A comparison of plastic cable ties based on physical,chemical and stable isotopic measurements

Plastic cable ties can be utilised in a range of serious criminal activities and a comparison of cable ties, or fragments, may form part of the physical evidence presented to a Court of law. This research assessed the potential value of evidence based on the analysis of plastic cable ties. Twenty packets of black coloured plastic cable ties (nominally 200 mm × 4.8 mm) were purchased in pack sizes ranging from 25 to 100 individual cable ties (Brisbane, Australia, March 2015). Representative samples from each packet were visually examined, compared and tested to determine their physical dimensions, chemical compositions and stable isotopic compositions (δ²H, δ¹³C and δ¹⁵N).All of the individual cable ties from a given packet were found to be indistinguishable with respect to appearance, physical, chemical and isotopic measurements (within-batch variability). Individual cable ties were also found to be isotopically homogeneous with respect to hydrogen, carbon and nitrogen. All of the cable ties analysed were found to have very similar chemical compositions and to be manufactured predominantly from nylon 6,6. The elemental compositions of composite samples, prepared from each packet, were found to be highly variable and, as such, were of very limited value.Cable ties from ten of the twenty packets were uniquely characterised by physical appearance (between-batch variability). Physical measurements such as the width, thickness and tooth-count of the grip section did not provide additional discrimination. Cable ties from nineteen of the twenty packets were uniquely characterised by isotopic composition, based on δ²H and δ¹⁵N measurements. Samples from two packets of Crescent brand cable ties were found to be indistinguishable with respect to all of the tests applied in this study. These two packets were inadvertently purchased from the same retailer and had the same barcode and batch number. It was considered a reasonable assumption that these two packets originated from the same manufacturing batch.The authors reason that a likelihood ratio (that might be presented to a Court of law) can be derived from this type of discrete data based on a calculation of the possible combinations of distinguishable objects (unordered sampling with replacement) in a convenience sample collected from the background population. In this example, a database of 19 distinguishable objects can yield a likelihood ratio as high as 210, with a verbal equivalent of “moderately strong support” for a proposition that two cable ties have the same isotopic composition because they originate from the same batch rather than by random chance.     

Changes in illicit cocaine hydrochloride processing identified and revealed through multivariate analysis of cocaine signature data

For nearly 30 years, the methods utilized in illicit cocaine hydrochloride production have remained relatively consistent. Cocaine hydrochloride is typically produced one kilogram at a time. As a result, each individual kilogram is unique and distinct from other kilograms in any particular seizure based on the total alkaloid profile, occluded solvent profile, and isotopic signature. Additionally, multi-kilogram cocaine seizures are often comprised of cocaine from several different coca growing regions. There has been a documented shift in this type of processing based on the recent analysis of a large cocaine seizure in the Eastern Pacific. Signature analyses of samples from 21 kg randomly selected from a 517 kg seizure were virtually identical. Triplicate analyses of each sample via gas chromatography with flame ionization detection, static headspace gas chromatography mass spectrometry, and isotope ratio mass spectrometry were completed. An initial outlier evaluation of the data and an in-depth univariate analysis indicated there was no statistically significant difference among the 21 samples at the 95% confidence interval. Principal components analysis did reveal consistent minor deviations between the samples and known authentic data from the Nariño coca growing region of Colombia. These deviations were only observed on the latter principal components and could be explained by differences in solvent selection during cocaine hydrochloride processing. Chemical analyses in addition to a thorough statistical evaluation suggest a shift in the traditional small-batch method of cocaine processing to a multi-kilogram, high throughput approach.     

Investigating Residential History Using Stable Hydrogen and Oxygen Isotopes of Human Hair and Drinking Water

The relationship between isotopic signals in human hair and geographic region has potential forensic applications for identifying unknown individuals' place of recent residence. This study analyzes δ²H and δ¹⁸O isotopes in residential tap water and bulk hair samples from 17 volunteers representing 12 locations in Ontario, Canada. There is a strong correlation (R² = 0.9) between δ²H and δ¹⁸O values of the water samples. In contrast, the δ²H and δ¹⁸O values of the hair samples are weakly correlated (R² = 0.3), and the greater variability in the data is linked to dietary factors. This study demonstrates that the δ²H and δ¹⁸O values of hair and drinking water can be used to help identify potential place of residence in forensic cases, particularly in relation to proximity to large bodies of water such as the Great Lakes, but interpretations are complicated by the contribution of both water and diet to δ²H and δ¹⁸O values in hair.     

A case study on the application of isotope ratio mass spectrometry (IRMS) in determining the provenance of a rock used in an alleged nickel switching incident

The application of isotope ratio mass spectrometry (IRMS) in forensic science to establish the provenance of a range of questioned substances including soils, drugs, explosives, currency, ivory and rhino horn has been widely documented. The present study wishes to highlight the applicability of IRMS and specifically stable carbon IRMS in determining the provenance of a carbonate rock that was switched for nickel metal exported from South Africa to Israel. The technique employed effectively argued against a South African origin for the rock whilst simultaneously supporting an Israeli origin, enabling investigators to focus their attention accordingly. The study represents the first documented instance known to the authors where IRMS has been employed in the forensic geo-location of a rock.     

Forensic isoscapes based on intra-individual temporal variation of δ18O and 206Pb/207Pb in human teeth

Isotopic signatures used in the georeferencing of human remains are largely fixed by spatially distinct geologic and environmental processes. However, location-dependent temporal changes in these isotope ratios should also be considered when determining an individual’s provenance and/or trajectory. Distributions of the relevant isotopes can be impacted by predictable external factors such as climate change, delocalisation of food and water sources and changes in sources and uses of metals. Using Multi-Collector Inductively-Coupled Plasma Mass Spectrometer (MC-ICP-MS) analyses of ²⁰⁶Pb/²⁰⁷Pb in tooth enamel and dentin from a population of 21 ± 1-year-old individuals born circa 1984 and isotope ratio mass spectrometry (IRMS) of δ¹⁸O in their enamel, we examined the expected influence of some of these factors. The resulting adjustments to the geographic distribution of isotope ratios (isoscapes) found in tooth enamel and dentin may contain additional useful information for forensic identification, but the shifts in values can also impact the uncertainty and usefulness of identifications if they are not taken into account.

KEY POINTS

• Isoscapes of ²⁰⁶Pb/²⁰⁷Pb and δ¹⁸O used for geolocation are not static.
• Within a few years, the enamel and dentin of a person may exhibit measurable differences in ²⁰⁶Pb/²⁰⁷Pb even without changing locations.
• Changes in climatic patterns tied to rising temperatures are more significant than the direct effect of increasing temperature on δ¹⁸O fixed in tooth bioapatite.
• Third molar (M3) enamel mineralisation includes material incorporated from before formal amelogenesis takes place.

     

Spatial Distributions of Oxygen Stable Isotope Ratios in Tap Water From Mexico for Region of Origin Predictions of Unidentified Border Crossers

One of the many difficulties associated with identifying undocumented border crossers stems from an inability to narrow down the search area for the region of origin and family members to obtain family reference samples for DNA comparison. While the geography of regions of origins is wide, the biological profiles of the undocumented border crossers often show strong similarities, young and male. The isotopic composition of human bones, teeth, and hair has been demonstrated to be useful biomarkers for tracing locations and movements of individuals and for aiding in the identification of human remains. Data obtained from human remains can be compared to and aligned with various reference sources, such as soils and bedrock, archaeological remains, or cultural data. Here, the spatial deficiency in isotopic reference data for Mexico, specifically for oxygen (δ¹⁸O) isotopes in tap water, is being addressed through the collection and analysis of over 150 water samples and explored with tooth enamel isotopic values from recently identified Mexican nationals. The isoscape was developed using a Spine with Barriers interpolation method and shows sufficient detail to narrow down the regions where specific isotopic values are represented. The individuals were plotted on the developed isoscape using conditional correlations. The methodology was successful in assigning the correct regions of origin for the two individuals, which shows the tremendous potential of the developed isoscape. Nonetheless, there is more research needed to further improve upon this geolocation method, including analysis of multiple isotopes in different tissues, and the development of new isotopic methods.     

Chemical fingerprinting of adhesive tapes by GCMS detection of petroleum hydrocarbon products

Pressure-sensitive adhesive tapes often represent key evidence of crimes such as assault, rape or homicide; thus, the development of analytical techniques able to contribute to a detailed characterization of these materials is of forensic importance. The gas chromatography-mass spectrometry (GCMS) analysis of the solvent extractable fractions of a suite of electrical and gaffer adhesive tapes spanning a range of colors and manufacturers identified a number of petroleum-derived hydrocarbons. Molecular and isotopic analyses of hydrocarbon constituents of complex materials have found wide analytical utility including the forensic investigation of oil spills and arson. Here, we investigate the utility of these techniques for characterizing the hydrocarbon composition of pressure-sensitive adhesive tapes for forensic correlation purposes. Subtle distinction of tape samples was evident in the GCMS distribution of several hydrocarbon groups including alkyl-naphthalenes, hopane and sterane biomarkers. Linear discriminant analysis of the abundances of these products provided high level differentiation of tape manufacturer. The distinction of different adhesive tape samples was further extended by measurement of their stable carbon isotopic values. The molecular and isotopic differences of the petroleum content of tapes are consistent with the use of different petroleum materials used in the manufacturing process and demonstrate the benefits of the combined use of complementary oil hydrocarbon characterization approaches. This study reveals the forensic potential of using established petroleum characterization methods for characterizing materials with a petroleum-derived hydrocarbon element.     

The Stable Isotope Ratios of Marijuana. II. Strontium Isotopes Relate to Geographic Origin

Abstract:  Effectively addressing marijuana trade is aided by understanding marijuana geographic sources. We analyzed the ⁸⁷Sr/⁸⁶Sr of marijuana samples grown in 79 counties across the United States to determine if a primary geologic signal is retained in marijuana, which could therefore be useful for geographic sourcing. The marijuana results were compared with modeled bedrock ⁸⁷Sr/⁸⁶Sr values based on ⁸⁷Rb decay rates and a generalized geologic map of the U.S.A. A significant correlation was observed between marijuana ⁸⁷Sr/⁸⁶Sr and modeled bedrock ⁸⁷Sr/⁸⁶Sr. Although values clustered near the 1:1 relationship, there was a predominance of positive anomalies, perhaps attributable to carbonate bedrock. A small number of negative anomalies were also observed, which were generally associated with granitic bedrocks. These results suggest that strontium isotopes in marijuana record the geographic origins of marijuana, and that refinement of the base strontium map (or strontium isoscape) and improved understanding of other strontium sources would be productive.     

Case of Fatal Starvation: Can Stable Isotope Analysis Serve to Support Morphological Diagnosis and Approximate the Length of Starvation?

The diagnosis of death as a result of starvation is established on anthropological measurements, visual appearance of the deceased on external and internal examination, microscopic analysis, laboratory testing, and exclusion of other causes of death. Herein, we present our findings on a case of 95‐year‐old man who died of starvation. After the diagnosis of starvation was established by traditional forensic medicine methods, we have conducted retrospective segmental analysis of stable carbon (δ¹³C) and nitrogen (δ¹⁵N) isotope ratios in hair sample. This method reveals periods of starvation through decrease in δ¹³C and increase in δ¹⁵N along the strand of hair. Our analysis revealed the decrease of 0.6 ‰ in δ¹³C during the last 10–12 weeks prior to death, similar as reported in other investigations. Also, a decrease of 0.7 ‰ in δ¹⁵N during the last 8–10 weeks prior to death was determined that was different than observed in previous studies.     

Paired stable carbon and oxygen isotope analyses of human enamel for forensic human geolocation: An exploratory study

Stable carbon isotope analysis has proven utility for reconstructing dietary information in humans in past populations. The usefulness of stable carbon for forensic geolocation has been little investigated, largely because of the globalization of the human diet seemingly rendering it inconsequential. This study queried this assumption at a country-wide level on a known sample group. Stable carbon isotope values were obtained from human enamel with known biographical and geographical information to determine whether stable carbon, when paired with stable oxygen isotope values, could differentiate Canadians from non-Canadians. Samples originating outside of Canada were separated into three regions, and a linear discriminant analysis was used to generate discriminant functions that best separate the regions according to the stable carbon and oxygen isotope values. The results revealed two functions, where the first function explained 92.1% and the second 7.9% of the variance. Although some overlap in stable carbon and oxygen values was observed for individuals from both the United States and Canada, differences were observed between those from Canada and other geographical regions. This study demonstrated that pairing the dietary isotope carbon with the geolocator stable oxygen isotope, produced an interesting separation geographically, one that might well be helpful when attempting a geolocation query on unknown human remains.