Food contamination from packaging material with special focus on the Bisphenol-A.

Additives, such as bisphenol A (BPA) that are added to packaging material to enhance functionality may migrate into food products creating a concern for food safety. BPA has been linked to various chronic diseases, such as: diabetes, obesity, prostate cancer, impaired thyroid function, and several other metabolic disorders. To safeguard consumers, BPA migration limits have been defined by regulatory bodies. However, it is important to address the underlying factors and mechanisms so that they can be optimized in order to minimize BPA migration. In this review, we determine the relative importance of the factors, i.e. temperature, contact time, pH, food composition, storage time and temperature, package type, cleaning, and aging, and packaging damage that promote BPA migration in foods. Packaging material seems to be the key source of BPA and the temperature (applied during food production, storage, can sterilization and cleaning processes) was the critical driver influencing BPA migration.

Sulfites in meat: Occurrence, activity, toxicity, regulation, and detection. A comprehensive review.

Sulfites are a class of chemical compounds, SO2 releasers, widely used as additives in food industry, due to their antimicrobial, color stabilizing, antibrowning, and antioxidant properties. As the results of these pleiotropic functions they can be added to a broad range of products including dried fruits and vegetables, seafood, juices, alcoholic and nonalcoholic beverage, and in few meat products. Sulfites ingestion has been correlated with several adverse and toxic reactions, such as hypersensitivity, allergic diseases, vitamin deficiency, and may lead to dysbiotic events of gut and oral microbiota. In many countries, these additives are closely regulated and in meat products the legislation restricts their usage. Several studies have been conducted to investigate the sulfites contents in meat and meat products, and many of them have revealed that some meat preparations represent one of the main sources of SO2 exposure, especially in adults and young people. This review discusses properties, technological functions, regulation, and health implications of sulfites in meat-based foods, and lays a special emphasis on the chemical mechanisms involved in their interactions with organic and inorganic meat components.

Innovative approaches for identifying a mechanically separated meat: evaluation of radiostrontium levels and development of a new tool of investigation.

Due to food safety concerns, the European Food Safety Authority (EFSA) asked to identify useful parameters for identifying the mechanically separated meat (MSM). In this work, the 90Sr levels of MSM products were assessed for evaluating the suitability of this parameter for MSM identification. Indeed, this contaminant may accumulate in animal bones and bone fragments may be present in MSM. One hundred samples of fresh meats and meat products composed of different MSM percentages and without MSM were analyzed by ultra-low-level liquid scintillation counting. The 90Sr activity concentrations detected in meat products with high percentage of MSM were significantly higher (p ≥ 0.05) (0.099 Bq kg-1) than those of fresh meats (0.024 Bq kg-1) and meat products containing low percentage of MSM (0.011 Bq kg-1). The percentage of correct MSM identification was 61%. In order to increase this percentage and to develop a new tool of investigation, the 90Sr was elaborated in combination with other three parameters: 88Sr, Ca and ash percentage, through a multivariate approach. The precision of this tool of investigation was significantly increased (87%), higher than the reference method (Ca level) (76%), representing a valid novel approach in the identification of MSM products.

Certification of nitrate in spinach powder reference material SPIN-1 by high-precision isotope dilution GC-MS.

A high-precision exact-matching quadruple isotope dilution method (ID4MS) was employed for the quantitation of nitrate in an air-dried spinach powder Certified Reference Material (CRM). The analyte was extracted in hot water following addition of 15NO[Formula: see text] internal standard. The blend was then treated with sulfamic acid to remove nitrite and with triethyloxonium tetrafluoroborate to promote aqueous conversion of nitrate into volatile EtONO2. The derivative was analyzed by headspace GC-MS with 3-min elution time. The method performance was validated with a series of tests which demonstrated adequate selectivity and ruggedness. This method supported the development of novel SPIN-1 CRM giving a modest contribution to its uncertainty (uchar = 0.85%). With respect to previous attempts, the SPIN-1 was proven stable, homogeneous (uhom = 0.44%), and suitable for spinach monitoring under EU regulations. On dried basis, the nitrate content of SPIN-1 was found to be 22.53 ± 0.43 mg/g (Uc = 1.9%, k = 2). The material was also used in an inter-laboratory study where four laboratories employed a total of ten measurement methods. Graphical Abstract SPIN-1 Certified Reference Material for nitrate in spinach powder.

Environmental monitoring of the area surrounding oil wells in Val d'Agri (Italy): element accumulation in bovine and ovine organs.

In this work, environmental heavy metal contamination in the Val d'Agri area of Southern Italy was monitored, measuring the accumulation of 18 heavy metals (U, Hg, Pb, Cd, As, Sr, Sn, V, Ni, Cr, Mo, Co, Cu, Zn, Ca, Mn, Fe, and Al) in the organs of animals raised in the surrounding area (kidney, lung, and liver of bovine and ovine species). Val d'Agri features various oil processing centers which are potentially a significant source of environmental pollution, making it essential to perform studies that will outline the state of the art on which any recovery plans and interventions may be developed. The analysis was carried out using official and accredited analytical methods based on inductively coupled plasma mass spectrometry, and the measurements were statistically processed in order to give a contribution to risk assessment. Even though five samples showed Pb and Cd concentrations above the limits defined in the European Commission Regulation (EC) No 1881/2006, the mean concentrations of most elements suggest that contamination in this area is low. Consequently, these results also suggest that there is no particular risk for human exposure to toxic trace elements. Nevertheless, the findings of this work confirm that element accumulation in ovine species is correlated with geographical livestock area. Therefore, ovine-specific organs might be used as bioindicators for monitoring contamination by specific toxic elements in exposed areas.

Monitoring of nitrites and nitrates levels in leafy vegetables (spinach and lettuce): a contribution to risk assessment.

BACKGROUND: Nitrites and nitrates are compounds considered harmful to humans and the major part of the daily intake of nitrates in foodstuffs is related to vegetable consumption. In this work, 150 leafy vegetables samples (75 spinach and 75 lettuce) were analysed in order to assess the levels of nitrites and nitrates. The analyses were carried out by a validated ion chromatography method and the samples with nitrate concentrations higher than legal limits and/or with quantifiable concentrations of nitrites were confirmed by an alternative ion chromatography method. RESULTS: Nitrate levels higher than legal limits were detected both in spinach (four samples) and in lettuce (five samples). Nitrite residues were registered both at low concentrations--lower than 28.5 mg kg⁻¹ (12 spinach samples)--and at high concentrations, up to 197.5 mg kg⁻¹ (three spinach and one lettuce sample). CONCLUSION: Considering the non-negligible percentage of 'not-compliant' samples for nitrates (6.0%), control is needed. Moreover, it is possible to suggest the introduction in the Communities Regulations of a 'maximum admissible level' for nitrites in leafy vegetables.

Monitoring of Animal Feed Contamination by Mycotoxins: Results of Five Years of Official Control by an Accredited Italian Laboratory.

Mycotoxin contamination of animal feed is a complex issue in both animal wellness and food safety. The most diffused mycotoxins subject to the official control of animal feed are Aflatoxin B1 (AF), Zearalenone (ZEA), Deoxynivalenol (DON), Ochratoxin A (OCRA), Fumonisins (FUMO), and T-2/HT-2 toxins. This work describes the results of five years of monitoring focused on the evaluation of mycotoxin contamination of animal feed. Analytical determinations were carried out by means of accredited ELISA. The obtained results showed a non-alarming scenario, with several samples resulting as "non-compliant" according to the Maximum Residue Limits (MRLs) set in European Regulation No. 574/2011. Out of 722 analyzed samples coming from 2 Italian regions, Apulia and Basilicata, 14 samples were characterized by mycotoxin concentrations higher than related MRL; in particular, 5, 4, and 5 non-compliant samples for DON, AF, and ZEA, respectively. This study also evaluated the possible correlations between mycotoxin type and feed use with a special focus on animal sensitivity to mycotoxins.

Red Meat Heating Processes, Toxic Compounds Production and Nutritional Parameters Changes: What about Risk-Benefit?

The heating process is a crucial step that can lead to the formation of several harmful chemical compounds in red meat such as heterocyclic aromatic amines, N-Nitrosamines, polycyclic aromatic hydrocarbons and acrylamide. Meat has high nutritional value, providing essential amino acids, bioactive compounds and several important micronutrients which can also be affected by heating processes. This review aims to provide an updated overview of the effects of different heating processes on both the safety and nutritional parameters of cooked red meat. The most-used heating processes practices were taken into consideration in order to develop a risk-benefit scenario for each type of heating process and red meat.

Microwave-Assisted Extraction/UHPLC-Q-Orbitrap-MS-Based Lipidomic Workflow for Comprehensive Study of Lipids in Soft Cheese.

In this work, Microwave-Assisted Extraction (MAE) was proposed as an alternative and environmentally friendly technique in lipidomics to study the lipid fingerprint of soft cheeses, such as mozzarella. For method development, a first step concerning an evaluation of extraction solvents was carried out via testing three different mixtures, including methanol/ethyl acetate, isopropanol/ethyl acetate, and ethanol/ethyl acetate, at a 1:2 v/v ratio. The latter was chosen as a solvent mixture for subsequent method optimization. MAE conditions, in terms of solvent volume, time, and temperature, were explored to define their effects on extraction capability through a full factorial experimental design. The best compromise to extract more lipids at the same time was obtained with 24 mL g-1 for solvent-to-solid ratio, 65 °C for temperature, and 18 min for time. Lipid analyses were conducted by UHPLC-Q-Orbitrap-MS associated with multivariate statistics. The developed lipidomic workflow allowed for the extraction of over 400 lipids grouped into 18 different subclasses. The results confirmed that MAE is a suitable technique for lipid extraction in the omics approach with high efficiency, even using low-cost and less toxic solvents. Moreover, a comprehensive structure characterization of extracted lipids, in terms of fatty acid composition and regiochemistry, was carried out.

Headspace Solid-Phase Microextraction/Gas Chromatography-Mass Spectrometry and Chemometric Approach for the Study of Volatile Profile in X-ray Irradiated Surface-Ripened Cheeses.

X-ray irradiation is an emerging non-thermal technology that is used as a preservation and sanitization technique to inactivate pathogens and spoilage organisms, increasing the shelf life of products. In this work, two different types of surface-ripened cheeses, Brie and Camembert, produced with cow milk, were treated with X-rays at three dose levels, 2.0, 4.0 and 6.0 kGy, to evaluate the irradiation effects on the volatile profile using a volatolomic approach. The headspace solid-phase microextraction (HS-SPME) technique combined with gas chromatography-mass spectrometry (GC-MS) was used to extract and analyze the volatile fraction from these dairy matrices. The HS-SPME method was optimized by a central composite design in combination with a desirability optimization methodology. The Carboxen/PDMS fiber, 50 °C for extraction temperature and 60 min for time extraction were found to be the best parameter settings and were applied for this investigation. The obtained fingerprints demonstrated that the irradiation-induced changes are dose dependent. The X-ray irradiation produced many new volatiles not found in the non-irradiated samples, but it also varied the amount of some volatiles already present in the control. Specifically, aldehydes and hydrocarbons increased with the irradiation dose, whereas alcohols, carboxylic acids, esters, methyl esters, ketones, lactones and sulfur-containing compounds showed a non-linear dependence on the dose levels; indeed, they increased up to 4.0 kGy, and then decreased slightly at 6.0 kGy. This trend, more evident in the Camembert profile, is probably due to the fact that these compounds are involved in different oxidation mechanisms of lipids and proteins, which were induced by the radiation treatment. In these oxidative chemical changes, the production and degradation processes of the volatiles are competitive, but at higher doses, the decomposition reactions exceed those of formation. A principal component analysis and partial least square discriminant analysis were used to discriminate between the treated and untreated samples. Moreover, this study allowed for the identification of potential markers of X-ray treatment for the two cheeses, confirming this approach as a useful tool for the control of irradiated surface-ripened cheeses.

Development of a highly sensitive method based on QuEChERS and GC-MS/MS for the determination of polycyclic aromatic hydrocarbons in infant foods.

Polycyclic aromatic hydrocarbons (PAHs) are environmental contaminants that can be found in various food products, including those intended for infants. Due to their potential health risks, it is crucial to develop sensitive analytical methods for the accurate determination of PAHs in infant foods. This study describes the development and validation of a highly sensitive method for the quantification of European PAH markers, namely benzo[a]pyrene, benzo[a]anthracene, chrysene, and benzo[b]fluoranthene, using gas chromatography-tandem mass spectrometry (GC-MS/MS), in baby food samples. The first step was the optimization of the sample preparation procedure, performed using different methods based on the QuEChERS approach, also testing different extraction solvents. Several factors such as extraction efficiency, selectivity, and recovery were evaluated to choose the most effective procedure for sample preparation. Furthermore, the GC-MS/MS method was optimized, evaluating parameters such as linearity, sensitivity, accuracy, and robustness using spiked infant food samples. The method demonstrated excellent linearities with a correlation coefficient higher than 0.999 over a wide concentration range, and limits of detection and limits of quantification in the range 0.019-0.036 µg/kg and 0.06-0.11 µg/kg, respectively. Extraction recoveries were between 73.1 and 110.7%, with relative standard deviations always lower than 8%. These findings are compliant with the indications of the European Commission (Reg. 836/2011). To assess the applicability of the method to official control activities, a survey was conducted on commercially available infant food products. Four markers were determined in commercial samples belonging to different food categories for infants and young children. The outcome of this monitoring showed that PAH contamination, in all samples, was below the quantification limits. In conclusion, the developed GC-MS/MS method provides a highly sensitive and reliable approach for the determination of PAHs in baby foods. The optimized sample preparation, instrumental parameters, and validation results ensure accurate quantification of 4 PAHs even at trace levels. This method could contribute to the assessment of PAH exposure in infants and it could support regulatory efforts to ensure the safety and quality of infant food products with regular monitoring.

A multiresidual method based on ion-exchange chromatography with conductivity detection for the determination of biogenic amines in food and beverages.

In the present work a sensitive and accurate method by ion chromatography and conductimetric detection has been developed for the determination of biogenic amines in food samples at microgram per kilogram levels. The optimized extraction procedure of trimethylamine, triethylamine, putrescine, cadaverine, histamine, agmatine, spermidine, and spermine from real samples, as well as the separation conditions based on a multilinear gradient elution with methanesulfonic acid and the use of a weak ionic exchange column, have provided excellent results in terms of resolution and separation efficiency. Extended calibration curves (up to 200 mg/kg, r > 0.9995) were obtained for all the analyzed compounds. The method gave detection limits in the range 23-65 µg/kg and quantification limits in spiked blank real samples in the range 65-198 µg/kg. Recovery values ranged from 82 to 103 %, and for all amines, a good repeatability was obtained with precision levels in the range 0.03-0.32 % (n = 4). The feasibility and potential of the method were tested by the analysis of real samples, such as tinned tuna fish, anchovies, cheese, wine, olives, and salami.

Effect of Different Cooking Treatments on the Residual Level of Nitrite and Nitrate in Processed Meat Products and Margin of Safety (MoS) Assessment.

Nitrite and nitrate are well-known food additives used in cured meats and linked to different food safety concerns. However, no study about the possible effect of cooking treatment on the residual level of these compounds before consumption is available. In this work, 60 samples of meat products were analyzed in order to evaluate the variation in residual nitrite and nitrate level after baking, grilling and boiling. The analyses by ion chromatography demonstrated that meat cooking leads to a decrease in nitrite and an increase in nitrate residual levels in the final products. Meat boiling caused an overall decrease in two additives' concentration, while baking and particularly grilling caused an increase in nitrate and, in some cases, nitrite as well. Some regulatory aspects were also considered, such as the possibility of revising the legal limit of nitrate from the actual 150 mg kg-1 to a more cautious 100 mg kg-1. Indeed, several meat samples (bacon and swine fresh sausage) resulted in a higher nitrate concentration than the legal limit after cooking by grilling (eleven samples) or baking (five samples). Finally, the Margin of Safety evaluation demonstrated a good level of food safety, all values being higher than the protective threshold of 100.

Novel Approaches in Food Preservation and Their Impact on the Food System.

The increase in consumer demand for safe, convenient, and fresh food with an extended shelf life is accompanied by an interest in the environmental impacts caused by the food industry [...].

Untargeted Lipidomics and Chemometric Tools for the Characterization and Discrimination of Irradiated Camembert Cheese Analyzed by UHPLC-Q-Orbitrap-MS.

In this work, an investigation using UHPLC-Q-Orbitrap-MS and multivariate statistics was conducted to obtain the lipid fingerprint of Camembert cheese and to explore its correlated variation with respect to X-ray irradiation treatment. A total of 479 lipids, categorized into 16 different lipid subclasses, were measured. Furthermore, the identification of oxidized lipids was carried out to better understand the possible phenomena of lipid oxidation related to this technological process. The results confirm that the lipidomic approach adopted is effective in implementing the knowledge of the effects of X-ray irradiation on food and evaluating its safety aspects. Furthermore, Partial Least Squares-Discriminant Analysis (PLS-DA) and Linear Discriminant Analysis (LDA) were applied showing high discriminating ability with excellent values of accuracy, specificity and sensitivity. Through the PLS-DA and LDA models, it was possible to select 40 and 24 lipids, respectively, including 3 ceramides (Cer), 1 hexosyl ceramide (HexCer), 1 lysophosphatidylcholine (LPC), 1 lysophosphatidylethanolamine (LPE), 3 phosphatidic acids (PA), 4 phosphatidylcholines (PC), 10 phosphatidylethanolamines (PE), 5 phosphatidylinositols (PI), 2 phosphatidylserines (PS), 3 diacylglycerols (DG) and 9 oxidized triacylglycerols (OxTG) as potential markers of treatment useful in food safety control plans.

Characterization and Quantification of Arsenic Species in Foodstuffs of Plant Origin by HPLC/ICP-MS.

Arsenic is a well-known carcinogenic, mutagenic and toxic element and occurs in the environment both as inorganic arsenic (iAs) and organoarsenical compounds (oAsCs). Since the toxicity of arsenic compounds depends on their chemical form, the identification and determination of arsenic species are essential. Recently, the European Food Safety Authority, following the European Commission request, published a report on chronic dietary exposure to iAs and recommended the development and validation of analytical methods with adequate sensitivity and refined extraction procedures for this determination. Moreover, the authority called upon new arsenic speciation data for complex food matrices such as seaweeds, grains and grain-based products. Looking at this context, an optimized, sensitive and fast analytical method using high performance liquid chromatography followed by inductively coupled plasma-mass spectrometry (HPLC/ICP-MS) was developed for the determination of iAs (sum of arsenite-AsIII and arsenate-AsV) and the most relevant oAsCs, arsenobetaine, dimethylarsinic acid and monomethylarsonic acid. The method was validated with satisfactory results in terms of linearity, sensitivity, selectivity, precision, recovery, uncertainty, ruggedness and matrix effect, and then successfully applied for the analysis of several matrices, i.e., processed and unprocessed cereal and cereal products, fruits, vegetables, legumes, seaweeds, nuts and seeds. The results obtained indicate that not only seaweed and rice matrices but also many cereals, legumes and plant-based foods for infants and young children contain significant concentrations of iAs and oAsCs. These findings contribute to the data collection necessary to assess the role of these matrices in the total arsenic exposure and if specific maximum limits have to be established.

Volatolomic approach by HS-SPME/GC-MS and chemometric evaluations for the discrimination of X-ray irradiated mozzarella cheese.

In this work, an untargeted screening of the volatile profile of X-ray irradiated mozzarella cheese was carried out to study the possible radio-induced modifications. A Central Composite Design (CCD) for Response Surface Methodology (RSM) was employed to optimise the HS-SPME analysis of volatile organic compounds (VOCs). The optimised HS-SPME conditions, in terms of sample amount (5.0 g), extraction temperature (50 °C) and extraction time (75 min), were used to analyse non-irradiated and irradiated samples at three dose levels, 1.0, 2.0, 3.0 kGy. Partial Least Squares-Discriminant Analysis (PLS-DA) and Linear Discriminant Analysis (LDA) were applied to explore the variation of volatile profile with respect to the X-ray irradiation treatment. Both methods highlighted a high discriminant capability with excellent values of accuracy, specificity and sensitivity, demonstrating the effectiveness of the volatolomic approach to evaluate the variations induced by the treatment and allowing to select a total of 35 VOCs as potential irradiation markers.

Monitoring of polyphosphate levels in animal source products collected in Italy by means of ion chromatography with suppressed conductivity detection.

Polyphosphates (PPs) constitute a class of food additives widely used due to their ability to exercise different useful activities. The food safety concern about the use of PPs in food is both the possible non-declared addition and some health effects, such as bile duct stones, decrease in oligo-element absorption, and allergic reactions in susceptible people. In this study, an analytical method based on ion chromatography with conductivity detection was applied for the detection and quantification of PPs in 238 samples of animal-derived products such as meat, dairy, and fish products. A contribution to risk assessment was also included. The monitoring confirmed the absence of non-compliant results. All concentrations of PPs were indeed lower than the legal limits set in European Regulation No. 1333/2008. Moreover, no residue of PPs was detected (> limit of quantification: 0.09 g kg-1) in samples where it was not reported on the product label. No PPs were detected in mollusks, meat-based preparations, semi-ripened, unripened, and spun paste cheese, while they are widely used in surimi, with concentrations in the range of 0.1-0.5 g kg-1. The highest concentrations were quantified in a würstel sample (4.7±0.3 g kg-1) and a spreadable cheese sample (8.9±0.7 g kg-1). Considering that the high exposure scenario together with a very susceptible population group (toddlers) were taken into account for this risk exposure study and that the highest admissible daily intake obtained was equal to 10.4%, the assessment demonstrated that the actual use of PPs in food does not pose a risk for food safety.

Effect of different cooking treatments on the residual level of sulphites in shrimps.

Sulphiting agents (or sulphites) are a class of food additives identified in Europe by codes E220-E228. Their addition in crustaceans is permitted with specific legal limits for avoiding the so-called "blackspot" that is a defect that compromises the marketability of these products. High levels of ingested sulphites may cause pseudoallergenic reactions in susceptible people. Moreover, they can exercise mutagenic and citotoxic effects other that destroy some vitamins such as thiamine, folic acid, nicotinamide and pyridoxal. The residual level of sulphites in crustaceans can be considerably affected by the specific method of cooking. In this study, 5 traditional procedures of cooking - grilling, oven, frying, steaming and stewed cooking - were compared to verify their effect on the residual concentration of sulphites in shrimp samples. The analytical determination was carried out using a fully validated and accredited analytical method by ion chromatography with conductivity detection. The results demonstrated that cooking leads to the decrease of sulphites levels in the products, with the highest percentage of reduction (55.3%) obtained by steaming and the lowest using oven (13.9%). The results of this study confirm that the specific method of cooking should be taken into account during "total diet studies" and risk assessment for appraising the effective number of sulphites ingested from crustaceans consumption.

Determination of Nitrate and Nitrite in Swiss Chard (Beta vulgaris L. subsp. vulgaris) and Wild Rocket (Diplotaxis tenuifolia (L.) DC.) and Food Safety Evaluations.

Nitrite and nitrate levels in vegetables are a matter of concern due to their toxicity at high levels and nitrate high accumulation. Moreover, there is a lack of knowledge about their levels in some types of widely consumed vegetables such as chard and rocket. In this study, 124 Swiss chard and wild rocket samples were analyzed for determining nitrite and nitrate using validated and accredited analytical methods by ion chromatography with conductivity detection. High nitrite concentrations, up to 219.5 mg kg−1 f.w., were detected in one Swiss chard and three wild rocket samples. One Margin of Safety (MoS) value was <1. Regarding nitrate, in Swiss chard samples the mean concentration (2522.6 mg kg−1) was slightly higher than those reported in the literature for spinach and lettuce. No MoS was <1, but 83% of values were <100. Nitrate concentrations higher than the legal limit were quantified in 11 rucola samples. The verification of 25% of wild rocket samples with nitrate concentration higher than the legal limit confirmed the need for official control. This study also suggests the introduction of legal limits for nitrite/nitrate in Swiss chard and nitrite in wild rocket.