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1.
Environ Sci Technol ; 56(10): 6391-6398, 2022 05 17.
Artigo em Inglês | MEDLINE | ID: mdl-35420785

RESUMO

Passive sampling devices (PSDs) offer key benefits for monitoring chemical water quality, but the uptake process of PSDs for hydrophilic compounds still needs to be better understood. Determining mass transfer coefficients of the water boundary layer (kw) during calibration experiments and in situ monitoring would contribute toward achieving this; it allows for combining calibration data obtained at different temperature and hydrodynamic conditions and facilitate the translation of laboratory-derived calibration data to field exposure. This study compared two kw measurement methods applied to extraction disk housings (Chemcatcher), namely, alabaster dissolution and dissipation of performance reference compounds (PRCs) from silicone. Alabaster- and PRC-based kw were measured at four flow velocities (5-40 cm s-1) and two temperatures (11 and 20 °C) in a channel system. Data were compared using a relationship based on Sherwood, Reynolds, and Schmidt numbers. Good agreement was observed between data obtained at both temperatures, and for the two methods. Data were well explained by a model for mass transfer to a flat plate under laminar flow. It was slightly adapted to provide a semi-empirical model accounting for the effects of housing design on hydrodynamics. The use of PRC-spiked silicone to obtain in situ integrative kw for Chemcatcher-type PSDs is also discussed.


Assuntos
Monitoramento Ambiental , Poluentes Químicos da Água , Sulfato de Cálcio , Calibragem , Monitoramento Ambiental/métodos , Hidrodinâmica , Silicones , Poluentes Químicos da Água/química
2.
Anal Bioanal Chem ; 414(17): 4987-4998, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35608670

RESUMO

Headspace solid-phase micro-extraction (SPME) is a promising technique for the characterisation and profiling of gunshot exhausts in spent cartridge casings, especially for health and environmental risk assessments, as well as forensic purposes. To date, however, no comprehensive investigation has been carried out to objectively assess the kinds of compound released during a discharge that can be recovered by this approach, the selectivity of the main commercially available fibres, and their relative performances for the analysis of gunshot exhausts and the discrimination of different ammunition types. This study aimed to fill this gap. Gunshot exhausts in spent cartridge casings from four different ammunition types were analysed by GC-MS, after extraction with four different commercial fibres: 100 µm polydimethylsiloxane (PDMS), 85 µm polyacrylate (PA), 65 µm polydimethylsiloxane/divinylbenzene (DVB), and 85 µm carboxen/polydimethylsiloxane (CAR). Results showed that, overall, a total of 120 analytes could be observed across the cartridges, but the different tested fibres also displayed distinct performances, which were, to some extent, complementary for the characterisation of gunshot exhausts. DVB, in particular, recovered the most compounds simultaneously. On the other hand, the observed variability between measurements was also high, making it a poor candidate for (semi-)quantitative applications (e.g. estimation of time since discharge and/or source profiling). In this regard, PA demonstrated the highest potential for broad use and implementation in multi-purpose methods.


Assuntos
Dimetilpolisiloxanos , Microextração em Fase Sólida , Cromatografia Gasosa-Espectrometria de Massas/métodos , Microextração em Fase Sólida/métodos
3.
Analyst ; 145(13): 4698, 2020 07 07.
Artigo em Inglês | MEDLINE | ID: mdl-32432581

RESUMO

Correction for 'Changes in latent fingermark glyceride composition as a function of sample age using UPLC-IMS-QToF-MSE' by Amanda A. Frick, et al., Analyst, 2020, DOI: .

4.
Analyst ; 145(12): 4212-4223, 2020 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-32393937

RESUMO

The composition of fingermark residue has been an important topic in forensic science, mainly in efforts to better understand and eventually improve the efficacy of latent fingermark detection methods. While the lipid fraction has been extensively studied, there is currently little information about how the glyceride fraction of latent fingermarks is chemically altered over time following deposition. A previously reported untargeted ultra performance liquid chromatography-ion mobility spectrometry-quadrupole time-of-flight mass spectrometry (UPLC-IMS-QToF-MSE) method was used to investigate changes over time in fingermark di- and triglycerides. Charged latent fingermark samples from 5 donors were analysed up to 28 days following deposition. Significant changes in glyceride composition occurred with increased sample age, attributed primarily to the oxidation of unsaturated triglycerides through ozonolysis. Considerably fewer unsaturated TGs were identified in samples 7 and 28 days following deposition, while mono- and diozonides of these lipids were identified as major components of aged samples. Additional compounds were identified as possible aldehyde and carboxylic acid derivatives resulting from the reaction of water with ozonolysis intermediates. While the onset of these processes occurred rapidly following deposition, continuing oxidation over time was seen via the progressive ozonolysis of diunsaturated triglycerides. These results represent a further step towards understanding the factors affecting fingermark composition, ageing and subsequent detection under operational conditions.


Assuntos
Dermatoglifia , Diglicerídeos/análise , Triglicerídeos/análise , Adulto , Cromatografia Líquida de Alta Pressão/métodos , Diglicerídeos/química , Ácidos Graxos Insaturados/química , Humanos , Espectrometria de Massas/métodos , Oxirredução , Ozônio/química , Fatores de Tempo , Triglicerídeos/química
5.
Analyst ; 144(11): 3590-3600, 2019 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-31065642

RESUMO

More detailed fundamental information is required about latent fingermark composition in order to better understand fingermark properties and their impact on detection efficiency, and the physical and chemical changes that occur with time following deposition. The composition of the glyceride fraction of latent fingermark lipids in particular is relatively under-investigated due in part to their high structural variability and the limitations of the analytical methods most frequently utilised to investigate fingermark composition. Here, we present an ultra performance liquid chromatography-ion mobility spectroscopy-quadrupole time-of-flight mass spectrometry (UPLC-IMS-QToF-MSE) method to characterise glycerides in charged latent fingermarks using data-independent acquisition. Di- and triglycerides were identified in fingermark samples from a population of 10 donors, through a combination of in silico fragmentation and monitoring for fatty acid neutral losses. 23 diglycerides and 85 families of triglycerides were identified, with significant diversity in chain length and unsaturation. 21 of the most abundant triglyceride families were found to be common to most or all donors, presenting potential targets for further studies to monitor chemical and physical changes in latent fingermarks over time. Differences in relative peak intensities may be indicative of inter- and intra-donor variability. While this study represents a promising step to obtaining more in-depth information about fingermark composition, it also highlights the complex nature of these traces.


Assuntos
Dermatoglifia , Diglicerídeos/análise , Triglicerídeos/análise , Adulto , Cromatografia Líquida de Alta Pressão/métodos , Diglicerídeos/química , Feminino , Humanos , Masculino , Espectrometria de Massas/métodos , Triglicerídeos/química , Adulto Jovem
6.
Analyst ; 144(4): 1128-1139, 2019 Feb 11.
Artigo em Inglês | MEDLINE | ID: mdl-30474092

RESUMO

Evidence association in forensic cases involving gunshot residue (GSR) remains very challenging. Herein, a new in silico approach, called quantitative profile-profile relationship (QPPR) modelling, is reported. This is based on the application of modern machine learning techniques to predict the pre-discharge chemical profiles of selected ammunition components from those of the respective post-discharge GSR. The obtained profiles can then be compared with one another and/or with other measured profiles to make evidential links during forensic investigations. In particular, the approach was optimised and successfully tested for the prediction of GC-MS profiles of smokeless powders (SLPs) from organic GSR in spent cases, for nine ammunition types. Results showed a high degree of similarity between predicted and experimentally measured profiles, after adequate combination and evaluation of fourteen machine learning techniques (median correlation of 0.982). Areas under the curve (AUCs) of 0.976 and 0.824 were observed after receiver operating characteristic (ROC) analysis of the results obtained in the comparisons between predicted-predicted and predicted-measured profiles, respectively, in the specific case that the ammunition types of interest were excluded from the training dataset (i.e., extrapolation). Furthermore, AUCs of 0.962 and 0.894 were observed in interpolation mode. These values were close to those of the comparison of the measured SLP profiles between themselves (AUC = 0.998), demonstrating excellent potential to correctly associate evidence in a number of different forensic scenarios. This work represents the first time that a quantitative approach has successfully been applied to associate a GSR to a specific ammunition.

7.
Sci Justice ; 59(1): 58-66, 2019 01.
Artigo em Inglês | MEDLINE | ID: mdl-30654969

RESUMO

The present study aimed at providing data to assess the secondary transfer of organic gunshot residues (OGSR). Three scenarios were evaluated in controlled conditions, namely displacing a firearm from point A to point B, a simple handshake and an arrest involving handcuffing on the ground. Specimens were collected from the firearm, the hands of the shooter and the non-shooter undergoing the secondary transfer in order to compare the amounts detected. Secondary transfer was observed for the three scenarios, but to a different extent. It was found that displacing a firearm resulted in secondary transfer in <50% of the experiments. The firearm also had an influence, as contrary to the pistol, no secondary OGSR were detected using the revolver. Shaking the hand of the shooter also transferred OGSR to the non-shooter's hand. In that case, the amount of OGSR was generally higher on the shooter than on the non-shooter. Finally, the largest secondary transfer was observed after the arrest with handcuffing with positive results in all cases using the pistol. In that scenario, the amounts on the shooter and the non-shooter were in the same range. This study highlights that the secondary transfer must be taken into account in the interpretation of OGSR. Indeed, an individual's hands might be contaminated by handling a firearm or having physical contact with a shooter.


Assuntos
Armas de Fogo , Balística Forense/métodos , Mãos , Manejo de Espécimes , Cromatografia Líquida de Alta Pressão , Humanos , Aplicação da Lei/métodos , Pele/química , Espectrometria de Massas por Ionização por Electrospray
8.
Sci Justice ; 58(1): 31-46, 2018 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-29332693

RESUMO

The development of an ink dating method requires an important investment of resources in order to step from the monitoring of ink ageing on paper to the determination of the actual age of a questioned ink entry. This article aimed at developing and evaluating the potential of three interpretation models to date ink entries in a legal perspective: (1) the threshold model comparing analytical results to tabulated values in order to determine the maximal possible age of an ink entry, (2) the trend tests that focusing on the "ageing status" of an ink entry, and (3) the likelihood ratio calculation comparing the probabilities to observe the results under at least two alternative hypotheses. This is the first report showing ink dating interpretation results on a ballpoint be ink reference population. In the first part of this paper three ageing parameters were selected as promising from the population of 25 ink entries aged during 4 to 304days: the quantity of phenoxyethanol (PE), the difference between the PE quantities contained in a naturally aged sample and an artificially aged sample (RNORM) and the solvent loss ratio (R%). In the current part, each model was tested using the three selected ageing parameters. Results showed that threshold definition remains a simple model easily applicable in practice, but that the risk of false positive cannot be completely avoided without reducing significantly the feasibility of the ink dating approaches. The trend tests from the literature showed unreliable results and an alternative had to be developed yielding encouraging results. The likelihood ratio calculation introduced a degree of certainty to the ink dating conclusion in comparison to the threshold approach. The proposed model remains quite simple to apply in practice, but should be further developed in order to yield reliable results in practice.

9.
Sci Justice ; 58(1): 17-30, 2018 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-29332691

RESUMO

The development of ink dating methods requires an important amount of work in order to be reliably applicable in practice. Major tasks include the definition of ageing parameters to monitor ink ageing. An adequate parameter should ideally fulfil the following criteria: it should evolve as a function of time in a monotonic way, be measurable in a majority of ink entries, be as accurate and reproducible as possible, and finally it should not be influenced too much by transfer and storage conditions. This work aimed at evaluating the potential of seven ageing parameters for ink dating purposes: the phenoxyethanol quantity, relative peak areas (RPA), three solvent loss ratios (R%, R%*, NR%) and two solvent loss parameters (RNORM, NRNORM). These were calculated over approximately one year for 25 inks selected from a large database to represent different ageing behaviours. Ink entries were analysed using liquid extraction followed by GC/MS analysis. Results showed that natural ageing parameters (NR% and NRNORM) were not suitable ageing parameters for ink entries older than a few weeks. RPA used other compounds present in ink formulations in combination to PE in order to normalise the results. However, it presented particular difficulties as they could not be defined for all inks and were thus applicable only for 64% of the studied inks. Finally, the PE quantity, R% and RNORM allowed to follow the ageing of the selected inks over the whole time frame and were identified as the most promising. These were thus selected to test three different interpretation models in the second part of this article. The possibilities and limitations of ink dating methods will be discussed in a legal perspective.

10.
Int J Legal Med ; 130(2): 475-88, 2016 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-25794687

RESUMO

Due to the rise of criminal, civil and administrative judicial situations involving people lacking valid identity documents, age estimation of living persons has become an important operational procedure for numerous forensic and medicolegal services worldwide. The chronological age of a given person is generally estimated from the observed degree of maturity of some selected physical attributes by means of statistical methods. However, their application in the forensic framework suffers from some conceptual and practical drawbacks, as recently claimed in the specialised literature. The aim of this paper is therefore to offer an alternative solution for overcoming these limits, by reiterating the utility of a probabilistic Bayesian approach for age estimation. This approach allows one to deal in a transparent way with the uncertainty surrounding the age estimation process and to produce all the relevant information in the form of posterior probability distribution about the chronological age of the person under investigation. Furthermore, this probability distribution can also be used for evaluating in a coherent way the possibility that the examined individual is younger or older than a given legal age threshold having a particular legal interest. The main novelty introduced by this work is the development of a probabilistic graphical model, i.e. a Bayesian network, for dealing with the problem at hand. The use of this kind of probabilistic tool can significantly facilitate the application of the proposed methodology: examples are presented based on data related to the ossification status of the medial clavicular epiphysis. The reliability and the advantages of this probabilistic tool are presented and discussed.


Assuntos
Determinação da Idade pelo Esqueleto , Determinação da Idade pelos Dentes , Funções Verossimilhança , Teorema de Bayes , Ciências Forenses , Humanos , Modelos Estatísticos
11.
Sci Justice ; 56(3): 165-180, 2016 May.
Artigo em Inglês | MEDLINE | ID: mdl-27162015

RESUMO

Despite the recurrence of fingermark dating issues and the research conducted on fingermark composition and aging, no dating methodology has yet been developed and validated. In order to further evaluate the possibility of developing dating methodologies based on the fingermark composition, this research proposed an in-depth study of the aging of target lipid parameters found in fingermark residue and exposed to different influence factors. The selected analytical technique was gas chromatography coupled with mass spectrometry (GC/MS). The effects of donor, substrate and enhancement techniques on the selected parameters were firstly evaluated. These factors were called known factors, as their value could be obtained in real caseworks. Using principal component analysis (PCA) and univariate exponential regression, this study highlighted the fact that the effects of these factors were larger than the aging effects, thus preventing the observation of relevant aging patterns. From a fingermark dating perspective, the specific value of these known factors should thus be included in aging models newly built for each case. Then, the effects of deposition moment, pressure, temperature and lighting were also evaluated. These factors were called unknown factors, as their specific value would never be precisely obtained in caseworks. Aging models should thus be particularly robust to their effects and for this reason, different chemometric tools were tested: PCA, univariate exponential regression and partial least square regression (PLSR). While the first two models allowed observing interesting aging patterns regardless of the value of the applied influence factors, PLSR gave poorer results, as large deviations were obtained. Finally, in order to evaluate the potential of such modelling in realistic situations, blind analyses were carried out on eight test fingermarks. The age of five of them was correctly estimated using soft independent modelling of class analogy analysis (SIMCA) based on PCA classes, univariate exponential linear regression and PLSR. Furthermore, a probabilistic approach using the calculation of likelihood ratios (LR) through the construction of a Bayesian network was also tested. While the age of all test fingermarks were correctly evaluated when the storage conditions were known, the results were not significant when these conditions were unknown. Thus, this model clearly highlighted the impact of storage conditions on correct age evaluation. This research showed that reproducible aging modelling could be obtained based on fingermark residue exposed to influence factors, as well as promising age estimations. However, the proposed models are still not applicable in practice. Further studies should be conducted concerning the impact of influence factors (in particular, storage conditions) in order to precisely evaluate in which conditions significant evaluations could be obtained. Furthermore, these models should be properly validated before any application in real caseworks could be envisaged.


Assuntos
Dermatoglifia , Lipídeos/análise , Adulto , Feminino , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Funções Verossimilhança , Modelos Lineares , Masculino , Pressão , Análise de Componente Principal , Propriedades de Superfície , Temperatura , Fatores de Tempo
12.
Anal Bioanal Chem ; 407(23): 7123-34, 2015 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-26168966

RESUMO

In forensic investigation of firearm-related cases, determination of the residual amount of volatile compounds remaining inside a cartridge could be useful in estimating the time since its discharge. Published approaches are based on following the decrease of selected target compounds as a function of time by using solid phase micro-extraction (SPME). Naphthalene as well as an unidentified decomposition product of nitrocellulose (referred to as "TEA2") are usually employed for this purpose. However, reliability can be brought into question given their high volatility and low reproducibility of the extracted procedure. In order to identify alternatives and therefore develop improved dating methods, an extensive study on the composition and variability of volatile residues in nine different types of cartridges was carried out. Analysis was performed using headspace sorptive extraction (HSSE), which is a more exhaustive technique compared to SPME. One hundred sixty six compounds were identified (several of which for the first time), and it was observed that the final compositional characteristics of each residue were strongly dependent on its source. Variability of single identified compounds within and between different types of cartridge as well as their evolution over time were also studied. Many explosion products containing up to four aromatic rings were found to be globally present in high proportions. Twenty-seven of them (excluding naphthalene) also presented detectable decreases during the first 24 h. Therefore, they could be used as complementary target analytes in future dating methods.


Assuntos
Substâncias Explosivas/análise , Substâncias Explosivas/química , Armas de Fogo , Balística Forense/métodos , Extração em Fase Sólida/métodos , Compostos Orgânicos Voláteis/análise , Adsorção , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Compostos Orgânicos Voláteis/química
13.
Sci Justice ; 64(5): 557-571, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39277338

RESUMO

During the investigation of firearm-related incidents, gunshot residues (GSR) can be collected on the scene and individuals (e.g., shooters or bystanders). Their analysis can give valuable information for the reconstruction of the events. Since GSR collection on persons of interest generally occurs a few minutes to hours after discharge, knowledge is needed to understand how organic (O), and inorganic (I) residues are transferred and persist. In this research, the quantities of OGSR and IGSR were assessed on the right and left hands, forearms, face, and nostrils of four shooters. Specimens were collected immediately before the discharge (shooter's blank specimens) and shortly after (30 min) using carbon adhesive stubs. Organic compounds were first extracted from the collection device and analysed using ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Subsequently, IGSR particles were detected on the same stub using scanning electron microscopy coupled with energy-dispersive X-ray spectrometry (SEM/EDS). Shooter's blank specimen analysis revealed background contamination of both O and IGSR in the shooter's environment, predominantly attributed to the presence of an indoor shooting range. However, the background quantities generally remained below the associated 30-minute specimen. Thirty minutes after a discharge, higher quantities were generally detected on the shooter's right and left hands than on other collection regions for both GSR types. Forearms and face emerged as interesting collection alternatives, especially in cases where a person of interest may have washed their hands in the interval between the discharge and collection. In contrast, very low amounts of GSR were detected in the nostrils. Furthermore, the results indicated that OGSR and IGSR have different transfer and persistence mechanisms.


Assuntos
Armas de Fogo , Balística Forense , Mãos , Humanos , Balística Forense/métodos , Face/anatomia & histologia , Microscopia Eletrônica de Varredura , Espectrometria por Raios X , Nariz , Antimônio/análise , Antebraço , Espectrometria de Massas em Tandem , Bário/análise , Ferimentos por Arma de Fogo , Cromatografia Líquida de Alta Pressão , Cicloexanonas
14.
Forensic Sci Int ; 360: 112020, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38781838

RESUMO

In this article, three main approaches to situate forensic traces in time were revisited under the prism of the Sydney Declaration and adapted to be applicable to a large range of physical and digital traces. The first approach is based on time tags which are time-based characteristics produced as the result of an activity at a specific time. They can either be directly related to time (i.e., time stamps) or indirectly (i.e., time indicators). While relatively straightforward, time tags require scientific knowledge to be correctly interpreted and to account for the risks of desynchronisation, anomalies and manipulation. The second approach is based on time dynamics and aim at measuring changes that occur as a function of time, such as caesium pulsation (i.e., on which international atomic time is based) or body cooling after death (i.e., from which time since death can be inferred). However, time dynamics phenomena are generally also influenced by other case-specific factors (e.g., environmental factors), and thus more difficult to reliably implement in practice. Finally, the third approach relies on relative sequences, using information unrelated to time, such as relative positions or dynamics of traces at the scene. As each approach has its potential and limitations, a combination of traces from different (both material and digital) sources and approaches is recommended to answer time questions in practice (When? How long? In which succession?) and enhance the reliability of the dating endeavours. It is strongly recommended to consider the principles of the Sydney Declaration when implementing or developing dating methods, as they point at potential issues that are often forgotten in forensic research and practice, such as uncertainties linked to the concept of trace, scene investigation, the asymmetry of time, the importance of context and the multiplicity of purposes. Future research should focus on improving the reliability of these dating approaches by combining and systematising their usage in investigative practice, as well as in broader intelligence processes.

15.
Forensic Sci Int ; 360: 112066, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38810589

RESUMO

The Sydney Declaration is an initiative led by an informal group of forensic scientists with diverse backgrounds. It offers a vision of forensic science based on the trace, as a vestige of a past event related to security or a possible law violation. An article published in Forensic Science International (FSI) introduces to this view [1]. Our investigation delves into how the forensic science literature has received this article (the SD article), nearly two years after its publication. One of the main challenges of this exploratory study was to define the appropriate scope of forensic scientific literature, within which the SD article must be located. In general, the publishing domain is quickly evolving, with many competing players, while still being structured around standard academic disciplines. The forensic literature, meanwhile, is scattered and poorly connected. This reflects the fragmentation of practice and research in forensic science, and the difficulty of situating a scientific activity in such a way as to bring out its forensic substance. Nonetheless, the SD article fills a gap. By deciphering the critical concept of trace, it highlights how pivotal forensic science is in addressing societal challenges. Scholarly literature expresses clear quantitative interest in the SD article. It has received significant qualitative citations on multiple levels and dimensions, in a highly relevant manner and in accordance with its aim of providing a forensic foundation for various debates that have been conducted separately, notably over the last fifteen years.


Assuntos
Ciências Forenses , Publicações Periódicas como Assunto , Humanos , Editoração , Bibliometria
16.
J Hazard Mater ; 475: 134853, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-38878431

RESUMO

Passive samplers are key tools to sample hydrophilic micropollutants in water. Two main approaches address the influence of hydrodynamics: (1) determining site-specific sampling rate (RS) by characterizing kw, the mass transfer coefficient of the water-boundary layer (WBL), and (2) reducing WBL impact using a diffusive material to control the uptake. The first requires calibration data and the second has only been achieved using fragile diffusive material. This study assesses the transfer of hydrophilic contaminants through polytetrafluoroethylene (PTFE; 30 µm thick), a new membrane material with lower sorption than commonly used polyethersulfone (PES). Combined for the first time in a Chemcatcher-like configuration, we calibrated the modified samplers for 44 micropollutants to provide RS - kw relationships for in-situ RS determination (approach 1). Micropollutants accumulated over 2000 times more on the sorbent than on PTFE. PTFE-based RS (0.027 to 0.300 L day-1) were 2.5 higher than previously reported with PES. Membrane property measurements (porosity, tortuosity) indicated that accumulation is primarily controlled by the membrane. Extrapolation indicated that using thicker PTFE membranes (≥ 100 µm) would shift uptake control entirely to the membrane in river conditions (approach 2). This finding could enable RS prediction based on contaminants properties, thus representing a significant advancement in passive sampling.

17.
Sci Justice ; 53(1): 41-8, 2013 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-23380061

RESUMO

Estimating the time since discharge of a spent cartridge or a firearm can be useful in criminal situations involving firearms. The analysis of volatile gunshot residue remaining after shooting using solid-phase microextraction (SPME) followed by gas chromatography (GC) was proposed to meet this objective. However, current interpretative models suffer from several conceptual drawbacks which render them inadequate to assess the evidential value of a given measurement. This paper aims to fill this gap by proposing a logical approach based on the assessment of likelihood ratios. A probabilistic model was thus developed and applied to a hypothetical scenario where alternative hypotheses about the discharge time of a spent cartridge found on a crime scene were forwarded. In order to estimate the parameters required to implement this solution, a non-linear regression model was proposed and applied to real published data. The proposed approach proved to be a valuable method for interpreting aging-related data.

18.
Sci Total Environ ; 871: 162037, 2023 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-36740052

RESUMO

When monitoring water quality with hydrophilic integrative passive sampling devices, it is crucial to use accurate sampling rates (RS) that account for exposure conditions such as hydrodynamics. This study aims at calibrating Chemcatcher-like passive samplers - styrene-divinylbenzene reverse phase sulfonate (SDB-RPS) extraction disk covered by a polyethersulfone (PES) membrane - at four water flow velocities (5 to 40 cm s-1) in a channel system. First, the four hydrodynamic conditions were characterized by measuring the mass transfer coefficients of the water boundary layer (kw) at the surface of the samplers using the alabaster dissolution method. Then, fifty-six samplers were deployed in the channels and exposed for 7 different intervals varying from 1 to 21 days. Thus, RS were determined at four different kw for 44 hydrophilic compounds, ranging from 0.015 to 0.115 L day-1. Relationships were established between kw and RS using models for mixed rate control by the membrane and the water boundary layer. The estimated parameters of those relationships are suitable for the determination of accurate RS when kw is measured in situ, for example by co-deploying silicone disks spiked with performance and reference compounds (PRC) as implemented in Part B.

19.
Forensic Sci Int ; 348: 111592, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-36775701

RESUMO

Many different issues have been identified in forensic science for more than 10 years. While quality management has often been suggested as a path forward, research is generally considered as an essential part of the solution. Through an overview of current forensic science research, this paper aims at evaluating if and how research answer the challenges forensic science is currently facing. While forensic related publications have massively increased over the years, approximately half of the publications were published in non-forensic sources, indicating that forensic science research tends to be led by other disciplines. Over the years, forensic science research has remained largely oriented towards methodological and technological development rather than relevance to the forensic science discipline and practice. Practical implementation of the techniques is rarely discussed from a forensic perspective, and thus research rarely move from the "proof-of-concept" stage to its utilisation in case investigation. The digital transformation also generated a massive increase of data, making it challenging to find the relevant pieces of information in the mass of "forensic" publications available on-line. Thus, we propose to refocus forensic science research on forensic fundamental and practical questions to strengthen the discipline and its impact on crime investigation and security issues. Our propositions represent an incentive to further discuss forensic science research and knowledge transmission through the definition of a common culture within the community, focusing on common fundamental knowledge such as a better understanding of the concept of trace and its case-based information content.


Assuntos
Medicina Legal , Ciências Forenses , Ciências Forenses/métodos , Pesquisa , Crime
20.
Forensic Sci Int ; 348: 111600, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-36801088

RESUMO

Gunshot residues (GSR) collected during the investigation of firearm-related incidents can provide useful information for the reconstruction of the events. Two main types of GSR traces can be targeted by forensic scientists, the inorganic (IGSR) and the organic GSR (OGSR). Up to now, forensic laboratories have mainly focused on the detection of inorganic particles on the hands and clothes of a person of interest using carbon stubs analysed by scanning electron microscopy coupled with energy dispersive X-ray spectrometry (SEM/EDS). Several approaches have been proposed to also analyse the organic compounds since they might bring additional information for the investigation. However, implementing such approaches might disrupt the detection of IGSR (and vice versa depending on the applied sequence of analysis). In this work, two sequences were compared for the combined detection of both types of residues. One carbon stub was used for collection, and the analysis was performed either by targeting the IGSR or the OGSR first. The aim was to evaluate which one allows maximum recovery of both types of GSR while minimising losses that might occur at different stages of the analysis process. SEM/EDS was used for the detection of IGSR particles while an ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) was used for the analysis of OGSR compounds. Extracting OGSR first required the implementation of an extraction protocol that did not interfere with the IGSR particles present on the stub. Both sequences allowed good recovery of the inorganic particles since no significant difference was observed in the detected concentrations. However, OGSR concentrations were lower after IGSR analysis than before for two compounds (ethyl and methylcentralite). Thus, it is advised to extract rapidly the OGSR before or after IGSR analysis to avoid losses during the storage and analysis processes. The data also indicated that there was a low correlation between IGSR and OGSR highlighting the potential of a combined detection and analysis of both types of GSR.

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