently dried in a vacuum oven at 40°C or by freeze drying. Sample δ18 O values were measured by HT-EA pyrolysis/IRMS using a zero-blank autosampler. RESULTS: Collagen samples exchanged O with both reagent waters and atmospheric water, which altered sample δ18 O values. Exchange with reagent waters occurred in all extraction methods, but was greater at lower pH. Damage to the collagen samples during extraction increased O exchange. The nature of exchange of O with atmospheric water depended on the temperature of exposure: kinetic fractionation of O was identified at 120°C but not at ambient temperature. Exchange was difficult to quantify due to the high variability of δ18 O values between experimental replicates. CONCLUSIONS: Studies of δ18 O values in collagen proteins should avoid extraction methods using acidic solutions.

Geographical variability in northern European sheep wool isotopic composition (δ(13) C, δ(15) N, δ(2) H values).

RATIONALE: Light stable isotopic analysis of herbivore proteinaceous tissues (hair, muscle, milk) is critical for authenticating the point of origin of finished agricultural or industrial products in both ancient and modern economies. This study examined the distribution of light stable isotopes in herbivores in northern Europe (Iceland to Finland), which is expected to depend on regional-level environmental inputs (precipitation, temperature) and local variables (vegetation type, fodder type, soil type). METHODS: Sheep wool was obtained from animals managed using traditional methods and located across a gradient of northern European environments. Defatted whole-year samples were analysed by isotope ratio mass spectrometry (IRMS) for carbon (δ(13) C values), nitrogen (δ(15) N values) and un-exchangeable hydrogen (δ(2) H values) isotopic composition. RESULTS: Wool δ(13) C, δ(15) N and δ(2) H values showed the same correlations to local mean annual precipitation and temperature as were expected for graze plants. Wool δ(2) H values were correlated with local modelled meteoric water δ(2) H values, mediated by plant solid tissue and leaf water fractionations. Cluster analysis distinguished wool from Sweden and the Baltic region from more western material. Local variation in vegetation or soil type did not disrupt dependence on climatic variables but did affect geospatial discrimination. CONCLUSIONS: Wool isotopic composition in northern Europe is controlled by the effects of local precipitation and temperature on graze plant inputs, and is only weakly affected by pasture type. Copyright © 2016 John Wiley & Sons, Ltd.

Reprint of: The effects of decomposition and environment on antemortem H-Pb-Sr isotope compositions and degradation of human scalp hair: Actualistic taphonomic observations.

Multi-isotope analysis (e.g., Sr-Pb-O-H-C-N) of human scalp hair is routinely used in forensic investigations of human remains to constrain the geographic origin of unidentified bodies, and to investigate antemortem mobility patterns. However, while it is known that postmortem processes can affect the preservation of, or even overprint, the biogenic isotopic signatures in hair, the speed and nature of these processes have rarely been studied. This study investigates the effects of decomposition and environment on the H-Pb-Sr isotope compositions of human hair as well as the relationship between structural hair shaft degradation and isotopic signature change over time. Human scalp hair samples from four body donations were collected at different stages throughout gross body decomposition. The willed-donated bodies were placed to decompose outdoors at the Forensic Anthropology Research Facility (FARF) at Texas State University. Hair fibres from two of the donations were examined using scanning electron microscopy (SEM) and high-resolution light microscopy (HRLM). Chemical and microbiological degradation of hair fibres occurred rapidly after placement of the body outdoors. Measurements of scalp hair isotopic composition demonstrated that H-Pb-Sr isotope ratios were altered within days after environmental exposure, presumably by deposition, leaching and/or exchange with the local bioavailable soil, and vapour. The degree of physical hair degradation and changes in H-Pb-Sr isotope composition were not correlated. We conclude that antemortem isotopic H-Pb-Sr isotope ratios are difficult to recover in hairs derived from decomposing whole bodies.

The effects of decomposition and environment on antemortem H-Pb-Sr isotope compositions and degradation of human scalp hair: Actualistic taphonomic observations.

Multi-isotope analysis (e.g., Sr-Pb-O-H-C-N) of human scalp hair is routinely used in forensic investigations of human remains to constrain the geographic origin of unidentified bodies, and to investigate antemortem mobility patterns. However, while it is known that postmortem processes can affect the preservation of, or even overprint, the biogenic isotopic signatures in hair, the speed and nature of these processes have rarely been studied. This study investigates the effects of decomposition and environment on the H-Pb-Sr isotope compositions of human hair as well as the relationship between structural hair shaft degradation and isotopic signature change over time. Human scalp hair samples from four body donations were collected at different stages throughout gross body decomposition. The willed-donated bodies were placed to decompose outdoors at the Forensic Anthropology Research Facility (FARF) at Texas State University. Hair fibers from two of the donations were examined using scanning electron microscopy (SEM) and high-resolution light microscopy (HRLM). Chemical and microbiological degradation of hair fibers occurred rapidly after placement of the body outdoors. Measurements of scalp hair isotopic composition demonstrated that H-Pb-Sr isotope ratios were altered within days after environmental exposure, presumably by deposition, leaching and/or exchange with the local bioavailable soil, and vapor. The degree of physical hair degradation and changes in H-Pb-Sr isotope composition were not correlated. We conclude that antemortem isotopic H-Pb-Sr isotope ratios are difficult to recover in hairs derived from decomposing whole bodies.

A bioavailable strontium isoscape for Western Europe: A machine learning approach.

Strontium isotope ratios (87Sr/86Sr) are gaining considerable interest as a geolocation tool and are now widely applied in archaeology, ecology, and forensic research. However, their application for provenance requires the development of baseline models predicting surficial 87Sr/86Sr variations ("isoscapes"). A variety of empirically-based and process-based models have been proposed to build terrestrial 87Sr/86Sr isoscapes but, in their current forms, those models are not mature enough to be integrated with continuous-probability surface models used in geographic assignment. In this study, we aim to overcome those limitations and to predict 87Sr/86Sr variations across Western Europe by combining process-based models and a series of remote-sensing geospatial products into a regression framework. We find that random forest regression significantly outperforms other commonly used regression and interpolation methods, and efficiently predicts the multi-scale patterning of 87Sr/86Sr variations by accounting for geological, geomorphological and atmospheric controls. Random forest regression also provides an easily interpretable and flexible framework to integrate different types of environmental auxiliary variables required to model the multi-scale patterning of 87Sr/86Sr variability. The method is transferable to different scales and resolutions and can be applied to the large collection of geospatial data available at local and global levels. The isoscape generated in this study provides the most accurate 87Sr/86Sr predictions in bioavailable strontium for Western Europe (R2 = 0.58 and RMSE = 0.0023) to date, as well as a conservative estimate of spatial uncertainty by applying quantile regression forest. We anticipate that the method presented in this study combined with the growing numbers of bioavailable 87Sr/86Sr data and satellite geospatial products will extend the applicability of the 87Sr/86Sr geo-profiling tool in provenance applications.

Provenancing Archaeological Wool Textiles from Medieval Northern Europe by Light Stable Isotope Analysis (δ13C, δ15N, δ2H).

We investigate the origin of archaeological wool textiles preserved by anoxic waterlogging from seven medieval archaeological deposits in north-western Europe (c. 700-1600 AD), using geospatial patterning in carbon (δ13C), nitrogen (δ15N) and non-exchangeable hydrogen (δ2H) composition of modern and ancient sheep proteins. δ13C, δ15N and δ2H values from archaeological wool keratin (n = 83) and bone collagen (n = 59) from four sites were interpreted with reference to the composition of modern sheep wool from the same regions. The isotopic composition of wool and bone collagen samples clustered strongly by settlement; inter-regional relationships were largely parallel in modern and ancient samples, though landscape change was also significant. Degradation in archaeological wool samples, examined by elemental and amino acid composition, was greater in samples from Iceland (Reykholt) than in samples from north-east England (York, Newcastle) or northern Germany (Hessens). A nominal assignment approach was used to classify textiles into local/non-local at each site, based on maximal estimates of isotopic variability in modern sheep wool. Light element stable isotope analysis provided new insights into the origins of wool textiles, and demonstrates that isotopic provenancing of keratin preserved in anoxic waterlogged contexts is feasible. We also demonstrate the utility of δ2H analysis to understand the location of origin of archaeological protein samples.