Migration Studies and Endocrine Disrupting Activities: Chemical Safety of Cosmetic Plastic Packaging.

The endocrine activity and endocrine disruptor (ED) chemical profiles of eleven plastic packaging materials covering five major polymer types (3PET, 1HDPE, 4LDPE, 2 PP, and 1SAN) were investigated using in vitro cell-based reporter-gene assays and a non-targeted chemical analysis using gas chromatography coupled to mass spectrometry (GC-MS). To mimic cosmetic contact, six simulants (acidic, alkaline, neutral water, ethanol 30%, glycerin, and paraffin) were used in migration assays performed by filling the packaging with simulant. After 1 month at 50 °C, simulants were concentrated by Solid Phase Extraction (SPE) or Liquid-Liquid Extraction (LLE). The migration profiles of seven major endocrine disrupting chemicals detected from GC-MS in the different materials and simulants were compared with Estrogen Receptor (ER) and Androgen Receptor (AR) activities. With low extraction of ED chemicals in aqueous simulants, no endocrine activities were recorded in the leachates. Paraffin was shown to be the most extracting simulant of antiandrogenic chemicals, while glycerin has estrogenic activities. Overall, ED chemical migration in paraffin was correlated with hormonal activity. The NIAS 2,4-di-tert-butyl phenol and 7,9-di-tert-butyl1-oxaspiro (4,5) deca-6,9-diene-2,8-dione were two major ED chemicals present in all polymers (principally in PP and PE) and in the highest quantity in paraffin simulant. The use of glycerin and liquid paraffin as cosmetic product simulants was demonstrated to be relevant and complementary for the safety assessment of released compounds with endocrine activities in this integrated strategy combining bioassays and analytical chemistry approaches.

Consumer Attitudes toward Pulses: Measuring the Implicit.

Research into consumer attitudes toward food products is important to help people adopt healthier, more sustainable diets. A positive attitude regarding an object is a prerequisite for its adoption. This study compares French consumers' implicit attitudes toward pulses and cereals. Many studies have measured attitudes by explicit methodologies (e.g., questionnaires). Such methods are often biased by social desirability, and consumers may not be consciously aware of their attitudes toward food. A Sorting Paired Feature Task measures the strength of automatic associations, pairing images of pulses or cereals and adjectives with positive or negative valence. Participants sorted 120 paired stimuli as fast as possible. Pairs composed of pulses and negative adjectives were sorted faster than pairs composed of cereals and negative adjectives. Cereals with positive adjectives were sorted more rapidly than pulses with positive adjectives. Mistaken associations were more frequent for pairs composed of cereals and negative adjectives than for pairs composed of pulses and negative adjectives. These results highlight more negative implicit attitudes toward pulses than cereals. This study provides the first potential evidence of negative implicit attitudes toward pulses, which could explain the low consumption of these products.

Profiles of Volatile Compounds from Seven New Hybrid Families Obtained by Crossings on Noir de Bourgogne Cultivar and Other Blackcurrant Varieties.

Berries of blackcurrant (Ribes nigrum L.) are popular for their strong and complex aroma and their benefits for health. In Burgundy (France), the most famous blackcurrant cultivar is the "Noir de Bourgogne". A blackcurrant breeding program was conducted to obtain new varieties, more resistant to infections and climate changes. The cultivar "Noir de Bourgogne" was crossed with seven other varieties in order to create a hybrid with good agronomic properties and organoleptic properties close to the ones of "Noir de Bourgogne". Several hybrids were created, and their aromatic profiles studied. Berries of eight cultivars, among which Noir de Bourgogne and hybrids resulting from crossings, were harvested during the summer of 2020. Volatile compounds of berries were analyzed by HS-SPME-GC-MS, and principal component analysis (PCA) was used as the most useful chemometric technique. The profiles in volatile compounds of hybrids were either different from those of the two parental varieties or close to that of varieties other than Bourgogne black. In all cases, the overall aroma strength of the hybrid did not equal that of the Noir de Bourgogne cultivar.

Identification of Volatile Compounds in Blackcurrant Berries: Differences among Cultivars.

Berries of blackcurrant are known to produce a strong flavor. Some previous studies have reported that a given cultivar of blackcurrant can produce berries with a specific profile of volatile compounds. For the Burgundy region in France, the Noir de Bourgogne cultivar is especially important because it is the main ingredient of a liquor with a designation of origin. The aim of the present study was to characterize the volatile fractions of berries from 15 cultivars in order to explore the possibility of using different cultivars for liquor production. The plants were cultivated under the same conditions and harvested in the same year. The volatile fractions of the harvested berries were analyzed using HS-SPME-GC-MS. Thorough univariate statistical analysis and multivariate analysis were applied to the dataset, which made it possible to identify groups within cultivars. The Rosenthal cultivar exhibited a quite flat profile; the Lositkia, Ben Tiran, and Barchatnaia cultivars shared common features; the Noir de Bourgogne cultivar showed the highest amounts of molecules such as 3-carene, limonene, ß-phellandrene, ocimene, α-terpinolene, and bicyclogermacrene. None of the studied varieties were close to the Noir de Bourgogne on the basis of VOC analysis.

Regionality in Australian Pinot noir wines: A study on the use of NMR and ICP-MS on commercial wines.

Wine quality and character are defined in part by the terroir in which the grapes are grown. Metabolomic techniques, such as nuclear magnetic resonance (NMR) spectroscopy and inductively coupled plasma mass spectrometry (ICP-MS), are used to characterise wines and to detect wine fraud in other countries but have not been extensively trialled in Australia. This paper describes the use of ICP-MS and NMR to characterise a selection of Pinot noir wines. Wines from varying terroirs could be somewhat distinguished by their mineral content using principal component analysis (PCA). PCA was able to separate wines by their Australian states more clearly than by region. Metabolomic analysis of the wines using NMR did not find any correlations with climate/daytime temperatures, or region. An analysis of coinertia suggested that the two datasets were not redundant, and it is proposed that ICP-MS data is the most useful for determining regionality.

A First Tentative for Simultaneous Detection of Fungicides in Model and Real Wines by Microwave Sensor Coupled to Molecularly Imprinted Sol-Gel Polymers.

A molecularly imprinted silica (MIS) coupled to a microwave sensor was used to detect three fungicides (iprodione, procymidone and pyrimethanil) present in most French wines. Chemometric methods were applied to interpret the microwave spectra and to correlate microwave signals and fungicide concentrations in a model wine medium, and in white and red Burgundy wines. The developed microwave sensor coupled to an MIS and to its control, a nonimprinted silica (NIS), was successfully applied to detect the three fungicides present in trace levels (ng L-1) in a model wine. The MIS sensor discriminated the fungicide concentrations better than the NIS sensor. Partial Least Squares models were suitable for determining iprodione in white and red wines. A preliminary method validation was applied to iprodione in the white and red wines. It showed a limit of detection (LOD) lower than 30 ng L-1 and a recovery percentage between 90 and 110% when the iprodione concentration was higher than the LOD. The determined concentrations were below the authorized level by far.

A review of the newly identified impurity profiles in methamphetamine seizures.

Forensic intelligence of synthetic illicit drugs suffers a problem of continuous introduction of new synthetic methods, modification of the existing routes of manufacture, and adulterations practiced by criminal networks. Impurity profiling has been indispensable in methamphetamine intelligence based on precursors, synthetic routes, and chemical modifications during trafficking. Law enforcement authorities maintain the credibility and integrity of intelligence information through constant monitoring of the chemical signatures in the illicit drug market. Changes in the synthetic pattern result in new impurity profiles that are important in keeping valuable intelligence information on clandestine laboratories, new synthetic routes, trafficking patterns, and geographical sources of illicit Methamphetamine. This review presents a critical analysis of the methamphetamine impurity profiles and more specifically, profiling based on impurity profiles from Leuckart, Reductive amination, Moscow, Emde, Nagai, Birch, Moscow route; a recent nitrostyrene route and stable isotope signatures. It also highlights the discrimination of ephedrine from pseudoephedrine sources and the emerging methamphetamine profiling based on stable isotopes.

Biophysical Stress Responses of the Yeast Lachancea thermotolerans During Dehydration Using Synchrotron-FTIR Microspectroscopy.

During industrial yeast production, cells are often subjected to deleterious hydric variations during dehydration, which reduces their viability and cellular activity. This study is focused on the yeast Lachancea thermotolerans, particularly sensitive to dehydration. The aim was to understand the modifications of single-cells biophysical profiles during different dehydration conditions. Infrared spectra of individual cells were acquired before and after dehydration kinetics using synchrotron radiation-based Fourier-transform infrared (S-FTIR) microspectroscopy. The cells were previously stained with fluorescent probes in order to measure only viable and active cells prior to dehydration. In parallel, cell viability was determined using flow cytometry under identical conditions. The S-FTIR analysis indicated that cells with the lowest viability showed signs of membrane rigidification and modifications in the amide I (α-helix and ß-sheet) and amide II, which are indicators of secondary protein structure conformation and degradation or disorder. Shift of symmetric C-H stretching vibration of the CH2 group upon a higher wavenumber correlated with better cell viability, suggesting a role of plasma membrane fluidity. This was the first time that the biophysical responses of L. thermotolerans single-cells to dehydration were explored with S-FTIR. These findings are important for clarifying the mechanisms of microbial resistance to stress in order to improve the viability of sensitive yeasts during dehydration.

Lebanese Population Exposure to Trace Elements via White Bread Consumption.

The objective of this study was to assess Lebanese population exposure to trace elements (TEs) via white pita consumption. A survey of white pita consumption was achieved among one thousand Lebanese individuals, grouped into adults (above 15 years old, men, and women) and young people (6-9 and 10-14 years old). The most consumed pita brands, labeled B1, B2, and B3, were selected. Levels of TEs (i.e., As, Cd, Co, Cr, Hg, Ni, and Pb) in B1, B2, B3 pitas were measured. The highest contents of TEs in pitas were: Ni (1292 µg/kg) and Co (91 µg/kg) in B1; As (400 µg/kg) and Cd (< 15 µg/kg) in B2; Cr (363 µg/kg), Pb (260 µg/kg), and Hg (0.89 µg/kg) in B3. The pita brand B3 was the source of the highest TEs exposure, except for Ni for which it was B1. Daily exposures to TEs due to the fact of pita consumption were compared to safety levels. There were no safety concerns for Hg, Cd, Cr or Co (except the 95th percentile of 6-9 years old). An excess of the Ni tolerable daily intake was observed for the most exposed populations. The very low margins of exposure for As and Pb suggest a worrying risk for the Lebanese population.

Fast and direct analysis of oxidation levels of oil-in-water emulsions using ATR-FTIR.

Oxidation of omega-3 fatty acids is a major limitation on its enrichment in food and beverages. An efficient and simple method to monitor lipid oxidation in complex systems is essential to limit lipid oxidation during formulation and processing. Fish oil-in-water emulsions (20% v/v) were exposed to iron or free radical initiated oxidation. Conjugated dienes (CDs) were rapidly measured using a previously developed fat extraction method. Fourier transform infrared (FTIR) spectroscopy has been used to directly record chemical changes occurring during oxidation. Variations were noticed in different spectral regions despite the presence of broad water bands near 3400 and 1640 cm-1. Partial least squares regression (PLSR) revealed correlations between CD values and full FTIR spectra (4000-600 cm-1), and different spectral regions (e.g., 1800-1500 cm-1, 1500-900 cm-1). These correlations confirm that FTIR spectroscopy is a rapid and simple method for measuring lipid oxidation in complex foods without prior fat extraction.

Analysis of multivariate images in fluorescence microscopy.

A multivariate image is an image stack in which each pixel contains several variables. Such images are common in many fields (medicine, imaging microscopy, satellite imaging...) and their analysis requires adapted multivariate statistical methods. In fluorescence imaging microscopy, different probes or different measurements such as intensity, fluorescence lifetime or spectral information can be observed from one view. However, this is not yet analysed as multivariate images. Here, we are presenting a full approach of multivariate analysis of fluorescence microscopy images and we are proposing a free R package (multifluo) to conduct it.

Understanding the Effects of High Pressure on Bacterial Spores Using Synchrotron Infrared Spectroscopy.

Bacterial spores are extremely resistant life-forms that play an important role in food spoilage and foodborne disease. The return of spores to a vegetative cell state is a three-step process, these being activation, germination, and emergence. High-pressure (HP) processing is known to induce germination in part of the spore population and even to inactivate a high number of Bacillus spores when combined with other mild treatments such as the addition of nisin. The aim of the present work was to investigate the mechanisms involved in the sensitization of spores to nisin following HP treatment at ambient temperature or with moderate heating leading to a heterogeneous spore response. Bacillus subtilis spores were subjected to HP treatment at 500 MPa at 20 and 50°C. The physiological state of different subpopulations was characterized. Then Fourier transform infrared (FTIR) microspectroscopy coupled to a synchrotron infrared source was used to explore the heterogeneity of the biochemical signatures of the spores after the same HP treatments. Our results confirm that HP at 50°C induces the germination of a large proportion of the spore population. HP treatment at 20°C generated a subpopulation of ungerminated spores reversibly sensitized to the presence of nisin in their growth medium. Regarding infrared spectra of individual spores, spores treated by HP at 50°C and germinated spores had similar spectral signatures involving the same structural properties. However, after HP was performed at 20°C, two groups of spores were distinguished; one of these groups was clearly identified as germinated spores. The second group displayed a unique spectral signature, with shifts in the spectral bands corresponding to changes in membrane fluidity. Besides, spores spectra in the amide region could be divided into several groups close to spectral properties of dormant, germinated, or inactivated spores. The part of the spectra corresponding to α-helix and ß-sheet-structures contribute mainly to the spectral variation between spores treated by HP at 20°C and other populations. These changes in the lipid and amide regions could be the signature of reversible changes linked to spore activation.

A study of cannabis potency in France over a 25 years period (1992-2016).

Cannabis contains a unique class of compounds known as the cannabinoids. Pharmacologically, the principal psychoactive constituent is Δ9-tetrahydrocannabinol (THC). The amount of THC in conjunction with selected additional cannabinoid compounds (cannabidiol/CBD, cannabinol/CBN), determines the strength or potency of the cannabis product. Recently, reports have speculated over the change in the quality of cannabis products, from nearly a decade, specifically concerning the increase in cannabinoid content. This article exploits the analytical data of cannabis samples analyzed in the five French forensic police laboratories over 25 years. The increase potency of both herbal and resin cannabis in France is proved through the monitoring of THC content. For cannabis resin, it has slowly risen from 1992 to 2009, before a considerable increase in the last four years (mean THC content in mid-2016 is 23% compared to 10% in 2009). For herbal cannabis, it has known three main stages of growth (mean THC content is 13% in 2015 and mid-2016 compared to 7% in 2009 and 2% in 1995). The calculation of THC/CBD ratios in both herbal and resin samples confirms the recent change in chemotypes in favor of high potency categories. Finally, the CBN/THC ratios in marijuana samples were measured in order to evaluate the freshness of French seized hemp.

IRMS to study a common cocaine cutting agent: phenacetin.

Phenacetin is a pharmaceutical closely related to acetaminophen that has been banned in France for a long time due to its nephritic and carcinogenic adverse effects. It frequently appears in cocaine seizures as a cutting agent. Following both sanitary and intelligence motivations, this molecule was chosen for this study, and stable isotopes seemed to be the most appropriate tool. A total of 228 seized samples were collected over a 6-year period, and 8 standards of known origin were purchased. They were submitted to gas chromatography (GC) or elemental analysis - isotope ratio mass spectrometry (EA-IRMS) measurements, depending on their complexity. Stable isotope ratios of carbon, hydrogen, and nitrogen for a part of the sample set, were acquired. The isotopic values of phenacetin standards acquired from various providers located worldwide are quite spread, which indicates that stable isotopes could be used to discriminate manufacturers. However, the measured values of most of the seized samples are concentrated in a narrow range, tending to demonstrate that phenacetin is smuggled from a single source or similar ones. Consequently, stable isotopes could only be used to exclude that several samples come from a common source. Copyright © 2016 John Wiley & Sons, Ltd.

What a validation strategy means for the quantitation of cocaine and heroin?

A method of separation by gas chromatography with a flame ionisation detector was developed for quantifying cocaine and heroin in powders seized by law enforcement. The method was validated by studying parameters of calibration, trueness, precision based on trueness error (or systematic bias) and random error. Total error, which is the combination of these errors, verified its adequacy with the objectives fixed by the analyst. Accuracy profile proved to be an efficient decision tool for that purpose. Results obtained with weighted regression model were analysed and allowed to conclude that the method enables quantitation of heroin and cocaine in powders on 2-100% concentration (w/w) range with acceptance limits fixed at 10% and a risk at 5%. The possible sources of uncertainty were evaluated and measurement of their contribution was integrated. The combined standard uncertainty and expanded uncertainty were determined.

Multidimensional analysis of cannabis volatile constituents: identification of 5,5-dimethyl-1-vinylbicyclo[2.1.1]hexane as a volatile marker of hashish, the resin of Cannabis sativa L.

The volatile constituents of drug samples derived from Cannabis sativa L. were investigated by means of headspace solid phase microextraction (HS-SPME) and gas chromatography techniques (GC-MS, GC×GC-MS). Samples of cannabis herb and hashish showed clear differences in their volatile chemical profiles, mostly resulting from photo-oxidation processes occurring during the transformation of fresh cannabis herb into hashish. Most unexpectedly, we could demonstrate hashish samples as containing remarkable amounts of a rare and unusual monoterpene - 5,5-dimethyl-1-vinylbicyclo[2.1.1]hexane - among the volatile compounds detected in their headspaces. We gave evidence for the formation of this compound from the light induced rearrangement of ß-myrcene during the manufacture of hashish. In view of its high abundance among volatile constituents of cannabis resin and its scarce occurrence in other natural volatile extracts, we propose to rename this specific monoterpene hashishene.

Different likelihood ratio approaches to evaluate the strength of evidence of MDMA tablet comparisons.

Two likelihood ratio (LR) approaches are presented to evaluate the strength of evidence of MDMA tablet comparisons. The first one is based on a more 'traditional' comparison of MDMA tablets by using distance measures (e.g., Pearson correlation distance or a Euclidean distance). In this approach, LRs are calculated using the distribution of distances between tablets of the same-batch and that of different-batches. The second approach is based on methods used in some other fields of forensic comparison. Here LRs are calculated based on the distribution of values of MDMA tablet characteristics within a specific batch and from all batches. The data used in this paper must be seen as examples to illustrate both methods. In future research the methods can be applied to other and more complex data. In this paper, the methods and their results are discussed, considering their performance in evidence evaluation and several practical aspects. With respect to evidence in favor of the correct hypothesis, the second method proved to be better than the first one. It is shown that the LRs in same-batch comparisons are generally higher compared to the first method and the LRs in different-batch comparisons are generally lower. On the other hand, for operational purposes (where quick information is needed), the first method may be preferred, because it is less time consuming. With this method a model has to be estimated only once in a while, which means that only a few measurements have to be done, while with the second method more measurements are needed because each time a new model has to be estimated.

Headspace profiling of cocaine samples for intelligence purposes.

A method for determination of residual solvents in illicit hydrochloride cocaine samples using static headspace-gas chromatography (HS-GC) associated with a storage computerized procedure is described for the profiling and comparison of seizures. The system involves a gas chromatographic separation of 18 occluded solvents followed by fully automatic data analysis and transfer to a PHP/MySQL database. First, a fractional factorial design was used to evaluate the main effects of some critical method parameters (salt choice, vial agitation intensity, oven temperature, pressurization and loop equilibration) on the results with a minimum of experiments. The method was then validated for tactical intelligence purposes (batch comparison) via several studies: selection of solvents and mathematical comparison tool, reproducibility and "cutting" influence studies. The decision threshold to determine the similarity of two samples was set and false positives and negatives evaluated. Finally, application of the method to distinguish geographical origins is discussed.

Drug intelligence based on MDMA tablets data I. Organic impurities profiling.

The main objectives of the European project "Collaborative Harmonization of Methods for Profiling of Amphetamine Type Stimulants" (CHAMP) funded by the sixth framework programme of the European Commission, included the harmonization of MDMA profiling methods and the creation of a common database in a drug intelligence perspective. In the preliminary stages of this project, the participating laboratories analysed the physical characteristics, the chemical composition and the organic impurities of MDMA tablets, using the previously harmonized methods. The aim of the present work was to apply statistical treatments to the recorded data in order to evaluate their potential in the fight against drug trafficking. Comparable working procedures were applied on the different types of data. The first part of this article deals with organic impurities data, while the second part focuses on the potential of the physical characteristics. Organic impurities data were recorded by a harmonized Gas Chromatography/Mass Spectrometry (GC/MS) method previously developed. Statistical analysis provided a selection of pertinent variables among the 46 organic impurities identified in the chromatograms. Correlation coefficients were used to yield separation between populations of samples coming from the same synthesis batch and samples coming from different batches. It was shown that correlation measurements based on Pearson and cosine functions applied to the data pre-treated by normalisation to the sum of peak responses followed by the square root provided an excellent discrimination between the two populations. The statistical methods applied to organic impurities profiles proved to be excellent techniques to differentiate samples from different batches and to highlight operational links between samples.

A quick and automated method for profiling heroin samples for tactical intelligence purposes.

A computerized procedure is presented for the profiling and comparison of illicit heroin seizures. The system involves the derivation and gas chromatographic separation of five major constituents followed by a fully automatic data analysis and transfer to a PHP/MySQL database. Comparisons via the square cosine function between a single chromatographic profile and the whole database (several hundred of samples) are performed in a few seconds. Advantages of this profiling method compared to the classical minor constituents one are discussed.