Showing papers by "German Criminal Police Office published in 2018"

Ambient-air ozonolysis of triglycerides in aged fingerprint residues.

Abstract: In forensic science, reconstructing the timing of events occurring during a criminal offense is of great importance. In some cases, the time when particular evidence was left on a crime scene is a critical matter. The ability to estimate the fingerprint age would raise the evidentiary value of fingerprints tremendously. For this purpose the most promising approach is the analysis of changes in the chemical compositions of fingerprint residues in the course of aging. The focus of our study is the identification of human specific compounds in fingerprint residues, characterized by a significant aging behavior that could analytically be used for the age determination of fingerprints in future. The first challenge is the sensitive detection of trace amounts of relevant human specific fingerprint compounds. Highly sensitive LC-MS methods were developed for the reliable structure identification of unsaturated triglycerides and their natural degradation products in order to proof the aging mechanism that takes place in fingerprint residues. Thus our results build the fundamental basis for further forensic method development and potential application in forensic investigation. Ozonolysis was found to be one of the major lipid degradation pathways in fingerprint residues in ambient air. High-resolution tandem mass spectrometry (HRMS2) was carried out to identify the ozonolysis products (TG48:0-monoozonide) formed under exposure to the highly reactive ozone in atmospheric air. The obtained products were confirmed by matrix assisted laser desorption ionization mass spectrometry imaging (MALDI-MSI). Despite several challenges and limitations in the age estimation of fingerprints, the identification of individual degradation products of specific unsaturated lipids in aged fingerprint samples represents a significant analytical progress, resulting in a strong increase in the validity of chemical analysis of fingerprints.

Characterisation of aqueous waste produced during the clandestine production of amphetamine following the Leuckart route utilising solid-phase extraction gas chromatography-mass spectrometry and capillary electrophoresis with contactless conductivity detection.

Abstract: Chemical waste from the clandestine production of amphetamine is of forensic and environmental importance due to its illegal nature which often leads to dumping into the environment. In this study, 27 aqueous amphetamine waste samples from controlled Leuckart reactions performed in Germany, the Netherlands, and Poland were characterised to increase knowledge about the chemical composition and physicochemical characteristics of such waste. Aqueous waste samples from different reaction steps were analysed to determine characteristic patterns which could be used for classification. Conductivity, pH, density, ionic load, and organic compounds were determined using different analytical methods. Conductivity values ranged from 1 to over 200 mS/cm, pH values from 0 to 14, and densities from 1.0 to 1.3 g/cm3 . A capillary electrophoresis method with contactless conductivity detection (CE-C4 D) was developed and validated to quantify chloride, sulphate, formate, ammonium, and sodium ions which were the most abundant ions in the investigated waste samples. A solid-phase extraction sample preparation was used prior to gas chromatography-mass spectrometry analysis to determine the organic compounds. Using the characterisation data of the known samples, it was possible to assign 16 seized clandestine waste samples from an amphetamine production to the corresponding synthesis step. The data also allowed us to draw conclusions about the synthesis procedure and used chemicals. The presented data and methods could support forensic investigations by showing the probative value of synthesis waste when investigating the illegal production of amphetamine. It can also act as starting point to develop new approaches to tackle the problem of clandestine waste dumping.

Identification of specific markers for amphetamine synthesised from the pre‐precursor APAAN following the Leuckart route and retrospective search for APAAN markers in profiling databases from Germany and the Netherlands

Abstract: α-Phenylacetoacetonitrile (APAAN) is one of the most important pre-precursors for amphetamine production in recent years. This assumption is based on seizure data but there is little analytical data available showing how much amphetamine really originated from APAAN. In this study, several syntheses of amphetamine following the Leuckart route were performed starting from different organic compounds including APAAN. The organic phases were analysed using gas chromatography-mass spectrometry (GC-MS) to search for signals caused by possible APAAN markers. Three compounds were discovered, isolated, and based on the performed syntheses it was found that they are highly specific for the use of APAAN. Using mass spectra, high resolution MS and nuclear magnetic resonance (NMR) data the compounds were characterised and identified as 2-phenyl-2-butenenitrile, 3-amino-2-phenyl-2-butenenitrile, and 4-amino-6-methyl-5-phenylpyrimidine. To investigate their significance, they were searched in data from seized amphetamine samples to determine to what extent they were present in illicitly produced amphetamine. Data of more than 580 cases from amphetamine profiling databases in Germany and the Netherlands were used for this purpose. These databases allowed analysis of the yearly occurrence of the markers going back to 2009. The markers revealed a trend that was in agreement with seizure reports and reflected an increasing use of APAAN from 2010 on. This paper presents experimental proof that APAAN is indeed the most important pre-precursor of amphetamine in recent years. It also illustrates how important it is to look for new ways to identify current trends in drug production since such trends can change within a few years.

Gemeinsame Empfehlungen der Projektgruppe „Biostatistische DNA-Berechnungen“ und der Spurenkommission zur biostatistischen Bewertung von Y‑chromosomalen DNA-Befunden

Abstract: Die Analyse von Y‑chromosomalen „Short-tandem-repeat“(Y-STR)-Markern kann eine wichtige Erganzung autosomaler DNA-Analysen darstellen. So ist es haufig moglich, bei DNA-Mischungen auch bei einem Uberschuss an weiblicher DNA Informationen zum mannlichen Spurenverursacher zu erhalten. Die Y‑STR-Analysen konnen den Nachweis fuhren, dass mannliche DNA in dem untersuchten Spurenmaterial vorliegt, und ermoglichen ggf. den Abgleich von Spurenmaterial mit Vergleichsmustern mannlicher Personen. Die hier vorgelegten Empfehlungen der Projektgruppe „Biostatistische DNA-Berechnungen“ der Landeskriminalamter in Zusammenarbeit mit der Spurenkommission der Deutschen Gesellschaft fur Rechtsmedizin sollen Sachverstandige bei der Bewertung von Y‑STR-Befunden und bei der Auswahl des geeigneten biostatistischen Berechnungsansatzes unterstutzen. Es werden Methoden zur Haufigkeitsschatzung von Y‑STR-basierten Haplotypen und zur Berechnung der Wahrscheinlichkeit der Ubereinstimmung von Haplotypen zwischen einer Spur und einem moglichen Spurenverursacher vorgestellt. Daraus werden Empfehlungen mit dem Ziel einer harmonisierten Verfahrensweise bei der Begutachtung von Y‑chromosomalen DNA-Befunden im Strafverfahren abgeleitet.

A Novel Impurity-Profiling Workflow with the Combination of Flash-Chromatography, UHPLC-MS, and Multivariate Data Analysis for Highly Pure Drugs: A Study on the Synthetic Cannabinoid MDMB-CHMICA

Abstract: In this paper we present a new, versatile workflow for a synthesis impurity profiling concept, using the combination of flash chromatography (F-LC), liquid chromatography coupled to mass spectrometry (LC-MS), and multivariate data analysis. For three highly pure, structurally different synthetic cannabinoids, we demonstrate that via F-LC more than 99% of the main component (API) can be removed from a sample to enrich present impurities and yield combined fractions of targeted synthesis impurities with reproducible chromatographic signatures via LC-MS. The maximum overall relative standard deviation (RSD) of the complete experimental procedure for isolation and measurement of the impurity profiles (FL-C + LC-MS) was found to be 13.8% on average. The impurity signatures of 40 1 kg samples of MDMB-CHMICA (methyl ( S)-2-(1-(cyclohexylmethyl)-1 H-indole-3-carboxamido)-3,3-dimethylbutanoate) from one large seizure by Luxembourg customs were assessed via UHPLC-MS and compared via principle component analysis (PCA) to possibly discriminate between individual synthesis pathways or production batches and to deduce batch sizes. Three of these 40 samples could be identified as outliers, i. a., as a result of a highly abundant impurity with m/ z 498, isolated via F-LC and identified as methyl 2-(2-(1-(cyclohexylmethyl)-1 H-indole-3-carboxamido)-3,3-dimethylbutanamido)-3,3-dimethylbutanoate, most probably manufactured with a varying synthesis pathway. The remaining 37 samples were subdivided via PCA and hierarchical cluster analysis into five clusters between five and ten samples, representing a maximum possible batch size of 10 kg of pure MDMB-CHMICA. Furthermore, the profiling concept was successfully applied to self-produced and seized "spice-products" to extract impurity profiles of MDMB-CHMICA without any ion suppression or chemical interference.

Dog breed affiliation with a forensically validated canine STR set

Abstract: We tested a panel of 13 highly polymorphic canine short tandem repeat (STR) markers for dog breed assignment using 392 dog samples from the 23 most popular breeds in Austria, Germany, and Switzerland. This STR panel had originally been selected for canine identification. The dog breeds sampled in this study featured a population frequency ≥1% and accounted for nearly 57% of the entire pedigree dog population in these three countries. Breed selection was based on a survey comprising records for nearly 1.9 million purebred dogs belonging to more than 500 different breeds. To derive breed membership from STR genotypes, a range of algorithms were used. These methods included discriminant analysis of principal components (DAPC), STRUCTURE, GeneClass2, and the adegenet package for R. STRUCTURE analyses suggested 21 distinct genetic clusters. Differentiation between most breeds was clearly discernable. Fourteen of 23 breeds (61%) exhibited maximum mean cluster membership proportions of more than 0.70 with a highest value of 0.90 found for Cavalier King Charles Spaniels. Dogs of only 6 breeds (26%) failed to consistently show only one major cluster. The DAPC method yielded the best assignment results in all 23 declared breeds with 97.5% assignment success. The frequency-based assignment test also provided a high success rate of 87%. These results indicate the potential viability of dog breed prediction using a well-established and sensitive set of 13 canine STR markers intended for forensic routine use.

Same, same but different!-matching entomological traces to a human food source by stable isotope analysis.

Abstract: Blow flies are important tools in forensic entomology, as they feed and develop on human bodies. This fact can be used to estimate the minimum post mortem interval (PMImin), by classifying the age of the immature stages found on corpses. The capacity to also be able to classify the age of adult flies, or even empty puparia, could increase the timeframe for a PMImin. However, the association of older developmental stages, such as adult flies or their empty cases, with a human cadaver may be challenged, as such specimens could stem from another food source. Analyzing the stable carbon (δ13C) and nitrogen (δ15N) isotopes in such specimens could be helpful here, as the isotope signatures reflect those of the food sources. We compared the δ15N and δ13C signatures of tissue from humans and 12 additional species by elemental analyzer-isotope ratio mass spectrometry (EA-IRMS). We did the same for adult flies and empty puparia of the blow fly Lucilia sericata, which were derived from juvenile stages developed on tissues from the mentioned species. The isotope signatures for the adult flies and their empty puparia linearly mirrored the isotope signatures for the respective tissues on which they developed as larvae. Results such as these are useful to indicate the flies' nutritional history, but they do not provide the same kind of evidence that a DNA analysis would. As individual dietary habits, global distribution and environmental effects can influence isotope ratios, we strongly recommend to analyzing entomological traces and muscle tissues of potential donors or for other food sources.

Isolation and whole genome analysis of endospore-forming bacteria from heroin.

Abstract: Infections caused by endospore-forming bacteria have been associated with severe illness and death among persons who inject drugs. Analysis of the bacteria residing in heroin has thus been biased towards species that affect human health. Similarly, exploration of the bacterial diversity of seized street market heroin correlated with the skin microflora of recreational heroin users insofar as different Staphylococus spp. or typical environmental endospore formers including Bacillus cereus and other Bacilli outside the B. cereus sensu lato group as well as diverse Clostridia were identified. In this work 82 samples of non-street market ("wholesale") heroin originating from the German Federal Criminal Police Office's heroin analysis program seized during the period between 2009 and 2014 were analyzed for contaminating bacteria. Without contact with the end user and with only little contaminations introduced by final processing, adulteration and cutting this heroin likely harbors original microbiota from the drug's original source or trafficking route. We found this drug to be only sparsely populated with retrievable heterotrophic, aerobic bacteria. In total, 68 isolates were retrieved from 49 out of 82 samples analyzed (60% culture positive). All isolates were endospore-forming, Gram-positive Bacilli. Completely absent were non-endospore-formers or Gram-negatives. The three most predominant species were Bacillus clausii, Bacillus (para)licheniformis, and Terribacillus saccharophilus. Whole genome sequencing of these 68 isolates was performed using Illumina technology. Sequence data sets were assembled and annotated using an automated bioinformatics pipeline. Average nucleotide identity (ANI) values were calculated for all draft genomes and all close to identical genomes (ANI>99.5%) were compared to the forensic data of the seized drug, showing positive correlations that strongly warrant further research on this subject.

Profiling of new psychoactive substances by using stable isotope ratio mass spectrometry: Study of the synthetic cannabinoid 5F-PB-22.

Abstract: In this paper, the results of a pilot study on the profiling of the synthetic cannabinoid receptor agonist 5F-PB-22 (5F-QUPIC, pentylfluoro-1H-indole-3-carboxylic acid-8-quinolinyl ester) via isotope ratio mass spectrometry are presented. It focuses on δ13 C, δ15 N and δ2 H isotope ratios, which are determined using elemental analyser (EA) and high temperature elemental analyser (TC/EA) coupled to an isotope ratio mass spectrometer (IRMS). By means of a sample of pure material of 5F-PB-22, it is shown that the extraction of 5F-PB-22 from herbal material, a rapid clean-up procedure, or preparative column chromatography had no influence on the isotope ratios. Furthermore, 5F-PB-22 was extracted from 14 different herbal blend samples ("Spice products" from police seizures) and analysed via IRMS, yielding 3 clusters containing 7, 5, and 2 samples, distinguishable through their isotopic composition, respectively. It is assumed that herbal blends in each cluster have been manufactured from individual batches of 5F-PB-22.

Database Binning and Retrieval in Multi-Fingerprint Identification Systems

Abstract: The increasingly large scale of deployed biometric systems necessitates approaches for computational workload reduction in order to perform identification queries efficiently. Simple database binning based on classification of features in biometric samples is amongst the most frequently used and researched methods for achieving said goal. However, multi-instance database binning appears to be a neglected topic in the scientific literature: best to the authors’ knowledge, for fingerprints there exists only one, entirely theoretical, study on this subject. In this paper, we propose a retrieval algorithm based on multi-instance binning of fingerprint databases, along with usage of statistical information on fingerprint classes and their correlations. The aforementioned statistics are obtained from NIST SD9 database and data obtained from the German Federal Criminal Police Office. Subsequently, the experimental evaluation of the proposed algorithm is performed on the NIST SD9 database. The proposed system is evaluated using a classifier based on the PCASYS tool and neuronal networks. The results show a significant workload reduction from a baseline exhaustive search scenario – down to 12.7% for this particular classifier and 5.8% for a theoretical perfect (completely accurate) classifier. The proposed method could be seamlessly integrated into operational systems, as it relies on well-established features and compatibility with the current acquisition methods.

Cyber Security Intelligence – Kollaborative Ansätze gegen Cyber- und Computerkriminalität

Abstract: Hans und Mark laufen durch den Wald. Hans ist Mark leicht voraus. Plotzlich ruft Mark: „Wir werden von einem Baren verfolgt! Wir mussen schneller laufen, um ihm zu entkommen!“ „Nein“, erwidert Hans darauf, „ich bin derjenige, der jetzt schneller laufen muss.“ Und sprintet seinem Laufpartner davon (Ross 2014: 4). Was hat diese Geschichte mit Cybersicherheit zu tun? Nun, Hans hat realisiert, dass er Ziel einer Attacke wurde und eine Gegenmasnahme (Countermeasure) eingeleitet, um der Gefahr zu entgehen. Sein Laufpartner Mark bleibt bei diesem Plan buchstablich auf der Strecke.