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Human exposure to contaminated food is a general health concern worldwide; it is necessary to evaluate food safety with respect to contaminants present in the edible parts of major food crops. This study evaluated the concentrations of 17 trace elements (As, Be, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se, Sn, Tl, V, and Zn) from 51 potato plantations in the Campania region, inside the area known as the "Triangle of Death," with inductively coupled plasma mass spectrometry analysis. Results confirm that the potatoes collected from the suburban area of Naples contained concentrations of trace elements below the safe limits prescribed by the Food and Agriculture Organization of the United Nations and the World Health Organization. The concentrations of elements were similar to those reported for potatoes grown in other countries. Monitoring the content of toxic and potentially toxic elements is one of the most important aspects of food quality assurance. The environmental persistence of metals may result in the accumulation of significant levels of these contaminants in plants. They are absorbed to different extents, depending on their source, soil and climatic factors, plant genotype, and agrotechnical conditions, thereby entering the food chain and representing a risk to human health. [ABSTRACT FROM AUTHOR]

Perfluorooctane sulfonate (PFOS) and Perfluorooctanoic acid (PFOA) are environmental contaminants belonging to a chemical group known as perfluoroalkyl substances (PFASs), which are very persistent in the environment. PFASs are potential reproductive and developmental toxicants and are considered to be endocrine disrupters. These compounds have been found with greater frequency in fish and other seafood compared to other food groups. In fact, aquatic ecosystems represent the final reservoir for PFASs due to their high affinity for sedimentary and living organic matter. Recommendation161/2010/EU stated that the Member States should carry out analysis of perfluoroalkylated substances in order to detect the presence of PFOS and PFOA by making use of an analytical method that has been proven to generate reliable results. The LC-MS/MS method described here has been developed for detecting PFOS and PFOA in fish and cereals. Validation of this method resulted in limits of quantification (LOQs) varying from 0.50 μg/kg for PFOA to 0.70 μg/kg for PFOS, fulfilling recoveries (95–109%), and showing a good linearity (R2 = 0.99). Precision varied from 4.43% to 8.97% of repeatability for PFOA and from 6.30% to 12.33% of repeatability for PFOS. [ABSTRACT FROM AUTHOR]

The presence and distribution of the 16 polycyclic aromatic hydrocarbons (PAHs) priority pollutant listed by US EPA (Naphthalene, Acenaphthylene, Acenaphthene, Fluorene, Phenanthrene, Anthracene, Fluoranthene, Pyrene, Benzo[a]anthracene, Chrysene, Benzo[b]fluoranthene, Benzo[k]fluoranthene, Benzo[a]pyrene, Dibenzo[a,h]anthracene, Benzo[g,h,i]perylene, Indeno[1,2,3-c,d]pyrene) were investigated in sediments from 35 stations of the Ligurian coast (Northern Italy). Results were shown as total PAH concentrations (PAHs) and molecular indices based on ratios of selected PAH concentrations were used to differentiate PAHs from pyrogenic and petrogenic origin. Analysis was performed by gas/chromatography mass spectrometry (GC/MS) with selected ion monitoring (SIM). Total PAHs concentrations ranged from 1113 to 17006 ng/g of dry matrix. PAH profiles varied according to the nature of the site and its proximity to sources; in general, the contamination levels of total PAHs were similar to those observed in contaminated and slightly contaminated sediments of the Mediterranean Sea. In some cases the concentration of contaminants is influenced by physical circulation processes that raise the concentrations of anthropogenic pollutants offshore an order of magnitude higher than those near industrial and harbors activities. [ABSTRACT FROM AUTHOR]

The presence and distribution of the 16 polycyclic aromatic hydrocarbons (PAHs) priority pollutant listed by US EPA (Naphthalene, Acenaphthylene, Acenaphthene, Fluorene, Phenanthrene, Anthracene, Fluoranthene, Pyrene, Benzo[a]anthracene, Chrysene, Benzo[b]fluoranthene, Benzo[k]fluoranthene, Benzo[a]pyrene, Dibenzo[a,h]anthracene, Benzo[g,h,i]perylene, Indeno[1,2,3-c,d]pyrene) were investigated in sediments from 35 stations of the Ligurian coast (Northern Italy). Results were shown as total PAH concentrations (PAHs) and molecular indices based on ratios of selected PAH concentrations were used to differentiate PAHs from pyrogenic and petrogenic origin. Analysis was performed by gas/chromatography mass spectrometry (GC/MS) with selected ion monitoring (SIM). Total PAHs concentrations ranged from 1113 to 17006 ng/g of dry matrix. PAH profiles varied according to the nature of the site and its proximity to sources; in general, the contamination levels of total PAHs were similar to those observed in contaminated and slightly contaminated sediments of the Mediterranean Sea. In some cases the concentration of contaminants is influenced by physical circulation processes that raise the concentrations of anthropogenic pollutants offshore an order of magnitude higher than those near industrial and harbors activities. [ABSTRACT FROM AUTHOR]

Highlights: [•] Selenium accumulation in tissues can be reverted after a Se withdrawal period. [•] Selenium concentration decreased slower in muscle than in liver and kidney. [•] Selenium induced changes in levels of antioxidant markers in liver and kidney. [•] Changes of biochemical markers persisted even after the withdrawal period. [Copyright &y& Elsevier]

Highlights: [•] Growth was faster, but not statistically significant in Se exposed crayfish after 8 weeks. [•] High Se levels were measured in exoskeleton and hepatopancreas of both Se exposed sexes. [•] Lower values of the health indicator HI were recorded in both Se exposed sexes. [•] Selenium can deplete the hepatopancreas energy reserves, mainly in male crayfish. [ABSTRACT FROM AUTHOR]

Abstract: 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 (HgTOT) from georeferenced areas and evaluated for their compliance with the European Union Maximum Residue Limits of 0.5 and 1.0mg/kgwet weight (ww). Accounting for the weekly estimated seafood intake in the Italian coastal population (mean 469–626g/person/week) it was then possible to recover threshold contamination values in seafood. Under a Tolerable Weekly Intake of 1.3μg/kg/bw/week, a threshold seafood contamination <0.10mg/kgww has been derived for sensitive groups. A suitable algorithm based on the parallel MeHg and HgTOT analysis on the most consumed species, helped to refine the uncertainties related to the conservative assumption in seafood all the HgTOT 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 HgTOT/MeHg overintakes in sensitive groups. [Copyright &y& Elsevier]

Abstract: The effects of a selenium (Se) diet (1.0mg Sekg−1) were investigated on growth, accumulation and antioxidant response in juvenile Tinca tinca at three endpoints (0, 4 and 8 weeks). Growth and condition factor (K >1.5) for both control (0.25mg Sekg−1) and Se tench were not significantly affected. Se exposed fish exhibited the highest Se level in the kidney and the liver after 4 weeks. By feeding more Se the accumulation capacity of tench did not increase and a plateau, mainly for the liver, was thus reached. Se level remained almost constant in the muscle if compared to own control and for each endpoint. Superoxide dismutase activity in both tissues was not affected by Se supplementation and the higher catalase level in the kidney might support the hypothesis that the enzyme was adequate to remove the hydrogen peroxide production following Se exposure. However, supplemented diet with higher Se level could be critical for tench, as it may cause a lowering of glutathione peroxidase and glutathione reductase activities facilitating the onset of oxidative damage. The enhancement of thiol level and glutathione S-transferase activity, mainly in the liver, could be the signals of the only protection against the oxidative damage induced by Se. [Copyright &y& Elsevier]

Bovine spongiform encephalopathy is a prion disease of ruminants that was first recognized in 1986 in the United Kingdom. Early in the epidemic, it became obvious that the presence of meat and bone meal in feed rations was a common factor in all bovine spongiform encephalopathy cases. The first ban of derived animal proteins in feed was enforced in Europe in 1994 and implemented by Regulation 999/2001 that prohibited the feeding of animal-derived protein to farm animals. The only official method currently accepted by the European Union Commission for test for the presence of animal-derived proteins in feedstuffs is feed microscopy. In Italy, monitoring of feedstuff safety is provided by both the Ministry of Health and the Ministry of Agriculture. The quality of official control, usually assessed by verifying the reproducibility and the accuracy of the testing method, is of fundamental importance for all laboratories and institutions using these results for comparative purposes. The aims of this study were to assess the reproducibility of the official method over all the Italian surveillance network and to provide a model for evaluating the performance of the monitoring system. The accuracy of the identification of the animal class of derived protein detected (avian, mammalian, or aquatic organism) was assessed. The interlaboratory agreement within the overall network reached 0.97 (95% confidence interval of 0.95 to 0.98) for determining the presence or absence of animal-derived proteins (e.g., for mammalian, avian, or aquatic species), and specificity of the identification of the animal class indicated that fish proteins are more easily recognized than are avian or mammalian proteins. [ABSTRACT FROM AUTHOR]

The Farm to Fork strategy promotes the development of organic farming and discourages the use of artificial fertilizers. The sustainable agricultural system increases the reduction of waste, allows the reuse of by-products and prefers renewable resources for the production of fertilizers. The European Union (EU) Regulation 2019/1009, called the Regulation on Fertilizer Products (FPR), enhances biomass conversion in organic fertilizers through the exploitation of certain animal by-products. High- and medium-risk animal by-products (Category 1 and 2 materials) must not be recycled in the food chain and therefore must be traceable and permanently marked with glyceroltriheptanoate (GTH) to discriminate them from low-risk materials [processed animal proteins (PAPs) and category 3 fat]. The EU regulates the use of category 2 meat and bone meal (MBM) and PAPs for fertilizers' production which can ensure a proper supply of macro, micronutrients and organic matter. This study aimed to improve fat extraction and to quantify with gas chromatography mass spectrometry (GC–MS) the detectable amount of GTH in organic fertilizer containing MBM, PAPs, and dry manure in different percentages. The following performance parameters were evaluated: fat recovery (%), GTH recovery (%), matrix effect (ME%), linearity range, coefficient of variation (CV%), and repeatability limit (r). This research represents a first evaluation of organic fertilizers produced from MBM, PAPs, and dry manure and its willing to be a starting point for a deeper investigation of a higher number of organic fertilizers produced from different kind of animal by-products' raw materials according to FPR regulation. [ABSTRACT FROM AUTHOR]

The implementation of the European Union strategy for polychlorodibenzo-dioxins and -furans (PCDD/Fs), and dioxin-like polychlorobiphenyls (DL-PCBs) is determining a general reduction of their presence in the environment and in the food chain. The most important route for human exposure to these substances is food consumption and, as a consequence, a progressive decrease of their dietary intake has been observed in the last decades. In this context, it seemed worth updating the PCDD/F and DL-PCB intake estimation for the Italian population. A total of 2659 samples of food of animal and vegetable origin analyzed for PCDD/Fs and DL-PCBs in the period 2013–2016 by accredited official laboratories and the national food consumption database were considered for the dietary intake assessment in different age groups of the Italian general population The median cumulative intake estimates expressed as pg WHO-TEQ/kg body weight per day and computed with a deterministic and a probabilistic approach were 1.40–1.52 for children, 0.82–0.85 for adolescents, and 0.64–0.61 for adults, respectively. Such results confirm the decreasing trend of PCDD/F and DL-PCB dietary intake even though the Tolerable Daily Intake (TDI) value of 2 WHO-TEQ/kg body weight per day is exceeded at the 95th percentile for all age groups, with children as sensitive group. Most contributing food categories to the intake resulted fish, food of vegetable origin, and cheese. A sensitivity analysis was also performed to calculate the target contamination levels able to keep the dietary exposure below the TDI. Computed target levels fall between P50 and P97 of the occurrence distribution of the main food groups, meaning that most of the Italian food production can be considered safe. [ABSTRACT FROM AUTHOR]

Following the bovine spongiform encephalopathy (BSE) in 2001, processed animal proteins (PAPs) reintroduction is envisaged in non-ruminant feed thanks to their high protein content, easy availability and cost-effective characteristics. PAPs must be submitted to rendering practices, providing sterilization of products, under standardized conditions of temperature and pressure, according to Regulation (EC) No 142/2011. However, the chemical risk associated to these raw materials has been never evaluated. The aim of this study was to develop and validate a reliable liquid chromatography tandem mass spectrometry (LC–MS/MS) method for the determination and quantification of tetracycline residues in PAPs at µg kg−1 level. The LC–MS/MS method performances were evaluated in terms of specificity, linearity (25–500 µg kg−1), limit of quantitation (LOQ) (25 µg kg−1), accuracy and precision (CV% < 25%), uncertainty, recovery (80–120%) and ruggedness. All the evaluated parameters fulfilled the analytical performance criteria, and the validated LC–MS/MS method fits for purpose as confirmatory method on the occurrence of residues (µg kg−1) of tetracyclines in PAPs. PAPs are a powerful product which could be used both as raw materials in feed and in organic fertilizer production in a circular economy context. Therefore, the lack of regulation and control over antibiotic occurrence should be implemented to avoid a misuse and an increment of antibiotic resistance pressure over the environment and to ensure safety of the feed and food chain. [ABSTRACT FROM AUTHOR]

Early in this century, the crisis connected to the spread of bovine spongiform encephalopathy caused a great concern related to the use of animal by-products (ABPs). According to the Commission Regulation (EU) No 1069/2009, these materials are classified in three categories according to their related risk. In 2011 Commission Regulation (EU) No 142/2011 established that meat and bone meal (MBM) and fat deriving from ABPs not intended for human consumption (category 1 and 2) are required to be permanently marked with glyceroltriheptanoate (GTH), at a minimum concentration of 250 mg kg–1 of fat, while category 3 processed animal proteins (PAPs) must not contain this compound. PAPs are bio resources, which could be used in a renewable and regenerative way in a circular economy model for a conscious usage of raw materials. The aim of this study was to provide information on GTH occurrence in MBM and, if any, in PAPs. Samples were collected from 2017 to 2021 and analysed by GC-MS. Detected non-compliant samples were exclusively of MBM category 1 and 2, probably due to the addition of an inadequate amount of GTH during the manufacturing processes. These results highlighted the importance of National Monitoring Programs as a useful tool to minimise safety related risk due to the misuse of GTH. Thus, investigating the critical points in feed supply-chain and sharing the information on its occurrence may help to improve animal and human wellness and safety. [ABSTRACT FROM AUTHOR]

Highlights: [•] Sturgeon accumulated selenium in tissues with a dose-response relationship. [•] The highest Se concentration was recorded in liver. [•] A dose-response relationship for antioxidant markers was recorded in liver. [•] GPx activity provided to sturgeon a great defense ability against selenium. [ABSTRACT FROM AUTHOR]

In 2007 and 2008, renal stone formation and kidney damage in human infants were linked to consumption of melamine (MEL)-contaminated infant formula, as well as renal failure and death in pets due to pet food containing both MEL and cyanuric acid (CYA). The aim of this study was to examine the effects of MEL and CYA administered individually or in combination on concentrations of certain metabolites and enzyme activities that serve as markers for oxidative stress in kidney and liver of rainbow trout. In addition, the levels of muscle MEL and renal crystal formation were determined. Trout were fed MEL and/or CYA for 8 wk at 250, 500, or 1000 mg of each compound/kg in feed. Fish muscle residues of MEL exhibited a dose-response relationship. Coexposure of trout to MEL and CYA at the highest dose led to lower MEL residue concentrations in muscle compared to exposure to MEL alone. Renal MEL–CYA complexes were found in kidneys of fish treated with combined MEL and CYA. A dose response was evident with respect to both (1) number of trout displaying renal crystals and (2) number of crystals per fish. Changes in concentration of antioxidant parameters, such as glutathione, superoxide dismutase, catalase, glutathione peroxidase, and glutathioneS-transferase, were recorded in both tissues of MEL- and CYA-dosed trout. Lipid peroxidation was more pronounced in kidney than liver. Therefore, feed contaminated with both MEL and CYA could be problematic for fish, as MEL administered to trout, individually or in combination with CYA, may facilitate the onset of oxidative damage in trout. [ABSTRACT FROM PUBLISHER]

Many diets employed in aquaculture are enriched with selenium to improve the diet quality and its conservation. The aim of the study was to investigate the effects of a diet enriched in selenium (1.21mgkg−1) on the antioxidant response of Procambarus clarkii (Girard, 1852). Crayfish fed a diet with lower selenium content (0.30mgkg−1) were the control. Selenium accumulation, enzymatic activities, and total glutathione were evaluated in hepatopancreas of adults of both sexes fed with both diets for 50 days at two experimental times (T 30, T 50 days). Treated females exhibited the highest selenium bioaccumulation during both experimental times, while treated males displayed the highest selenium concentration after 30 days, compared to control crayfish. A sex-related difference was found for the response of the analyzed enzymes in the selenium diet-treated specimens. In fact, superoxide dismutase, glutathione peroxidase and glyoxalase I activities in males were more sensitive compared with females, showing depleted activities in both experimental times. Catalase activity was induced in females (T 50), while glutathione S-transferase activity was the highest in treated females and the lowest in treated males, compared with own controls. Only glutathione reductase activity and glutathione content showed the same trend in both sexes, which were both lowered in treated specimens, when compared with control crayfish. This result might be due to the effect of selenium toxicity on this freshwater species. Males and females of P. clarkii showed a different susceptibility to the prooxidant effects in a Se-enriched diet. [Copyright &y& Elsevier]

To date, the occurrence of rare earth elements (REEs) in freshwater ecosystems has garnered limited attention in the scientific literature. Furthermore, a dearth of data exists regarding their potential bioaccumulation in freshwater fish. To fill this knowledge gap, we studied REEs concentrations in water, sediment, and fish specimens collected along the Po River (northwest Italy) and calculated biota-sediment accumulation (BSAF) and bioconcentration (BCF) factors, while taking into account fish feeding behavior and trophic level effects on the overall content of total REEs (ƩREEs). The fish communities were composed of native and non-native species. Remarkably low concentrations of REEs (<0.0003 mg/L) were detected in the water samples, indicating REEs insolubility. In contrast, sediment samples were found to be a good sink for REEs, with a higher mean ƩREEs recorded for the samples from the Moncalieri station (70.93 mg/kg). Notably, no significant differences in ƩREEs concentration were observed in the muscle tissue of fish samples from the three stations. The highest mean ƩREEs was recorded in the samples from the Murazzi station (0.027 mg/kg). The BSAF was very low, consistently below the unit, indicating an absence of bioaccumulation in fish muscle from sediment. In contrast, the BCF was high for several REEs, mainly for Sc and Y. While feeding ecology did not appear to affect REEs accumulation in muscle, there was a significant negative relationship between the trophic level and ΣREEs, indicating a trophic dilution of REEs from predator (Silurus glanis) to planktivorous (Alburnus arborella) fish. This study provides baseline concentrations, trophic transfers, and patterns of REEs in a river system. Further studies are needed to understand the transfer of REEs to other biotic components of lotic ecosystems. [Display omitted] • Sediment samples were found to be a good sink for REEs. • Bioconcentration factor values were high for several REEs, mainly for Sc and Y. • Feeding ecology had no influence on the REEs content in fish. • An inverse relationship between trophic levels of fish and REEs content was found. [ABSTRACT FROM AUTHOR]

Rare earth elements (REEs) are emergent contaminants in aquatic ecosystems in parallel with their growing use in science, technology, and industry. In this study we measured the concentration of 16 REEs in freshwater marcobenthic invertebrates from 6 watercourses in northeast Italy to determine their potential use as ecological tracers of REEs in aquatic ecosystems. The total REE concentration at the sampling sites followed this order: site 6 (7.05 mg Kg−1) > site 3 (5.76 mg Kg−1) > site 4 (3.58 mg Kg−1) > site 1 (3.0 mg Kg−1) > site 5 (2.36 mg Kg−1) > site 2 (1.95 mg Kg−1). There were no significant differences in REE concentrations across the six samplings sites (Kruskal Wallis test, p = 0.1773), but two (site 3 and 6) had higher amount of REEs and were classified with the ecological status "Moderate" sensu Water Framework Directive since affected by anthropogenic activities. Light REE were always greater than heavy REE concentrations at all six sites. A positive correlation was observed between certain REEs (La, Ce, Gd) and the density of genera Caenis and Baetis (Ehemeroptera, collector-gatherers) (ρS range 0.795–0.812), suggesting that non-predatory macrobenthic invertebrates accumulate more REEs than predatory organisms and that the intake of sediment is the most effective route of assimilation. Unlabelled Image • Rare earth elements were detected in macrobenthic communities from six watercourses. • Higher concentrations were measured in sites affected by anthropogenic activities. • A positive correlation exists between La, Ce, Gd and collector-gatherer density. • Functional feeding guilds of macrobenthic invertebrates influenced REE accumulation. • Macrobenthic invertebrates appear to be good indicators of REEs. [ABSTRACT FROM AUTHOR]

Rare earth elements (REEs), also called lanthanides, are emerging contaminants worldwide, due to their unique physical and chemical characteristics that make them essential in a variety of industrial applications. However, there is still a gap in the knowledge of occurrence and accumulation of REEs in biota, and no investigations have yet been performed in penguin feathers, which have already been widely utilized as a non-invasive tool for the biomonitoring of trace elements. The concentrations of 16 REEs were investigated in a colony of Humboldt penguins (Spheniscus humboldti) housed at the Acquario di Cattolica (Italy). Multielement determination of REEs was performed by an Inductively Coupled Plasma-Mass Spectrometer after a microwave digestion of feathers. As this colony lives indoors in a controlled environment, it was the ideal choice for studying lanthanide occurrence in penguin feathers. Since there is a strict link between metal levels in feathers and the diet of penguins, their food (capelin) was also tested for REEs. Chondrite normalized values revealed the same pattern for REEs in feathers and fish, but REE concentrations were an order of magnitude higher in penguin feathers, demonstrating the suitability of this tissue as a bioindicator of REEs. Unlabelled Image • The levels of 16 REE were investigated in Spheniscus humboldti feathers and food. • REE concentrations were order of magnitude higher in penguin feathers than in food. • Feathers are a suitable tool to biomonitor the presence of REE in the environment. • REE levels were strictly related to penguins' diet. [ABSTRACT FROM AUTHOR]

Farmed trout are commonly fed carotenoid-enriched diets during the finishing period to acquire typical red-to-pink flesh color in salmonid muscle. The aim of this study was to examine the effects of two xanthophylls, astaxanthin (Ax) or canthaxanthin (Cx), administered individually or in combination, on oxidative stress biomarkers in kidney and liver of rainbow trout. Specimens were fed Ax (75 mg/kg) or Cx (25 mg/kg) individually or in combination in the diets for 8 weeks. Changes in concentration of oxidative stress biomarkers, including total glutathione, superoxide dismutase, glutathione peroxidase, glutathione reductase, and glutathione S-transferase, were recorded in Ax- and Cx-dosed trout. These two carotenoids, predominantly Cx, initiated enzymatic responses in rainbow trout. It is noteworthy that lipid peroxidation processes were not apparent in all Ax or Cx-dosed trout. Further, both combined xanthophylls did not exert significant synergistic effects in liver and kidney. Biomarker responses were generally altered in both tissues through the 4 and 8 weeks suggesting that different time-dependent mechanisms led to enhanced antioxidant defense in Ax and/or Cx-fed trout. Data demonstrated that these two xanthophylls did not exert detrimental effects on rainbow trout. [ABSTRACT FROM AUTHOR]

Abstract Rare earth elements (REEs) are central in several critical technologies; their use is constantly increasing as is their release into the environment. For this reason, it is important to investigate REE concentrations in different matrices to evaluate human exposure and environmental risk of these emerging contaminants. REEs were measured by ICP-MS in matrices of terrestrial (plant feed, fruit, honey, wildlife livers) and marine origin (seaweeds, zooplankton, bivalves, fish) collected from Northwestern Italy. Highest REE concentrations were measured at low trophic levels, both in terrestrial and marine environments, such as plants (ΣREE 1.8 mg kg−1) and seaweed (ΣREE 12 mg kg−1), the major source of exposure and transfer of REEs to food webs. REE concentrations were several orders of magnitude lower in fruit, honey, and livers from terrestrial wildlife, suggesting a negligible risk of exposure by these matrices. Marine biota, such as bivalves (ΣREE 0.16 mg kg−1) and fish (ΣREE 0.21 mg kg−1) may constitute a pathway for human or animal dietary exposure. The study confirmed that REEs have low potential for biomagnification, but instead are subject to trophic dilution. However, given the numerous sources of dietary introduction of REEs, they should be monitored for a possible harmful cumulative effect. Owing to the scarcity of data regarding REEs worldwide, our results contribute to assessment of the occurrence of these emerging contaminants. Graphical abstract Unlabelled Image Highlights • Rare earth elements are emerging as contaminants worldwide. • REEs were detected by ICP-MS in terrestrial and marine matrices from NW Italy. • Plant and seaweed are major sources of exposure. • Marine samples showed higher ΣREE levels than terrestrial samples. • REEs were detectable in all sample types. [ABSTRACT FROM AUTHOR]

Abstract Avian feathers have the potential to accumulate trace elements originating from contaminated food and polluted environments. In fact, in feathers, metals bind to keratin, a sulphur-containing protein for which several metals have a strong affinity. Here, the concentrations of 18 essential and non-essential elements were investigated in a Humboldt penguin (Spheniscus humboldti) colony housed at the Acquario di Cattolica (Italy). This species is listed as vulnerable in the Red List of the International Union for Conservation of Nature. According to the literature, there is usually a link between metal levels in the diet of birds and levels detected in their feathers. Thus, metals were also determined in the penguins' food (capelin, Mallotus villosus). We hypothesize that the controlled conditions in which birds are kept in captivity, and the homogeneous diet that they follow could allow a better understanding of metal bioaccumulation (such as mercury) or bio-dilution (such as arsenic) in the marine food chain, indicated by penguins' feathers. Moreover, comparisons with our previous investigations performed on an ex-situ African penguin (Spheniscus demersus) colony suggest that penguins living indoors have lower body burden of metals than those living outdoors. Indeed, environmental contaminants usually found in areas subjected to anthropogenic impact, where zoos and aquaria are often located, are not accumulated to levels of concern. Graphical abstract Unlabelled Image Highlights • The levels of 18 metals were investigated in Spheniscus humboldti feathers and food. • Al, Co, Cr, Hg, Mn, Ni, Pb, Se, Sn and Zn were higher in feathers than in food. • Mercury concentration was in the range of moderate polluted environment. • Penguins living indoor have lower feathers metals concentrations than penguin hosted outdoor. • Metals levels were related to diet and environment. [ABSTRACT FROM AUTHOR]

Arsenic (As) is a global contaminant of terrestrial and aquatic environments posing concern for environmental and human health. The effects of subacute concentrations of arsenic trioxide (AsIII) and dimethylarsinic acid (DMAV) were examined using Crandell Rees feline kidney (CRFK), human hepatocellular carcinoma (PLC/PRF/5), and epithelioma papulosum cyprini (EPC). Whole monolayer with suffering cells (confluence 100%, pyknosis and refractive cells; value scale = 2) led to identification of subacute As concentrations for the three cell lines. The selected AsIII concentrations were 1.33 µM for CRFK and 33.37 µM for PLC/PRF/5 and EPC, at 48 hr time point. The selected DMAV concentrations were 0.67 mM for PLC/PRF/5, 1.33 mM for CRFK, and 2.67 mM for EPC for 48 hr. Unlike the AsIII test, the three cell lines did not exhibit marked susceptibility to DMAV-mediated toxicity. Several oxidative stress biomarker levels, directly or indirectly associated with reactive oxygen species (ROS) elimination including superoxide dismutase, catalase, glutathione peroxidases, glutathione reductase, glutathione S-transferase, glyoxalase I, glyoxalase II, and total glutathione, were determined in the three cell lines at 24 and 48 hr. Antioxidant responses in metal-treated cells were significantly altered compared to controls, suggesting a perturbation of redox state. The weakening of antioxidant pathway in either healthy or tumoral cells was greater using AsIII than DMAV. Differences in level of several oxidative stress biomarkers suggest that the oxidative stress mechanism induced by AsIII is distinctly different from DMAV. Multifaceted mechanisms of action underlying ROS generation in tumor and nontumor cells versus AsIII and DMAV exposure are thus involved. Since As-mediated toxicity is quite complex, more data regarding both oxidant-enhancement and oxidant-lowering strategies may be useful to improve knowledge regarding the influence of As on human and animal cells. [ABSTRACT FROM AUTHOR]

Human HT-29 and HepG2 cell lines were employed to test the effects of increasing concentrations of two rare earth elements (REEs), namely cerium (Ce) and lanthanum (La), alone or in combination. Effects on cell proliferation were measured using MTT assay, luciferase-based assays and proliferating cell nuclear antigen expression, while cell mortality and type of cell death was determined by Annexin V-FTC test using flow cytometry. Modulation of 84 genes involved in oxidative stress pathways was also studied using RT-PCR based arrays. Major alterations in selected genes compared to basal expression levels of respective control groups were found in the cells exposed to 600 μM Ce for 48 h. In HepG2 cells, 51 out of 84 genes were significantly up- or down-regulated, while in HT-29 cells only 16 genes were significantly up- or down-regulated. Dosage of REEs seems to be the pivotal factor for switching the biological effects from down- to up-regulation of cell growth; thus, low concentrations promoted cell survival and proliferation, but when concentrations increased, REEs exerted anti-proliferative and cytostatic/cytotoxic effects. The molecular mechanisms underlying these effects are still not well-defined and further analysis of the mechanisms that result in inhibition or induction of cell proliferation are crucially important. [ABSTRACT FROM AUTHOR]

We analyzed the concentrations of 20 trace elements in Eurydice spinigera (Isopoda) and Flaccisagitta enflata (Chaetognatha), which represent a hyperbenthic and a zooplanktonic marine species respectively, sharing the same predaceous feeding strategy, from a highly productive coastal region (Ligurian Sea, Northwestern Mediterranean). The same elements were also quantified in marine sediments, where geological anomalies were found for arsenic, chromium and nickel. Metal transfer seems to be deeply influenced by different habitats. The carnivorous isopod E. spinigera, which spends most of its lifetime on the seabed, was found to have the highest concentrations of most trace elements, such as Al, As, Cd, Ce, Cr, Fe, La, Mn, Ni, Pb, Se, V and Zn, and consequently have the highest bioaccumulation factors (BAFs). Moreover, the estimation of biota sediment accumulation factors (BSAFs) revealed that cadmium, copper and zinc concentrations were higher in the isopod than in the sediment. Conversely, in the carnivorous chaetognath F. enflata, which is not a benthonic species, the highest levels of copper and tin were found. Moreover, arsenic speciation analysis confirmed the presence of inorganic As (III + V) in E. spinigera. In the context of utilizing a marine organism as a bio-indicator of metal transfer, it is crucial to consider both feeding behavior and feeding habitat. [ABSTRACT FROM AUTHOR]

The applicability to the determination of mercury in tuna of square wave anodic stripping voltammetry (SW-ASV) conducted at both solid gold electrode (SGE) and a gold nanoparticle-modified glassy carbon electrode (AuNPs-GCE) was demonstrated. Mercury content in two certified materials and in ten samples of canned tuna was measured. The performances of the electrodes were compared with one another as well as with two spectroscopic techniques, namely cold vapour atomic absorption spectroscopy (CV-AAS) and a direct mercury analyser (DMA). The results found pointed out that both SW-ASV approaches were suitable and easy-to-use method to monitor mercury concentration in tunas, since they allowed accurate quantification at concentration values lower than the maximum admissible level in this matrix ([Hg] = 1 mg/kg wet weight,ww ). In particular, mercury detection at the AuNPs-GCE showed a LOQ in fish-matrix of 0.1 μg/l, corresponding to 0.06 mg/kg ww , with performance comparable to that of DMA. [ABSTRACT FROM AUTHOR]

Transition metals are cofactors for a wide range of vital enzymes and are directly or indirectly involved in the response against reactive oxygen species (ROS), which can damage cellular components. Their altered homeostasis has been studied in neurodegenerative disorders such as Alzheimer's disease (AD), Parkinson's disease (PD) and amyotrophic lateral sclerosis (ALS), but no data are available on rarer conditions. We aimed at studying the role of essential trace elements in ataxia telangiectasia (A-T), a rare form of pediatric autosomal recessive cerebellar ataxia with altered antioxidant response. We found an increased level of copper (Cu, p = 0.0002) and a reduced level of zinc (Zn, p = 0.0002) in the blood of patients (n. 16) compared to controls, using inductively coupled plasma mass spectrometry (ICP-MS). Other trace elements involved in the oxidative stress response, such as manganese (Mn) and selenium (Se), were unaltered. Cu/Zn-dependent superoxide dismutase (SOD1) was shown to have a 30% reduction in gene expression and 40% reduction in enzyme activity upon analysis of lymphoblastoid cell lines of patients (Student's t -test, p = 0.0075). We also found a 30% reduction of Mn-SOD (SOD2; Student's t -test, p = 0.02), probably due to a feedback regulatory loop between the two enzymes. The expression of antioxidant enzymes, such as erythrocyte glutathione peroxidase ( GPX1 ), and SOD2 was unaltered, whereas catalase ( CAT ) was increased in A-T cells, both at the mRNA level and in terms of enzyme activity (~ 25%). Enhanced CAT expression can be attributed to the high ROS status, which induces CAT transcription. These results suggest that alterations in essential trace elements and their related enzymes may play a role in the pathogenesis of A-T, although we cannot conclude if altered homeostasis is a direct effect of A-T mutated genes ( ATM ). Altered homeostasis of trace elements may be more prevalent in neurodegenerative diseases than previously thought, and it may represent both a biomarker and a generic therapeutic target for different disorders with the common theme of altered antioxidant enzyme responses associated with an unbalance of metals. [ABSTRACT FROM AUTHOR]

Lead, cadmium and chromium levels were determined in different raw and boiled portions of Norway lobster caught in the central Adriatic Sea (Italy). In raw specimens, the lowest concentrations were always detected in the white meat. Lead and cadmium content in the edible portion never exceeded the maximum levels set by European legislation. The highest cadmium and chromium values (0.47 ± 0.04 and 0.62 ± 0.13 mg/kg wet weight, respectively) were detected in the brown meat, while the highest lead concentrations were found in the exoskeleton (0.21 ± 0.01 mg/kg wet weight). Also, the boiled samples showed the lowest metal levels in the white meat, even if a significant increase (p < 0.01) was found for lead and cadmium compared to the corresponding raw portions. Among metals, chromium showed the highest concentrations in both raw and boiled portions, but up to now, the European legislation did not envisage any limits in seafood. [ABSTRACT FROM AUTHOR]

Highlights: [•] We present a rapid and sensitive method to detect melamine in milk based on SERS. [•] Interaction of melamine with AuNPs enhances melamine Raman signal in the analysis. [•] Different size AuNPs were tested to achieve the highest SERS enhancement. [•] Melamine detection in milk is in accordance with the European law limits. [•] SERS analysis is validated for sensitivity, linearity, recovery and repeatability. [Copyright &y& Elsevier]

Highlights: [•] Local seafood supply relevant for MeHg intake in Mediterranean coastal population. [•] Seafood consumption questionnaire broken into 42 seafood species administered to 278 adults. [•] 30% of 18–45years vulnerable women (N =98) exceeds the TWI for MeHg (1.3μg/kg bw). [•] The choice of consumed species appears as the main determinant in over-exposure. [•] The empowerment about a more responsible choice of seafood is envisaged. [Copyright &y& Elsevier]

Abstract: The general term “pesticide” includes a large number of substances that belong to many different chemical classes. Pesticides are applied to crops at various stages of cultivation to provide protection against weeds and pests, and during post-harvest storage to preserve quality. The list of which pesticides are authorized for use in Europe is available on EU pesticides Database. The QuEChERS approach is a method designed for the analysis of pesticides in fruits and vegetables. This method is based on an extraction and clean-up step; it has been designed to be Quick Easy Cheap Effective Rugged and Safe. The aim of this study was to modify the QuEChERS method to be applied in the analysis of 9 organophosphate and 1 pyrethroid pesticides in raw materials for animal feeding introducing an additional liquid–liquid partition step. This additional step allowed us to concentrate the samples, avoiding any solvent evaporation, prior to the instrumental analysis. Once the method was optimized, it was carried out a pesticides quantization study using a GC–MS SIM multi-residue analysis. 45 samples of maize and soy coming from Northern Italy (Piedmont Region) were analysed during ten months. In 30 samples organophosphate pesticides were found up to 12.4 mg kg−1 of Chlorpyrifos, while no Deltamethrin was detected. [Copyright &y& Elsevier]

Abstract: Gene expression experiments were targeted in order to monitor the ABC efflux transporters, which is potentially involved in cellular detoxification/defense. Changes in expression levels of different ABC genes in kidney of Oncorhynchus mykiss fed with melamine and melamine+cyanuric acid enriched diets were recorded in both treated groups by mRNA ΔΔCT relative quantification method. Expression profiles of eight different ABC genes basically showed low alterations in melamine group and more consistent changes in melamine+cyanuric acid treated fish, compared with own control. In the last group ABCC2 gene over expression was the more evident alteration. These results suggest that ABC efflux system could be involved in mobilization of hydrophilic molecules in the forcing condition of chronic exposure. [Copyright &y& Elsevier]

Spinocerebellar ataxia type15 (SCA15) is a pure ataxia characterized by very slow progression. Only seven families have been identified worldwide, in which partial deletions and a missense mutation of the inositol triphosphate receptor type I gene ( ITPR1) have been reported. We examined a four-generation Italian family segregating an autosomal dominant cerebellar ataxia, in which linkage analysis was positive for the SCA15 locus. We performed a genomic real-time polymerase chain reaction to search for ITPR1 gene deletions in this family and in 60 SCA index cases negative for mutations in the SCA1–3, 6–8, 10, 12, and dentatorubral-pallidoluysian atrophy genes. The deleted segments were characterized using a custom array comparative genomic hybridization analysis. We have identified two families with an ITPR1 gene deletion: in one, the deletion involved ITPR1 only, while in the other both sulfatase-modifying factor 1 and ITPR1. Clinical data of ten patients and brain MRI (available for six) showed that the phenotype substantially overlapped known SCA15 cases, but we also noted buccolingual dyskinesias, facial myokymias, and pyramidal signs never reported in SCA15. ITPR1 expression analysis of two deleted cases showed a half dose. Our results further support ITPR1 gene as causative of SCA15. The families reported show that SCA15 is present in Italy and has a greater variability in the age at onset and clinical features than previously reported. We propose that the search for ITPR1 deletions is mandatory in the clinical hypothesis of SCA15 and that ITPR1-reduced expression in blood may be a useful marker to identify SCA15 patients harboring genomic deletions and possibly point mutations causing reduction of mRNA level. [ABSTRACT FROM AUTHOR]

The article presents findings of the study which aims to evaluate the performances of a dissociation enhanced lanthanide fluorescence immunoassay (DELFIA) for rapid screening of 17 β-estradiol in bovine serum. The researchers performed the validation based on the European Union (EU) Decision 2002/657/EC. Accordingly, they found that the method is appropriate for qualitative screening analysis of 17 β-estradiol.

This study aimed at investigating the extent of accumulation of selenium in the hepatopancreas of the crayfish Procambarus clarkii and its effects on the enzymatic activities of catalase, glutathione peroxidase, and glutathione reductase. Crayfish were fed for 15 days either a diet enriched in Se, ED (1.21 mg kg-1) or a standard diet, SD (0.30 mg kg-1). Results showed that Se accumulation is higher in the sample subject to ED rather than to SD. A sexual difference was found for the response of the analyzed enzymes in the ED sample only. Catalase activity and glutathione peroxidase activity decreased in females and males, respectively, whereas glutathione reductase activity showed significant reductions in both sexes. These preliminary data might provide information about prooxidant effects of Se on P. clarkii when fed a Se enriched diet. [ABSTRACT FROM AUTHOR]

• A portable procedure for determination of mercury and methylmercury is proposed. • Anodic stripping voltammetry using a solid gold electrode is adopted. • Home-made cartridges containing a new modified resin are adopted. • Comparison between direct mercury analyser and voltammetry is made. A portable measurement and speciation procedure for inorganic mercury (Hg IN) and methylmercury (CH 3 Hg) was developed. A portable sample pretreatment was optimized to determine total mercury content. A new home-made sorbent (CYXAD, CHYPOS 101 modified Amberlite XAD), was prepared to separate Hg IN and CH 3 Hg. Mercury species were determined using square wave anodic stripping voltammetry (SW-ASV) with a solid gold electrode (SGE) and using a portable potentiostat. A certified reference material, five freeze-dried samples and three fresh samples were analysed with conventional voltammetric analyzer, after dissolution of the samples in microwave oven, and with a portable potentiostat after the mild eating procedure. The results obtained by SW-ASV were compared with those obtained using Direct Mercury Analyser (DMA). The quantification with the portable method is comparable to that obtained with the DMA. Retention tests showed the selectivity of CYXAD for Hg IN , its stability and the possibility to re-use the same aliquot of resin. [ABSTRACT FROM AUTHOR]

Crassostrea gigas is a sentinel species along the Italian coast. In mussels, the levels of oxidative stress biomarkers can be modulated by several environmental pollutants or pathogens and also fluctuate in response to reproductive stages and seasonal changes. In this study, adult Crassostrea gigas were sampled during summer and autumn from two lagoon and two offshore sites along the Adriatic coast of Italy in order to investigate the influence of seasonality on oxidative stress biomarkers. Trace elements load of Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Se and Zn suggests low contamination for lagoon and offshore sites. Levels of total glutathione, superoxide dismutase, catalase, glutathione peroxidases, glutathione reductase and glutathione S-transferase were analyzed in digestive gland and gills of the Pacific oysters in June, July, September and October. OsHV-1 and Vibrio aestuarianus were detected in lagoon sites, but both pathogens did not affect the biomarkers levels in both tissues. Although several biological responses were found different among the four sites in the same month, principal component analysis revealed similar trend in biomarkers levels between sites during the whole sampling period. On the other hand, a different biochemical pattern through the months emerged, suggesting that the level of oxidative stress biomarkers in both tissues may be related to seasonal progress and biological cycle of oysters sampled from the two lagoons and offshore sites along the Italian coasts of the Mediterranean Sea. Unlabelled Image • Trace elements and oxidative stress biomarkers were measured in Crassostrea gigas. • Trace elements load suggested low contamination in lagoons and offshores. • OsHV-1 and Vibrio aestuarianus were detected in oysters of lagoon sites. • Both pathogens did not affect biomarkers response. • A monthly-dependent fluctuation of biomarkers levels was recorded in oyster tissues. [ABSTRACT FROM AUTHOR]

Though mountain lakes are generally much less influenced by human activities than other habitats, anthropogenic threats can still alter their natural condition. A major source of global environmental pollution in mountain ecosystems is trace element contamination. For this study we investigated for the first time the accumulation of As, Cd, Pb, and Zn in sediment, Diptera Chironomidae (prey), and bullhead Cottus gobio (predator) in a typical high-mountain lake (Dimon Lake) in the Carnic Alps. Significant differences in trace element levels were observed between sediment, Diptera Chironomidae, and C. gobio liver and muscle samples (Kruskal-Wallis test; p <.03 for all elements). As and Pb levels were highest in sediment, Cd and Zn levels were highest in Diptera Chironomidae, and the lowest values for all elements were measured in C. gobio muscle and liver. Bioaccumulation factor values were much higher in Diptera Chironomidae than fish muscle and liver, with the highest values recorded for Cd (5.16) and Zn (4.37). Trophic transfer factor values were very low for all elements in fish muscle and liver, suggesting a biodilution effect along the food chain. Further studies are needed to expand on these first findings that provide useful insights to inform environmental monitoring and policy in remote high-mountain lakes. Unlabelled Image • Levels of As, Cd, Pb, and Zn were detected in a high-mountain lake dietary pathway. • Trace element concentration decreased with increasing trophic level. • The highest BAF values were recorded for Cd and Zn in Diptera Chironomidae. • Very low TTF values were recorded in fish muscle and liver. • Diptera Chironomidae seems to be a good matrix for trace element monitoring. [ABSTRACT FROM AUTHOR]

High-mountain lakes are pristine ecosystems characterized by extreme environmental conditions. The atmospheric transport of pollutants from lowlands may add further stress to organisms inhabiting these environments. We investigated the environmental stress pressure on brook trout (Salvelinus fontinalis) from a high-mountain lake in the Cottian Alps (Piedmont, northwest Italy). To do this, males and females of brook trout were sampled from Balma Lake in summer (August) and autumn (October) 2017 in order to assess the influence of trace elements accumulation and environmental parameters (physicochemical parameters and nutrient characteristics of water) on oxidative stress biomarkers. Bioaccumulation of Al, As, Cd, Cr, Cu, Fe, Hg, Pb, Ni, Se, and Zn and metallothionein levels were measured in muscle tissue of males and females. Liver, gills, kidney, and spleen tissue samples were analyzed for superoxide dismutase, catalase, total glutathione peroxidase, selenium-dependent glutathione peroxidase, glutathione reductase, and glutathione S-transferase activity. Analysis of environmental parameters showed changes in biomarker levels with seasonal variations. Water temperature was significantly higher in summer than autumn (Wilcoxon test; p =.0078), while pH was significantly higher in autumn than in summer (Wilcoxon test; p =.0078). Sex-related differences in oxidative stress biomarkers in tissues were unremarkable, whereas seasonal variability of oxidative stress biomarkers was observed, with major differences occurred for liver in summer and for gills, kidney, spleen and muscle in autumn. Positive correlations between environmental parameters and biomarkers were noted. Major fluctuations in water temperature, pH, Cu, Pb and Hg produced changes in biomarker levels; however, increased food intake during the ice-free season was probably the main factor that influenced changes in oxidative stress biomarker levels in brook trout in this extreme ecosystem. Unlabelled Image • The influence of environmental factors on oxidative stress biomarkers was assessed. • Temperature, pH, Cu, Pb and Hg showed the major fluctuation during seasons. • A seasonal-linked variability of oxidative stress biomarkers level was recorded. • Both sexes showed similar level of oxidative stress biomarkers. • Food intake in summer mainly affected oxidative stress biomarkers. [ABSTRACT FROM AUTHOR]

Identification and quantification of Non Intentionally Added Substances (NIAS) at low concentrations and eventually their distribution on Low Density Polyethylene (LDPE) films is an important issue. As Raman spectroscopy techniques are innovative and sensitive analytical methods and do not require pretreatment and manipulation of the sample, these were used for the identification of NIAS in LDPE pellet and films, which are commonly used for food packaging applications. The aggregation state of NIAS in LDPE were observed by Raman imaging with micrometric resolution. Four main NIAS compounds were identified in granule and film surfaces by confocal Raman spectroscopy: calcite (CaCO 3), calcium sulphate (CaSO 4), polystyrene (PS) and titanium dioxide (TiO 2) in anatase form. By a semi-quantitative evaluation of the inorganic NIAS, 9.93 mg/kg of CaCO 3 , 1.62 mg/kg of CaSO 4 and 0.17 mg/kg of TiO 2 were estimated. The experimental findings achieved by Raman analysis were confirmed by the results obtained by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Moreover, the toxicity of the identified compounds was examined according to the Cramer rules. • Rapid and non-destructive identification of Non-Intentionally Added Substances by Raman spectroscopy. • Determination of the aggregation state of the NIAS by Raman Imaging. • Determination of the distribution of the NIAS in the LDPE matrix by Raman imaging. • Semi-quantitative analysis of the NIAS. • Comparison of Raman data and ICP-MS data. [ABSTRACT FROM AUTHOR]

A simple procedure for field fish sample pretreatment was developed. This treatment in combination with square wave anodic stripping voltammetry (SW-ASV) with solid gold electrodes (SGE) and gold nanoparticle-modified glassy carbon electrodes (AuNPs-GCE) was applied for the determination of total mercury content. A certified reference material (CRM, Tuna Fish BCR 463), ten freeze-dried samples of canned tuna and two fresh fish samples were analysed both with a bench-top voltammetric analyser after microwave digestion and with a portable potentiostat after mild eating using a small commercial food warmer. The results obtained by the two SW-ASV approaches and by a Direct Mercury Analyser (DMA), the official method for mercury determination, were in very good agreement. In particular, (i) the results obtained with in field procedure are consistent with those obtained with the conventional microwave digestion; (ii) the presence of gold nanoparticles on the active electrode surface permits an improvement of the analytical performance in comparison to the SGE: the Limit of Quantification (LOQ) for mercury in fish-matrix was 0.1 μg L−1 (Hg cell concentration), corresponding to 0.06 mg kg−1 wet fish, which is a performance comparable to that of DMA. The pretreatment proposed in this study is very easy and applicable to fresh fish; in combination with a portable potentiostat, it proved to be an interesting procedure for on-site mercury determination. [ABSTRACT FROM AUTHOR]