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Toxics
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Analysis of Chemical Contaminants in Food
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Analysis of Chemical Contaminants in Food

A special issue of Toxics (ISSN 2305-6304). This special issue belongs to the section "Environmental Chemistry".

Deadline for manuscript submissions: closed (31 October 2018) | Viewed by 64486

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editor

Prof. Dr. Claudio Medana

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Guest Editor
Department of Molecular Biotechnology and Health Sciences, University of Torino, Via Pietro Giuria 5, 10125 Torino, Italy
Interests: mass spectrometry; chromatography; food chemistry; metabolomics
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The presence of contaminants in foods is a topic of concern both in science and popular culture. A growing attention is devoted to main and side effects of foodstuffs from the nutritional and dietary point of view, but furthermore toxicology and epidemiology research show new cases of correlation between food contaminants and development of pathologies. The undesirable contaminant compounds may have a different origin: They may be degradation products of food components (natural or anthropogenic), environmental pollutants or substances deriving from technological processes. Many of the components of the food that seem indifferent at first glance can reveal to be harmful by deeper investigation.

The recognized classes of undesirable food contaminants based on their origin can be summarized as: i) endogenous toxins, which are natural food components, ii) microbial toxins produced by molds or bacteria, iii) toxic residues carried over into food from procedures applied to living animals and plants, and iv) toxic contaminants originating from technological operations such as packaging, food processing, preservation and cooking.

The availability of analytical techniques of increasing selectivity and sensitivity has boosted the ability to detect traces of food contaminants in a more and more accurate and reproducible way. The development of molecular screening techniques such as -omics continuously raises the list of molecules with toxicological properties. Knowledge about acute toxicity, chronic toxicity (e.g. carcinogenicity, endocrine-disrupting effects, etc.) or subjective toxicity (as in the case of allergens) is crucial both for overall human health and in the development of personalized medicine.

The broad extension of this issue should be focused on the development and application of analytical technologies for the targeted and non-targeted detection of food contaminants. Particular attention should be paid to the correlation of their levels in food with toxicological risk and with the onset of diseases. Food chemical safety control methods have to involve both small molecules and macromolecules analytical determination; matrix effects should be studied in detail.

Prof. Claudio Medana
Guest Editor

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Keywords

  • food undesirables
  • analytical methods
  • food pollutants
  • contaminant quantitation
  • endogenous toxins analysis
  • toxic residues
  • food-borne toxins
  • matrix effect
  • food contaminant risk assessment

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Published Papers (12 papers)

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Editorial

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3 pages, 175 KiB  
Editorial
Analysis of Chemical Contaminants in Food
by Claudio Medana
Toxics 2020, 8(2), 27; https://doi.org/10.3390/toxics8020027 - 8 Apr 2020
Cited by 4 | Viewed by 3308
Abstract
Food chemical analysis is recognized as a unique tool for the characterization of nutritional value, quality and safety of foods and feeds [...] Full article
(This article belongs to the Special Issue Analysis of Chemical Contaminants in Food)

Research

Jump to: Editorial

12 pages, 1310 KiB  
Article
Multi-Analyte MS Based Investigation in Relation to the Illicit Treatment of Fish Products with Hydrogen Peroxide
by Federica Dal Bello, Riccardo Aigotti, Michael Zorzi, Valerio Giaccone and Claudio Medana
Toxics 2020, 8(1), 2; https://doi.org/10.3390/toxics8010002 - 8 Jan 2020
Cited by 8 | Viewed by 4054
Abstract
Fishery products are perishable due to the action of many enzymes, both endogenous and exogenous. The latter are produced by bacteria that may contaminate the products. When fishes age, there is a massive bacteria growth that causes the appearance of off-flavor. In [...] Read more.
Fishery products are perishable due to the action of many enzymes, both endogenous and exogenous. The latter are produced by bacteria that may contaminate the products. When fishes age, there is a massive bacteria growth that causes the appearance of off-flavor. In order to obtain “false” freshness of fishery products, an illicit treatment with hydrogen peroxide is reported to be used. Residues of hydrogen peroxide in food may be of toxicology concern. We developed two mass spectrometry based methodologies to identify and quantify molecules related to the treatment of fishes with hydrogen peroxide. With ultra-high-performance liquid chromatography–mass spectrometry (UHPLC-MS) we evaluated the concentration of trimethylamine-N-oxide (TMAO), trimethylamine (TMA), dimethylamine (DMA), and cadaverine (CAD) in fish products. After evaluating LOQ, we measured and validated the lower limits of quantification (LLOQs as first levels of calibration curves) values of 50 (TMAO), 70 (TMA), 45 (DMA), and 40 (CAD) ng/mL. A high ratio between TMAO and TMA species indicated the freshness of the food. With a GC-MS method we confirmed the illicit treatment measuring the levels of H2O2 after an analytical reaction with anisole to give 2-hydroxyanisole as a marker. This latter product was detected in the headspace of the homogenized sample with simplification of the work-up. A LLOQ of 50 ng/mL was checked and validated. When fish products were whitened and refreshed with hydrogen peroxide, the detected amount of the product 2-hydroxyanisole could be very important, (larger than 100 mg/kg). The developed analytical methods were suitable to detect the illicit management of fishery products with hydrogen peroxide; they resulted as sensitive, selective, and robust. Full article
(This article belongs to the Special Issue Analysis of Chemical Contaminants in Food)
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14 pages, 867 KiB  
Article
Assessment of Antibiotic and Pesticides Residues in Breast Milk of Syrian Refugee Lactating Mothers
by Nadia Smadi, Adla Jammoul and Nada El Darra
Toxics 2019, 7(3), 39; https://doi.org/10.3390/toxics7030039 - 31 Jul 2019
Cited by 14 | Viewed by 5157
Abstract
Occupational exposures and current diet are both sources of environmental contaminants that can be transferred in the mother’s body. These chemicals can definitely penetrate to the developing foetus and the nursing infant from contaminated breast milk during the lactation period. Nowadays, one of [...] Read more.
Occupational exposures and current diet are both sources of environmental contaminants that can be transferred in the mother’s body. These chemicals can definitely penetrate to the developing foetus and the nursing infant from contaminated breast milk during the lactation period. Nowadays, one of the special interests is the exposure of new-borns to toxic chemicals such as pesticides and antibiotics reported in human milk due to their potential harms, especially developmental deficits in early childhood. The aim of our current study was to assess the occurrence of pesticide residues and antibiotic residues contamination in breast milk collected from Syrian refugee lactating mothers residing in North Lebanon Camps. A total of 120 breast milk samples (40 in triplicate) were collected from camps in Akkar, North Lebanon using an electrical pump. A survey was administrated to determine socio-demographic characteristics, dietary and smoking habits and medical history of participating lactating mothers. The milk samples were analysed for the presence of antibiotic residues and pesticide residues using liquid and gas chromatography tandem mass spectroscopy (LC-MS/MS) and Gas Chromatography-Tandem Mass Spectrometry (GC-MS/MS). This study reported the absence of antibiotic residues in 96.66% of our samples (n = 120) and the presence of pesticides residues in only 5% of our total breast milk sample. Our results considered the breast milk collected from Syrian refugee lactating mothers as safe from chemical contamination. It is worth conducting more studies on other Syrian refugee camps to test the effect of camp living conditions on breast milk safety. Full article
(This article belongs to the Special Issue Analysis of Chemical Contaminants in Food)
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8 pages, 1286 KiB  
Article
Consumption of Minerals, Toxic Metals and Hydroxymethylfurfural: Analysis of Infant Foods and Formulae
by Christian Vella and Everaldo Attard
Toxics 2019, 7(2), 33; https://doi.org/10.3390/toxics7020033 - 8 Jun 2019
Cited by 21 | Viewed by 5313
Abstract
Infant foods and formulae may contain toxic substances and elements which can be neo-formed contaminants or derived from raw materials or processing. The content of minerals, toxic elements, and hydroxymethylfurfural (HMF) in infant foods and formulae were evaluated. The effect of storage temperature [...] Read more.
Infant foods and formulae may contain toxic substances and elements which can be neo-formed contaminants or derived from raw materials or processing. The content of minerals, toxic elements, and hydroxymethylfurfural (HMF) in infant foods and formulae were evaluated. The effect of storage temperature on HMF formation in infant formulae and its potential as a quality parameter was also evaluated. Prune-based foods contained the highest HMF content. HMF significantly increased when the storage temperature was elevated to 30 °C for 21 days. All trace elements were present in adequate amounts, while the concentration of nickel was higher when compared to those of other studies. The study indicates that HMF can be used as a quality indicator for product shelf-life and that the concentrations of minerals and toxic elements vary greatly due to the diverse compositions of foods and formulae. Such contaminants need to be monitored as infants represent a vulnerable group compared to adults. Full article
(This article belongs to the Special Issue Analysis of Chemical Contaminants in Food)
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13 pages, 2407 KiB  
Article
Magnetic Stirring Assisted Demulsification Dispersive Liquid–Liquid Microextraction for Preconcentration of Polycyclic Aromatic Hydrocarbons in Grilled Pork Samples
by Jitlada Vichapong, Yanawath Santaladchaiyakit, Rodjana Burakham and Supalax Srijaranai
Toxics 2019, 7(1), 8; https://doi.org/10.3390/toxics7010008 - 13 Feb 2019
Cited by 6 | Viewed by 3439
Abstract
A simple microextraction method, magnetic stirring assisted demulsification dispersive liquid–liquid microextraction, for preconcentration of five polycyclic aromatic hydrocarbons (fluorene, phenanthrene, anthracene, fluoranthrene, and pyrene) was investigated prior to analysis by high performance liquid chromatography. In this method, a mixture of extraction solvent and [...] Read more.
A simple microextraction method, magnetic stirring assisted demulsification dispersive liquid–liquid microextraction, for preconcentration of five polycyclic aromatic hydrocarbons (fluorene, phenanthrene, anthracene, fluoranthrene, and pyrene) was investigated prior to analysis by high performance liquid chromatography. In this method, a mixture of extraction solvent and disperser solvent was rapidly injected into sample solution. The magnetic stirrer agitator aided the dispersion of the extraction solvent into the sample solution. After the formation of an emulsion, the demulsifier was added, resulting in the rapid separation of the mixture into two phases. No centrifugation step was required. Several parameters affecting the extraction efficiency of the proposed method were studied, including addition of salt, kind and volume of extraction solvent, volume of demulsifier solvent, and extraction times. Under the optimum conditions, high enrichment factor, low limit of detections (LODs) and good precision were gained. The proposed method was successfully applied to analysis of polycyclic aromatic hydrocarbon residues in grilled pork samples. Full article
(This article belongs to the Special Issue Analysis of Chemical Contaminants in Food)
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13 pages, 702 KiB  
Article
Potential Antagonistic Effects of Acrylamide Mitigation during Coffee Roasting on Furfuryl Alcohol, Furan and 5-Hydroxymethylfurfural
by Dirk W. Lachenmeier, Steffen Schwarz, Jan Teipel, Maren Hegmanns, Thomas Kuballa, Stephan G. Walch and Carmen M. Breitling-Utzmann
Toxics 2019, 7(1), 1; https://doi.org/10.3390/toxics7010001 - 21 Dec 2018
Cited by 43 | Viewed by 7930
Abstract
The four heat-induced coffee contaminants—acrylamide, furfuryl alcohol (FA), furan and 5-hydroxymethylfurfural (HMF)—were analyzed in a collective of commercial samples as well as in Coffea arabica seeds roasted under controlled conditions from very light Scandinavian style to very dark Neapolitan style profiles. Regarding acrylamide, [...] Read more.
The four heat-induced coffee contaminants—acrylamide, furfuryl alcohol (FA), furan and 5-hydroxymethylfurfural (HMF)—were analyzed in a collective of commercial samples as well as in Coffea arabica seeds roasted under controlled conditions from very light Scandinavian style to very dark Neapolitan style profiles. Regarding acrylamide, average contents in commercial samples were lower than in a previous study in 2002 (195 compared to 303 µg/kg). The roasting experiment confirmed the inverse relationship between roasting degree and acrylamide content, i.e., the lighter the coffee, the higher the acrylamide content. However, FA, furan and HMF were inversely related to acrylamide and found in higher contents in darker roasts. Therefore, mitigation measures must consider all contaminants and not be focused isolatedly on acrylamide, specifically since FA and HMF are contained in much higher contents with lower margins of exposure compared to acrylamide. Full article
(This article belongs to the Special Issue Analysis of Chemical Contaminants in Food)
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14 pages, 1374 KiB  
Article
Optimization of Sample Preparation for Detection of 10 Phthalates in Non-Alcoholic Beverages in Northern Vietnam
by Thanh-Thien Tran-Lam, Yen Hai Dao, Duong Thanh Nguyen, Hoi Kim Ma, Trung Quoc Pham and Giang Truong Le
Toxics 2018, 6(4), 69; https://doi.org/10.3390/toxics6040069 - 19 Nov 2018
Cited by 7 | Viewed by 4709
Abstract
A novel method was developed for the sensitive, cheap and fast quantitation of 10 phthalates in non-alcoholic beverages by liquid–liquid extraction (LLE) combined with gas chromatography tandem mass spectrometry (GC-MS/MS). The best results were obtained when n-hexane was used as extraction solvent. [...] Read more.
A novel method was developed for the sensitive, cheap and fast quantitation of 10 phthalates in non-alcoholic beverages by liquid–liquid extraction (LLE) combined with gas chromatography tandem mass spectrometry (GC-MS/MS). The best results were obtained when n-hexane was used as extraction solvent. A central composite design (CCD) was applied to select the most appreciated operating condition. The method performance was evaluated according to the SANTE/11945/2015 guidelines and was linear in the 0.1 to 200 µg/L range for 10 phthalate compounds, with r2 > 0.996 and individual residuals <15%. Repeatability (RSDr), within-laboratory reproducibility (RSDwr), and the trueness range were from 2.7 to 9.1%, from 3.4 to 14.3% and from 91.5 to 118.1%, respectively. The limit of detection (LOD) was between 0.5 to 1.0 ng/L and the limit of quantitation (LOQ) was between 1.5 to 3.0 ng/L for all 10 compounds. The developed method was successfully applied to the analysis of non-alcoholic beverages. Full article
(This article belongs to the Special Issue Analysis of Chemical Contaminants in Food)
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13 pages, 1382 KiB  
Article
Pressurized Solvent Extraction with Ethyl Acetate and Liquid Chromatography—Tandem Mass Spectrometry for the Analysis of Selected Conazole Fungicides in Matcha
by Renata Raina-Fulton and Aisha A. Mohamad
Toxics 2018, 6(4), 64; https://doi.org/10.3390/toxics6040064 - 25 Oct 2018
Cited by 9 | Viewed by 5367
Abstract
The extraction of powdered nutraceuticals is challenging due to the low water content and high concentration of matrix components that can lead to significant matrix effects in liquid chromatography-positive ion electrospray ionization-tandem mass spectrometry (LC-ESI+-MS/MS). In this study we assess the [...] Read more.
The extraction of powdered nutraceuticals is challenging due to the low water content and high concentration of matrix components that can lead to significant matrix effects in liquid chromatography-positive ion electrospray ionization-tandem mass spectrometry (LC-ESI+-MS/MS). In this study we assess the feasibility of using pressurized solvent extraction with ethyl acetate to reduce the co-extraction of polar matrix components. Pigment attributed to chlorophyll was removed with in-cell clean-up utilizing Anasorb 747, Florisil®, and C18. Visible inspection of the extracts showed that pigment was removed from matcha, a powdered green tea sample. Pressurized solvent extraction with in-cell clean-up can be utilized to remove pigments from powdered samples such as nutraceuticals. Average matrix effect of the 32 target analytes that observed mass spectrometric signal suppression or soft MS signal enhancement was −41 ± 19% with the majority of analytes having a protonated molecular ion with m/z of 250 to 412. As generally moderate signal suppression was observed for conazole fungicides and structurally related compounds analyzed by LC-ESI+-MS/MS, it is recommended that matrix matched or standard addition calibration is used for quantitation. Catachins, other polyphenols, and caffeine are expected to contribute to the matrix effects observed in LC-ESI+-MS/MS. Diniconazole, fenbuconazole, and tebufenozide were the only target analytes with severe MS signal enhancement. Low levels (0.002–0.004 mg/kg) of prothioconazole-desthio and flusilazole were detected, along with trace levels of tebuthiuron in matcha. Full article
(This article belongs to the Special Issue Analysis of Chemical Contaminants in Food)
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12 pages, 3153 KiB  
Article
Characterization of MS/MS Product Ions for the Differentiation of Structurally Isomeric Pesticides by High-Resolution Mass Spectrometry
by Alberto Nuñez, Yelena Sapozhnikova and Steven J. Lehotay
Toxics 2018, 6(4), 59; https://doi.org/10.3390/toxics6040059 - 2 Oct 2018
Cited by 12 | Viewed by 4845
Abstract
Structural isomeric pesticides are used in agriculture and may be challenging to differentiate for accurate identification in pesticide monitoring programs. Due to structural similarity, isomeric pesticides are difficult to separate chromatographically, and thus, their accurate identification may rely solely on mass spectrometric analysis [...] Read more.
Structural isomeric pesticides are used in agriculture and may be challenging to differentiate for accurate identification in pesticide monitoring programs. Due to structural similarity, isomeric pesticides are difficult to separate chromatographically, and thus, their accurate identification may rely solely on mass spectrometric analysis (MS). In this study, we challenged the ability of high-resolution quadrupole-orbitrap (Q-Orbitrap) mass spectrometry to produce and evaluate the tandem mass spectrometry (MS/MS) product ions for the selected five pairs of isomeric pesticides from different classes: Pebulate and vernolate, methiocarb and ethiofencarb, uniconazole and cyproconazole, sebuthylazine and terbuthylazine, and orbencarb and thiobencarb. The use of Q-Orbitrap instrument with a mass error <3 ppm allowed proposed elucidation of the product ion structures with consideration of the ion formulae, data interpretation, and literature searches. Product ions unique to pebulate, vernolate, methiocarb, ethiofencarb, and uniconazole were observed. Elucidation of the observed MS/MS product ion structures was conducted, and the fragmentation pathways were proposed. This information is valuable to increase selectivity in MS/MS analysis and differentiate isomeric pesticides, and thereby reduce the rates of false positives in pesticide monitoring programs. Full article
(This article belongs to the Special Issue Analysis of Chemical Contaminants in Food)
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7 pages, 1084 KiB  
Article
Perfuorooctane Sulfonate (PFOS), Perfluorooctanoic Acid (PFOA), Brominated Dioxins (PBDDs) and Furans (PBDFs) in Wild and Farmed Organisms at Different Trophic Levels in the Mediterranean Sea
by Elena Fattore, Renzo Bagnati, Andrea Colombo, Roberto Fanelli, Roberto Miniero, Gianfranco Brambilla, Alessandro Di Domenico, Alessandra Roncarati and Enrico Davoli
Toxics 2018, 6(3), 50; https://doi.org/10.3390/toxics6030050 - 22 Aug 2018
Cited by 9 | Viewed by 4941
Abstract
The present study shows the results of perfuorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), brominated dioxins (PBDDs) and furans (PBDFs) measured in several marine fish and seafood of commercial interest at different trophic levels of the food chain. The aims were to investigate the [...] Read more.
The present study shows the results of perfuorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), brominated dioxins (PBDDs) and furans (PBDFs) measured in several marine fish and seafood of commercial interest at different trophic levels of the food chain. The aims were to investigate the level of the contamination in Mediterranean aquatic wildlife, and in farmed fish, to assess human exposure associated to fishery products consumption. Samples of wild fish were collected during three different sampling campaigns in different Food and Agriculture Organization (FAO) 37 areas of the Mediterranean Sea. In addition, farmed fish (gilthead sea bream and European sea bass) from off-shore cages from different marine aquaculture plants. Results showed contamination values of PFOS and PFOA were lower than those detected in sea basins other than the Mediterranean Sea. Concentration values of PFOS were generally higher than those of PFOA; moreover, levels in farmed fish were lower than in wild samples from the Mediterranean Sea. Intake of PFOS and PFOA through fishery products consumption was estimated to be 2.12 and 0.24 ng/kg·BW·day, respectively, for high consumers (95th percentile). Results of 2,3,7,8-substituted congeners of PBDDs and PBDFs were almost all below the limit of detection (LOD), making it difficult to establish the contribution of these compounds to the total contamination of dioxin-like compounds in fish and fishery products. Full article
(This article belongs to the Special Issue Analysis of Chemical Contaminants in Food)
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10 pages, 257 KiB  
Article
Harmful Elements (Al, Cd, Cr, Ni, and Pb) in Wild Berries and Fruits Collected in Croatia
by Michaela Zeiner and Iva Juranović Cindrić
Toxics 2018, 6(2), 31; https://doi.org/10.3390/toxics6020031 - 8 Jun 2018
Cited by 16 | Viewed by 5115
Abstract
Fruits and vegetables are considered a beneficial contribution to the human diet. Especially, berries contain a great deal of bioactive compounds, such as anthocyanins, organic acids, tannins, phenols, and antioxidants. Apart from organic substances, inorganic nutrients are also present in fruits. Some metals [...] Read more.
Fruits and vegetables are considered a beneficial contribution to the human diet. Especially, berries contain a great deal of bioactive compounds, such as anthocyanins, organic acids, tannins, phenols, and antioxidants. Apart from organic substances, inorganic nutrients are also present in fruits. Some metals and metalloids are essential for humans, whilst others may exhibit harmful effects. Wild grown berries, collected in so-called unpolluted areas, are considered to be free of any potentially toxic ingredients. However, due to transmission processes pollutants can also reach remote areas and, furthermore, metal uptake from the soil via roots has to be taken into account. Thus, the presented study focused on the determination of Al, Cd, Cr, Ni, and Pb in lingonberries, blueberries, and rose hips collected in a non-polluted area in Croatia. Neither Cd nor Cr could be found in any sample. Ni levels were mainly up to 25 mg/kg, in a comparable range to the literature data. No health threat is to be expected by eating these fruits and berries regarding Cd, Cr, and Ni. Rose hips, however, contain Pb beyond the stipulated limit in fruits, and also Al is present at a high level (8 mg/g). Full article
(This article belongs to the Special Issue Analysis of Chemical Contaminants in Food)
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413 KiB  
Communication
The Food and Beverage Occurrence of Furfuryl Alcohol and Myrcene—Two Emerging Potential Human Carcinogens?
by Alex O. Okaru and Dirk W. Lachenmeier
Toxics 2017, 5(1), 9; https://doi.org/10.3390/toxics5010009 - 11 Mar 2017
Cited by 48 | Viewed by 9117
Abstract
For decades, compounds present in foods and beverages have been implicated in the etiology of human cancers. The World Health Organization (WHO) International Agency for Research on Cancer (IARC) continues to classify such agents regarding their potential carcinogenicity in humans based on new [...] Read more.
For decades, compounds present in foods and beverages have been implicated in the etiology of human cancers. The World Health Organization (WHO) International Agency for Research on Cancer (IARC) continues to classify such agents regarding their potential carcinogenicity in humans based on new evidence from animal and human studies. Furfuryl alcohol and β-myrcene are potential human carcinogens due to be evaluated. The major source of furfuryl alcohol in foods is thermal processing and ageing of alcoholic beverages, while β-myrcene occurs naturally as a constituent of the essential oils of plants such as hops, lemongrass, and derived products. This study aimed to summarize the occurrence of furfuryl alcohol and β-myrcene in foods and beverages using literature review data. Additionally, results of furfuryl alcohol occurrence from our own nuclear magnetic resonance (NMR) analysis are included. The highest content of furfuryl alcohol was found in coffee beans (>100 mg/kg) and in some fish products (about 10 mg/kg), while among beverages, wines contained between 1 and 10 mg/L, with 8 mg/L in pineapple juice. The content of β-myrcene was highest in hops. In conclusion, the data about the occurrence of the two agents is currently judged as insufficient for exposure and risk assessment. The results of this study point out the food and beverage groups that may be considered for future monitoring of furfuryl alcohol and β-myrcene. Full article
(This article belongs to the Special Issue Analysis of Chemical Contaminants in Food)
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