Microplastics in bulk atmospheric deposition along the coastal region of victoria land, Antarctica.

The increasing global concern over microplastic pollution has driven a surge in research efforts aimed at detecting microplastics across various ecosystems. Airborne microplastics (MPs) have been identified in remote environments worldwide, including Antarctica. However, data on bulk atmospheric deposition remain scarce. From January to December 2020, atmospheric deposition was directly collected using passive samplers placed in eight sites across Victoria Land. Using Raman Microspectroscopy, MPs were identified in six out of the seven samples collected (one sample was lost due to the extreme weather conditions). The average daily MP deposition for Victoria Land was 1.7 ±â€¯1.1 MPs m-2 d-1, with values ranging from 0.76 to 3.44 MPs m-2 d-1. The majority (53 %) of MPs found in the atmospheric deposition were in the size class of 5-10 µm, and the main shape of MPs was fragments (95 %). The predominant plastic type was polypropylene (31 %), followed by polyethylene (19 %) and polycarbonate (12 %). Polystyrene, polyester, styrene and polyethylene terephthalate each accounted for ~6 %. Microplastics identified in the coastal sites may have local origins, potentially associated with scientific activities at research stations. Conversely, a backward trajectories analysis suggested a potential contribution of atmospheric transport to microplastic deposition at Larsen Glacier and Tourmaline Plateau, the two most remote sites of the study area, where the highest MP concentrations were detected. Our findings present the first evidence of microplastics in the Antarctic atmospheric deposition directly collected via passive samplers, highlighting the need for continued monitoring and research to assess the environmental impact of MPs, particularly in sensitive and remote ecosystems like Antarctica.

Unlocking the elemental signature of European tea gardens: Implications for tea traceability.

This study presents a comprehensive analysis of the elemental profiles of tea leaves coming from plants grown in several European gardens, with a focus on the bioaccumulation of essential and potentially toxic trace elements in relation to processing and location of tea garden. Samples were collected from various gardens across Europe, including Portugal, the Azores, Germany, the Netherlands, and Switzerland. Elemental analysis was conducted on fresh tea leaves, dried leaves, and leaves processed for the production of green and black tea, along with soil samples from the root zones of tea plants. The results reveal no significant differences in elemental content based on the processing of tea leaves. However, distinct elemental profiles were observed among tea leaves of plants grown in gardens from different European regions. Utilizing chemometric and machine learning tools, the study highlights the potential of these elemental profiles for enhancing the traceability of tea products.

Insights on the Nutraceutical Properties of Different Specialty Teas Grown and Processed in a German Tea Garden.

European countries have recently started experimenting with growing and producing their own teas in small quantities, mainly for the specialty tea sector. To characterize European teas, this study investigated a set of five tea types obtained from different Camellia sinensis varieties/cultivars, representing various oxidation grades (green, white, yellow, oolong, black), all grown and processed in the only tea garden in Europe (in Germany) that focuses on all five types. Hot and cold brews were studied by measuring the total phenolic (TPC) and flavonoid contents (TFC), the antioxidant capacity and UV-Vis spectra, also with the objective of discriminating between the different tea types and the different plant varieties. The dried leaves were analyzed to measure the content of essential and toxic elements and by ATR-FTIR spectroscopy to determine a chemical fingerprint for identifying the tea varieties and types. The average levels of TPC (hot brew = 5.82 ± 2.06; cold brew = 5.4 ± 2.46 mM GAEq), TFC (hot brew = 0.87 ± 0.309; cold brew = 0.87 ± 0.413 mM CAEq), and antioxidant capacity (ORAC assay-hot brew = 20.9 ± 605; cold brew = 21.8 ± 8.0 mM TXEq, ABTS assay-hot brew = 15.2 ± 5.09; cold brew = 15.1 ± 5.8 mM TXEq, FRAP assay-hot brew = 9.2 ± 3.84; cold brew = 10.4 ± 5.23 mM AAEq) observed compared well with those from other parts of the world such as China, Africa, and Taiwan. The hazard quotient <1 and the hazard index of 0.14 indicate that there is no non-carcinogenic risk from consumption of these teas. The obtained information is essential for elucidating the characteristics and the impact of tea processing and tea variety on the health benefits of these tea products coming from a single European tea garden. This multifaceted approach would help tea growers in Europe increase their knowledge on the health attributes of the teas they grow, ultimately leading to optimization of the nutraceutical properties of these teas.

Determination of Hg and Se in swordfish (Xiphias gladius) from Mediterranean Sea: Implications for nutritional recommendations during pregnancy and childhood.

Swordfish (Xiphias gladius) are important marine predators facing potential mercury (Hg) contamination. This study analyzed Hg levels in swordfish muscle tissue from two Mediterranean Sea stocks. Italian specimens showed significantly higher Hg concentrations (1.4 ± 0.8 mg kg-1 ww) than Spanish ones (0.8 ± 0.5 mg kg-1 ww), with many samples exceeding EU's safety limit (1 mg kg-1 ww). Selenium (Se) content and Se:Hg ratios were examined, along with the maximum safe fish meals per month for vulnerable consumers. These results highlight the urgent need for monitoring and mitigation strategies to reduce health risks, especially for susceptible populations.

Bioaccumulation and biomagnification of heavy metals in marine micro-predators.

Nematodes represent >3/5 of the abundance of the world's metazoans and usually account for nearly 90% of the total benthic fauna, playing a key ecological role in the benthic ecosystem functioning on a global scale. These small metazoans include a relevant number of microscopic predators and, in turn, are the most abundant preys of macro-megafauna and fish juveniles thus playing a key role in marine food webs. Here, using two independent approaches, we test the bioaccumulation in marine nematodes of several heavy metals present in contaminated sediments. We report here that nematodes, despite their short life cycle and small size, bioaccumulate significantly heavy metals. Bioaccumulation increases from deposit feeders and microalgal grazers to predators of microbes and other tiny metazoans. These results suggest that nematodes also contribute to their biomagnification along the food webs and can contribute to increase the transfer of contaminants from the sediments to larger organisms.

Mercury in honey from the Marche region (central Italy). Risk assessment from human consumption and its use as bioindicator of environmental pollution.

Honey is a natural product made by honeybees (Apis mellifera) from nectar or honeydew. It is a very popular and appreciated product all over the world as it represents a rapidly available energy source and exerts several beneficial properties for humans. However, it has been demonstrated that honey can be contaminated by potentially toxic elements (PTEs) of natural or anthropogenic origin. Among them, mercury (Hg) represents one of the most dangerous for its toxicity and its capacity to biomagnify along the trophic web. In the present study, 100 honey samples from the Marche Region (Central Italy) produced in the year 2021, were analyzed by thermal decomposition amalgamation atomic absorption spectrometry to determine the Hg content. The overall mean concentration was 0.2 ± 0.2 µg kg-1. The results showed that no statistically significant differences were found in Hg content among honey from different pollen origin, but honeydew had a significantly higher Hg content with respect to all other honey samples (0.6 ± 0.3 µg kg-1). The Hg content in honey depends mainly on local pollution, while geographical origin did not play a key role. Furthermore, considering the regulatory limits and provisional tolerable weekly intake (PTWIs) identified by FAO/WHO, the Hg Hazard Quotient (HQ) measurement revealed that this product is safe for human consumption.

Essential and Potentially Toxic Elements (PTEs) Content in European Tea (Camellia sinensis) Leaves: Risk Assessment for Consumers.

Tea (Camellia sinensis) is the second most consumed beverage worldwide, playing a key role in the human diet. Tea is considered a healthy drink, as its consumption has been linked to a lower risk of cardiovascular disease-related events and death, stroke, metabolic syndrome and obesity. However, several studies have shown that C. sinensis is a hyperaccumulator of Al and other elements that are considered potentially toxic. In the present study, the contents of 15 elements (both essential and toxic) were determined for the first time in tea leaves collected in tea gardens located in six different European countries and processed to provide black and green tea. The results showed that Al was the major toxic element detected, followed by Ni, Cr, Pb, As, Cd, Ag, and Hg. Essential elements were detected in the order of Mn, Fe, Zn, Cu, Co, and Se. Statistically significant correlations (p < 0.05) were found in the distribution of some elements, highlighting mechanisms of synergic or antagonist interaction. Multivariate analysis revealed that geographical origin was the main driver in clustering the samples, while the different treatment processes (black or green) did not significantly affect the contents of elements in the leaves. The estimation of potential non-carcinogenic risk revealed no risk for the consumption of European teas for consumers in terms of potentially toxic elements.

Mercury levels in Merluccius merluccius muscle tissue in the central Mediterranean Sea: Seasonal variation and human health risk.

In this study we analysed total mercury (THg) levels in European hake (Merluccius merluccius) - an ecologically and commercially important species throughout the Mediterranean - caught in the northern and central Adriatic Sea. To the best of our knowledge, this is the first study evaluating THg levels in hake fillets in relation to ecological (season) and biological (body size, sex, sexual maturity, lipid content) parameters. THg levels in muscle showed no sex-related differences; in contrast, significant season-related differences were found in females, with higher levels in spring-summer compared with autumn-winter. No season-related differences were seen in males. A significant sex effect was found for body size and sexual maturity. Females showed a correlation between THg level and length, THg being significantly higher in mature compared with immature specimens. No significant sex effect was found for muscle lipid content, because a correlation between THg concentration and tissue lipids was found in both sexes. Since the mean THg concentration found in M. merluccius fillets (0.64 ± 0.29 mg kg-1 dry weight; range, 0.20-1.53) was consistently under the level set by EU regulations, this study demonstrates that European hake caught in the northern and central Adriatic is safe for human consumption.

New Eco-Sustainable Feed in Aquaculture: Influence of Insect-Based Diets on the Content of Potentially Toxic Elements in the Experimental Model Zebrafish (Danio rerio).

According to the concept of circular economy, insects represent good candidates as aquafeed ingredients. Nevertheless, there are some potential chemical risks linked with insect consumption. In this study, we reared the teleost Danio rerio, used as an experimental model, with five experimental diets characterized by increasing levels (0%, 25%, 50%, 75%, and 100%) of full-fat Hermetia illucens (Hi) prepupae, substituting for fish meal (FM) and fish oil (FO). We investigated the presence of potentially toxic elements (PTEs) Cd, Pb, Ni, As, and Hg in larval (20 days), juvenile (2 months), and adult (6 months) fish. Quantitative determinations of Cd, Pb, Ni, and As were made with an atomic absorption spectrometer; the total mercury content was determined by a direct mercury analyzer. The substitution of FM and FO with Hermetia illucens meal led to a reduction in the content of some PTEs, such as Pb, As, and Ni, in fishfeed, leading to concentrations below the legal limit of undesirable substances in animal feed. By increasing the Hi meal dietary content, we observed in the Danio rerio specimens an increase in Cd, Pb, and Ni content and a reduction in As content for all life stages. Moreover, a general increase in the content of Cd, Pb, Hg, and Ni from larvae to juvenile was measured, while the shift of Danio rerio from the juvenile to the adult stage involved a significant increase in the content of Pb, Hg, and Ni. Larvae had a reduced ability to bioaccumulate metal(loid)s compared to juveniles and adults. In conclusion, the content of PTEs in Danio rerio is influenced both by the type of diet administered and by the life stage of the animal itself. This research demonstrates the possibility of using Hi prepupae as an aquafeed ingredient without exposing fish to a chemical risk and, in perspective, allows applying these eco-sustainable diets for the breeding of edible fish species, without endangering human health.

Erratum: Illuminati et al. Determination of Cd, Pb, and Cu in the Atmospheric Aerosol of Central East Antarctica at Dome C (Concordia Station). Molecules 2021, 26, 1997.

The authors wish to make the following corrections to the paper [...].

Determination of Cd, Pb, and Cu in the Atmospheric Aerosol of Central East Antarctica at Dome C (Concordia Station).

Trace heavy metals Cd, Pb, and Cu were determined (by square wave anodic stripping voltammetry) in aerosol samples collected at Dome C (the Italo-French Station Concordia), a remote site of the Central East Antarctic plateau, for which no data are available until now. During the Austral Summer 2005-2006, three PM10 high-volume impactors were installed in two locations nearby of Concordia station: the first one very close and downwind of the station (about 50 m north), the other two (very close to each other) in a 'distant' site, upwind of the station and close to the astrophysics tent (not used in that expedition) at ~800 m south of Station Concordia. For each sample, the availability of the mass of the aerosol collected (obtained by differential weighing carried out on site), in addition to the volume of the filtered air, allowed us to express results both in terms of metal mass fractions in the aerosol and in the usual way of metal atmospheric concentrations. Metal contents increased in the order Cd < Pb < Cu with the following ranges of values: Cd 1.0-8.4 µg g-1 (0.09-3.1 pg m-3), Pb 96-470 µg g-1 (12-62 pg m-3), and Cu 0.17-20 mg g-1 (0.027-2.4 ng m-3). From the metal temporal profiles obtained we estimated the following background values for the area of Dome C, expressed both in mass fractions and in atmospheric concentrations: Cd 1.2 ± 0.2 µg g-1 (0.24 ± 0.13 pg m-3), Pb (here fixed as upper limit) 113 ± 13 µg g-1 (21 ± 8 pg m-3), and Cu 0.91 ± 0.48 mg g-1 (0.12 ± 0.07 ng m-3). The highest values were observed in the first part of the season, and particularly for the site close to the station, possibly related to sample contamination linked to intense activity at the Concordia station connected with the beginning of the expedition, including aircraft arrivals/departures. Increments of up to 10 times (and even 20 times for Cu) were recorded with respect to the background values. The metal excesses of the contaminated over background samples were found approximately, except for Cu, in the same proportion of the metal contents of the special Antarctic blend (SAB) diesel fuel, which is used almost exclusively at Concordia Station. The effect of the wind direction was also observed. Thus in the intermediate period of the campaign, when the wind direction reversed for several days with respect to the prevailing one, Cd and Pb metal contents decreased at the sampling point installed close to the station, now upwind of Concordia station, and increased at the 'clean' site astrophysics tent, turned downwind at the main station. No simple and easily interpretable effect of the wind direction was observed for Cu, which suggests that some other extemporaneous and not clearly identified factor may have intervened in this case. These results suggest that the human impact at Dome C influences mainly the zone very close to the station, but also the area in the neighborhood, including the supposed clean site of the astrophysics tent (about 800 m far from the station), when the wind direction reverses with respect to the prevailing one, leaving the site downwind of the station Concordia. Since no other data are reported for the Dome C area, our results are compared with literature data referred to the South Pole Station (the only other plateau site for which data are available) and several other coastal Antarctic sites, observing that our results (excluding Cu) are the lowest ever observed for Antarctic aerosol.

Seasonal Evolution of Size-Segregated Particulate Mercury in the Atmospheric Aerosol Over Terra Nova Bay, Antarctica.

Size-fractionated particulate mercury (PHg) measurements were performed from November 2017 to January 2018 at Terra Nova Bay (Antarctica) for the first time. Samples were collected every 10 days by a six-stage high-volume cascade impactor with size classes between 10 µm and 0.49 µm. Total PHg concentrations were maxima (87 ± 8 pg m-3) in November, then decreased to values ~40% lower and remained almost constant until the end of the sampling period (~30 pg m-3). The trimodal aerosol mass distribution reveals that from 30% to 90% of the total PHg came in the size > 1.0 µm. Hg in the two coarse fractions was probably produced by the adsorption of oxidized Hg species transported by air masses from the Antarctic plateau or produced locally by sea ice edges. PHg in accumulation mode seemed to be related to gas-particle partitioning with sea salt aerosol. Finally, average dry deposition fluxes of PHg were calculated to be 0.36 ± 0.21 ng m-2 d-1 in the accumulation mode, 47 ± 44 ng m-2 d-1 in the first coarse mode, and 37 ± 31 ng m-2 d-1 in the second coarse mode. The present work contributed to the comprehension of the Hg biogeochemical cycle, but further research studies are needed.

A Chemically Safe Way to Produce Insect Biomass for Possible Application in Feed and Food Production.

Black soldier fly (Hermetia illucens, HI, Diptera, Stratiomydae) has great potential as a food and feed ingredient in the European Union (EU). The production of insects as livestock feed or as food ingredients requires strict monitoring of the content of potentially toxic elements (PTEs) in the growth substrate, to meet the security requirements. This study aims to investigate the presence of PTEs, like cadmium, lead, mercury, arsenic, and nickel, in HI prepupae and in their growth substrates based on coffee roasting by-product and microalgae Schizochytrium sp. and Isochrysis sp. Analyses were carried out via graphite furnace atomic absorption spectrophotometry for Cd, Pb, Ni, and As, and via Direct Mercury Analyzer for Hg. All element concentrations found in growth substrates were below the legal limit of undesirable substances in animal feed (2002/32/EC). Elements concentrations in HI prepupae were in the range (mg kg-1 wet weight) of 0.072 to 0.084 for Cd, 0.018 to 0.026 for Pb, 0.010 to 0.032 for Hg, 0.036 to 0.047 for As, and 0.18 to 0.76 for Ni. Even if HI prepupae accumulated Cd, Pb, and Hg, our results indicated that the risk of exposure to PTEs from HI prepupae consumption is relatively low and in compliance with EU regulations.

Influence of Feeding Substrates on the Presence of Toxic Metals (Cd, Pb, Ni, As, Hg) in Larvae of Tenebrio molitor: Risk Assessment for Human Consumption.

Larvae of Tenebrio molitor L. (Coleoptera: Tenebrionidae) are particularly suitable as novel food for the human consumption; nevertheless, there are some potential safety risks linked with insect consumption. In this study we investigated the presence of Cd, Pb, Ni, As, Hg in new feeding substrates coming from solid residues generated by olive fruits processing, called olive-pomace, and their influence on the metal content in larvae of T. molitor. Morover, bioaccumulation factor and the mercury-selenium balance were evaluated. Analyses were carried out via graphite furnace atomic absorption spectrophotometry for Cd, Pb, Ni, As and Se, and via Direct Mercury Analyzer for Hg. All metal concentrations found in feeding substrates were below the legal limit of undesirable substances in animal feed (2002/32/EC). Concentrations in larvae were in the range (mg kg-1 wet weight): Cd 0.008-0.016, Pb 0.063-0.079, Ni 0.03-0.63, As 0.021-0.023, Hg 0.12 × 10-3-0.49 × 10-3, and Se 0.057-0.085. Statistically significant correlation between metal content in feeding substrates and in larvae was evidenced only for Hg, which bioaccumulates. Se protects from mercury toxicity, with a Selenium Health Benefit Value (HVBSe) of > 0. Overall, our results indicate that the risk of exposure to metals from consumption of mealworm larvae is relatively low and in compliance with European Union regulations.

Mercury Content in Central and Southern Adriatic Sea Sediments in Relation to Seafloor Geochemistry and Sedimentology.

Mercury contents were determined in surface sediments from the Central and Southern Adriatic Sea to gain insight into the processes, factors, and variables affecting its distribution. Mercury concentration was measured by thermal decomposition amalgamation atomic absorption spectrometry in samples collected by box-corer from Ancona to Santa Maria di Leuca during the CNR-PERTRE cruise (16/9-4/10/2016). Sediments were also evaluated for chemical-physical parameters (pH, Eh), biogeochemical composition (total carbon, inorganic carbon, total organic carbon, organic matter) and grain size. The average mercury concentration in the Adriatic Sea sediment was 0.053 mg/Kg (d.w.), range 0.011-0.12 mg/Kg (d.w.). Mercury content was mainly affected by grain size and organic matter (OM) distribution, whereas anthropic factors exerted a limited influence. Concentrations followed the distribution of sediment types (clay > silt > sand) due to Adriatic Sea hydrodynamics and were well below the regulatory limits in all samples.

Determination of Hg in Farmed and Wild Atlantic Bluefin Tuna (Thunnus thynnus L.) Muscle.

Mercury (Hg) is a well-known toxic element, diffused in the environment, especially in the Mediterranean Sea which is rich in cinnabar deposits. Mercury bioaccumulation in fish is of great concern, especially for top-level aquatic predators (e.g., shark, tuna, swordfish) and above all for species of large human consumption and high nutritional value. This work aimed to determine Hg concentrations in farmed and wild Atlantic Bluefin tuna (Thunnus thynnus) caught in the Mediterranean area in order to evaluate the level of Hg bioaccumulation. selenium (Se) content was also determined, since this element is an antagonist of mercury toxicity. Mercury and Se were analysed by atomic absorption spectrometry after microwave digestion of the samples. Hg content in farmed tuna was below the legal limit (1 mg/kg, wet weight, w.w.) for all specimens (0.6 ± 0.2 mg/kg), whereas the wild ones had a content over the limit (1.7 ± 0.6 mg/kg); Se concentration was higher in farmed specimens (1.1 ± 0.9 mg/kg) compared to wild ones (0.6 ± 0.3 mg/kg). A safe seafood could show a Se/Hg ratio >1 and a health benefit value (HBVSe) > 0: farmed tuna had higher values than the wild specimens (Se/Hg 5.48 vs. 1.32; HBVSe 11.16 vs. 0.29). These results demonstrate that for Hg, there is a better risk/benefit ratio in farmed T. thynnus. making it safer than wild tuna.

Heavy Metals in Spring and Bottled Drinking Waters of Sibylline Mountains National Park (Central Italy).

Heavy metal concentrations (cadmium, lead, and copper) in spring, tap, and bottled waters of the Sibylline Mountains National Park (central Italy) were investigated using square wave anodic stripping voltammetry from 2004 to 2011. The mean (±SD) concentrations detected (1.3 ± 0.4 ng L-1 cadmium, 14 ± 6 ng L-1 lead, and 0.16 ± 0.10 µg L-1 copper) were below the limits stipulated by Italian and European legislation for drinking and natural mineral water. In the three studied areas of the park (Mount Bove north, Mount Bove south, and springs of River Nera) with very few exceptions, both mineral waters bottled in the area and aqueduct waters from public fountains had approximately the same metal concentrations as did the spring waters from which they were derived. Conversely, substantially higher metal concentrations were found at some sites in private houses, which may be due to release of metals from old metal pipes. At the time of this study, waters of Sibylline Mountains National Park were of good quality, and no influence of the bottling process on heavy metal concentrations was found.

Pb, Cu and Cd distribution in five estuary systems of Marche, central Italy.

Heavy metals are subjected to monitoring in estuarine and marine water by the European Union Water Framework Directive, which requires water body health to be achieved by 2021. This is the first survey of heavy metals content in five estuaries of Marche, a region in central Italy. Results showed that total Pb and Cu concentrations decreased by 70-80%, from 1000-2000 to 100-200 ng L(-1) (Pb) and from 2000-3000 to 500-1000 ng L(-1) (Cu) from river to sea. Cd was consistently 20-40 ng L(-1). Dissolved Pb and Cu concentrations declined by 50% and 70% respectively passing from oligohaline to euhaline water, from 150 to 70 ng L(-1) and from 2000-1000 to 600-400 ng L(-1). Cd decreased slightly from ∼20 to ∼10 ng L(-1). Although such concentrations are in the range allowed by the Water Framework Directive, they far exceed (up to 10×) the ground content ceiling set for 2021.

Physicochemical properties of honey from Marche, Central Italy: classification of unifloral and multifloral honeys by multivariate analysis.

The purpose of this study was the physicochemical characterization and classification of Italian honey from Marche Region with a chemometric approach. A total of 135 honeys of different botanical origins [acacia (Robinia pseudoacacia L.), chestnut (Castanea sativa), coriander (Coriandrum sativum L.), lime (Tilia spp.), sunflower (Helianthus annuus L.), Metcalfa honeydew and multifloral honey] were considered. The average results of electrical conductivity (0.14-1.45 mS cm(-1)), pH (3.89-5.42), free acidity (10.9-39.0 meq(NaOH) kg(-1)), lactones (2.4-4.5 meq(NaOH) kg(-1)), total acidity (14.5-40.9 meq(NaOH) kg(-1)), proline (229-665 mg kg(-1)) and 5-(hydroxy-methyl)-2-furaldehyde (0.6-3.9 mg kg(-1)) content show wide variability among the analysed honey types, with statistically significant differences between the different honey types. Pattern recognition methods such as principal component analysis and discriminant analysis were performed in order to find a relationship between variables and types of honey and to classify honey on the basis of its physicochemical properties. The variables of electrical conductivity, acidity (free, lactones), pH and proline content exhibited higher discriminant power and provided enough information for the classification and distinction of unifloral honey types, but not for the classification of multifloral honey (100% and 85% of samples correctly classified, respectively).

Recent temporal variations of trace metal content in an Italian white wine.

For the first time in Italy, the temporal variations of Cd, Pb and Cu content in an Italian white wine were studied over the period 1995-2010. A previously set up and optimized Square-Wave Anodic Stripping Voltammetric technique was used. Cd showed a first decrease (∼30%) due to the use of pesticides with progressively low Cd residues. Since 2000 Cd had constant and extremely low values (0.17±0.07 µg L(-1)). A significant decrease (∼74%) from 1995 to 2010 was observed for Pb (mean concentration, 18±10 µg L(-1)) probably due to the recent decrease in Pb emissions in the atmosphere following the phasing out of metal from gasoline (in Italy since 2002). The Cu reduction (mean value, 32±15 µg L(-1)) of ∼74% from 1995 to 2010 was related to the use of phytoiatric products with a progressively low Cu content.