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Metals (trace elements and rare earth elements, REEs) were analysed by inductively coupled plasma-mass spectrometry in blood, the liver, the kidney and muscle of ex situ spotted dogfish (Scyliorhinus stellaris). The controlled environment in which these elasmobranchs were hosted allowed to assess a baseline level of metals in the different organs since exposure via water and food can be easily monitored. The highest arsenic, chromium, copper, and iron values were found in the liver, cobalt in the kidney, and cadmium and rubidium in muscle. The highest total trace elements content was found in the trend liver (75 mg kg

Animal hair is a useful biomonitoring tool for assessing the occurrence of trace elements in ecosystems. Essential (chromium, copper, iron, manganese, nickel, and zinc) and nonessential (aluminum, arsenic, cadmium, mercury, lead, palladium, platinum, rubidium, tin, and vanadium) elements were investigated in hair of badger (Meles meles), wild boar (Sus scrofa), marmot (Marmota marmota), wolf (Canis lupus), fox (Vulpes vulpes) and deer (Cervus elaphus) from Northwestern Italy. Badger was found to be the highest bioaccumulator of metals, while wolf, fox and deer recorded the lowest values. Essential elements contribute in higher degree to the sum of metals for all species except for wild boar. Results have shown that animals with omnivorous diet such as badger, marmot and wild boar have metal content (especially Al, As, Cr, Cu, Fe, Ni, V) higher than carnivores (wolf and fox) and herbivores (deer) and could represent an effective sentinel of environmental exposure to metals.

Insects represent a valuable and environmentally friendly protein alternative in food and feed. The Farm to Fork strategy encouraged the reintroduction of animal by-products in feed production to optimize recycling and to valorise under-used resources. In order to grant safe and valuable feed products, this study investigated the black soldier fly (BSF) (Hermetia illucens) chemical risk.Samples collected in different steps of production (8 samples of substrate for culturing, 7 samples of larvae, 15 samples of protein meal, 18 samples of spent substrate) were analysed for essential elements (chromium, copper, iron, nickel, selenium and zinc) and inorganic contaminants (aluminium, arsenic, cadmium, lead, tin and vanadium) by Inductively Coupled Plasma Mass Spectrometer (ICP-MS). Essential elements were found in the following order Fe>Zn>Cu>Ni>Se>Cr (mg kg-1). Non-essential elements concentrations were found lower than the set limits according to the European Union Regulations. The growing demand for alternative protein sources for feed production could be partially compensated by black soldier fly (BSF) (Hermetia illucens) meal, as it appears a good source for high quality proteins and essential elements which play a pivotal role in animal growth. In the foreseeable future the current legislation and the official monitoring plans may be implemented and broaden, to focus and assess limits for upcoming matrices, and to ensure feed and food safety.

The toxicity of water samples from water distribution plants needs to be investigated further. Indeed, studies on the pro-oxidant effects driven by tap water are very limited. In this study, the water quality, pro-oxidant effects, and potential health risks driven by exposure to groundwater samples from two water plants (sites A and B) located in Northwestern Italy were investigated in a multi-level system. Physicochemical parameters and the absence of pathogens, cyanotoxins, and endocrine active substances indicated a good water quality for both sites. The 25 metals analyzed were found under the limit of quantification or compliant with the maximum limits set by national legislation. Water samples were concentrated by the solid-phase extraction system in order to assess the aquatic toxicity on Epithelioma papulosum cyprini (EPC) cell line. Levels of superoxide dismutase, catalase, glutathione peroxidase, glutathione S-transferase, and glutathione reductase were evaluated through the Integrated Biomarkers Response (IBRv2) index. EPC cell line was found a sensible model for assessing the antioxidant responses driven by both water concentrates. A similar antioxidant response was shown by plots and IBRv2 suggesting a muted risk for the two sampling sites.

Honey is a very unusual food - a natural substance produced by bees from the nectar or secretion of plants and elaborated by the bees themselves. Differences in trace elements and rare earth elements (REEs) are related to botanical and geographical origin, and, as such, honey could be a suitable indicator for metal occurrence in the environment within the bee forage area. A total of 40 metals were analyzed by inductively coupled plasma-mass spectrometry in multi-floral honey samples from different geographical areas. The highest levels of trace elements and REEs were found in honey from Tanzania, while lower concentrations were recorded in Italian, Kazakhstan, the Balkans, and South American honeys. Tanzanian honey is of interest due to its different content of metals, related to the peculiar lithology and the mineral resources of this country. Rubidium and aluminum were the most represented nonessential elements, while manganese, iron, zinc, and copper registered the highest values of the essential elements. Very low concentrations were found for the toxic elements lead, cadmium, and arsenic. The present study showed differences in metal concentrations in multi-floral honey from different countries, confirming the strong influence of the area of origin on the chemical composition of honeys.

The present study aimed to determine trace elements in Mediterranean mussels (

Alpine lakes are extreme ecosystems located in remote areas and populated by few but well-adapted species. Because of their remote location, they are often considered pristine, unpolluted ecosystems. Since the 1980s, however, they have been affected by global anthropogenic impacts. Macrobenthic invertebrates play a pivotal role in these ecosystems and can be used as bioindicators also for monitoring the accumulation of trace elements. We characterized the macrobenthic invertebrates community of Balma Lake (Cottian Alps, Northwest Italy) and Dimon Lake (Carnic Alps, Northeast Italy) in summer and autumn and measured the levels of nine trace elements (As, Cd, Cr, Cu, Fe, Ni, Pb, Se, Zn) in the most abundant taxa (Chironomidae and Oligochaeta in both lakes and Hirudinea in Dimon Lake) in both seasons. The highest levels of trace elements were recorded for Fe, Cu, and Zn according to their environmental availability and their function as essential elements. The total amount of trace elements was highest for the Chironomidae from both lakes compared to the other two taxa. As, Cd, Pb, and Zn were measured in sediment to calculate bioaccumulation factor (BAF) values. The amount of elements in sediment and macrobenthic invertebrates was higher for Dimon Lake, suggesting a greater flux via precipitation of contaminants from the lowland. The BAF values were decreased with increasing trace elements concentration in sediment, indicating mechanisms of elements excretion in biota where the environment is contaminated. This study is the first to report on the use of macrobenthic invertebrates to monitor trace elements in Alpine lakes.

Processed animal products (PAPs) could be a great alternative to common protein supplements and represent a good example of recycling and valorization of by-products. Due to the reintroduction of certain types of PAPs in feed, a deeper knowledge of these heterogeneous matrices is needed. Thus, the aim of this study is to evaluate the levels of essential elements and inorganic contaminants in 55 PAPs considered as potential alternatives to common protein supplements.PAPs samples were analysed for essential (cobalt, nickel, chromium, copper, zinc, iron and manganese) and non-essential elements (arsenic, cadmium, lead and mercury) by Inductively Coupled Plasma Mass Spectrometer (ICP-MS), Graphite Furnace Atomization Atomic Absorption Spectrometer (GF-AAS) and dual cell Direct Mercury Analyzer spectrometer (DMA-80).Essential elements were found with the following decreasing order ironzinccoppermanganesechromiumnickelcobalt (mg kgThis study suggests that PAPs could be a useful supplement for animal diet due to their natural content of essential elements. A careful monitoring of chemical elements should be required and eventually guidelines have to be drafted for a correct use of PAPs to ensure a safe and sustainable feed production.

Microplastics are contaminants of great concern all over the world. Microplastics constitute pollutants themselves; moreover, other contaminants such as metals are easily absorbed on their plastic surface, becoming bioavailable to marine biota such as zooplankton.We collected marine zooplankton from Mediterranean Sea to investigate trace elements associated with microplastics. Samples were subjected to visual sorting by a stereomicroscope, collected with sterile tweezers, pooled and subjected to sonication, filtration, and drying before being subjected to acid extraction. An ICP-MS was utilized for multi-elemental determination.Aluminum, iron, chromium, zinc, nickel, molybdenum, manganese, lead cobalt, and copper were found at concentrations of mg/kg while arsenic, vanadium, rubidium, and cadmium at level of μg kg-1. Other elements such as silver, beryllium, bismuth, selenium, tin, and thallium were under the limit of quantitation. Lower levels of iron and manganese in samples from Italy were found in comparison to England and Brazil, while aluminum, copper, and zinc registered comparable values. The presence of metals in marine waters is strictly related to sediment lithology and anthropogenic inputs, but plastic plays a key role as vectors for metal ions in the marine system, being able to concentrate metals several order of magnitude higher than in surrounding waters and exerting potential toxicity for living beings after chronic exposure.

A portable measurement and speciation procedure for inorganic mercury (HgIN) and methylmercury (CH3Hg) 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 HgIN and CH3Hg. 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 HgIN, its stability and the possibility to re-use the same aliquot of resin.

The occurrence of 21 trace elements in native Mediterranean mussel (Mytilus galloprovincialis) from the Calich Lagoon, a typical brackish area of the northwest of Sardinia (Italy), was investigated. The seasonal variation of metals in bivalves was considered, and the highest values were found in spring and summer; in particular, a high significant (P

Nickel (Ni) is an essential element in plants and animals, but elevated levels can exert toxicity in living beings, as recently highlighted by the European Food Safety Authority opinion. However, literature regarding the presence of nickel in the environment is scarce. In 2016, the EU Commission Recommendation n°1110 recommended monitoring the presence of Ni in feed in order to set maximum levels or to adopt other risk management measures to ensure a high level of animal health protection and consequently of human health. A total of 200 samples of feedingstuffs, drinking water, and milk were collected from dairy cow farms in Piedmont, and analyzed for Ni concentration by Z-ETA-AAS. Results showed the presence of nickel in feedingstuffs in a range from 0.20 to 16 mg/kg, while Ni concentrations in water and milk were close to or below the limit of quantitation. There was no carry-over from feed to milk in this food chain. Nickel concentrations were not of concern for animal health despite being in the upper range of those observed in vegetables from Europe.

The potential threat of both metals and antibiotics to the environment and human health has raised significant concerns in the last decade. Metal-resistant and antibiotic-resistant bacteria are found in most environments, including water, and the risk posed to humans and animals due to the spread of antibiotic-resistant bacteria and antibiotic-resistant genes in the environment is increasing. Bacteria have developed the ability to tolerate metals even at notable concentrations. This ability tends to favor the selection of antibiotic-resistant strains, even in pristine water environments, with the potential risk of spreading this resistance to human pathogens. In this mini-review, we focus on investigations performed in marine and freshwater environments worldwide, highlighting the presence of co-resistance to metals and antibiotics.

Background Metals are a minor constituent in honey, but they have been suggested to be a potential tool to characterize honeys according to their botanical or geographical origin. Methods A total of 40 metals were analyzed by Inductively Coupled Plasma-Mass Spectrometry in monofloral and multifloral honeys from Northwestern Italy. PCA and ANOVA were used to discriminate honeys according to the various floral types. Results The highest levels of trace elements and rare earth elements (REEs) were found in chestnut honey, while the lowest concentrations were recorded in acacia and rhododendron honeys. Rubidium and aluminum were the most represented nonessential elements, while manganese, iron, zinc and copper had the highest values of the essential elements. Potentially toxic elements arsenic, cadmium and lead were close to or below the limit of quantification. Conclusions The present study showed significant differences in metal concentrations according to honey floral type, reflecting the strong influence of botanical origin on the chemical composition of this particular food.

The Indo-Pacific lionfish is a saltwater fish that inhabits the Red Sea waters and the Indian and Pacific oceans; it is an invasive species in the western Atlantic and was recently introduced into the local diet in the USA, Central and South America, and the Caribbean with the aim of controlling the invasion of this species. Due to its predatory nature, it tends to bioaccumulate metals and other contaminants via the marine food web and could thus constitute a suitable species for monitoring aquatic ecosystems. The presence and distribution of 23 trace elements and 16 rare earth elements (REEs) were investigated by inductively coupled plasma-mass spectrometry (ICP-MS) in the muscle, liver, and kidneys of lionfish from Cuba. Significant differences in metal concentrations were found in the different fish organs. The liver and kidneys registered the highest concentrations for most trace elements and for ΣREE, thus demonstrating that they are effective bioindicators of possible pollution on the environment in which fish live, and assuming great importance in the choice of early biomonitoring. Trace element concentrations in the muscle are instead of crucial interest for consumer safety. The limits set by EU regulations and Cuban guidelines for Cd and Pb in fish muscle were never exceeded, suggesting that lionfish from Cuba could therefore represent a good source of minerals and proteins for the local population. Graphical abstract.

The anthropogenic contamination of water bodies with metals via fertilizer, industrial sewage and urban wastewater has resulted in widespread problems in aquatic organisms, but also poses a risk to consumer health. Shellfish from coastal and estuarine environments bioaccumulate toxic metals in their tissues due to their ability to concentrate inorganic contaminants several orders of magnitude above ambient levels. The aim of this study was to evaluate the presence of trace elements in adult specimens of indigenous clams (Ruditapes decussatus). To this end, wild clams were collected from four different brackish areas of Sardinia (Western Mediterranean Sea, Italy) devoted to extensive aquacultural practices. The concentration of 16 trace elements (Al, Ag, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, Sn, Tl and Zn) in the tissues of the clams was quantified. The legal limits set by European Regulations for cadmium; mercury and lead were never exceeded. However, unexpectedly high values for aluminium and iron (mean 207 mg kg⁻1 and 113 mg kg⁻1 wet weight) were found in Santa Gilla lagoon, which is close to industrial settlements and had the highest values for the majority of chemical elements investigated. The highest values of the metalloid arsenic (As) were reported in the Porto Pozzo and San Teodoro lagoons (9.6 and 6.8 mg kg⁻1 w.w., respectively). The clam R. decussatus confirmed the capacity of bivalves as suitable bioindicators of trace elements pollution. Further investigations are necessary for constant monitoring of clams, 32 which constitute an important traditional resource for the fishing activity in Sardinia.

Bird feathers have been proven to be reliable indicators of metal exposure originating from contaminated food and polluted environments. The concentrations of 15 essential and non-essential metals were investigated in African penguins (Spheniscus demersus) feathers from a Northwestern Italian zoological facility. These birds are exclusively fed with herring from the northeast Atlantic Ocean. Certain elements, such as Hg and Cd, reflected the bioaccumulation phenomena that occur through the marine food chain. The levels of Cr, Mn, and Ni were comparable to those registered in feathers of birds living in polluted areas. These results are important for comparative studies regarding the health, nutrition and welfare of endangered seabirds kept under human care.

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.

A thresher shark poached by fishermen in the stretch of sea between the island of Ponza and the coast of Terracina (Lazio, Central Italy, Mediterranean Sea) and confiscated by the Italian health authorities was evaluated for the presence of chemical contaminants. Hg mean concentration of 2.1 mg kg−1 was found in muscle; speciation analysis confirmed it was almost in the toxic organic form of MeHg (2.0 mg kg−1). The Se:Hg molar ratio was

Copepods are the most numerous taxonomic group in marine mesozooplankton communities. These planktonic organisms have an essential role in the function of marine trophic webs, as they are the link between phytoplankton and secondary consumers. The concentrations of 20 essential and non-essential trace elements were investigated by Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) in calanoid copepods with different feeding behaviors. The sampling was performed in the Northwestern Mediterranean Sea, at the border between the Northern Tyrrhenian Sea and the Ligurian Sea (Italy). Aluminum, iron, zinc and copper were present in the highest concentrations in herbivorous calanoids ( Temora stylifera, Nannocalanus minor, Neocalanus gracilis) . Conversely, the nonessential element – arsenic – and the essential elements selenium and molybdenum – were present in the highest levels in carnivores ( Pontella mediterranea, Candacia ethiopica). In the omnivorous copepod Centropages typicus, metal concentrations were found at an intermediate level between herbivores and carnivores, reflecting the importance of dietary pathways in metal intake and bioaccumulation. Finally, the bioaccumulation factors (BAFs), expressed as a ratio of the total metal levels in copepods compared to the seawater metal levels, were as follows: herbivores (83699) > omnivores (47855) > carnivores (41648).

Huntington' disease (HD) is an autosomal dominant neurodegenerative disease characterized by progressive motor, psychiatric, and cognitive deterioration. HD is, together with spinocerebellar ataxias, spinobulbar muscular atrophy and dentatorubral-pallido- luysian atrophy, one of the nine disorders caused by an expansion of glutamine residues in the causative protein where the polyglutamine expansion cause aberrant protein folding. Since an excessive metal's accumulation in organs may induce protein misfolding and oxidative stress, we have studied the blood concentration of essential (Cr, Co, Cu, Fe, Mn, Mo, Ni, Se, Zn) and nonessential (As, Cd, Sb, Sn, V) trace elements in HD patients. We found increased levels of the essential elements iron, chromium, selenium and zinc and of the nonessential element arsenic in the blood of HD patients. Since alteration in metals homeostasis may contribute to the pathogenesis of neurodegenerative disease and could eventually constitute a target for therapy, we may suggest the utilize of the blood metal profile as a further in vivo tool to study and characterize Huntington disease.

Trace elements are common contaminants in aquatic ecosystems; their detection in biota yields information on their availability in the environment and provides an indirect indication of freshwater ecological status. We analyzed samples of freshwater macrobenthic invertebrates from six watercourses in Friuli Venezia-Giulia (Northeast Italy) to verify whether trace elements accumulation is related to their ecological status sensu Water Framework Directive (WFD), and to determine tropic level influences on the accumulation of 18 trace elements in macrobenthic communities. Observed concentrations could be in line with results of ecological status assessment defined by the WFD, in fact two sites classified as “Moderate” had the highest trace elements content. The genus Calopteryx (Odonata, predator) was positively correlated with Be, Cr, Fe, Mn, Mo, Ni, Sn, and V (ρS range 0.777–0.844). Positive correlations were also determined for the genus Rhyacophila (Trichoptera, predator) with Cu (ρS = 0.757), suggesting bioaccumulation in macroinvertebrate tissue. Ephemeroptera of the genus Caenis (collector-gatherers) were positively correlated with Be, Fe, Mn, Pb, Sb, and V (ρS range 0.757–0.802), indicating that ingestion of sediment is the most effective uptake of these metals. Results of this study, albeit preliminary, showed that trace elements detection in aquatic macrobenthic invertebrates is a useful analysis for obtaining information about the status of freshwater course. Our study provides evidence for a greater accumulation of trace elements in predators and collector-gatherers, suggesting that the tropic level of macrobenthic communities influence the accumulation of trace elements.

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.

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 &mu, g L&minus, 1 (Hg cell concentration), corresponding to 0.06 mg kg&minus, 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.

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.

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.

The presence of Norovirus (NoV) and Hepatitis E virus (HEV) in non-depurated and depurated oysters raised in the north-west Italian coast was investigated by quantitative real-time RT-PCR. Total and inorganic arsenic (As) and the presence of marine biotoxins (DSP, ASP, PSP) by LC-MS were also investigated. NoV was detected through all the sampling period in non depurated and depurated oysters with highest levels during wintertime (>104 genome copies per gram, gc/g) and minimum values in summer below the LOQ (

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.

Background Transfer of metals from soil to plant is a possible route of contamination for the food chain. This investigation focused on the occurrence of 40 elements in the “Red Apple of Cuneo”, an Italian excellence and a Protected Geographical Indication (P.G.I.). Four cultivars were considered: Red Delicious (Jeromine) and Gala (Bukeye, Brookfield, Schniga). Methods Trace elements and rare earth elements (REEs) detection was performed by an Inductively Coupled Plasma-Mass Spectrometer (ICP-MS) previous homogenization of samples and microwave acid digestion. One-way analysis of variance (ANOVA) with Bonferroni correction was employed to for statistical analysis. Results Concentrations of metals in the four apples cultivars were quite comparable, Al and Rb were the most represented nonessential elements while Fe, Cu and Zn between the essential; REEs were found at negligible concentrations. Bioaccumulation factors demonstrated an extremely low capacity of bioaccumulation from soil to fruit. Conclusions The analysis performed on the “Red Apple of Cuneo” has shown that this product is safe for human consumption since metals were recovered at concentrations of no concern and lower than those registered in apples from other countries. Since each production area is characterized by a typical elemental pattern the multielemental profile based on the analysis of 40 elements could be useful to relate products to their region of origin. Differences between the four apple cultivars were instead not significant to discriminate between them.

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.

The concentrations of rare earth elements (REEs) were determined by ICP-MS in feed for farm animals in three regions of Northwestern Italy. This is the first study aimed at defining the levels and patterns of REEs in feed for different animal species. REEs are in fact emerging as contaminants worldwide, following their applications in industry, technology, medicine, and agriculture. Moreover, in 2016, the first REE-based feed additive—a zootechnical additive for weaned piglets—was authorized in the EU. Therefore, information about the natural content of REEs in animal feed of vegetal origin is required to evaluate the potential use of REEs as a growth promoter. There was a high variability in the REEs content of the animal feed in three different Italian regions, and REEs content varied according to the different animal species for which the feed was intended. Concentrations of light REE (LREE) were higher than those of heavy REE (HREE) in each feed typology. Raw materials were shown to have higher ΣREE concentrations (mean concentration 2.4 mg kg−1) than complete or complementary feed. Considering the animal species, mean ΣREE concentrations were as follows: horse feed (2.7 mg kg−1) > poultry feed > bovine feed > swine feed (0.61 mg kg−1). REE levels in feed were in line with values available in the literature on vegetables; thus, REE concentrations in feed do not constitute a concern for animal health.

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.

In this study, arsenic content in 200 cat- and dog-food samples was estimated by means of electro thermal atomic absorption (Z-ETA-AAS), after using the wet digestion method, that were imported or commercialised in Italy from 2007 to 2012. The maximum value of total arsenic (As) in the samples was 12.5 mg kg-1. Some imported pet food was intercepted as a result of the Rapid Alert System for Food and Feed (RASFF) and rejected at the border or withdrawn from the Italian market, because they exceeded the maximum level of arsenic content imposed in Italy at the time of this study (2002/32/EC). All the samples with a signi cant arsenic level were sh-based. Recently, the 2013/1275/EC raised the maximum level of As permitted in sh-based pet food. However, the analysis of As species is required (EFSA 2014) in order to identify correctly the di erent contributions of dietary exposure to inorganic As and to assure pet food quality.

The occurrence of trace elements, REE and iAs was investigated in macroalgae collected from Giglio Island (Grosseto, Italy), 3 years after the Costa Concordia shipwreck recovery operations. There was a high variability of metals and REE between species, even those belonging to the same phylum. Arsenic level was found within the range of the Tuscany marine environment; the inorganic fraction was from 9% to 31%. Al, Be, Pb and Zn levels in seaweeds from Giglio Island were found to be significantly higher than in macroalgae from other islands of the Tuscany archipelago. REE were double the values found in the Tuscan islands of Elba and Capraia. We suggest that concentrations of metals and REE were influenced by the 3-year-long naval operations carried out for the Costa Concordia shipwreck rescue, and that macroalgae could be suitable bioindicators of perturbations in metal concentrations in the marine environment. Capsule Inorganic contaminants in seaweeds for Giglio Island.

Seaweeds have been used as animal feed since a long time and are consumed as food in several cultures. In fact, macroalgae are a source of protein, fiber, polyunsaturated fat, and minerals. The concentration of trace elements was determined in dominant macroalga species from three sites of the northwestern Mediterranean Sea. A high interspecies variability was observed, with higher metal levels in brown and green than those in red seaweeds. The maximum values set by European regulations for arsenic, mercury, and cadmium in food and feed were never exceeded, but a few samples were very close to limits set for mercury. Conversely, the maximum limit for lead in feed was exceeded in all species from one of the considered sites. Analogously, lead in seaweeds could constitute a potential risk for human health, due to the exceeding of the maximum value set for food supplements.

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 600μM Ce for 48h. 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.

The concentrations of trace and non-trace elements were determined in blood and fibers of alpacas (Vicugna pacos) from a north Italian area, as well as in their pasture forages. This is the first investigation regarding this species in Italy, and the first considering alpaca’s fiber as bioindicator worldwide. Metal contents in blood were in the decreasing order: copper > zinc > aluminum > selenium > lead > nickel > manganese > chromium > arsenic and cadmium, while in fiber, metal levels were in the following order: aluminum > zinc > copper > manganese > chromium > nickel > selenium > lead > arsenic and cadmium. Antimony, beryllium, mercury, tin, and thallium were below the limit of quantification (0.010 mg kg−1). The analysis of the alpacas’ forage confirmed the same trend found in fiber, suggesting that metal bioaccumulation was affected by diet. These preliminary results have shown that all the trace elements studied bioaccumulated to a greater extent in the fibers of the alpaca than in the blood. Accordingly, we may suggest that alpaca fibers could be used for monitoring exposure especially to non-essential metals like aluminum, cadmium, and lead, and could constitute a suitable non-invasive method for measuring trace and non-trace element exposure in camelids.

The presence of xenobiotics, such as metals, in ecosystems is concerning due to their durability and they pose a threat to the health and life of organisms. Moreover, mercury can biomagnify in many marine food chains and, therefore, organisms at higher trophic levels can be adversely impacted. Although feathers have been used extensively as a bio-monitoring tool, only a few studies have addressed the effect of both age and sex on metal accumulation. In this study, the concentrations of trace elements were determined in the feathers of all members of a captive colony of African Penguins (Spheniscus demersus) housed in a zoological facility in Italy. Tests were performed by inductively coupled plasma-mass spectrometry to detect aluminum, arsenic, cadmium, cobalt, chromium, copper, iron, manganese, nickel, lead, selenium, tin, vanadium, and zinc. Mercury was detected by a direct mercury analyzer. Sexing was performed by a molecular approach based on analyzing the chromo-helicase-DNA-binding1 gene, located on the sex chromosomes. Sex- and age-related differences were studied in order to investigate the different patterns of metal bioaccumulation between male and female individuals and between adults and juveniles. Juvenile females had significantly higher arsenic levels than males, while selenium levels increased significantly with age in both sexes. Penguins kept in controlled environments-given that diet and habitat are under strict control-represent a unique opportunity to determine if and how metal bioaccumulation is related to sex and age.

PCDD/Fs and PCBs are environmentally persistent substances that have been associated with adverse effects on human health. Contamination of soils, animal feed and pastures leads to their bioaccumulation of in food products of animal origin, which are considered the major source of intake of these contaminants in humans. We analyzed eggs from free-range hens, sampled from small farms, located within a distance of 4.5 km from a secondary aluminum smelter in Northern Italy. The concentrations of PCDD/Fs, DL-PCBs and NDL-PCBs were higher in eggs from locations close to the plant, and strongly exceeded the limits set by EU Regulation 1259/2011 (2.5 pg WHO TEQ fat g(-1) for PCDD/Fs, 5.0 pg WHO TEQ g(-1) for PCDD/Fs and DL-PCBs L, 40 ng g(-1) for NDL-PCBs). Without the prompt and immediately applied control strategies, the consumption of contaminated eggs may have posed [corrected] a risk for human health, especially for children (≤9 years) and infants (≤3 years), due to the 2-fold excess of the current exposure limits.

Mass stranding of sperm whales (Physeter macrocephalus) is a rare event in the Mediterranean Sea. In September 2014, a pod of seven sperm whales became stranded along the Adriatic coast of Southern Italy. This is the seventh occurrence of this type since 1555 in this sea basin. Total concentrations of mercury (T-Hg), methylmercury (MeHg) and selenium (Se) were measured from brain, muscle, liver and kidney of three female sperm whales, which died in this event. Analyses showed considerable, age-dependent variations in Hg and Se concentrations in the different organs. The contamination levels of T-Hg in the liver (up to 200 mg kg(-1)) and brain (up to 21 mg kg(-1)) samples were markedly higher than those in the kidney and muscle samples. The liver and brain also showed the highest Se levels. Se:Hg molar ratios ⩾1 were observed in all the organs of the three sperm whales, suggesting that Se could protect the animals from Hg toxicity. The risk of Hg-associated neurotoxicity was assessed by comparing our values to thresholds set for neurotoxicity in mammals, and the role of Se in the detoxification process of T-Hg/MeHg is discussed herein.

In September 2014, a pod of seven sperm whales ( Physeter macrocephalus ) was stranded along the Adriatic coast of Southern Italy. Concentrations of 20 essential and non-essential trace elements were quantified in the brain, muscle, liver and kidneys of three female sperm whales, which died in this event. The essential elements copper, iron, manganese and zinc showed low ranges of variability, suggesting a homeostatic physiological control, while selenium concentrations were associated with age. Molybdenum, nickel and chromium showed low ranges of concentrations and no evidence of preferential accumulation in selected organs. Very low concentrations of the non-essential elements cadmium, lead, tin and vanadium were detected in all tissues, suggesting a minor impact of these pollutants on the sperm whale populations of the Mediterranean Sea. Aluminum was revealed to have relatively high concentrations, together with a high variability between tissues and individuals, reaching the highest values in the kidneys and muscle of the oldest female, which was pregnant; the rare earth elements – lanthanum and cerium – were also detected in the kidneys of this female, indicating that pregnancy probably influenced metal concentrations in body tissues.