Effects of Age, Fulton's Condition Index (K) and Muscle Fat on Total Mercury Content in Raw, Pre-Canning and Canned Samples of Atlantic Bluefin Tuna (Thunnus thynnus).

A total of 30 samples of Atlantic bluefin tuna were analysed for total mercury concentration. Relationships between total mercury content and age, Fulton's condition index (K) and fat content were statistically evaluated. The effect of muscle status (raw, pre-canning, canned) on mercury content was also investigated. The average total mercury content was: 1.185 ± 0.662 mg/kg in raw, 1.481 ± 0.893 mg/kg in pre-canning and 1.393 ± 0.882 mg/kg in canned samples, respectively. Canning promotes a statistically significant increase in the concentration of mercury. The weight of fish, K and fat content are useful tools to estimate the mercury accumulation in Atlantic bluefin tuna. The results of the present study represent a contribution to the assessment of the EU mercury levels in Atlantic bluefin tuna.

Analytical Approaches in Official Food Safety Control: An LC-Orbitrap-HRMS Screening Method for the Multiresidue Determination of Antibiotics in Cow, Sheep, and Goat Milk.

The presence of unauthorized substances, such as residues of veterinary medicines or chemical contaminants, in food can represent a possible health concern. For this reason, a complete legislative framework has been established in the European Union (EU), which defines the maximum limits allowed in food and carries out surveillance programs to control the presence of these substances. Official food control laboratories, in order to ensure a high level of consumer protection, must respond to the challenge of improving and harmonizing the performance of the analytical methods used for the analysis of residues of authorized, unauthorized, or prohibited pharmacologically active substances. Laboratories must also consider the state of the art of the analytical methodologies and the performance requirements of current legislation. The aim of this work was to develop a multiresidue method for the determination of antibiotics in milk, compliant with the criteria and procedures established by Commission Implementing Regulation (EU) 2021/808. The method uses an LC-Orbitrap-HRMS for the determination of 57 molecules of antibiotic and active antibacterial substances belonging to different chemical classes (beta-lactams, tetracyclines, sulfonamides, quinolones, pleuromutilins, macrolides, and lincosamides) in bovine, ovine, and goat milk samples. It provides a simple and quick sample pretreatment and a subsequent identification phase of analytes, at concentrations equal to or lower than the maximum residual limit (MRL), in compliance with Commission Regulation (EU) 2010/37. The validation parameters: selectivity, stability, applicability, and detection capability (ccß), are in agreement with the requirements of Commission Implementing Regulation (EU) 2021/808 and demonstrated the effectiveness of the method in detecting veterinary drug residues at the target screening concentration (at the MRL level or below), with a false positive rate of less than 5%. This method represents an effective solution for detecting antibiotics in milk, which can be successfully applied in routine analyses for official food control plans.

Anti- and Pro-Oxidant Activity of Polyphenols Extracts of Syrah and Chardonnay Grapevine Pomaces on Melanoma Cancer Cells.

The phenolic composition of Syrah and Chardonnay grape pomaces was studied to assess their antioxidant and prooxidant properties. Polyphenols were extracted by a "green" hydroalcoholic solvent (ethanol/water 1:1 v/v), and a detailed chemical and electrochemical characterization of the phenolic compounds was performed. The antioxidant and prooxidant capacity of the pomace was first studied by cyclic voltammetry (CV) and other reference analytical assays, then with biological tests on B16F10 metastatic melanoma cancer cells. Electrochemical data showed that, when a +0.5 V potential was applied, a low to moderate antioxidant capacity was observed. MTT test showed an increasing viability of melanoma cells, after treatments at low concentration (up to 100 µg/mL) and for a short time (6 h), but when cells were treated with higher doses of extract (≥250 µg/mL for 12/24 h), their viability decreased from 25 to 50% vs. control, depending on treatment time, dose, and extract origin. A stronger prooxidant activity resulted when 250 µg/mL of extract was combined with non-toxic doses of H2O2; this activity was correlated with the presence of copper in the extracts. This study shows the potential of winemaking by-products and suggests the opportunity to exploit them for the production of cosmeceuticals, or for combined therapies with approved anticancer drugs.

A representative sampling of tuna muscle for mercury control.

The mechanisms of mercury accumulation and distribution in fish tissues are related to its high affinity for sulfhydryl groups in proteins. There is evidence that mercury is distributed unevenly based on the different reactivity of these groups in the various muscle proteins. Tuna fish also shows numerous specialized anatomical features including the structure of the swimming muscles and some form of endothermy, which generates variations in the mercury content between dark and white muscle and between muscle tissues with different lipid content. The aim of the study is to verify, through a suitable sub lot of Thunnus thynnus caught by a static trap in south-western Sardinia, the effective uneven distribution of mercury in the various muscles and also identify the sites representative of the entire carcass. In agreement with other authors, the results show that even in the Bluefin tuna of the Mediterranean, the site "anterior extremity of upper loin (schienale in Italian)" is representative of the mercury average content of muscle tissues as a whole.

Occurrence of hexabromocyclododecanes and tetrabromobisphenol A in fish and seafood from the sea of Sardinia - FAO 37.1.3 area: Their impact on human health within the European Union marine framework strategy directive.

Levels of hexabromocyclododecane isomers α, ß, γ, (HBCDDs) and tetrabromobisphenol A (TBBP-A) were determined in 24 representative samples of different wild fish and seafood species (benthic: N = 16; pelagic: N = 8) and 16 samples of farmed bivalve molluscs from the West Mediterranean Sea (FAO 37, 1.3 sub-area). An LC-MS/MS-based method with limits of quantification (LOQS) in the range of 0.01-0.05 ng g-1 fresh weight (fw) was utilized. While α HBCDD was found in 80% of the 24 wild species samples, ß and γ congeners were found in 33% and 25%, respectively. ΣHBCDD content ranged from 0.03 (Aristeus antennatus) to 0.68 (Sardina pilchardus) ng g-1 fw as Upper Bound values across 2.00-4.46 trophic levels. In farmed molluscs, HBCDD congeners were always present and ranged from 0.22-0.52 ng g-1 fw, with the exception of one farm (1.23-2.06 ng g-1 fw), whose values suggest the presence of a regular emission source. TBBP-A levels always fell below the LOQ of 0.05 ng g-1 fw in all samples. The results are in good agreement with results of previous studies from the Mediterranean Sea. The Environmental Quality Standard for human health from fish and seafood local consumption was set at 165 µg g-1 fw. The Margin of Exposure of 490,020 as the ratio between the considered Health Based Guidance Level of 0.79 mg kg-1 body weight and the geo-referenced HBCDD intake (P95 fish and seafood intake; mean ΣHBCDD contamination) indicates no threat to food safety.

[Monitoring plan of environmental contaminants in sheep milk from areas next to an Italian contaminated site named «Aree industriali di Porto Torres e discarica di Calancoi¼ (Industrial areas of Porto Torres and landfill of Calancoi) in Sardinia Region (Southern Italy)]. / Piano di monitoraggio per la ricerca di contaminanti ambientali in latte ovino prodotto in aree prossime al sito di interesse nazionale denominato «Aree industriali di Porto Torres e discarica di Calancoi¼ in Sardegna.

OBJECTIVES: to assess concentration levels of dioxins, PCBs, and chemical elements in sheep milk produced in areas close to the Italian contaminated site (CS) located in the North-West of Sardinia (Southern Italy), named «Aree industriali di Porto Torres e discarica di Calancoi¼ (i.e., industrial areas of Porto Torres and landfill of Calancoi). DESIGN: monitoring plan of environmental contaminants on zootechnical productions based on analysis of dioxins, PCBs, heavy metals (Cd, Hg, Pb), and other elements (As, Be, Cr, Ni, Tl , Zn) in sheep bulk milk. SETTING AND PARTICIPANTS: 60 samples of sheep bulk milk were collected in rural farms where animals were fed mainly with forage and feed produced in the CS: 30 samples from farms located near the industrial area of Porto Torres and 30 taken from farms spread out the landfill area of Calancoi, a former waste dump in the East of Sassari city. MAIN OUTCOME MEASURES: the concentration levels of target substances were determined and compared to legal thresholds fixed on EU regulations. RESULTS: concentrations of target substances in all samples were below the maximum limits set by EU regulations. Dioxins and DL-PCBs (expressed as the sum) were in the range 0.20-1.30 pg WHO-TEQ/g fat, NDL-PCB (sum of the six marker congeners) were in the range 0.50-7.50 ng/g, while concentrations of all heavy metals were not detectable or were near the limit of quantitation of the method. Undetectable concentrations were also observed for the toxic elements beryllium and thallium. CONCLUSIONS: concentration levels of micro-pollutants in milk samples were significantly lower than the legal thresholds. Concentrations and congener profiles showed no relevant differences compared to milk samples from areas with low environmental impact, therefore consumption of milk from the studied area do not produce a higher intake of contaminants respect to the regional milk. The results of this study do not make the resident population safe from health risks caused by critical issue of the CS, but provide information limited to the safety of the milk from these areas, without showing peculiar contamination and hazard for food from local sheep farms.

Mercury occurrence in Italian seafood from the Mediterranean Sea and possible intake scenarios of the Italian coastal population.

Mercury (Hg) settlements in the Mediterranean Sea determine a potential toxicological relevance of seafood intakes for coastal populations. To assess this possibility, fish, molluscs, and crustaceans of commercial size of 69 different species were sampled and analyzed for total mercury (Hg(TOT)) from georeferenced areas and evaluated for their compliance with the European Union Maximum Residue Limits of 0.5 and 1.0 mg/kg wet weight (ww). Accounting for the weekly estimated seafood intake in the Italian coastal population (mean 469-626 g/person/week) it was then possible to recover threshold contamination values in seafood. Under a Tolerable Weekly Intake of 1.3 µg/kg/bw/week, a threshold seafood contamination <0.10 mg/kg ww has been derived for sensitive groups. A suitable algorithm based on the parallel MeHg and Hg(TOT) analysis on the most consumed species, helped to refine the uncertainties related to the conservative assumption in seafood all the Hg(TOT) present is in form of MeHg. This work aims to improve the link between the risk management and risk assessment strategies, with the identification of those fish and seafood species, that, when regularly consumed, could determine or prevent potential Hg(TOT)/MeHg overintakes in sensitive groups.

Liquid chromatography electrospray ionization tandem mass spectrometric determination of quassin and neoquassin in fruits and vegetables.

Quassia amara wood chips are used by organic farmers as a valid alternative to synthetic insecticides. The powder of Q. amara contains high levels of quassin, neoquassin and picrasinoside B. In this study we developed a liquid chromatography mass spectrometry method for the rapid and accurate quantification of the insecticide quassinoids on fruits and vegetables. Quassinoids were extracted from fruits and vegetables with acetonitrile and separated on a Zorbax Column Eclipse XDB C8 by isocratic elution with a mobile phase consisting of water and methanol with 0.1% of formic acid. Using a high-performance liquid chromatograph coupled with an electrospray ionization tandem mass spectrometer (HPLC/ESI-MS/MS), quassinoids were selectively and simultaneously detected monitoring the multiple reaction (MRM) transitions of proton adduct precursor ions: m/z 389.5 --> 222.9 for quassin, 391.5 --> 372.9 for neoquassin and 576.1 --> 394.5 for picrasinoside B. For all quassinoids calibration was linear over a working range of 1 and 100 microg/kg with r > 0.991. Limit of determination (LOD) and limit of quantification (LOQ) for both quassinoids were 0.5 and 1 microg/kg respectively while for picrasinoside B they were 5 and 10 microg/kg. Quassinoid recoveries ranged from 85.3% to 105.3% with coefficients of variation between 2.5% and 12.8% for fruit and vegetables. The presence of interfering compounds in the fruit and vegetable extract was evaluated and found to be minimal. Due to the linear behavior it was concluded that the multiple reaction transitions of precursor ions can be used for analytical purposes, i.e. for identification and quantification of quassin, neoquassin, and picrasinoside B in fruit and vegetable extracts at trace levels.