Uncovering the Counterfeit: A study of whiskey authenticity through volatile organic compound fingerprinting, aroma and color sensory analysis.

This study presents a method employing gas chromatography coupled with mass spectrometry and headspace solid-phase microextraction (HS-SPME-GC-MS), supplemented with chemometrics (Soft independent modelling of class analogies - SIMCA), to analyze volatile organic compound (VOCs) profiles in suspect whiskey samples. Furthermore, a sensory analysis of aroma and color was conducted with a panel of 52 non-trained volunteers to evaluate their ability to discriminate and preference for counterfeit whiskeys. The HS-SPME-GC-MS method successfully distinguished 41 seized samples from authentic beverages. Interestingly, sensory analysis revealed that panelists could differentiate between counterfeit and authentic samples with a reference standard but did not consistently show a preference for aroma. In some cases, there was even a preference for the color of counterfeit whiskeys. The findings suggest that sensorial tests alone may not effectively distinguish counterfeit from authentic whiskeys, especially for non-expert consumers, highlighting the need for analytical instrumentation methods in fraud detection.

From inspection to analysis: A combined approach to identifying counterfeit whiskeys using HS-GC-FID and bottle integrity.

Counterfeiting of alcoholic beverages, particularly high-value spirits such as whiskey, presents significant challenges for regulators, manufacturers, and consumers. In this study, we introduce and validate a novel application of headspace extraction (HS) followed by gas chromatography with flame ionization detection (GC-FID) for the quantitative determination of ethanol content in 42 suspected counterfeit brazilian samples of whiskeys. This method, in conjunction with visual inspection of material inconsistencies, offers a combined approach to identify potential cases of fraud. The HS-GC-FID findings revealed that only 19% of the analyzed samples had ethanol content in the limits declared on the label, emphasizing the role of ethanol content as a chemical marker for suspected beverage fraud.

Levels of organic pollutants and metals/metalloids in infant formula marketed in Brazil: Risks to early-life health.

Infant formula intake is recommended to ensure comprehensive nutritional and caloric fulfillment when exclusive breastfeeding is not possible. However, similarly to breast milk, infant formulas may also contain pollutants capable of inducing endocrine-disrupting and neurotoxic effects. Thus, considering the sensitivity of their developing physiological systems and that infants have heightened susceptibility to environmental influences, this study was aimed at assessing the contents of essential elements, and inorganic and organic pollutants in infant formulas marketed in Brazil. Additionally, health risk assessments for selected contaminants were also performed. Measured contents of essential elements (Ca, Fe, Mg, Mn, Cu, Se, and Zn) were congruent with label information. Nevertheless, some toxic elements (Pb, Cd, As, Ni, and Al) were also detected. Notably, in the upper-bound scenario, Pb and Cd surpassed established threshold values when comparing the estimated daily intake (EDI) and tolerable daily intake (TDI - 3.57 and 0.36 µg/kg bw, respectively). Bisphenol P (BPP) and benzyl butyl phthalate (BBP) were frequently detected (84 % detection rate both) with elevated contents (BPP median = 4.28 ng/g and BBP median = 0.24 ng/g). Furthermore, a positive correlation (0.41) was observed between BPP and BBP, implying a potential co-occurrence within packaging materials. Methyl-paraben also correlated positively with BBP (0.57), showing a detection rate of 53 %. The cumulative PBDE contents ranged from 0.33 to 1.62 ng/g, with BDE-154 and BDE-47 the dominant congeners. When comparing EDI values with TDIs, all organic pollutants remained below the thresholds across all exposure scenarios. Moreover, non-carcinogenic risks were below the threshold (HQ > 1) when dividing the EDIs by the respective reference doses for chronic exposure. While the current findings may suggest that infant formula intake poses no immediate risk in terms of the evaluated chemicals, it remains imperative to conduct further research to safeguard the health of infants considering other chemicals, as well as their potential cumulative effects.

Hybrid volatilomics in cancer diagnosis by HS-GC-FID fingerprinting.

Assessing volatile organic compounds (VOCs) as cancer signatures is one of the most promising techniques toward developing non-invasive, simple, and affordable diagnosis. Here, we have evaluated the feasibility of employing static headspace extraction (HS) followed by gas chromatography with flame ionization detector (GC-FID) as a screening tool to discriminate between cancer patients (head and neck-HNC,n= 15; and gastrointestinal cancer-GIC,n= 19) and healthy controls (n= 37) on the basis of a non-target (fingerprinting) analysis of oral fluid and urine. We evaluated the discrimination considering a single bodily fluid and adopting the hybrid approach, in which the oral fluid and urinary VOCs profiles were combined through data fusion. We used supervised orthogonal partial least squares discriminant analysis for classification, and we assessed the prediction power of the models by analyzing the values of goodness of prediction (Q2Y), area under the curve (AUC), sensitivity, and specificity. The individual models HNC urine, HNC oral fluid, and GIC oral fluid successfully discriminated between healthy controls and positive samples (Q2Y = 0.560, 0.525, and 0.559; AUC = 0.814, 0.850, and 0.926; sensitivity = 84.8, 70.2, and 78.6%; and specificity = 82.3; 81.5; 87.5%, respectively), whereas GIC urine was not adequate (Q2Y = 0.292, AUC = 0.694, sensitivity = 66.1%, and specificity = 77.0%). Compared to the respective individual models, Q2Y for the hybrid models increased (0.623 for hybrid HNC and 0.562 for hybrid GIC). However, sensitivity was higher for HNC urine and GIC oral fluid than for hybrid HNC (75.6%) and hybrid GIC (69.8%), respectively. These results suggested that HS-GC-FID fingerprinting is suitable and holds great potential for cancer screening. Additionally, the hybrid approach tends to increase the predictive power if the individual models present suitable quality parameter values. Otherwise, it is more advantageous to use a single body fluid for analysis.

Alternative matrices in forensic toxicology: a critical review.

PURPOSE: The use of alternative matrices in toxicological analyses has been on the rise in clinical and forensic settings. Specimens alternative to blood and urine are useful in providing additional information regarding drug exposure and analytical benefits. The goal of this paper is to present a critical review on the most recent literature regarding the application of six common alternative matrices, i.e., oral fluid, hair, sweat, meconium, breast milk and vitreous humor in forensic toxicology. METHODS: The recent literature have been searched and reviewed for the characteristics, advantages and limitations of oral fluid, hair, sweat, meconium, breast milk and vitreous humor and its applications in the analysis of traditional drugs of abuse and novel psychoactive substances (NPS). RESULTS: This paper outlines the properties of six biological matrices that have been used in forensic analyses, as alternatives to whole blood and urine specimens. Each of this matrix has benefits in regards to sampling, extraction, detection window, typical drug levels and other aspects. However, theses matrices have also limitations such as limited incorporation of drugs (according to physical-chemical properties), impossibility to correlate the concentrations for effects, low levels of xenobiotics and ultimately the need for more sensitive analysis. For more traditional drugs of abuse (e.g., cocaine and amphetamines), there are already data available on the detection in alternative matrices. However, data on the determination of emerging drugs such as the NPS in alternative biological matrices are more limited. CONCLUSIONS: Alternative biological fluids are important specimens in forensic toxicology. These matrices have been increasingly reported over the years, and this dynamic will probably continue in the future, especially considering their inherent advantages and the possibility to be used when blood or urine are unavailable. However, one should be aware that these matrices have limitations and particular properties, and the findings obtained from the analysis of these specimens may vary according to the type of matrix. As a potential perspective in forensic toxicology, the topic of alternative matrices will be continuously explored, especially emphasizing NPS.

Alcohol and Alcohol Combined with Texting: Evaluation of Driving Impairment Effects in a Closed-Course Section.

OBJECTIVE: Examine the driving impairment effects of alcohol alone and of alcohol combined with texting. METHODS: Fifteen drivers (nine male, six female; mean age: 31.1 ± 6.9 years, range: 23 to 43 years) with similar drinking habit (i.e., social drinkers) completed a lap in a closed-course section in six different situations: (I) sober; (II) sober and while texting; (III) 30 minutes after ingesting a moderate dose of ethanol (0.50 g/kg); (IV) 30 minutes after drinking and while texting; (V) 60 minutes after drinking, (VI) 60 minutes after drinking and while texting. Driving performance was analyzed by means of maximum and mean speed, braking time and braking distance; and ability to control the car (i.e., evaluating if the drivers hit a traffic cone or exceeded the boundaries of the course). P values of < 0.05 were considered significant. RESULTS: Pre and post-alcohol consumption results show a significant increase concerning the drivers' mean and maximum speed after drinking (p < 3.2x10-8). However, neither alcohol nor texting had significant effects on braking parameters (p > 0.05). Traffic cones were knocked down only in texting experiments. In addition, when using the cell phone drivers tended to reduce the speed, and to accelerate abruptly right after they finish texting. CONCLUSION: Our findings strengthen the hypothesis that even moderate alcohol doses may significantly impair the driving performance. Additionally, alcohol and texting have complementary effects on driving impairment, and their combination represents a significant risk factor for crashes.

Caffeine content of energy drinks marketed in Brazil.

Energy drinks represent a multibillionaire industry that has been growing continuously worldwide. These drinks are especially consumed by young people, athletes, and military personnel due to their claimed "boost" effects. However, there have been concerns about their consumption since incompatibilities regarding the accuracy of the declared caffeine content of these drinks have been reported. Therefore, in this study, we have developed a fast and simple method to quantify caffeine in energy drinks. Sample preparation consisted of a dilute-and-shoot process, and analyses were performed by gas chromatography with nitrogen-phosphorus detector (GC-NPD). The method was applied to quantify caffeine in 37 energy drinks marketed in Brazil. Compared with the labeled caffeine content, 84% of the tested drinks presented caffeine levels in accordance with the specifications. The determined caffeine concentrations ranged from 10 to 67 mg/100 ml, with an average value of 31 mg/100 ml. According to the recommended serving size, no drinks exceeded the safe caffeine daily intake for the general population (400 mg). These findings are more favorable than the results of similar studies. Nevertheless, to avoid caffeine intoxication, energy drink consumers should be aware of three aspects. First, they need to avoid consuming multiple serving doses in short periods of time. Additionally, some energy drinks are labeled as "nutritional supplements," so they may present much more caffeine than similar products commonly regulated as beverages. Finally, despite the growing interest in energy drinks, their consumption by children and early adolescents is being discouraged by the health authorities.

Pre-workout supplements marketed in Brazil: Caffeine quantification and caffeine daily intake assessment.

The stimulating and performance-enhancing properties of caffeine are often explored in one the most consumed types of supplements: the pre-workout supplements (PWS). However, despite the popularity of PWS, previous studies have reported incompatibilities between what is described in their labels and their actual caffeine content. This study aimed to develop, to optimize, and to validate a gas-chromatography coupled to nitrogen-phosphorus detector (GC-NPD) method to quantify caffeine in PWS and to analyze commercial PWS marketed in Brazil to estimate the caffeine daily intake. For this purpose, three different extraction procedures were evaluated: agitation in vortex, shaker, and sonication. Sonication yielded the best extraction results. Next, the parameters' temperature and time were optimized by using central composite rotatable design (CCRD) and response surface methodology, which revealed the optimal values of 70°C and 10 min. The method was validated and applied to quantify caffeine in 52 PWS. From the 36 PWS labels that specified the caffeine amount, seven (19%) presented more than 120% of the declared quantity, whereas 15 (42%) contained less than 80% of the labeled caffeine. Additionally, six products presented undeclared caffeine. Considering the label stated doses, five supplements exceeded the safe caffeine daily intake (400 mg). On the basis of these findings, supplement quality control remains an issue that deserves more attention from consumers, manufacturers, and regulatory agencies. Finally, we suggest that PWS consumers be careful of the habit of ingesting caffeine through other sources and avoid ingesting two or more different PWS products in the same day.

Analysis of urinary VOCs using mass spectrometric methods to diagnose cancer: A review.

The development of non-invasive screening techniques for early cancer detection is one of the greatest scientific challenges of the 21st century. One promising emerging method is the analysis of volatile organic compounds (VOCs). VOCs are low molecular weight substances generated as final products of cellular metabolism and emitted through a variety of biological matrices, such as breath, blood, saliva and urine. Urine stands out for its non-invasive nature, availability in large volumes, and the high concentration of VOCs in the kidneys. This review provides an overview of the available data on urinary VOCs that have been investigated in cancer-focused clinical studies using mass spectrometric (MS) techniques. A literature search was conducted in ScienceDirect, Pubmed and Web of Science, using the keywords "Urinary VOCs", "VOCs biomarkers" and "Volatile cancer biomarkers" in combination with the term "Mass spectrometry". Only studies in English published between January 2011 and May 2020 were selected. The three most evaluated types of cancers in the reviewed studies were lung, breast and prostate, and the most frequently identified urinary VOC biomarkers were hexanal, dimethyl disulfide and phenol; with the latter seeming to be closely related to breast cancer. Additionally, the challenges of analyzing urinary VOCs using MS-based techniques and translation to clinical utility are discussed. The outcome of this review may provide valuable information to future studies regarding cancer urinary VOCs.

A fast method for bisphenol A and six analogues (S, F, Z, P, AF, AP) determination in urine samples based on dispersive liquid-liquid microextraction and liquid chromatography-tandem mass spectrometry.

In this study, a novel method combining dispersive liquid-liquid microextraction (DLLME) and fast liquid chromatography coupled to mass spectrometry (LC-MS/MS) was developed and validated for the extraction and determination of bisphenol A (BPA) and six bisphenol analogues, namely bisphenol S (BPS), bisphenol F (BPF), bisphenol P (BPP), bisphenol Z (BPZ), bisphenol AP (BPAP) and bisphenol AF (BPAF) in human urine samples. Type and volume of extraction and disperser solvents, pH sample, ionic strength, and agitation were evaluated. The matrix-matched calibration curves of all analytes were linear with correlation coefficients higher than 0.99 in the range level of 0.5-20.0ngmL(-1). The relative standard deviation (RSD), precision, at three concentrations (1.0, 8.0 and 15.0ngmL(-1)) was lower than 15% with accuracy ranging from 90 to 112%. The biomonitoring capability of the new method was confirmed with the analysis of 50 human urine samples randomly collected from Brazilians. BPA was detected in 92% of the analyzed samples at concentrations ranging