The role of isotope ratio mass spectrometry as a tool for the comparison of physical evidence

This paper considers how likelihood ratios can be derived for a combination of physical, chemical and isotopic measurements. Likelihood ratios were formulated based on the characteristics of a small convenience sample of 20 duct tapes. The propositions considered were:

• H_ptwo samples are from the same batch
• H_dtwo samples are from different batches.

The physical and isotopic characteristics of ten rolls of duct tape were shown to be consistent throughout each roll.The width and thickness of the tapes and the density of the scrim fibres provided equivalent information and the combined physical characteristics provided a basis upon which to discriminate between many of the samples.Scatter-plots and confidence ellipses provided a convenient method to group the isotopic composition of the tape backing material and provided a basis to discriminate between samples which were physically indistinguishable. Considering both the physical and isotopic characteristics it was possible, at best, to ascertain that the evidence provided moderately strong support for the proposition that two samples of tape were derived from the same batch (LR = 400).Kernel density estimates were used to model the distribution of isotopic compositions of the backing material. Using this technique it was possible to estimate objectively the probability that a sample with given characteristics could be drawn, at random, from the background population and to calculate a likelihood ratio based on the propositions above.The strength of evidence which could be presented by either model was ultimately limited by the size of the background sample.     

Use of nitrogen cryogun for separating duct tape and recovery of latent fingerprints with a powder suspension method

Duct tape is sometimes recovered as physical evidence in crimes. The purpose of this study was to determine the quality of latent prints on the adhesive and non-adhesive surfaces of duct tape samples that were separated using three methods. Three hundred donor fingerprint impressions were deposited on duct tape. Sections of duct tape were affixed to sections of cardboard and a fingerprint placed on the non-adhesive surface of the tape. A second layer of duct tape was prepared and a fingerprint placed on the adhesive side of the tape and then the tape was affixed to the piece of tape on the cardboard. After a 24-h period, the samples were separated using gradual force, liquid nitrogen applied with a cryogun and an adhesive neutralizer to separate the layers of tape. The recovered fingerprints were processed with a fingerprint powder suspension method. The recovered fingerprint images were evaluated and rated as +1, +2, or +3. The liquid nitrogen spray separation method yielded the highest number of +3 prints.     

A validation study for duct tape end matches

Fracture matches are considered to be the strongest association achievable in forensic examinations of glass, metal, wood, plastic, paint, tape, and other trace evidence. Despite being fairly routine examinations, few publications exist to support their admissibility in court. This study was designed, using duct tape as the fractured medium, to determine the validity and error rate associated with conducting end match (fracture match) examinations on this material. Five test designs, which varied either the source roll of tape or manner of separation (torn or cut) from the roll, were administered to four analysts with instructions to examine the assigned test sets for end matches. If an end match was not identified by the initial analyst, the entire test set was independently evaluated by the remaining three analysts. Results indicated that while tape grade did not hinder end match identification, the manner of separation could affect results.     

Forensic utility of carbon isotope ratio variations in PVC tape backings

Forensic interest in adhesive tapes with polyvinyl chloride (PVC) backings (electrical tape) derives from their use in a variety of illicit activities. Due to the range of physical characteristics, chemical compositions, and homogeneity within a single roll of tape, traditional microscopic and chemical analyses can offer a high degree of discrimination between tapes, permitting the assessment of potential associations between evidentiary tape samples. The carbon isotope ratios of tapes could provide additional discrimination among tape samples. To evaluate whether carbon isotope ratios may be able to increase discrimination of electrical tapes, particularly with regards to different rolls of tape of the same product, we assessed the δ(13)C values of backings from 87 rolls of PVC-based black electrical tape (~20 brands, >60 products) Prior to analysis, adhesives were removed to prevent contamination by adhering debris, and plasticizers were extracted because of concern over their potential mobility. This result is consistent with each of these tapes having approximately the same plasticizer δ(13)C value and proportion of carbon in these plasticizers. The δ(13)C values of the 87 PVC tape backings ranged between -23.5 and -41.3 (‰, V-PDB), with negligible carbon isotopic variation within single rolls of tape, yet large variations among tape brands and tape products. Within this tape population, carbon isotope ratios permitted an average exclusion power of 93.7%, using a window of +/-0.3‰; the combination of carbon isotope ratio measurement with additional chemical and physical analyses raises the discrimination power to over 98.9%, with only 41 out of a possible 3741 pairs of tape samples being indistinguishable. There was a linear relationship between the δ(13)C value of tape backings and the change in δ(13)C value with the extraction of plasticizers. Analyses of pre- and post-blast tape sample pairs show that carbon isotope signatures are within 0.3‰ of pre-blast values, indicating that carbon isotope values are largely preserved during an explosion.     

Capturing high-resolution digital images for use in forensic document examination

In the past, pattern disciplines within forensic science have periodically faced criticism due to their subjective and qualitative nature and the perceived absence of research evaluating and supporting the foundations of their practices. Recently, however, forensic scientists and researchers in the field of pattern evidence analysis have developed and published approaches that are more quantitative, objective, and data driven. This effort includes automation, algorithms, and measurement sciences, with the end goal of enabling conclusions to be informed by quantitative models. Before employing these tools, forensic evidence must be digitized in a way that adequately balances high-quality detail and content capture with minimal background noise imparted by the selected technique. While the current work describes the process of optimizing a method to digitize physical documentary evidence for use in semi-automated trash mark examinations, it could be applied to assist other disciplines where the digitization of physical items of evidence is prevalent. For trash mark examinations specifically, it was found that high-resolution photography provided optimal digital versions of evidentiary items when compared to high-resolution scanning.     

A Novel Solvent-based Method to Separate Duct Tape from Porous Surface for Fingerprint Development

In this study, we have proposed a novel solvent-based method using a specific concentration of 3M™ Novec™ HFE-72DE and 7200 solvents to untangle duct tape from porous article with minimal impact to the quality of latent fingerprint deposited on the sticky-side surface of duct tape. A series of experiments determined that a mixture of 30% HFE-72DE:7200 (v/v) was found to be the most effective to separate various brands of duct tape from different types of porous surface, including office copy paper, newspaper, cardboard, and tissue wipe, which had been stored for up to 30 days before untangling. Further studies also revealed that 30% HFE-72DE:7200 was compatible with three common fingerprint development methods for porous articles, namely ninhydrin, indanedione-zinc, and physical developer. The nonflammability and low toxicity nature of this novel solvent mixture also make it ideal for separating duct tape from porous surface in laboratory or at crime scene.     

Simultaneous hair testing for opiates, cocaine, and metabolites by GC-MS: a survey of applicants for driving licenses with a history of drug use

A sensitive GC-MS method for the simultaneous determination of opiates, cocaine, and metabolites in hair at a cut-off level of 0.1 ng/mg was adopted to assess past exposure to these drugs in applicants for driving licenses with a history of drug use. The sampling protocol consisted of collection of one hair (sample A, 5-cm length) and one urine sample. When hair and urine (EMIT Syva, cut-off levels: 0.3 mg/l for opiates, 0.15 mg/l for cocaine, GC-MS confirmation of positives) were both positive or negative the protocol was concluded. In the other cases, the assessment of 'current exposure' to drugs was carried out, in order to avoid seriated random urinalysis, by collecting a second hair sample (sample B) 6 weeks later and analysing the proximal 1-cm segment. Out of the 214 'A' hair samples analyzed, 14 (6.5%) tested positive for morphine and/or 6-acetylmorphine (6AM), and 26 (12%) for cocaine and/or benzoylecgonine (BE), whereas none of the samples tested positive for both drugs. Levels between 0.1 and 1 ng/mg of the single analytes were found in eight out of the 14 morphine-6AM positives (57%) and in 18 out of the 26 cocaine-BE positives (69%). The time course of positive cases showed a progressive decrease of morphine-6AM positives and a corresponding increase of cocaine-BE positives within the study period September 1995-February 1999. No cases with positive urine and negative hair were observed. Among the 40 positive cases, seven (four and three for opiates and cocaine, respectively) were found to be 'currently exposed to drug', four by urinalysis (three and one) and three by analysis of the hair sample B (1 and 2).     

A survey of extraction techniques for drugs of abuse in urine

Sixty nine participants in the United Kingdom national external quality assessment scheme for drugs of abuse in urine reported details of their sample extraction technique by questionnaire. Laboratories were categorised by differences in technique and their analytical test results compared for samples containing D-amfetamine 0.4 (4) and 0.8 (3) mg/l, morphine 0.4 (4) and 0.8 (4)mg/l, and benzoylecgonine 0.15/0.2 (2) and 0.45/0.5 (4) mg/l. Values in parentheses are numbers of samples. For amfetamine, there was no significant difference in the frequency of true positive results between liquid-liquid or solid phase extraction and the Toxi-Lab A system at 0.8 mg/l. Toxi-Lab A gave significantly fewer positives when operating below its specified threshold at 0.4 mg/l. Paradoxically, laboratories using >5 ml urine volume performed less well. Acidification of the extract before volume reduction gave significantly more true positives. For extraction of morphine, solid phase systems significantly outperformed both liquid-liquid and the Toxi-Lab A system at both 0.8 and 0.4 mg/l. No significant differences between extraction techniques were demonstrated for analysis of benzoylecgonine.     

Applicability of DNA analysis on adhesive tape in forensic casework

Adhesive tape is commonly used in crimes and is often the subject of forensic evaluation. DNA analysis of adhesive tape can provide DNA profiles of suspects. The object of this study was to evaluate the applicability of DNA analysis on adhesive tape samples in forensic casework. We retrospectively reviewed all cases involving adhesive tape or similar items received by our institute for DNA analysis during the past 11 years. From 100 forensic cases reviewed, 150 adhesive tape samples were examined. A total of 98 DNA profiles were obtained from these samples. Sixty-two of the profiles provided feasible case-relevant information. In conclusion, DNA profiling of adhesive tape samples can be useful in a variety of forensic cases.     

How the probability of a false positive affects the value of DNA evidence

Errors in sample handling or test interpretation may cause false positives in forensic DNA testing. This article uses a Bayesian model to show how the potential for a false positive affects the evidentiary value of DNA evidence and the sufficiency of DNA evidence to meet traditional legal standards for conviction. The Bayesian analysis is contrasted with the "false positive fallacy," an intuitively appealing but erroneous alternative interpretation. The findings show the importance of having accurate information about both the random match probability and the false positive probability when evaluating DNA evidence. It is argued that ignoring or underestimating the potential for a false positive can lead to serious errors of interpretation, particularly when the suspect is identified through a "DNA dragnet" or database search, and that ignorance of the true rate of error creates an important element of uncertainty about the value of DNA evidence.     

Development and Assessment of Postcranial Sex Estimation Methods for a Guatemalan Population

This study tests whether postcranial sex estimation methods generated from Hispanic, and mainly Mexican samples, can be successfully applied to other increasingly common migrant populations from Central America. We use a sample of postcranial data from a modern (1980s) Guatemalan Maya sample (n = 219). Results indicate a decrease in classification accuracies for previously established univariate methods when applied to the Guatemalan study sample, specifically for males whose accuracies ranged from 30 to 84%. This bias toward inaccuracies for Guatemalan males is associated with the smaller skeletal sizes for the Guatemalan sample as compared to the samples used in the tested sex estimation methods. In contrast, the tested multivariate discriminant function classification yielded less sex bias and improved classification accuracies ranging from 82 to 89%. Our results highlight which of the tested univariate and multivariate methods reach acceptable levels for accuracy for sex estimation of cases where the region of origin may include Guatemala.     

Hair analysis by using radioimmunoassay, high-performance liquid chromatography and capillary electrophoresis to investigate chronic exposure to heroin, cocaine and/or ecstasy in applicants for driving licences

The present paper describes an integrated diagnostic strategy to check the physical fitness of subjects, formerly users of illicit drugs, to obtain a driving license, after having quit their addiction. According to the Italian law, applicants for a driving license with a history of drug abuse must give evidence to have quit this behaviour and to show no risk of relapse in the future. To prove this, at our institute, they undergo medical examination, hair analysis and a urinalysis program on eight seriate samples, collected over about 40 days. About 700 subjects per year are investigated with this strategy. The hair samples are screened for opiates (morphine), cocaine and ecstasy, the most abused illicit substances in our region, by using commercial radioimmunoassays adopting cut-off levels of 0.1 ng/mg. All positive samples and about 10% of negatives are confirmed by high-performance liquid chromatography. Further confirmation of results can be carried out by capillary electrophoresis (and/or GC/MS or MS/MS). In 1998, the prevalence of positives for morphine, cocaine and ecstasy was 4.8, 11.3 and 2.6%, respectively. In this year, for the first time, the percentage of hair samples positive for cocaine was greater than that for opiates. The results of this integrated diagnostic strategy are presented and discussed, with particular emphasis on the comparison between hair analysis on a single sample and seriate urinalyses (on eight samples).     

Analysis of pressure sensitive adhesive tape: I. Evaluation of infrared ATR accessory advances

Attenuated total reflection (ATR), also known as internal reflection spectroscopy (IRS), is a forensically accepted method for infrared (IR) analysis of pressure sensitive adhesive tapes. Advancements of ATR accessories in the last decade have provided the forensic examiner several ATR methods to choose from. These accessories offer a variety of ATR crystal choices with a variety of prices and capabilities. Four different types of pressure sensitive adhesive tapes including duct tape, electrical tape, packaging tape and office tape have been used to compare six different ATR methods. Each of the methods tested offers both benefits and limitaltions which must be considered for the type of sample to be analyze. The intent of this paper is to assist the reader in better understanding ATR techniques, the many differences among currently available ATR accessories and how the method is applied to the analysis of pressure sensitive adhesive tape.     

Firearms discharge residue sample collection techniques.

Critical comparisons of Ba and Sb in firearms discharge residue were made on samples collected by three independent collection technqiues. Collection materials studied were transparent adhesive tape, (Scotch Brand), a solution of cellulose acetate in acetone ("Film Lift"), and plastic-shafted cotton swabs wetted with dilute nitric acid. Flameless atomic absorption analyses were performed with a Jarrell-Ash Model 810 instrument equipped with a tantalum strip atomizer. Tape and cotton swabs gave comparable positive indications of residue, with frequencies of 90 and 80%, respectively. The plastic Film Lift gave fewer positives, with a frequency of 50%. With the transparent tape lift, gunshot residue particles are discernible, making nondestructive microscopic identification possible prior to destructive elemental analysis.     

Identification and comparison of electrical tapes using instrumental and statistical techniques: I. Microscopic surface texture and elemental composition

Comparisons of polyvinyl chloride electrical tape typically rely upon evaluating class characteristics such as physical dimensions, surface texture, and chemical composition. Given the various techniques that are available for this purpose, a comprehensive study has been undertaken to establish an optimal analytical scheme for electrical tape comparisons. Of equal importance is the development of a quantitative means for sample discrimination. In this study, 67 rolls of black electrical tape representing 34 different nominal brands were analyzed via scanning electron microscopy and energy dispersive spectroscopy. Differences in surface roughness, calendering marks, and filler particle size were readily apparent, including between some rolls of the same nominal brand. The relative amounts of magnesium, aluminum, silicon, sulfur, lead, chlorine, antimony, calcium, titanium, and zinc varied greatly between brands and, in some cases, could be linked to the year of manufacture. For the first time, quantitative differentiation of electrical tapes was achieved through multivariate statistical techniques, with 36 classes identified within the sample population. A single-blind study was also completed where questioned tape samples were correctly associated with known exemplars. Finally, two case studies are presented where tape recovered from an improvised explosive device is compared with tape recovered from a suspect.     

Rapid and non-destructive approach for characterization and differentiation of sealing wax using ATR-FTIR spectroscopy

Sealing wax is used for maintaining the integrity and authenticity of a document or physical evidence. Any tampering with the seal calls into question the overall integrity and authenticity of the tangible evidence or document. In these circumstances, determining the authenticity of the sealing material (physical and chemical) becomes imperative. In this study, ATR-FTIR spectroscopy supported by chemometrics has been used to differentiate sealing wax samples belonging to 12 different brands available across India. All the samples were first melted, cooled, and then analyzed using ATR-FTIR spectroscopy in the mid-infrared region (4000–600 cm⁻¹). The obtained spectra were first examined visually for the presence of different functional groups. Principal component analysis (PCA) and principal component analysis-linear discriminant analysis (PCA-LDA) were employed to analyze the sample clustering patterns and to categorize them into their respective groups, respectively. For classification, a PCA-LDA training model was applied, and it demonstrated 95.83% accuracy. The validation test resulted in an accuracy of 83.33%. PCA-LDA model offered 100% accurate prediction for samples on various substrates, including cloth, cardboard, and paper. A blind study was also performed using five unknown samples, which were accurately classified into their respective groups. PCA-LDA model will be helpful in providing investigative leads by linking a questioned sealing wax sample with its respective group.     

Analysis of forensic soil samples via high-performance liquid chromatography and ion chromatography

Traditional forensic soil comparisons are performed via physical and/or chemical examinations of color, texture, and mineral content, leaving any organic- or water-soluble fractions unexamined. This study uses high-performance liquid chromatography (HPLC) and ion chromatography (IC) to assess the qualitative and quantitative variation in these fractions of soil. Soil samples (n=120) were collected over the course of 3 weeks from urban, suburban, and rural locations in and around Lansing, MI. Additional samples from six of these locations (two urban, two suburban, and two rural) were collected once a week for 10 weeks for temporal analysis. Nine additional samples, equally spaced over a 1 m(2) grid, from these same six locations were collected for spatial analyses. Qualitative and quantitative analysis of the resultant chromatograms separated the 120 samples into 10 groups by HPLC and 23 groups by IC. This study shows that using HPLC and IC to analyze the organic- and water-soluble fractions of soil can successfully discriminate samples. Quantitative analysis of the results eliminates some false inclusions by providing further differentiation of samples. The results of this study indicate that adding HPLC and IC analyses to traditional forensic soil analysis schemes can improve overall sample differentiation. The methods used in this study were also able to detect both qualitative and quantitative variations in soil over a relatively small geographic area. This demonstration of soil heterogeneity underscores the importance of the collection of a representative known sample population when assessing a forensic soil comparison. Significant temporal variation was also demonstrated over the course of 10 weeks of sampling; however, samples were found to be consistent over shorter periods of time. Baseline levels of inorganic anions were determined via IC; these levels may be useful in assessing the significance of anions detected in soil from cases involving low explosives.     

Paint and tape: collection and storage of microtraces of paint in adhesive tape

The collection and preservation of microtrace evidence with the aid of an adhesive tape is a method of choice in forensic science. This technique is rapid and easy and allows the concentration of microtraces on a carrier, which facilitates further investigations in the laboratory. Adhesive tapes are currently used to secure microtraces of fibers and glass, but hardly for traces of automotive paint and other lacquers for fear of interference with the analysis of binders. A collection of automotive paint consisting of original and repair lacquers collected by tape has been evaluated. After various times of storage within the tape, these samples were compared with untreated references by microscope FT-IR and microspectrophotometry (MSP). Another set of paints was collected in 1984, stored within the tape until 1995, and examined the same way. About 170 layers of lacquer with various types of binder were examined. With the exception of one clear lacquer no difference between treated samples and references was detected. This small difference observed could be correlated to the exposure to xylene (extractant) and was not caused by the storage within the adhesive tape.     

Validation of an ELISA-based screening assay for the detection of amphetamine, MDMA and MDA in blood and oral fluid

The use of amphetamine and 'ecstasy' (MDMA) has increased exponentially in many European countries since the late nineties, leading to a rapid growth in the number of clinical and forensic analyses. Therefore, a rapid screening procedure for these substances in biological specimens has become an important part of routine toxicological analysis in forensic laboratories. The objective of this study was to evaluate the Cozart amphetamine enzyme-linked immunosorbent assay (ELISA) for the screening of plasma samples and oral fluid samples (collected with the Intercept device). Authentic plasma samples from drivers (n=360) were screened, using an 1:5-fold dilution. True positive, true negative, false positive and false negative results were determined relative to the in-house routine GC-MS analysis. Samples consisted of 144 amphetamine-only positives, 141MDMA/MDA-only positives, and 74 negatives when using the limit of quantitation as the cut-off level for confirmation (10 ng/mL). Using these results, receiver operating characteristic (ROC) curves were generated and optimal cut-off values for the screening assay were calculated. Analysis showed that the ELISA is able to predict the presence of either amphetamine or *MDMA/MDA (*MDMA as its metabolite MDA) in plasma samples with 98.3% sensitivity and 100% specificity at a cut-off value of 66.5 ng/mL d-amphetamine equivalents. A similar analysis was conducted on 216 oral fluid specimens collected from a controlled double blind study. Subjects received placebo or a high (100 mg) or low (75 mg) dose of MDMA. Oral fluid samples were collected at 1.5 and 5.5h after administration. Combined results of the analysis of the high and low dose oral fluid samples indicated a screening cut-off of 51 ng/mL d-amphetamine equivalents with both a sensitivity and specificity of 98.6% (using a LC-MS/MS confirmation cut-off of 10 ng/mL). In conclusion, these data indicate that the Cozart AMP EIA plates constitute a fast and accurate screening technique for the identification of amphetamine and MDMA/MDA positive plasma samples and oral fluid specimens (collected with Intercept. It should be emphasized that method validation should be performed for each type of biological matrix.