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We explored whether isotope ratio mass spectrometry (IRMS) is useful to investigate the origin of falsified antimalarials. Forty-four falsified and genuine antimalarial samples (artesunate, artemether-lumefantrine, dihydroartemisinin-piperaquine and sulphamethopyrazine-pyrimethamine) were analyzed in bulk for carbon (C), nitrogen (N), and oxygen (O) element concentrations and stable isotope ratios. The insoluble fraction ("starch") was extracted from 26 samples and analyzed. Samples of known geographical origin maize, a common source of excipient starch, were used to produce a comparison dataset to predict starch source. In both an initial (n = 18) and a follow-on set of samples that contained/claimed to contain artesunate/artemether (n = 26), falsified antimalarials had a range of C concentrations less than genuine comparator antimalarials and δ13C values higher than genuine comparators. The δ13C values of falsified antimalarials suggested that C4 plant-based organic material (e.g., starch derived from maize) had been included. Using the known-origin maize samples, predictions for growth water δ18O values for the extracted "starch" ranged from - 6.10 to - 1.62. These findings suggest that IRMS may be a useful tool for profiling falsified antimalarials. We found that C4 ingredients were exclusively used in falsified antimalarials versus genuine antimalarials, and that it may be possible to predict potential growth water δ18O values for the starch present in falsified antimalarials.
Assuntos
Antimaláricos , Antimaláricos/uso terapêutico , Artesunato , Projetos Piloto , Artemeter , Combinação Arteméter e Lumefantrina , Espectrometria de Massas/métodos , Isótopos , Amido , ÁguaRESUMO
19-Norandrosterone (19NA) is the preferred urinary target compound to identify doping with nandrolone or related 19-norsteroids. At concentrations between 2.5 and 15 ng/mL, isotope ratio mass spectrometry (IRMS) is required to establish exogenous origin of urinary 19NA. An absolute difference of 3 between urinary 19NA and an endogenous reference compound (ERC) constitutes a finding for exogenous origin of 19NA. Over the last 3 years, 77 samples containing urinary 19NA between 2.5 and 15 ng/mL were analyzed at our laboratory. The measured δ13 C values for 19NA ranged from -29.5 to -16.8. In comparison, the δ13 C values for the corresponding urinary ERCs ranged from -22.4 to -16.2. Due to the considerable overlap in values between the target compound and the natural range of urinary ERCs, it can be challenging to distinguish between endogenous and exogenous origins of urinary 19NA. In addition, it is well known that consumption of offal from non-castrated pigs can produce 19NA in urine. To determine whether this could cause a positive IRMS finding under the current IRMS positivity criteria, meat from non-castrated boars fed a mixture of corn and soy was consumed by 13 volunteers. Two volunteers produced 19NA findings above 2.5 ng/mL, and the measured isotope values, while inconsistent with documented 19-norsteroid preparations, did meet IRMS positivity criteria. However, these increases in 19NA urinary concentrations were short-lived due to rapid elimination. Timely follow-up collections may help support a claim for dietary exposure when low urinary concentrations of 19NA with pseudo-endogenous isotope values are observed.
Assuntos
Estranos , Carne , Suínos , Masculino , Humanos , Animais , Cromatografia Gasosa-Espectrometria de Massas/métodos , Estranos/análise , Isótopos de Carbono/análise , Carne/análiseRESUMO
Determining coffee region-of-origin is most appropriately addressed through analyses of the product available to the consumer. We analyzed the concentrations of 44 trace elements in 53 samples of roasted Arabica coffee beans (Coffea arabica) from 21 different countries. Variations in absolute elemental concentrations of coffee beans arise through varying degrees of roasting (from green through dark roasts). Since trace elements are not volatilized at roasting temperatures, we conducted analyses of element ratios to evaluate concentration-related differences among beans of different origins. We used kernel density estimates to compare the distributions of 1892 element ratios for each of these countries with the combined distribution of coffee samples from the other countries. Using this quantitative approach, we demonstrated that many of the world's coffee-producing regions can be distinguished from other regions of the world on the basis of element ratios.
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Café/química , Geografia , Oligoelementos/análise , Coffea , Café/classificação , Sementes/químicaRESUMO
RATIONALE: Fraudulent region-of-origin labeling is a concern for high-value, globally traded commodities such as coffee. The oxygen isotope ratio of cellulose is a useful geographic tracer, as it integrates climate and source water signals. A predictive spatial model ("isoscape") of the δ18 O values of coffee bean cellulose is generated to evaluate coffee region-of-origin claims. METHODS: The oxygen isotope ratio of α-cellulose extracted from roasted coffee beans was measured via high-temperature conversion elemental analyzer/isotope ratio mass spectrometry (TC-EA/IRMS) and used to calculate the δ18 O value of coffee bean water. The 18 O enrichment of coffee bean water relative to the δ18 O value of local precipitation was modeled as a function of local temperature and humidity. This function was incorporated into a mechanistic model of cellulose δ18 O values to predict the δ18 O values of coffee bean cellulose across coffee-producing regions globally. RESULTS: The δ18 O values of analyzed coffee bean cellulose ranged from approximately +22 to +42 (V-SMOW). As expected, coffees grown in the same region tended to have similar isotope ratios, and the δ18 O value of coffee bean cellulose was generally higher than the δ18 O value of modeled stem cellulose for the region. Modeled δ18 O values of coffee cellulose were within ±2.3 of the measured δ18 O value of coffee cellulose. CONCLUSIONS: The oxygen isotope ratio of coffee bean cellulose is a useful indicator of region-of-origin and varies predictably in response to climatic factors and precipitation isotope ratios. The isoscape of coffee bean cellulose δ18 O values from this study provides a quantitative tool that can be applied to region-of-origin verification of roasted coffee at the point-of-sale.
Assuntos
Celulose/análise , Coffea/química , Café/química , Isótopos de Oxigênio/análise , Café/provisão & distribuição , Análise de Alimentos , Manipulação de Alimentos , Temperatura Alta , Espectrometria de Massas , Modelos Biológicos , Folhas de Planta/química , Caules de Planta/química , Sementes/química , Água/análiseRESUMO
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.
Assuntos
Ecologia , Isótopos , América , Animais , Ciências Forenses , Humanos , PlantasRESUMO
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.
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RATIONALE: Elemental analyzer systems generate N(2) and CO(2) for elemental composition and isotope ratio measurements. As quantitative conversion of nitrogen in some materials (i.e., nitrate salts and nitro-organic compounds) is difficult, this study tests a recently published method - thermal decomposition without the addition of O(2) - for the analysis of these materials. METHODS: Elemental analyzer/isotope ratio mass spectrometry (EA/IRMS) was used to compare the traditional combustion method (CM) and the thermal decomposition method (TDM), where additional O(2) is eliminated from the reaction. The comparisons used organic and inorganic materials with oxidized and/or reduced nitrogen and included ureas, nitrate salts, ammonium sulfate, nitro esters, and nitramines. Previous TDM applications were limited to nitrate salts and ammonium sulfate. The measurement precision and accuracy were compared to determine the effectiveness of converting materials containing different fractions of oxidized nitrogen into N(2). RESULTS: The δ(13) C(VPDB) values were not meaningfully different when measured via CM or TDM, allowing for the analysis of multiple elements in one sample. For materials containing oxidized nitrogen, (15) N measurements made using thermal decomposition were more precise than those made using combustion. The precision was similar between the methods for materials containing reduced nitrogen. The %N values were closer to theoretical when measured by TDM than by CM. The δ(15) N(AIR) values of purchased nitrate salts and ureas were nearer to the known values when analyzed using thermal decomposition than using combustion. CONCLUSIONS: The thermal decomposition method addresses insufficient recovery of nitrogen during elemental analysis in a variety of organic and inorganic materials. Its implementation requires relatively few changes to the elemental analyzer. Using TDM, it is possible to directly calibrate certain organic materials to international nitrate isotope reference materials without off-line preparation.
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Isotope ratio analysis allows forensic investigators to discriminate materials that are chemically identical but differ in their isotope ratios. Here we focused on the discrimination of pentaerythritol tetranitrate (PETN), an explosive with military and civilian applications, using carbon (δ(13)C) and nitrogen (δ(15)N) isotope ratios. Our goal was to understand some of the factors influencing the isotope ratios of commercially manufactured PETN. PETN was isolated from bulk explosives using preparative HPLC, which reduced chemical and isotopic within-sample variability. We observed isotope ratio variation in a survey of 175 PETN samples from 22 manufacturing facilities, with δ(13)C values ranging from -49.7 to -28.0 and δ(15)N values ranging from -48.6 to +6.2. Both within-sample variability and variation of PETN within an explosive block were much smaller than between-sample variations. Isotopic ratios of PETN were shown to discriminate explosive blocks from the same manufacturer, whereas explosive component composition measurements by HPLC were not able to do so. Using samples collected from three industrial PETN manufacturers, we investigated the isotopic relationship between PETN and its reactants, pentaerythritol (PE) and nitric acid. Our observations showed that δ(13)C values of PETN were indistinguishable from that of the reactant pentaerythritol. Isotopic separation between nitric acid and PETN was consistent within each sampled manufacturer but differed among manufacturers, and was likely dependent upon reaction conditions. These data indicate that δ(13)C variation in PETN is dependent on δ(13)C variation of PE supplies, while δ(15)N variation in PETN is due to both nitric acid δ(15)N and reaction conditions.
Assuntos
Isótopos de Carbono/análise , Substâncias Explosivas/química , Isótopos de Nitrogênio/análise , Tetranitrato de Pentaeritritol/química , Cromatografia Líquida de Alta Pressão , Ácido Nítrico/química , Propilenoglicóis/químicaRESUMO
RATIONALE: Because of the threat of bombings using improvised explosives containing ammonium nitrate (AN), law enforcement and intelligence communities have been interested in stable isotope techniques for tracking and discriminating AN sources. Separate analysis of the AN component ions ammonium and nitrate would add discriminatory power to these techniques. METHODS: Ammonium ions in dissolved AN solution were isolated from samples by precipitation using sodium tetraphenylborate solution. We tested the isolation of ammonium from nitrates using solutions of ammonium and nitrate salts with different (15)N/(14)N isotope ratios. Ammonium tetraphenylborate and AN were separately analyzed for their (15)N/(14)N isotope ratios using EA-ConFlo-IRMS, and the (15)N/(14)N isotope ratios of the nitrate ions were calculated using mass balance. Ammonium and nitrate nitrogen isotope ratios were plotted as two separate variables. RESULTS: Isolation of ammonium precipitate from solutions containing dissolved nitrates did not influence the nitrogen isotope ratios of test ammonium salts. A survey set of 42 AN samples showed that the ammonium and nitrate (15)N/(14)N isotope ratios were not significantly correlated, and the paired mean differences were not statistically significant. Both ammonium and nitrate were depleted in (15)N relative to their theoretical atmospheric sources. CONCLUSIONS: Isolation of the ammonium ion from AN adds another dimension for the discrimination of forensic AN samples. This technique using sodium tetraphenylborate is robust and does not require specialized equipment. Our observations indicated that ammonium nitrogen and nitrate nitrogen have independent sources of isotopic variation.
Assuntos
Compostos de Amônio/química , Nitratos/química , Isótopos de Nitrogênio/análise , Tetrafenilborato/química , Substâncias Explosivas , Ciências Forenses/métodos , Espectrometria de Massas , Isótopos de Nitrogênio/química , Isótopos de Nitrogênio/isolamento & purificação , Reprodutibilidade dos TestesRESUMO
RDX and HMX are explosive compounds commonly used by the military and also occasionally associated with acts of terrorism. The isotopic characterization of an explosive can be a powerful approach to link evidence to an event or an explosives cache. We sampled explosive products and their reactants from commercial RDX manufacturers that used the direct nitration and/or the Bachmann synthesis process, and then analyzed these materials for carbon and nitrogen isotope ratios. For manufacturers using the Bachmann process, RDX (13)C enrichment relative to the hexamine substrate was small (+0.9) compared to RDX produced using the direct nitration process (+8.2 to +12.0). RDX (15)N depletion relative to the nitrogen-containing substrates (-3.6) was smaller in the Bachmann process than in the direct nitration process (-12.6 to -10.6). The sign and scale of these differences agree with theorized mechanisms of mass-dependent fractionation. We also examined the isotopic relationship between RDX and HMX isolated from explosive samples. The δ(13)C and δ(15)N values of RDX generally matched those of the HMX with few exceptions, most notably from a manufacturer known to make RDX using two different synthesis processes. The range in δ(13)C values of RDX in a survey of 100 samples from 12 manufacturers spanned 33 while the range spanned by δ(15)N values was 26; these ranges were much greater than any previously published observations. Understanding the relationship between products and reactants further explains the observed variation in industrially manufactured RDX and can be used as a diagnostic tool to analyze explosives found at a crime scene.
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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.