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Benzothiazoles are high production volume chemicals widely used in many industrial and household applications. However, information on their occurrence in aquatic organisms is very limited, although a high level of bioaccumulation is expected. In this study and for the first time, a method was developed involving subcritical water extraction followed by solid-phase microextraction coupled to gas chromatography-ion trap-tandem mass spectrometry for the determination of five benzothiazoles in seafood. The repeatability and reproducibility of the method were under 21% (%RSD, n = 5, 100 ng g−1 (dw)), while method detection limits and method quantification limits were between 0.5 and 10 ng g−1 (dw) and 1 and 50 ng g−1 (dw), respectively. Ten widely consumed fish and shellfish species from the county of Tarragona (Catalonia, Spain) were selected in order to estimate dietary exposure and to assess the human health risks. The most frequently determined compounds were benzothiazole and 2-(methylthio)-benzothiazole, with squid being the species which showed the highest level of benzothiazole (82 ng g−1 (dw)). In terms of human exposure, the current concentrations of benzothiazoles found in fish and shellfish could not be compared to threshold values because of the lack of toxicological data.

The concentrations of 19 brominated flame retardants (BFRs) (8 polybrominated diphenyl ethers (PBDEs), 8 methoxylated PBDEs (MeO-PBDEs) and 3 emerging flame retardants) were determined in 10 species of fish and shellfish widely consumed in Tarragona County (Catalonia, Spain), by pressurized liquid extraction followed by gas chromatography coupled to tandem mass spectrometry. A higher occurrence of PBDEs was found in all the analyzed samples, while MeO-PBDEs were only detected in a few ones and the levels of emerging pollutants were relatively low. In contrast, hexabromobenzene was found in almost all samples at concentrations ranging between non detected and 0.2 ng g−1 wet weight (w.w.). Salmon, sole, hake, cod and tuna showed the highest concentrations of ΣPBDEs (>0.8 ng g−1 w.w.), while mussel was the species with the highest level of MeO-PBDEs (1.5 ng g−1 w.w.). The dietary exposure of BFRs through consumption of these 10 species of fish and shellfish by the population of Tarragona County was estimated for different subpopulations, classified according to age and gender. Furthermore, calculations were performed in upper-, middle- and lower-bound risk scenarios. According to our data, the current concentrations of BFRs in fish and shellfish suggest no significant health risks for the consumers.

A novel solid phase microextraction Arrow (SPME Arrow) system has been applied for the first time to determine synthetic musk fragrances in fish samples. The lack of regulation concerning the concentration of musk fragrances in fish along with the risk associated to these compounds has led to an increased development of analytical methods on this topic. This study applies SPME Arrow followed by gas chromatography coupled to tandem mass spectrometry (ion trap) to determine nine musk fragrances and compares this novel technique with its predecessor (SPME). Parameters such as type of coating, extraction time and temperature as well as water addition were optimized to achieve higher sensitivity. Results show that detection limits ranging between 0.5 ng g−1 (for cashmeran, celestolide, phantolide, tonalide and musk ketone) and 2.5 ng g−1 (dry weight) (for musk xylene) when SPME Arrow is used instead of a conventional fibre, with an up to ten-fold increase in sensitivity. Moreover, commercial fish samples were analysed using the method developed and galaxolideand tonalidewere quantified at concentrations ranging from 6.5 ng g−1 to 17.5 ng g−1 (d.w.) and 2.9 ng g−1 and 5.1 ng g−1 (d.w.) in all the species analysed.

Generally, dietary intake assessment and risk characterization are evaluated using contaminant concentration in raw fish while it is usually ingested cooked, which can cause an overestimation because one of the essential issues for risk-benefit analysis is to determine the maximum amount of a contaminant that can be released from the food matrix and be absorbed by the human body, called bioaccessibility. Moreover, despite most seafood products are cooked before consumption, risk assessment is still evaluated in raw products, strongly affecting public health guidelines. In the present study, an in vitro bioaccessibility assay was performed for Galaxolide (HHCB) in fish samples. Raw spiked hake samples were in vitro digested and aliquots of each fraction of the digestion process were analysed. HHCB was quantitatively present in the bioaccessibility fraction. The effect of fish cooking on HHCB was also evaluated in cod and mackerel samples. Results demonstrate that steaming and grilling processes lead to a loss of 50-70% HHCB in fish.

Seafood consumption is a major route for human exposure to environmental contaminants of emerging concern (CeCs). However, toxicological information about the presence of CeCs in seafood is still insufficient, especially considering the effect of cooking procedures on contaminant levels. This study is one among a few who evaluated the effect of steaming on the levels of different CeCs (toxic elements, PFCs, PAHs, musk fragrances and UV-filters) in commercially relevant seafood in Europe, and estimate the potential risks associated with its consumption for consumers. In most cases, an increase in contaminant levels was observed after steaming, though varying according to contaminant and seafood species (e.g. iAs, perfluorobutanoate, dibenzo(ah)anthracene in Mytilus edulis, HHCB-Lactone in Solea sp., 2-Ethylhexyl salicylate in Lophius piscatorius). Furthermore, the increase in some CeCs, like Pb, MeHg, iAs, Cd and carcinogenic PAHs, in seafood after steaming reveals that adverse health effects can never be excluded, regardless contaminants concentration. However, the risk of adverse effects can vary. The drastic changes induced by steaming suggest that the effect of cooking should be integrated in food risk assessment, as well as accounted in CeCs regulations and recommendations issued by food safety authorities, in order to avoid over/underestimation of risks for consumer health. info:eu-repo/semantics/acceptedVersion

The levels of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in 8 passive air samples (PAS) and 6 lichen transplants (Ramalina fastigiata) deployed for a period of 2 months in different zones of Tarragona County (Catalonia, Spain), an area with an important number of chemical and petrochemical industries. The accumulated amount of the sum of the 16 PAHs ranged between 1363 to 7866 ng/sample in air samples. The highest concentration was found in the neighborhood of Puigdelfi (village of Perafort), in the vicinity of a big oil refinery and well under the potential influence of the petrochemical emissions. In lichen samples, the sum of the 16 PAHs ranged between 247 and 841 ng/g (dry weight), being the greatest value also observed in Puigdelfi. Data on the levels and profiles of PAHs in both passive monitoring methods were compared. A significant positive linear correlation was found between the concentrations of low molecular weight PAHs in lichens and the amounts accumulated in passive air samples (R = 0.827, P

In the framework of the FP7 ECsafeSeafood project, 62 seafood samples commercialized in Europe Union from several representative species - mackerel, tuna, salmon, seabream, cod, monkfish, crab, shrimp, octopus, perch and plaice - were analysed for residues of 21 personal care products (PCPs), including 11 UV-filters (UV-Fs) and 10 musk fragrances (musks). PCPs analysis were performed by Quick, Easy, Cheap, Effective Rugged, Safe (QuEChERS), combined with liquid-liquid extraction (LLE) or dispersive solid-phase extraction (dSPE), followed by gas chromatography-tandem mass spectrometry (GC-MS/MS). The results showed the presence in a wide range of samples of nine out of eleven UV-Fs compounds analysed, namely 2-ethylhexyl salicylate (EHS), 2-ethylhexyl,4-methoxycinnamate (EHMC), 4-methylbenzylidenecamphor (4-MBC), benzophenone-1 (BP1), benzophenone-3 (BP3), isoamyl-4-methoxycinnamate (IMC), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (DHMB), homosalate (HS), and octocrylene (OC), whereas galaxolide (HHCB), galaxolide lactone (HHCB-lactone), and tonalide (AHTN) were the most found musks. The potential risks to human health associated with the exposure to eight of the more prevalent PCPs - EHS, EHMC, 4-MBC, BP1, BP3, IMC, HHCB, and AHTN - through seafood consumption were assessed for consumers from five European countries (Belgium, Ireland, Italy, Portugal and Spain). Results showed that the human exposure to UV-Fs and musks estimated from the concentration values found in seafood and the daily consumption of concerned seafood species, were far below toxicological reference values.

The occurrence of ten synthetic musks in samples of 10 widely consumed fish and shellfish species from Tarragona (Catalonia, Spain) was determined. The most used nitro and polycyclic musks, as well as a well-known transformation product in tissues, were analyzed. Furthermore, the human health risks derived from the musk exposure through seafood consumption were characterized. None of the nitro musks were detected in any of the analyzed samples. In contrast, most of the polycyclic musks were found, being galaxolide (HHCB) and tonalide (AHTN) present in all the samples. HHCB was the greatest contributor, with maximum levels in sardine and mackerel (367 and 304 ng g−1 (d.w.) (dry weight), respectively). The highest exposure to individual musks was estimated for HHCB and HHCB-Lactone, with average values of 19.7 and 6.8 ng kg−1 bw day−1, respectively, in adults. A notably lower mean exposure was calculated for AHTN, cashmeran (DPMI) and traseolide (ATII), being ranged between 1.1 and 3.7 ng kg−1 bw day−1. The current concentrations of musks in fish and shellfish should not mean human health risks for the adult population living in Tarragona. However, a continuous monitoring would be desirable to assure that the exposure does not follow increasing temporal trends.