Mass Spectrometry

Sex Determination Through the Chemical Analysis of Fingerprints
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Sex Determination Through the Chemical Analysis of Fingerprints

Fingerprints have been a staple of forensic science for decades, providing a reliable (though not perfect) means of identifying suspects and placing people at crime scenes. In recent years, scientists have turned their attention towards exploring the additional information that could be extracted from fingerprints, in particular, chemical information for police intelligence. Fingerprints are composed of a mixture of chemical compounds both excreted through our skin and picked up from the environment.

Over the past decade, analytical chemists have shown that there may be sufficient chemical differences in the fingerprints of male and female donors to differentiate between the sexes. By studying these chemical differences, it may be possible to build a model capable of predicting the sex of a fingerprint donor based on the chemical compounds within the fingerprint.

In a recent study published in Forensic Chemistry, a method was developed to predict the sex of a donor based on the presence of peptides and proteins in fingermarks. The study used MALDI-MS (Matrix-assisted laser desorption/ionization mass spectrometry), a type of mass spectrometry that enables both the measurement and identification of the chemical constituents in a material, in addition to the imaging of samples. MALDI has already been demonstrated to be a powerful technique in the chemical analysis of fingermarks, including imaging fingermarks and detecting the presence of blood and drugs in the mark. Much of the research in the area has been led by Professor Simona Francese of Sheffield Hallam University in the UK, senior author on this recent paper.

In the study, 199 participants donated multiple fingermarks, culminating in hundreds of samples for analysis. The fingermarks used for the analysis were natural, that is to say, deposited with no fingertip preparation beforehand. Many studies in the chemical analysis of fingerprints use “groomed” marks, in which the fingers are rubbed on the face or forehead in order to load the fingers with skin secretions prior to deposition. Although this provides rich samples for analysis, they are not applicable to fingermarks encountered in the real world.

After fingermark collection, MALDI-MS was then used to analyse the samples, focusing on the measurement of peptides and proteins in the deposited marks. To further mimic realistic scenarios, fingermarks were analysed both undeveloped and enhanced by common fingerprint visualisation techniques (white powder and vacuum metal deposition). Based on the chemical profiles produced, a predictive model was then constructed for the purpose of predicting the sex of the donor of unknown fingermarks, such as those that may be discovered at crime scenes.

The technique had a predictive power of up to 86%, demonstrating the potential to differentiate between male and female donors to a degree. There were, however, challenges in this study. Polyethylene glycol (PEG)-based contaminants, routinely used in cosmetics and personal care products, were commonly encountered, interfering with the detection of the actual targets of the analysis. Furthermore, the application of fingermark development techniques also caused interference, with many mass spectra being dominated by the gold nanoparticles used in the vacuum metal deposition method. This suggests the technique may only be truly applicable in the case of undeveloped fingermarks.

Although the technique has a high predictive power, it was not able to determine the sex of the donor in all cases, rendering it unsuitable for conclusively excluding suspects from an investigation based on their sex. However the method could be used to triage fingermarks, allowing investigators to establish which marks are of the greatest importance and which should be prioritised for further study, potentially speeding up forensic investigations.

 

Heaton & Bury et al. Investigating sex determination through MALDI MS analysis of peptides and proteins in natural fingermarks through comprehensive statistical modelling. 2020, Forensic Chemistry, DOI: 10.1016/j.forc.2020.100271

Speeding Up Sexual Assault Investigations with Chemistry
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Speeding Up Sexual Assault Investigations with Chemistry

A recent study has demonstrated a new technique for the rapid detection of semen and the chemical differentiation of condoms, offering a new potential tool to assist sexual assault investigations.

Hundreds of thousands of cases of sexual assault and rape are reported each year, though this is undoubtedly a fraction of the actual number. The successful identification and prosecution of offenders in sexual assault cases often hinges on the ability to detect and collect biological fluids such as semen, essential for supporting victim statements and identifying the offender. In the past, the identification of semen has relied on destructive, non-specific presumptive tests, often based on a colour change reaction in the presence of a specific chemical in semen. In recent years, there has been a push for the development of preparation-free analytical techniques that could be used for the analysis of sexual assault evidence at crime scenes or in hospitals.

In a recent study published in Forensic Chemistry, a method using ambient ionisation mass spectrometry has been developed for the analysis of sexual assault evidence, specifically semen and condoms. Ambient ionisation MS refers to a type of mass spectrometry which allows the rapid, direct analysis of a material, eliminating the need for the time-consuming and destructive sample preparation steps that limit traditional techniques.

This particular technique, called sheath-flow probe electrospray ionisation MS, uses a small, cheap-to-construct probe that is simply touched to the surface of the sample. The probe is then placed in front of a mass spectrometer inlet and a voltage applied to produce an instant unique chemical profile. In all, a sample can be analysed in a matter of seconds.

In this study, semen was successfully detected on various materials, such as fabric and condoms, mimicking the kind of environments the body fluid could be encountered during a sexual assault investigation and, crucially, showing the ability of the technique to work with different surfaces. Whereas presumptive tests for semen are focused on the presence of one chemical, making them prone to “false positives”, this new technique harnesses a suite of chemicals, allowing a more confident identification of semen. It was also shown that semen could still be detected after 40 days of ageing. This is important as during a criminal investigation it may be days, weeks or even longer before evidence is seized and analysed. After 40 days, the chemical profile was remarkably unchanged, indicating that even older semen could potentially be identified.

The study then took this technique one step further, applying it to the analysis of condoms. As criminals become more knowledgeable about forensic evidence such as DNA, there has been an increase in the use of condoms by criminals to protect their identity. By analysing the surface of different brands and types of condom, it was demonstrated that unique chemical profiles were associated with the different condoms, with notable chemicals relating to the condom’s material or flavouring being detected. This has two major implications. Firstly, the ability to detect lubricants and traces from condoms could prove beneficial in confirming condom use, particularly important when biological evidence is lacking. Furthermore, the unique chemical profiles could even open up the possibility of indicating what type of condom was used by the offender, offering more information to the investigation.

Direct analysis techniques such as this have great potential to speed up forensic investigations, but it will no doubt be years before such technology is considered for adoption by police forces.

 

Rankin-Turner et al. Using mass spectrometry to transform the assessment of sexual assault evidence. Forensic Chemistry, 2020, DOI: 10.1016/j.forc.2020.100262

If you don’t have a subscription to Forensic Chemistry, see the 50-day free access link or get in touch with the authors.

Maggot Analysis with Mass Spectrometry
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Maggot Analysis with Mass Spectrometry

A new proof-of-concept study by researchers at the University at Albany in New York has developed a mass spectrometry-based technique for the rapid species prediction of blow fly larvae for use in forensic investigations.

Entomological evidence (evidence relating to insects) has proven invaluable to forensic investigations for decades, particularly in the estimation of time since death. Insects which feed on decomposing remains, known as necrophagous insects, will colonise a body in a reasonably predictable pattern, with different insects arriving at different stages throughout the decomposition process. Different species of flies, beetles and mites are commonly encountered. Blow flies in particular will often arrive at the scene within minutes of death to lay eggs on the body. As these eggs hatch, larvae (or maggots) emerge to feed on the decomposing remains. By studying the type and age of insects present at a scene, it may be possible to estimate the time since death, or postmortem interval.

The ability to achieve this hinges on the correct identification of insect species, which is unfortunately not always straightforward. The larvae of different species of blow fly are visually very similar, thus difficult to distinguish by eye. For this reason, maggots are often reared to maturity for species identification, with adult blow flies exhibiting more distinguishing physical differences. Inevitably the rearing of maggots to adulthood is a time-consuming process that requires the expertise of a forensic entomologist.

In recent years, researchers have tried to develop more rapid approaches to insect species identification, particularly using chemical analysis. Researchers at the University at Albany in New York have been applying direct analysis in real time mass spectrometry (DART-MS) to the analysis of insect evidence to provide a rapid species identification tool. In DART-MS, the sample is placed between the DART ion source and the inlet of the mass spectrometer, allowing chemical components in the sample to be ionised and drawn into the MS for direct analysis. DART-MS requires minimal or no sample preparation and results can be obtained almost instantly. Using this technique, Rabi Musah and her team have already demonstrated the ability to determine the species of larvae, pupae and adult flies, highlighting a promising new tool in rapid species identification in forensic entomology.

However, until now this research has focused on the analysis of individual species. In a real-world scenario, maggots present on the body may consist of multiple different species, therefore any techniques developed for rapid species identification of larvae must be able to work with mixed samples. In a recent study, the team have taken the method one step further by examining the potential to identify larvae from mixed species.

Blow flies of various species were collected from Manhattan, New York. Maggots were submerged in 70% ethanol and the solution exposed to the ion source of the DART-MS to produce chemical signatures of both individual species and combinations of species. Mixtures of two, three, four, fix and six different species were analysed. Using the chemical profiles produced, a predictive model was constructed for the subsequent identification of unknown insect samples. Using this model, maggot species could be established with an accuracy of up to 94% and a confidence interval of 80-95%. Individual insect species are readily differentiated, with different species producing distinct chemical profiles. Similarly, mixtures of two different species could also be differentiated. As might be expected, samples containing a higher number of species were more difficult to differentiate.

Although only a proof-of-concept study and further validation is required, the study demonstrates that DART-MS could offer a way of rapidly determining the species of blowfly larvae, thus allowing investigators to establish which insects are present at the scene of a death and work out postmortem interval faster.

 

Beyramysoltan, S. Ventura, M. I. Rosati, J. Y. Giffen, J. E. Musah, R. A. Identification of the Species Constituents of Maggot Populations Feeding on Decomposing Remains—Facilitation of the Determination of Post Mortem Interval and Time Since Tissue Infestation through Application of Machine Learning and Direct Analysis in Real Time-Mass Spectrometry. Analytical Chem, 2020, In Press. 

Fingerprint Drug Testing to Detect Drug Use or Contact
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Fingerprint Drug Testing to Detect Drug Use or Contact

The detection and identification of drugs to demonstrate the use of illicit substances has long since been achieved through the collection and analysis of bodily fluids such as urine or blood. However with the inconvenience and invasiveness of collecting bodily fluids from people combined with the risks associated with handling biological fluids, scientists have examined alternative matrices for the detection of drug abuse.

In recent years researchers have demonstrated the possibility of detecting drugs in a less invasive manner, using only a fingerprint. In a recent study published in the Journal of Analytical Toxicology, researchers at the University of Surrey have developed a mass spectrometry-based technique to not only detect illicit drugs in fingerprints, but also differentiate between drug use and drug contact.

Fingerprints were collected from recent drug users undergoing treatment at a drug rehabilitation centre, specifically those who had taken heroin or cocaine in the last 24 hours. Fingerprints were collected both before and after thorough handwashing, with the aim of establishing whether drugs could be detected from both the surface of the hands but also in sweat excreted by the participants. Fingerprint samples were also collected from non-drug users who had simply handled heroin to further establish the detectable differences between those who have used or handled drugs. The fingerprints collected were analysed by liquid chromatography-high resolution mass spectrometry, with a focus on both the drugs and their metabolites (for instance 6-monoacetylmorphine, a compound formed in the body following heroin use).

The experiment successfully detected heroin or its metabolites in every scenario, even if an individual had washed their hands prior to fingerprint collection. However in some instances, the process of hand-washing removed all detectable traces of the drugs, such as in the case of morphine, acetylcodeine and noscapine. Importantly, the technique was able to distinguish between those who had handled illicit drugs and those who had actually taken them, due to the presence of metabolites only formed in the body following drug use. Furthermore, the research demonstrated that it was also possible to detect heroin in the fingerprints of someone who had simply shaken hands with another person who had handled heroin. This highlights an essential factor should such techniques ever become operational in the detection of drug use, stressing the importance of handwashing prior to fingerprint collection to ensure any drugs detected are the result of drug use rather than inadvertent contact with illicit drugs.

The ability to detect drugs in fingerprint could aid legal investigations in a number of ways. Firstly, by demonstrating drug use in known individuals through the analysis of their fingerprints. And secondly, by analysing fingerprints recovered from crime scenes to indicate a person of interest has recently used or handled illicit drugs, potentially guiding police investigations. The full study was published in the Journal of Analytical Toxicology.

 

Catia Costa, Mahado Ismail, Derek Stevenson, Brian Gibson, Roger Webb, Melanie Bailey, Distinguishing between Contact and Administration of Heroin from a Single Fingerprint using High Resolution Mass Spectrometry, Journal of Analytical Toxicology. https://doi.org/10.1093/jat/bkz088

Rapid & Safer Drug Testing with Mass Spectrometry
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Rapid & Safer Drug Testing with Mass Spectrometry

Scientists have demonstrated a new method that allows police to quickly predict the contents of suspected drugs packages using Direct Analysis in Real Time mass spectrometry.

When faced with a suspected illicit drug, police officers will not know the identity or potency of the substance. Investigators will often perform something called a presumptive test to indicate what kind of drug they are dealing with. These tests typically involve scooping up a small amount of the material and adding a few drops of a specific chemical reagent to the sample. If the drug is present, a chemical reaction will occur resulting in a distinctive colour change to indicate a positive result.

Unfortunately, these tests can be somewhat hazardous, necessitating both the potential exposure to harmful substances in order to sample the drug, as well as the use of chemicals in the field. This has become particularly problematic in recent years as more uncharacterised and potentially harmful illicit drugs have hit the market. For instance, recent news reports have seen first responders complain of exposure to the drug fentanyl, a particularly potent opioid harmful even in small quantities.

In light of this, the need for rapid, reliable and safe drug screening techniques is greater than ever before.

Researchers at the National Institute of Standards and Technology (NIST) have teamed up with Maryland State Police and Vermont Forensic Laboratory to develop a method of quickly predicting the contents of a suspicious package without the need to handle the contents. We’ve all seen how airport staff check luggage for traces of explosives. They swipe an absorbent material over the surface of the bag, introduce that swab to an analyser, and receive a rapid alert to the presence of specific controlled substances. This new method essentially follows the same process. Upon discovering a package suspected of containing illicit drugs, the investigator simply swipes an absorbent wipe across the surface of the package, and that swab is then exposed to the mass spectrometer.

The new method utilises Direct Analysis in Real Time mass spectrometry (DART-MS) analysis. DART-MS is a form of ambient ionisation mass spectrometry in which the sample is placed between the DART ion source and the inlet of the mass spectrometer, allowing chemical components in the sample to be ionised and drawn into the mass spectrometer for rapid analysis. The major advantage of this technique is that it requires no form of sample preparation, so the sample itself (or in this case a swab of the sample) can be analysed directly for almost instantaneous results. You can read more about how DART works here.

In a study recently published in the journal Forensic Science International, the technique was applied to almost 200 suspicious packages, including plastic baggies, pill bottles, envelopes, and tin foil bags. From these samples, a range of illicit substances were detected, including fentanyl, cocaine, heroin, methamphetamine and synthetic cannabinoids. Also detected on a couple of the packages was carfentanil, a particularly powerful opioid thousands of times more potent than heroin and a great concern for first responders. It was shown that only a few micrograms of drug on the outside of the packages could be detected. The study has successfully demonstrated the possibility of rapidly screening for the presence of harmful drugs such as fentanyl, even when mixed with other substances like heroin. In fact, the contents of the packages were successfully predicted 92% of the time.

This new technique enables police officers to rapidly screen suspicious bags and packages for the presence of illicit drugs, whilst reducing the risk of exposure to harmful substances. By quickly and safely predicting the contents of a package, steps can then be taken to ensure the evidence is processed under appropriate conditions, for instance in a laboratory fume hood and with appropriate protective equipment. Although a complete analysis by standardised laboratory methods would still be required for legal purposes, this new technique at least allows for the rapid, and safe screening of suspected drugs.

 

Sisco, E. Robinson, E. L. Burns, A. Mead, R. What’s in the Bag? Analysis of Exterior Drug Packaging by TD-DART-MS to Predict the Contents. For. Sci. Int., 2019, In Press.

 

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The Smell of Death: Confirming Decomposition using Volatiles in the Air

Odour mortis, or the ‘smell of death’, refers to the chemicals released from the body during decomposition. Renowned forensic anthropologist Arpad Vass, who has studied the chemical changes occurring in the body after death for many years, recently shared the details of a particularly interesting scenario. The article, published in the May 2019 issue of Forensic Science International, details a fascinating case in which the occurrence of human decomposition was demonstrated based solely on chemical compounds in the air for the first time, without any human remains actually being found at the scene. The article doesn’t specify suspect or victim details, but anyone familiar with the case will recognise it instantly.

First, a brief introduction. In 2008, a woman was charged with the murder of her daughter, allegedly storing the victim’s body in the boot of her car for several days before disposing of the remains and dumping the car. Police had initially been alerted to the incident by the suspect’s parents, who had picked up their daughter’s abandoned car and noticed a foul decomposition-like odour coming from the vehicle. Coupled with the fact they had not seen their granddaughter in several weeks, the suspect’s mother promptly called 911.

The police soon took possession of the car and agreed that the scent of decomposition was emanating from the vehicle. Numerous cadaver dogs, specifically trained to detect odours from decaying bodies, alerted to the back of the car, further suggesting some kind of decomposing remains had been stored in the boot of the car. Fly pupae were also discovered. Entomological evidence is frequently associated with decomposing human remains, with flies and various other insects known to visit corpses to feed or lay eggs. Although no human remains were found in the car, several weeks later the body of the missing girl was found in a wooded area near the suspect’s home, and the case promptly turned into a murder investigation, with the victim’s mother as the prime suspect. However with minimal physical evidence linking the body to the suspect’s car, law enforcement turned to a somewhat unconventional tool to aid their investigation.

Various pieces of evidence were recovered from the vehicle, including segments of carpet, scrapings from the tyre wells, and various pieces of rubbish found in the car. Interestingly, investigators also collected some air samples from the boot of the car. Air can be sampled from remote locations using a technique that utilises air pumps to draw in gaseous analytes from the environment and capture them in a sorbent trap. This collection of trapped compounds can then be transported to a laboratory for analysis. In this case, about 35L of air was collected from the vehicle into a type of sorbent tube, then analysed using gas chromatography/mass spectrometry (GC/MS). GC/MS is a well-established analytical technique, allowing scientists to separate the individual chemicals in a mixture and identify those components. You can read more about how mass spectrometry works here.

This process allowed researchers to figure out exactly which volatile chemicals were present in the suspect’s vehicle and establish whether these are everyday compounds likely to be found in a car, or if they had some other source.

In the years leading up to this case a great deal of research had been conducted at the University of Tennessee’s Anthropological Research Facility. At this facility researchers were investigating, among other things, the odours produced during the decomposition of a human body. The odours created during this process are the result of volatile compounds produced as the body decomposes, and research has demonstrated that hundreds of individual chemical components are formed during this complex process. As part of research at the university, researchers had constructed a vast database of hundreds of chemicals detected during the process of human decomposition, including the different decomposition stages at which those chemicals appear. By comparing the chemicals detected in the vehicle with those stored in the database, it was possible to identify compounds known to be produced during the decomposition process. There was an 80% match between the compounds detected in the boot of the car and those chemicals considered to be relevant to human decomposition. Furthermore, unusually high levels of chloroform were also detected in the boot of the car.

The results from the air samples collected and chemical extracts from various other artefacts in the car led the researcher to conclude that there was a very high likelihood of a decomposition event occurring in the boot of the car. Many of the compounds detected in the vehicle could only be logically explained by the presence of decomposing remains.

Despite these findings (and various other pieces of evidence presented in court), the jury reached a verdict of not guilty for the charge of murder. Not too surprising an outcome, considering the use of air analysis to detect decomposition had not previously been used in a legal investigation. However in closing arguments, the defence stated that the victim had in fact been placed in the vehicle for transport (claiming the victim’s death had been accidental), ultimately confirming the results of the analysis.

 

Vass, A. A. Death is in the air: confirmation of decomposition without a corpse. Forensic Sci. Int. (2019). doi:10.1016/j.forsciint.2019.05.005

Vass, A. A. Odor mortis. Forensic Sci. Int. 222, 234–241 (2012).

 

Detecting Homemade Bombs & Explosives in Sweat
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Detecting Homemade Bombs & Explosives in Sweat

Improvised explosive devices (IEDs) are often used in the implementation of terrorist attacks, for instance the 2005 London underground bombings, the suicide bomb attack during a concert in Manchester, and the 2015 Paris attacks. Unfortunately the components required for building these devices are commercially available and the bombs relatively easy to construct.

Many explosives leave a characteristic trace after being handled or detonated, and it is essential that investigators can rapidly identify the components used in homemade explosives. Furthermore, the ability to trace the explosives back to particular individuals and terrorist cells is essential in preventing future attacks. Unfortunately effectively detecting and tracing explosives and explosive precursors can prove difficult. On top of this, after the production and implementation of IEDs, it can be difficult to prove a suspects’ involvement in bomb construction.

Researchers at King’s College London and Northumbria University have been working on developing new ways to detect homemade explosives.

The newly developed approach, recently published in the journal Analytica Chimica Acta, uses a technique known as ion chromatography high resolution mass spectrometry (IC-HRMS) to separate and detect chemical components. By applying the technique to compounds commonly encountered in the analysis of explosive residues, the method was shown to be effective in detecting a large number of components used to make bombs, capable of detecting just trace amounts of the chemicals faster than previous techniques.

Upon developing this method, the team of researchers then demonstrated that the approach could be applied to the analysis of human sweat, with the aim of indicating an individual has recently handled explosives. Participants were made to handle Pyrodex powder, a black powder propellant used in firearm cartridges. After handling the powder for a few minutes, palm sweat and fingermark samples were then collected at numerous timepoints over several hours. Analytes related to the explosive material were readily detected using the method. The real-world implementation of this technique could help prove contact between a suspect and explosive material or explosive precursors.

 

Gallidabino et al. Targeted and non-targeted forensic profiling of black powder substitutes and gunshot residue using gradient ion chromatography – high resolution mass spectrometry (IC-HRMS). Analytica chimica acta. 2019, In Press.

Developing Fingerprints on Metals to Aid Knife & Gun Crime Investigations
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Developing Fingerprints on Metals to Aid Knife & Gun Crime Investigations

Fingerprints are something of a staple in forensic science. For over 100 years we have used the unique details of fingerprints to identify victims and suspects, and draw connections between people and objects to place suspects at crime scenes. Fingermarks are encountered on all kinds of surfaces that can have an effect on how easy it is to visualise the mark and for how long the mark persists. As a result, the market is flooded with products for developing fingerprints, from powders to glues to chemical reagents.

Despite the options available, some surfaces, for instance metals, still prove somewhat tricky when it comes to developing prints. This is due to various factors, such as how the chemical results in the fingermark and developing reagents may react with the surface. This is obviously problematic when trying to obtain fingerprints from knives and firearms, a matter of particular importance right now worldwide. For years researchers have been examining methods of improving the detection of fingerprints on metals, including metal vapour deposition and different chemical reagents, but reliable techniques are still few and far between.

Researchers at the University of Nottingham and University of Derby in the UK are using analytical chemistry to solve this problem. Using a technique called Time-of-Flight Secondary Ion Mass Spectrometry, or ToF-SIMS, researchers have developed a way of producing images of fingerprints of various metal surfaces. ToF-SIMS utilises an ion beam which is passed along the surface of the sample, causing ions (charged chemical components) to be emitted from the sample. These are then analysed by mass spectrometry and the results used to produce a kind of map of the surface.

Researchers deposited fingermarks on various types of commonly-encountered metals, such as stainless steel and aluminium, and studied the effects of time on the ability to visualise the prints. Cyanoacrylate (or superglue) fuming, a traditional technique particularly popular when analysing metal surfaces, proved to be unreliable, with the print’s quality degrading rapidly or disappearing completely in just a matter of days. However using this new mass spectrometry-based approach, fingermarks could be visualised in samples up to 26 days old, a vast improvement on traditional methods.

The high-resolution images produced sufficient detail to not only observe ridge detail in the marks, but even the shape and position of individual sweat pores. Furthermore, and perhaps most importantly in a forensic context, the technique is non-destructive. Current methods of visualising fingerprints tend to involve adding a powder or chemical to the print, inevitably altering and potentially contaminating it. But the use of ToF-SIMS ensures the print remains intact, so further development or analysis techniques can be employed if required.

By enabling the visualisation of fingerprints that previous techniques may have failed to reveal, this method has the potential to not only aid investigators as they face the ongoing rise of knife and gun crime, but could also be applied to cold cases. However it is important to note that fingermarks deposited as part of research are not always indicative of real-world samples. In reality the fingerprints we leave behind can vary greatly in the amount of material deposited and the type of material being left behind. Traces of anything handled can be deposited in the fingermark, adding many potential variables to the real-world applicability of this kind of work. Despite this, the study demonstrates a promising new technique for the development of fingermarks on metals, which could have great implications in the investigation of violent gun and knife crimes.

 

Thandauthapani et al. Exposing latent fingermarks on problematic metal surfaces using time of flight secondary ion mass spectroscopy. Science & Justice. 2018, 58(6).

Tracking Movements with Fingernails
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Tracking Movements with Fingernails

When human remains are discovered, investigators will often turn to routine methods such as fingerprinting, DNA profiling and the use of dental records to identify the individual. But in the absence of database records for comparison, such traditional techniques may not prove all that useful, and forensic scientists must look for new ways to identify the unknown.

In recent years the use of stable isotope analysis has aided forensic investigations, particularly in establishing the geographic origin of unidentified human remains. Isotopes are different forms of an element. For example, oxygen has three naturally occurring stable isotopes: O16, O17 and O18.  These isotopes are incorporated into substances in the environment (such as water) in varying ratios. The relative abundance of isotopes can be influenced by various factors in a process known as isotopic fractionation. It has been found that isotopic ratios can be related to different regions of the world. For example, the tap water in one country may have a completely different isotopic signature in comparison to water in another country. How does this relate to the isotopes found in our bodies? Well, you are what you eat. As you consume food and water from a particular area, the atoms in our bodies express abundances similar to the food and water consumed.

This provides the basis for using isotope analysis to trace materials back to a certain geographic region. It has already been demonstrated that the isotopic analysis of bones, teeth and other bodily tissues can allow for individuals to be traced to particular locations, typically through the analysis of oxygen, hydrogen and sulphur isotopes. However last year, researchers at the University of Utah took a different approach, this time focusing on fingernails.

As with bones and teeth, the isotopic content of our fingernails will be affected by factors such as the food and water we consume. As fingernails are estimated to grow at a rate of 3-4mm per month, they are a prime target for studying isotopic patterns in an individual over a shorter timespan (less than six months as oppose to years). This is by no means the first study of isotope abundances in fingernails, but previous research has typically focussed on single timepoints rather than tracking the same individuals over time. As global travel becomes more commonplace, it is increasingly likely that human remains could have originated from any part of the world. Therefore, we need to understand how travel can cause changes in isotope abundances within the body.

This study aimed to establish whether fingernail isotope ratios were different in a group of local people in comparison to non-locals who had recently moved to the area (in this case Salt Lake City in the United States). Over a period of a year, fingernail clippings were collected at multiple timepoints from a group of volunteers, about half of which were local residents and the rest individuals who had recently arrived from various locations across the US and the world. The fingernail clippings were cleaned (to remove surface components and contaminants that could interfere with the analysis) and subjected to analysis by isotope ratio mass spectrometry (IRMS). IRMS is a particular type of mass spectrometry that allows us to measure the isotopic abundance of certain elements typically hydrogen, carbon, nitrogen, and oxygen. You can read more about IRMS here.

The isotope values of samples from residents were used to construct a baseline of expected values for the area, with isotope values from non-residents’ samples being compared with these. Initially, samples from non-residents showed a wide range of isotopic values, which is to be expected given they had only recently moved to the area. Some residents did fall within the expected range of locals, but these participants had moved from relatively nearby locations, which could explain the similar relative isotopic abundances. However after about 3 months, the fingernail isotopic patterns shifted until the non-residents could no longer be distinguished from the residents. This indicates that although the relative abundance of isotopes in our fingernails can shed some light on geographical movement, it can only provide information relating to the past few months. Inevitably there will always be a certain amount of error associated with such analyses, with variation from the likes of short-term travel and random dietary changes being impossible to account for.

 

Mancuso, C. J, Ehleringer, J. R. Resident and Nonresident Fingernail Isotopes Reveal Diet and Travel Patterns. Journal of Forensic Sciences. 2019, 64(1).

 

Tracking Illicit Drugs with Strontium Isotope Analysis
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Tracking Illicit Drugs with Strontium Isotope Analysis

The manufacture and distribution of illicit drugs such as heroin is a primary focus of many major law enforcement organisations worldwide, including the Drug Enforcement Agency (DEA) in the United States and the National Crime Agency (NCA) in the United Kingdom. Unfortunately, as drug shipments pass hands between dealers and cross borders so rapidly, it can be difficult if not impossible to trace a batch of drugs back to an initial manufacturer. As a result of this, the chances of locating and arresting the manufacturers of illicit drugs can be slim.

To a forensic drugs analyst, a whole range of characteristics can be examined and used to classify and compare different batches of the same drug, including physical appearance, packaging, and chemical composition. To an extent, heroin chemical signatures are already beneficial in comparing different batches of the drug in attempts to establish links and possible sources of the narcotics. This may be based on agents or adulterants a product has been cut with, and the relative concentrations of those substances. The manufacturing process itself can vary in terms of chemicals and apparatus used and the skills of the manufacturer, resulting in further characteristic differences in the chemical profile. However these differences may not be distinct enough to be valuable and are certainly not able to pinpoint the country from which a batch originated. Though there is still no reliable method of tracing an illicit drug back to a particular location, ongoing research is aiming to change this.

One method of studying the history and even origin of a sample is to use isotopic composition. Isotopes are different forms of elements that are incorporated into substances in the environment in varying ratios and abundances, influenced by a number of factors that can alter these ratios. These processes can be described as isotopic fractionation. Interestingly, isotopic ratios can be characteristic to different regions of the world, enabling certain materials to be traced back to the geographic region based on the ratios of particular isotopes contained within that material. With this in mind, they have often been used to trace unidentified human remains to a particular location or study the origin of food products. Focusing on isotopes allows for heroin samples to be studied and compared based on regional characteristics as oppose to the variation caused by the production process.

For the first time, researchers at Florida International University have utilised strontium isotope ratio analysis to determine the provenance of illicit heroin samples. 186 unadulterated, undiluted heroin samples of known origin were obtained from a number of geographic regions including Southeast Asia, Southwest Asia, South America, and Mexico. Of a particularly challenging nature is South American heroin and SA-like Mexican heroin, which can be extremely difficult to differentiate based on their chemical compositions alone. Heroin samples were dissolved via a microwave-assisted acid digestion method before being subjected to a technique known as a multi-collector inductively-coupled plasma mass spectrometry (MC-ICP-MS). This instrument utilises an inductively coupled plasma ion source to ionise target analytes, which are then separated and analysed by the mass spectrometer. The use of MC-ICP-MS allows for the strontium concentration of particular samples to be determined. The strontium isotope ratio (87Sr/86Sr) value of each individual sample was then compared with the overall mean values of ratios from different regions in order to establish the likely origin of that particular heroin sample. Samples from the same geographic region would be expected to exhibit a similar isotope ratio.

icpms

Multi-collector inductively-coupled plasma mass spectrometer (MC-ICP-MS) Source: www.thermofisher.com

The results demonstrated the possibility of differentiating between heroin of different geographic origin. South American and Mexican heroin samples were correctly classified 82% and 77% of the time respectively. South East and South West Asian heroin samples were somewhat more difficult to differentiate due to more of an overlap between strontium isotope ratio values. SE Asian samples were correctly classified 63% of the time and SW Asian samples only 56% of the time. It is not clear whether this elemental strontium is endogenous or the result of external contamination, but either way it is sufficiently characteristic to be associated with a particular geographic location.

The strontium isotope composition of heroin can be affected by a number of factors, including the soil in which components are grown and groundwater in the area, which can result in region-specific isotope compositions. The use of strontium isotope ratio analysis has presented promising results in the origin determination of illicit heroin. Although a larger scale study incorporating samples of a more worldwide origin would be ideal, initial results suggest that this technique could allow for an unknown illicit drug sample to be traced back to a country of origin, aiding criminal intelligence agencies in the war against drugs.

 

Debord, J., Pourmand, A., Jantzi, S., Panicker, S. & Almirall, J. Profiling of Heroin and Assignment of Provenance by 87Sr/86Sr Isotope Ratio Analysis. Inorg Chim Acta. In press (2017).