Maurizio Masci

The fatty acid composition of some seed oils from plants of emerging interest was studied. The benefits towards human health were evaluated by taking into account current recommendations regarding dietary intake of essential, polyunsaturated, and monounsaturated fatty acids and by discussing the pathologies for which such fatty acids exert protective action. Species studied were Hemp (Cannabis sativa), Flax (Linum usitatissimum), Milk Thistle (Silybum marianum), Perilla (Perilla frutescens), Borage (Borago officinalis), and Black Cumin (Nigella sativa). Seeds were subjected to cold milling in order to maintain their original nutritional characteristics. Chemical analyses were performed via the dual-detector gas chromatography technique by means of Flame Ionization Detection (FID) and mass spectrometry (MS) and by applying a modified version of the AOAC Official Method 991.39, thanks to which it was possible to obtain the fatty acid composition expressed as mg per gram of oil: such information is not always available in the literature for the species studied here. Comparison with the fatty acid international guidelines about the recommended intakes in g/day was made. This allowed us to evaluate whether such oils are suitable to be used as fatty acid food supplements to rebalance the Western diet, which is shown to be inadequate by numerous studies. Results show that seed oils from Cannabis sativa, Linum usitatissimum, and Perilla frutescens are suitable to be used as food supplements while seed oils from Silybum marianum, Borago officinalis, and Nigella sativa are not. It is important to note that any possible benefits from other parts of the plant (leaves, stems, flowers, and roots) are not studied or questioned by the present research, which focuses solely on fatty acids in the oil extracted from the seeds.

Polychlorinated biphenyls (PCBs) and polybrominated biphenyls (PBBs) are persistent organic pollutants still widespread in the environment and in the food chain. Both groups of these synthetic xenobiotics consist of 209 possible congeners depending on the number and position of halogens. PCBs with the same number of chlorine atoms and PBBs with the same number of bromine atoms are isomers: ten different degrees of halogenation are allowed, which results in a lot of existing isomers for both groups. The isomers have perfect correspondence in the number and type of atoms with differences only in positioning, so their mass spectra are expected to be identical with a consequent significant analytical problem in the event of coelution of the chromatographic peaks. This is not always the case, since the mass spectrometric ortho effect is capable of effectively discriminating many coeluting PCB or PBB isomers, although not all possible ones. The present paper investigates, for the first time, the reliability of qualitative and quantitative analysis by using the ortho effect: this was conducted through targeted experimental measurements on real samples of food by using different detectors. In this context, it is shown how to recognize the presence of a PCB that does not have the ortho effect when coeluting with an isomer that has. This is an important aspect that has never been studied until now. The ortho effect is extremely simple to operate once the ordinary GC-MS runs have been performed: the analyst only needs to recheck the mass spectrum for measuring the intensity of the first dehalogenation ion. The topic is of practical relevance since two different isomers can have different health hazards, and the presence of a very toxic isomer could be masked by a less toxic one. The same mass spectrometric ortho effect also deals with PXBs (i.e., mixed poly-brominated/chlorinated biphenyls), which are emerging contaminants.

The European Union’s recent decision to renew the authorization for the use of glyphosate until 15 December 2033 has stimulated scientific discussion all around the world regarding its toxicity or otherwise for humans. Glyphosate is a chemical of which millions of tons have been used in the last 50 years worldwide to dry out weeds in cultivated fields and greenhouses and on roadsides. Concern has been raised in many areas about its possible presence in the food chain and its consequent adverse effects on health. Both aspects that argue in favor of toxicity and those that instead may indicate limited toxicity of glyphosate are discussed here. The widespread debate that has been generated requires further investigations and field measurements to understand glyphosate’s fate once dispersed in the environment and its concentration in the food chain. Hence, there is a need for validated analytical methods that are available to analysts in the field. In the present review, methods for the analytical determination of glyphosate and its main metabolite, AMPA, are discussed, with a specific focus on chromatographic techniques applied to cereal products. The experimental procedures are explained in detail, including the cleanup, derivatization, and instrumental conditions, to give the laboratories involved enough information to proceed with the implementation of this line of analysis. The prevalent chromatographic methods used are LC-MS/MS, GC-MS/SIM, and GC-MS/MS, but sufficient indications are also given to those laboratories that wish to use the better performing high-resolution MS or the simpler HPLC-FLD, HPLC-UV, GC-NPD, and GC-FPD techniques for screening purposes. The concentrations of glyphosate from the literature measured in wheat, corn, barley, rye, oats, soybean, and cereal-based foods are reported, together with its regulatory status in various parts of the world and its accumulation mechanism. As for its accumulation in cereals, the available data show that glyphosate tends to accumulate more in wholemeal flours than in refined ones, that its concentration in the product strictly depends on the treatment period (the closer it is to the time of harvesting, the higher the concentration), and that in cold climates, the herbicide tends to persist in the soil for a long time.

The European Union's recent decision to renew the authorization for the use of glyphosate until 15 December 2033 stimulates the scientific discussion all around the world regarding its toxicity or otherwise for humans. Glyphosate is a chemical used by millions of tons in the last 50 years worldwide to drying weeds in cultivated fields, greenhouses, roadsides. Concern has been raised in many quarters about the possible presence in the food chain and the consequent adverse effects on health: both aspects that argue in favor of toxicity and those that instead may indicate limited toxicity of glyphosate are here discussed. The great debate that has been generated requires further investigations and field measurements to understand its fate once dispersed in the environment and its concentration in the food chain. Hence the need for validated analytical methods that are available to analysts in the field. In the present review, methods for the analytical determination of glyphosate and its main metabolite, AMPA, are discussed, with a specific focus on chromatographic techniques applied to cereal products. The experimental procedures are explained in any detail, including cleanup, derivatization, and instrumental conditions to give the laboratories involved enough information to proceed with the implementation of this line of analysis. The prevalent chromatographic methods used are LC-MS/MS, GC-MS/SIM, and GC-MS/MS but sufficient indications are also given to those laboratories that wish to use the simpler HPLC-FLD, HPLC-UV, GC-NPD or GC-FPD techniques for screening purposes. Concentrations from literature measured in wheat, corn, barley, rye, oats, soybean, and cereal-based foods are reported together with the regulatory status in various parts of the world and the accumulation mechanism. As for the accumulation in cereals, available data show that glyphosate tends to accumulate more in wholemeal flours than in refined ones, that its concentration in the product strictly depends on the treatment period (the closer it is to the time of harvesting, the higher the concentration) and that in cold climates the herbicide tends to persist in the soil for a long time.

In the present work, experimental measurements were carried out on dietary fats purchased in stores or bought online and produced in different countries of the world. Shortenings of animal origin (lard, butter) or vegetable-made (margarine, coconut oil, hydrogenated palm/soybean oil) were selected. The concentrations of organochlorines (OC pesticides and PCBs) were measured to ascertain whether the level of these contaminants in food has decreased since they were banned and to assess the today consumer exposure to such xenobiotics. Analyses were carried out by GC-ECD and GC-MS according to the United Nations Environment Program on persistent organic pollutants. Organochlorines were detected in 85% of the samples analysed. The observed levels were not high (maximum value 5.54 ± 2.33 ng g^-1) and point out a slow decline over the last years. Butter from Europe was the most studied matrix showing HCB and 4,4'-DDE as the main organochlorines that were constantly detected above the limit of quantitation. This can be explained if the past use of the two pesticides is considered. Consumption data from the EFSA database were combined with the HCB and 4,4'-DDE concentrations measured in the present research to obtain the Estimated Daily Intakes (EDIs) of the two contaminants from butter. The comparison with the Tolerable Daily Intakes (TDIs) set by World Health Organization indicates that the observed EDIs are far below the TDIs, so allowing to conclude that the risk deriving from the intake of the investigated organochlorines through butter is acceptably low for European consumers. Results relating to some non-Aroclor PCBs detected in shortenings, such as PCB 47, which have recently been discovered to be released into the environment are also reported.

The global market of food supplements is growing rapidly with a large turnover. Fish oil supplements represent a significant part of this turnover as they are believed to have important health benefits. Conversely, there are few papers in the literature about the quality control of fish oil capsules. As prior studies illustrate, a perfect agreement with the label is rarely found, and in some isolated cases, large amounts of soybean oil are also detected, indicating a true adulteration rather than a non-compliance with the label. None of the available studies refer to the Italian market, which ranks first in Europe in the consumption of food supplements. In this present communication, a quality control of fish-oil-based supplements from the Italian market was carried out for the first time. With minor deviations, all results showed substantial agreement with the label. However, the most important conclusion from this research is that compliance with the label is not enough to judge a product of good quality. The analysis of the overall fatty acid composition showed that some supplements have a high level of saturated fatty acids, and therefore they did not undergo a proper purification process. This may represent a safety issue since the purification process also allows the removal of toxic contaminants.

Milk and derivatives are a very important part in the diet of the world population. Products from goat, buffalo, and sheep species have a greater economic value than the cow ones, therefore, authenticity frauds by improperly adding cow's milk occur frequently: dairy products are among the seven more attractive foods for adulteration. Milk from each of the above‐cited animal species has its own definite profile of whey proteins (variants of α‐lactalbumin and β‐lactoglobulin) and its definite profile of caseins (variants of α_S1‐, α_S2‐, β‐, and κ‐casein). Such proteins can be usefully exploited as markers of authenticity by using capillary electrophoresis which is the technique of choice for the analysis of proteins. Due to the multiple adjustable parameters that are unknown to other analytical techniques, capillary electrophoresis is able to detect frauds in milk mixtures and cheese with little use of solvents, fast analysis time, and ease of operation. This makes it attractive and competitive for routine checks that are very important to fight the adulteration market. Advantages and limitations are discussed.

A sampling campaign from 21 sites in Italy was conducted: 15 species from fishery and three species from aquaculture, for a total of 40 determinations, were considered. A careful sample preparation preceded the instrumental analysis that was carried out by means of GC-ECD and GC-MS. Good laboratory practice was achieved by the participation in proficiency tests, by the use of certified reference materials and by applying other directives recommended by international organisations. Concentrations measured in this work were compared with a TDI proposed by some international bodies: for a person weighing 70 kg one-third of the samples from fishery, when consumed, lead to exceed this TDI if the average fish daily consumption per capita is considered. Based on the data obtained here some hypotheses on environmental spreading and influence of PCBs on human health are made. Some suggestions about the preparation of fish for consumption are also given.