Evaluation of neodymium isotope analysis of human dental enamel as a provenance indicator using 1013 Ω amplifiers (TIMS)

Human provenance studies employing isotopic analysis have become an essential tool in forensic and archaeological sciences, with multi-isotope approaches providing more specific location estimates compared to single isotope studies. This study reports on the human provenancing capability of neodymium isotopes (¹⁴³Nd/¹⁴⁴Nd), a relatively conservative tracer in the environment. Neodymium isotope ratios have only recently been determined on human remains due to low concentrations in human dental enamel (ppb range), requiring thermal ionisation mass spectrometry (TIMS) using 10¹³ Ω resistors. Dental elements (third molars) from 20 individuals born and raised in the Netherlands were analysed for Nd concentration (n = 12) and Nd isotope ratios (n = 15). The geological control on Nd isotope composition was examined using coupled Nd-Sr isotope analysis of the same third molar. Teeth from different geological environments were also analysed (Caribbean, Columbian, and Icelandic, n = 5). Neodymium elemental concentrations in dental elements ranged between 0.1 and 7.9 ppb (median 0.5 ppb). The Dutch ¹⁴³Nd/¹⁴⁴Nd ratios of the provinces of Limburg and Friesland were between 0.5118 and 0.5121, with Dutch ⁸⁷Sr/⁸⁶Sr ratios in agreement with the previously established local range (0.708–0.710). The current findings were compared to previously published results on Nd concentration and composition from Dutch individuals. The concentration of Nd and ¹⁴³Nd/¹⁴⁴Nd ratios were weakly correlated (R² = 0.47, n = 17) in Dutch human dental enamel. The majority (n = 25, 83.3%) of individuals had Nd and Sr isotope values isotopically indistinguishable from the geological environment in which their third molars formed and mineralised. However, the Nd isotope ratios of the Icelandic individual and several Dutch individuals (n = 4) suggested that Nd in enamel is not solely influenced by geological environment. In order for neodymium isotopes to be quantitatively applied in forensic and archaeological settings further analyses of individuals from various geographical regions with well-defined dietary Nd isotope data are required.     

A City‐wide Investigation of the Isotopic Distribution and Source of Tap Waters for Forensic Human Geolocation Ground‐truthing

Human geolocation is prefaced on the accuracy of the geographic precision of mapped isotopic values for drinking water. As most people live in cities, it becomes important to understand city water supplies and how the isotopic values uniquely reflect that city. This study investigated the isotopic distribution of δ²H and δ¹⁸O from sourced tap waters that were collected from across the Metro Vancouver (MV) area (n = 135). The results revealed that the isotopic values reflect their water sources with a range of 5.3‰ for δ¹⁸O_tap and 29.3‰ for δ²H_tap for MV. The results indicate that individual cities need higher resolution studies to determine their tap water isotopic ranges, and a good understanding of the water supply network itself for human geolocation work. With an extended high‐resolution understanding of each city, human tissue may be compared with more certainty for geolocation.     

Discrimination of Geographical Origin of Asian Garlic Using Isotopic and Chemical Datasets under Stepwise Principal Component Analysis

Isotopic compositions of δ²H, δ¹⁸O, δ¹³C, and δ¹⁵N and concentrations of 22 trace elements from garlic samples were analyzed and processed with stepwise principal component analysis (PCA) to discriminate garlic's country of origin among Asian regions including South Korea, Vietnam, Taiwan, and China. Results indicate that there is no single trace‐element concentration or isotopic composition that can accomplish the study's purpose and the stepwise PCA approach proposed does allow for discrimination between countries on a regional basis. Sequentially, Step‐1 PCA distinguishes garlic's country of origin among Taiwanese, South Korean, and Vietnamese samples; Step‐2 PCA discriminates Chinese garlic from South Korean garlic; and Step‐3 and Step‐4 PCA, Chinese garlic from Vietnamese garlic. In model tests, countries of origin of all audit samples were correctly discriminated by stepwise PCA. Consequently, this study demonstrates that stepwise PCA as applied is a simple and effective approach to discriminating country of origin among Asian garlics.     

Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS) — Preliminary study on TATP and PETN

The application of isotopic techniques to investigations requiring the provision of evidence to a Court is limited. The objective of this research was to investigate the application of light stable isotopes and isotope ratio mass spectrometry (IRMS) to solve complex forensic cases by providing a level of discrimination not achievable utilising traditional forensic techniques.Due to the current threat of organic peroxide explosives, such as triacetone triperoxide (TATP), research was undertaken to determine the potential of IRMS to differentiate samples of TATP that had been manufactured utilising different starting materials and/or manufacturing processes. In addition, due to the prevalence of pentaerythritoltetranitrate (PETN) in detonators, detonating cord, and boosters, the potential of the IRMS technique to differentiate PETN samples from different sources was also investigated.Carbon isotope values were measured in fourteen TATP samples, with three definite groups appearing in the initial sample set based on the carbon data alone. Four additional TATP samples (in a second set of samples) were distinguishable utilising the carbon and hydrogen isotopic compositions individually, and also in combination with the oxygen isotope values. The 3D plot of the carbon, oxygen and hydrogen data demonstrated the clear discrimination of the four samples of TATP. The carbon and nitrogen isotope values measured from fifteen PETN samples, allowed samples from different sources to be readily discriminated.This paper demonstrates the successful application of IRMS to the analysis of explosives of forensic interest to assist in discriminating samples from different sources. This research represents a preliminary evaluation of the IRMS technique for the measurement of stable isotope values in TATP and PETN samples, and supports the dedication of resources for a full evaluation of this application in order to achieve Court reportable IRMS results.     

Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS) — Discrimination of ammonium nitrate sources

An evaluation was undertaken to determine if isotope ratio mass spectrometry (IRMS) could assist in the investigation of complex forensic cases by providing a level of discrimination not achievable utilising traditional forensic techniques. The focus of the research was on ammonium nitrate (AN), a common oxidiser used in improvised explosive mixtures.The potential value of IRMS to attribute Australian AN samples to the manufacturing source was demonstrated through the development of a preliminary AN classification scheme based on nitrogen isotopes. Although the discrimination utilising nitrogen isotopes alone was limited and only relevant to samples from the three Australian manufacturers during the evaluated time period, the classification scheme has potential as an investigative aid.Combining oxygen and hydrogen stable isotope values permitted the differentiation of AN prills from three different Australian manufacturers. Samples from five different overseas sources could be differentiated utilising a combination of the nitrogen, oxygen and hydrogen isotope values. Limited differentiation between Australian and overseas prills was achieved for the samples analysed.The comparison of nitrogen isotope values from intact AN prill samples with those from post-blast AN prill residues highlighted that the nitrogen isotopic composition of the prills was not maintained post-blast; hence, limiting the technique to analysis of un-reacted explosive material.     

Strontium and geolocation, the pathway to identification for deceased undocumented mexican border-crossers: a preliminary report

Much of the difficulty associated with identifying and repatriating deceased undocumented border-crossers stems from an inability to narrow down the search area to more probable options. Analysis of the isotopic variation in the tooth enamel of modern Mexican populations is currently underway at the University of California Santa Cruz. Using Thermo Ionization Mass Spectrometry, the pilot research analyzed strontium isotopes located in the donated permanent teeth of Mexican-born individuals of known origin from four states. The preliminary results reveal the formation of three distinctly significant regions in the data set. Using the technology outlined here, a map documenting the isotopic variation in modern Mexican tooth enamel is being complied to use for cross comparison with deceased border crossers of unknown origin.     

Carbon and nitrogen stable isotopes as indicative of geographical origin of marijuana samples seized in the city of São Paulo (Brazil)

The drug trafficking is one of the most serious problems related to the Public Safety in Brazil, especially in the most populous areas of the country, as is the case of the city of São Paulo. In this work, it was developed a methodology that can help tracking the traffic routes of marijuana samples seized in the city of São Paulo, based on stable carbon and nitrogen isotopes, which are related to the climate and plant growth conditions. A model to classify the origin of unknown samples was built using linear discriminant analysis based on about 150 samples apprehended in the main producing regions of the country. Results for 76 samples seized in the city of São Paulo showed that most of them were cultivated in a humid region with the same origin as those from Mato Grosso do Sul. The provenance of 13 outliers samples from Northeast region (an important producing region) also were evaluated and some of them presented same profile of those from Mato Grosso do Sul, pointing to the existence of the traffic routes between the Northeast and Midwest region, probably as a consequence of the intensive field raids by Brazilian Federal Government since 1999.     

Variation of δ2H, δ18O & δ13C in crude palm oil from different regions in Malaysia: Potential of stable isotope signatures as a key traceability parameter

A total of 33 crude palm oil samples were randomly collected from different regions in Malaysia. Stable carbon isotopic composition (δ¹³C) was determined using Flash 2000 elemental analyzer while hydrogen and oxygen isotopic compositions (δ²H and δ¹⁸O) were analyzed by Thermo Finnigan TC/EA, wherein both instruments were coupled to an isotope ratio mass spectrometer. The bulk δ²H, δ¹⁸O and δ¹³C of the samples were analyzed by Hierarchical Cluster Analysis (HCA), Principal Component Analysis (PCA) and Orthogonal Partial Least Square-Discriminant Analysis (OPLS-DA). Unsupervised HCA and PCA methods have demonstrated that crude palm oil samples were grouped into clusters according to respective state. A predictive model was constructed by supervised OPLS-DA with good predictive power of 52.60%. Robustness of the predictive model was validated with overall accuracy of 71.43%. Blind test samples were correctly assigned to their respective cluster except for samples from southern region. δ¹⁸O was proposed as the promising discriminatory marker for discerning crude palm oil samples obtained from different regions. Stable isotopes profile was proven to be useful for origin traceability of crude palm oil samples at a narrower geographical area, i.e. based on regions in Malaysia. Predictive power and accuracy of the predictive model was expected to improve with the increase in sample size. Conclusively, the results in this study has fulfilled the main objective of this work where the simple approach of combining stable isotope analysis with chemometrics can be used to discriminate crude palm oil samples obtained from different regions in Malaysia. Overall, this study shows the feasibility of this approach to be used as a traceability assessment of crude palm oils.     

Using Carbon,Oxygen, Strontium,and Lead Isotopes in Modern Human Teeth for Forensic Investigations: A Critical Overview Based on Data from Bulgaria

Isotopic data obtained from human remains can provide information about an individual's origin, migration, and diet. We evaluate the usefulness of carbon, oxygen, strontium, and lead isotopes for forensic investigations by comparing data from Bulgarian teeth with data from other regions. Geo‐referencing based on oxygen or strontium isotopes can be misleading due to overlap with other countries in Europe and other continents. Carbon and lead isotopes, in combination with oxygen and strontium isotopes, provide the most useful information for identification of local vs foreigner status. In particular, high‐precision Pb isotopes show a distinct “Bulgarian” range; however, it is possible that individuals from other countries in Eastern Europe and/or central to western Asia could have overlapping isotopic values. Additional high‐precision multi‐isotope data from modern humans from different regions in the world are required to transition from speculative to more quantitative estimation of a geographical place of origin for unidentified human remains.     

Refining Stable Oxygen and Hydrogen Isoscapes for the Identification of Human Remains in Mississippi,

Isoscape refinement is an essential component for accurately predicting region‐of‐origin in forensic investigations involving isotope analysis of unidentified human remains. Stable oxygen (δ¹⁸O) and hydrogen (δ²H) isotopes were measured from 57 tap water samples collected across Mississippi to model refined isoscapes for the state. A tap water conversion equation, δ¹⁸O_tw=1.64 δ¹⁸Op?31.35, was developed for the southeastern USA to test the prediction accuracy of the δ¹⁸O_tw isoscape using individuals with known residential histories. A local Mississippi resident (USAFA‐134) was assigned with 90% probability to the correct region‐of‐origin reported by the participant. Assignments for Georgia residents (USAFA‐118 and USAFA‐205) had variable results, predicting USAFA‐118 from Mississippi and USAFA‐205 as a nonlocal resident. Stable isotope values often overlap geographically and a multi‐isotope approach should be used when narrowing region(s)‐of‐origin(s). This study demonstrates the utility of refining isoscapes and the importance of tissue calibration in prediction assignments of human remains.