Radiocarbon dating of seized ivory confirms rapid decline in African elephant populations and provides insight into illegal trade.

Carbon-14 measurements on 231 elephant ivory specimens from 14 large ivory seizures (≥0.5 ton) made between 2002 and 2014 show that most ivory (ca 90%) was derived from animals that had died less than 3 y before ivory was confiscated. This indicates that the assumption of recent elephant death for mortality estimates of African elephants is correct: Very little "old" ivory is included in large ivory shipments from Africa. We found only one specimen of the 231 analyzed to have a lag time longer than 6 y. Patterns of trade differ by regions: East African ivory, based on genetic assignments of geographic origin, has a much higher fraction of "rapid" transit than ivory originating in the Tridom region of Cameroon-Gabon-Congo. Carbon-14 is an important tool in understanding patterns of movement of illegal wildlife products.

Applying the principles of isotope analysis in plant and animal ecology to forensic science in the Americas.

The heart of forensic science is application of the scientific method and analytical approaches to answer questions central to solving a crime: Who, What, When, Where, and How. Forensic practitioners use fundamentals of chemistry and physics to examine evidence and infer its origin. In this regard, ecological researchers have had a significant impact on forensic science through the development and application of a specialized measurement technique-isotope analysis-for examining evidence. Here, we review the utility of isotope analysis in forensic settings from an ecological perspective, concentrating on work from the Americas completed within the last three decades. Our primary focus is on combining plant and animal physiological models with isotope analyses for source inference. Examples of the forensic application of isotopes-including stable isotopes, radiogenic isotopes, and radioisotopes-span from cotton used in counterfeit bills to anthrax shipped through the U.S. Postal Service and from beer adulterated with cheap adjuncts to human remains discovered in shallow graves. Recent methodological developments and the generation of isotope landscapes, or isoscapes, for data interpretation promise that isotope analysis will be a useful tool in ecological and forensic studies for decades to come.

Hydrogen and oxygen isotope values in hydrogen peroxide.

Hydrogen peroxide (H(2)O(2)) is a widely used oxidizer with many commercial applications; unfortunately, it also has terrorist-related uses. We analyzed 97 hydrogen peroxide solutions representing four grades purchased across the United States and in Mexico. As expected, the range of hydrogen (δ(2)H, 230‰) and oxygen (δ(18)O, 24‰) isotope values of the H(2)O(2) solutions was large, reflecting the broad isotopic range of dilution waters. This resulted in predictable linear relationships of δ(2)H and δ(18)O values of H(2)O(2) solutions that were near parallel to the Meteoric Water Line (MWL), offset by the concentration of H(2)O(2) in the solution. By grade, dilute (3 to 35%) H(2)O(2) solutions were not statistically different in slope. Although the δ(2)H values of manufactured H(2)O(2) could be different from those of water, rapid H(2)O(2)-H(2)O exchange of H atoms eliminated any distinct isotope signal. We developed a method to measure the δ(18)O value of H(2)O(2) independent of dilution water by directly measuring O(2) gas generated from a catalase-induced disproportionation reaction. We predicted that the δ(18)O values of H(2)O(2) would be similar to that of atmospheric oxygen (+23.5‰), the predominant source of oxygen in the most common H(2)O(2) manufacturing process (median disproportionated δ(18)O=23.8‰). The predictable H-O relationships in H(2)O(2) solutions make it possible to distinguish commercial dilutions from clandestine concentration practices. Future applications of this work include synthesis studies that investigate the chemical link between H(2)O(2) reagents and peroxide-based explosive products, which may assist law enforcement in criminal investigations.

TATP isotope ratios as influenced by worldwide acetone variation.

Isotope ratio analysis has been shown to discriminate samples of forensic interest and to link many synthesized and natural materials to their precursors when traditional chemical and physical analyses cannot. Successful application of stable isotope analysis to chemicals of interest requires a background of likely variations in stable isotope ratios; often, this background population can be generated from analysis of possible precursors and the relationships of stable isotopes of precursor(s) to product(s), which may depend on synthesis techniques. Here we measured the carbon (13C/12C) and hydrogen (2H/1H) isotope ratios of the oft-illicitly manufactured explosive triacetone triperoxide, TATP, and one of its precursors, acetone. As acetone is the sole source of carbon and hydrogen to TATP, a survey of acetone from 12 countries was conducted to explore the breadth of 13C/12C and 2H/1H variation in the precursor, and therefore, its product. Carbon and hydrogen isotope ratios were measured using continuous flow isotope ratio mass spectrometry (IRMS) techniques. We observed greater ranges in both C and H isotope ratios of acetone than previously published; we also found that country-of-purchase was a large contributing factor to the observed variation, larger than acetone grade and brand. Following clandestine production methods, we observed that the stable isotope ratios of TATP retained the stable isotope signatures of acetone used in synthesis. We confirmed the robustness of TATP carbon isotope ratios to both recrystallization and time-dependent sublimation, important considerations when faced with the task of practical sampling of potential unexploded TATP from a crime scene.

The influences of cultivation setting on inflorescence lipid distributions, concentrations, and carbon isotope ratios of Cannabis sp.

While much is known about how the growth environment influences many aspects of floral morphology and physiology, little is known about how the growth setting influences floral lipid composition. We explored variations in paraffin wax composition in Cannabis sp., a cash crop grown both indoors and outdoors across the United States today. Given an increased focus on regulation of this crop, there are additional incentives to certify the setting of Cannabis cultivation. To understand the impacts of the growth environment, we studied distributions, concentrations, and carbon isotope ratios of n-alkanes isolated from Cannabis sp. inflorescences to assess if variations within these lipid parameters were related to known growth settings of specimens seized by federal agents. We found that Cannabis plants cultivated under open-field settings had increased inflorescence paraffin wax abundances and greater production of lower molecular weight n-alkanes relative to plants grown in enclosed environments. Further, the carbon isotope ratios of n-C29 from Cannabis plants grown in enclosed environments had relatively lower carbon isotope (δ(13)C) values compared to plants from open-field environments. While this set of observations on seized plant specimens cannot address the particular driver behind these observations, we posit that (a) variations in irradiance and/or photoperiod may influence the distribution and concentration of inflorescence lipids, and (b) the δ(13)C value of source CO2 and lipid concentration regulates the δ(13)C values of inflorescence n-C29 and bulk Cannabis plant materials. Nonetheless, by using a cultivation model based on δ(13)C values of n-C29, the model correctly identified the growth environment 90% of time. We suggest that these lipid markers may be used to trace cultivation methods of Cannabis sp. now and become a more powerful marker in the future, once the mechanism(s) behind these patterns is uncovered.

Urban water - a new frontier in isotope hydrology.

Isotope hydrology has focused largely on landscapes away from densely inhabited regions. In coming decades, it will become increasingly more important to focus on water supplies and dynamics within urban systems. Stable isotope analyses provide important information to water managers within large cities, particularly in arid regions where evaporative histories of water sources, vulnerabilities, and reliabilities of the water supplies can be major issues. Here the spatial and vertical understanding of water supporting urban systems that comes from stable isotope analyses can serve as a useful management tool. We explore this research frontier using the coupled natural-human landscape of the Salt Lake Valley, USA, with its greater than one million inhabitants. We first provide data on the stable isotope ratios of the hydrologic system's primary components: precipitation, incoming surface waters, and terminus waters in this closed basin. We then explore the spatial and temporal patterns of drinking waters within the urban landscape and the new opportunities to better link isotope ratio data with short- and long-term management interests of water managers.

The potential for application of ink stable isotope analysis in questioned document examination.

We investigated a novel application of stable isotope abundance analysis of nitrogen (15N), carbon (13C), hydrogen (2H), and oxygen (18O) to characterize pen ink. We focused on both ballpoint and gel pen inks. We found that the isotope ratios of ink from pens purchased together in a package were similar and within-package stable isotope ratio variability was not significantly larger than the variability of isotope reference materials used during analysis. In contrast, the isotope ratios of ink from pens of the same brand purchased in three states of the continental USA were significantly different from each other and there was isotope ratio variation among pens of the same brand but different, unknown production periods. The stable isotope ratios of inked paper were statistically distinguishable using measured δ15N values. Paper inked with different gel pens was statistically distinguishable using measured δ2H values. The capacity of stable isotope ratios to differentiate among ballpoint inks as well as gel inks shows that stable isotope analysis may be a useful and quantifiable investigative technique for questioned document examination, although current sample size requirements limit its utility. Application of the technique in casework will require the development of micro-scale sampling and analysis methods.

14C analyses quantify time lag between coca leaf harvest and street-level seizure of cocaine.

Measurements were made on the natural abundance (14)C content (Δ(14)C) of cocaine specimens seized between 2003 and 2009. The objective of this study was to determine the extent to which Δ(14)C analyses could quantify the "age" of recent cocaine seizures. Here "age" of a seized cocaine specimen is defined as the time period between when a coca leaf was harvested in South America and its seizure as cocaine at either the international or domestic street levels. Based on Δ(14)C analyses of seizure specimens, there were no statistically significant differences in the ages of domestic cocaine HCl and cocaine base specimens seized on the streets in different locations across the United States. Between 2007 and 2009, the average age of a street-level cocaine seizure in the United States was 24.6±1.1 months. Cocaine shipment seizures that were in excess of 150 kg during this time period had an average age of 18.2±1.4 months, whereas smaller shipment seizures were significantly older with an average age of 22.3±0.6 months. Analyses of the largest cocaine shipment seizures suggested that these seizures were composed of specimens with different ages, possibly representing accumulations over as much as a 31-month period.

Accuracy and precision of a laser-spectroscopy approach to the analysis of δ²H and δ¹8O in human urine.

The isotope ratio analysis of body water often involves large sample numbers and lengthy sample processing. Here we demonstrate the ability of isotope ratio infrared spectroscopy (IRIS) to rapidly and accurately analyse the isotope ratios of water in urine. We analysed water extracted from human urine using traditional isotope ratio mass spectrometry (IRMS) and compared those values with IRIS-analysed extracted water and un-extracted urine. Regression analyses for δ²H and δ¹8O values between (1) extracted water analysed via IRMS and IRIS and (2) urine and extracted water analysed via IRIS were significant (R²=0.99). These results indicate that cryogenic distillation of urine was not required for an accurate estimate of the isotopic composition of urine when using IRIS.

PKCgamma regulates syndecan-2 inside-out signaling during xenopus left-right development.

The transmembrane proteoglycan syndecan-2 cell nonautonomously regulates left-right (LR) development in migrating mesoderm by an unknown mechanism, leading to LR asymmetric gene expression and LR orientation of the heart and gut. Here, we demonstrate that protein kinase C gamma (PKCgamma) mediates phosphorylation of the cytoplasmic domain of syndecan-2 in right, but not left, animal cap ectodermal cells. Notably, both phosphorylation states of syndecan-2 are obligatory for normal LR development, with PKCgamma-dependent phosphorylated syndecan-2 in right ectodermal cells and nonphosphorylated syndecan-2 in left cells. The ectodermal cells contact migrating mesodermal cells during early gastrulation, concurrent with the transmission of LR information. This precedes the appearance of monocilia and is one of the earliest steps of LR development. These results demonstrate that PKCgamma regulates the cytoplasmic phosphorylation of syndecan-2 and, consequently, syndecan-2-mediated inside-out signaling to adjacent cells.