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The purpose of this paper is to investigate the trace metal content in edible biomonitors (i.e., mollusks) in the Beagle Channel (southern Patagonia) and to assess the human health risks associated with their consumption. Rationale: The monitoring breakdown structure (MBS) conceptual model was applied to four sampling campaigns (2005 → 2012) that collected 729 samples of Mytilus chilensis and Nacella magellanica. The composition of trace elements (Cd, Cr, Cu, Ni, Pb and Zn) in the mollusks was determined using graphite furnace (GFAAS) or flame atomic absorption spectrometry (FAAS). We compared the mean obtained values with the maximum levels (MLs) of each element established by international organizations. Then, based on semi-structured interviews, we calculated the estimated daily intake (EDI) of local residents and compared it with safety reference doses, i.e., the provisional tolerable daily intake (PTDI), provisional maximum tolerable daily intake (PMTDI), and tolerable daily intake (TDI), as well as the benchmark dose level lower confidence limit for Pb (BMDL01, a reference point (RP)/point of departure (POD). Moreover, to obtain information about the potential health risks of ingesting heavy metals (HMs) through mollusk consumption, we evaluated the target hazard quotient (THQ) and the hazard index (HI). Findings: For Cd and Pb, 65% and 40% of bivalves exceeded the MLs established by the Mercado Común del Sur (Mercosur), respectively. Except for Cd in N. magellanica (i.e., 1.20 µg/kg/bw/day), EDI values were clearly lower than the safety reference doses. For Cr, Cu, Ni, Pb and Zn, mussels were safe for consumption and did not raise concerns for public health. Likewise, THQ values were well below one for most of the studied metals, indicating that the exposed human population is assumed to be safe. Occasional high consumers of mollusks from the most contaminated sites may be at some health risk. Originality: The food production system and the environment are complex systems; this is crucial to understand when we consider ecosystems as a food source (i.e., marine ecosystems). Here we consider edible biomonitors, that are organisms that can have a dual function. They are food, and at the same time, if properly calibrated, they can act as indicators of environmental quality. This study is the first to investigate relevant essential and non-essential trace metal content in two edible mollusks from the Beagle Channel in a long-term survey (2005 → 2012). The information variety was high; approximately thirteen thousand determinations were conducted to support the risk assessment for mollusk consumption. Other aspects connected with the health risks and the uncertainty factors related to the presence of essential and non-essential minerals in edible mollusks as well as the use of the MBS are also discussed.

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Lichen Usnea barbata transplants were tested as a biomonitor of atmospheric deposition in an apparently pristine environment that is Tierra del Fuego region (Patagonia, Argentina). The present survey is connected with the volcanic eruption that started in north Patagonia on June 4, 2011 from the Puyehue-Cordón Caulle volcano, Chile (north Patagonia, at 1700 km of distance of our sampling sites). Lichens were collected in September 2011 (one month of exposure) and September 2012 (1 year of exposure) in 27 sites covering the northern region of the province where trees are not present. The atmospheric deposition of 27 elements by using Neutron Activation Analysis (NAA) was determined in the collected samples. The first aim of the study was to evaluate the influence of the volcanic eruption on the regional atmospheric deposition comparing our results with baseline data we determined in U. barbata in 2006 in the same sites. The second aim was to test possible patterns of bioaccumulation between the two sampling campaigns after the volcanic eruption. With respect to 2006 baseline levels, we found significant higher levels for As, Ba, Co, Cr, Cs, Na, Sb and U in lichens collected after 1 month of exposure (first sampling campaign--2011). Between the two sampling campaigns (2011-2012) after the eruption, lichens reflected the natural contamination by volcanic ashes with significantly higher median levels of Br, Cr, Fe, K, Na, Sc, and Se. Results confirmed the very good aptitude of U. barbata to reflect the levels of elements in the environment at global scale and to reflect the volcanic emissions at distant places. Volcanic eruptions cause the emission in the atmosphere of elevated levels of particulate matter. In this regard, our findings demonstrate the importance to evaluate the metal composition of the particles to avoid possible health effects.

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BACKGROUND: The levels of 19 elements (As, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Se, Tl, U, V, Zn) from sixteen different Argentine production sites of unifloral [eucalyptus (Eucaliptus rostrata), chilca (Baccharis salicifolia), Algarrobo (Prosopis sp.), mistol (Ziziphus mistol) and citric] and multifloral honeys were measured with the aim to test the quality of the selected samples. Typical quality parameters of honeys were also determined (pH, sugar content, moisture). Mineral elements were determined by using inductively coupled plasma mass spectrometer (ICP-MS DRC). We also evaluated the suitability of honey as a possible biomonitor of environmental pollution. Thus, the sites were classified through cluster analysis (CA) and then pattern recognition methods such as Principal Component Analysis (PCA) and discriminant analysis (DA) were applied. RESULTS: MEAN VALUES FOR QUALITY PARAMETERS WERE: pH, 4.12 and 3.81; sugar 82.1 and 82.0 °brix; moisture, 16.90 and 17.00% for unifloral and multifloral honeys respectively. The water content showed good maturity. Likewise, the other parameters confirmed the good quality of the honeys analysed. Potassium was quantitatively the most abundant metal, accounting for 92,5% of the total metal contents with an average concentration of 832.0 and 816.2 µg g(-1) for unifloral and multifloral honeys respectively. Sodium was the second most abundant major metal in honeys with a mean value of 32.16 and 33.19 µg g(-1) for unifloral and multifloral honeys respectively. Mg, Ca, Fe, Mn, Zn and Cu were present at low-intermediate concentrations. For the other 11 trace elements determined in this study (As, Be, Cd, Co, Cr, Ni, Pb, Se, Tl, U and V), the mean concentrations were very low or below of the LODs. The sites were classified through CA by using elements' and physicochemical parameters data, then DA on the PCA factors was applied. Dendrograms identified three main groups. PCA explained 52.03% of the total variability with the first two factors. CONCLUSIONS: In general, there are no evidences of pollution for the analysed honeys. The analytical results obtained for the Argentine honeys indicate the products' high quality. In fact, most of the toxic elements were below LODs. The chemometric analysis combining CA, DA and PCA showed their aptness as useful tools for honey's classification. Eventually, this study confirms that the use of honey as biomonitor of environmental contamination is not reliable for sites with low levels of contamination.

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With the aim to evaluate the mollusk Nacella (P)magellanica as biomonitor of elemental pollution in seawater of the Beagle Channel, more than one hundred individuals of the gastropod were sampled, separated in viscera and muscle, and then examined with respect to the accumulation of Cd, Cr, Cu, Ni, Pb and Zn. Collection was performed in seven strategic locations along 170 km of the coastal area of the Beagle Channel (Tierra del Fuego, Argentina) in two campaigns during 2005 and 2007. Samples of surrounding seawater in the different sites were obtained and tested for the same metals as well. The accumulation capacity of Nacella (P)magellanica and thus its aptitude as biomonitor, was evaluated through the calculus of the preconcentration factors of the metals assayed. A discussion involving the comparison with other mollusks previously tested will be given. Several statistical approaches able to analyze data with environmental purposes were applied. Non parametric univariate tests such as Kruskal-Wallis and Mann-Whitney were carried out to assess the changes of the metal concentrations with time (2005 and 2007) in each location. Multivariate methods (linear discriminant analysis on PCA factors) were also applied to obtain a more reliable site classification. Johnson's probabilistic method was carried out for comparison between different geographical areas. The possibility of employing these results as heavy metals' background levels of seawater from the Beagle Channel will be debated.

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Lichen, Usnea barbata, transplants taken from Tierra del Fuego (south Patagonia, Argentina) were tested as potential biomonitors of atmospheric airborne deposition in an apparently pristine environment. In 2005, lichens were sampled in a reference site (n = 31) and transplanted in the northern Region of Tierra del Fuego. After, respectively, 1 month and 1 year of exposure, we collected them. The aim of the study was to determine the bioaccumulation of 26 elements in order to evaluate the background levels in the selected area. Samples were analyzed by the sector field inductively coupled plasma mass spectrometry. Discriminant analysis on principal component analysis factors was applied in order to explore the relationship among the different elements as far as time and spatial variation in transplants regards. The analysis was tested by Monte Carlo test based on 999 replicates. The most important contamination source resulted to be the atmospheric soil particle deposition. Furthermore, the results were compared with those obtained from the lichens collected in central and southern Tierra del Fuego. This study confirms the ability of U. barbata to reflect the background levels of the 26 elements in that environment. Compared with other background sites in the world, we did confirm that Tierra del Fuego lichens have a low content of the studied elements. Tierra del Fuego turned out not to be a pristine environment as supposed, but it can be considered as a reference basal ecosystem for useful comparisons among different geographical areas. These findings can be very relevant and useful for environmental conservation programs.

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In order to test the aptitude of individuals of Mytilus chilensis as biomonitors of heavy metals pollution in seawater, several samples of this mollusk together with surrounding seawater samples were collected along 170 km of the coastal area of the Beagle Channel (Tierra del Fuego, Argentina) in 2005 and 2007. The study, performed in seven locations strategically selected, involved the determination of Cd, Cr, Cu, Ni, Pb and Zn in seawaters and mollusks by atomic absorption spectrometry (AAS) and the calculation of the respective concentration factors (CFs). Obtained data were standardized and analyzed by multivariate techniques in order to establish differences between sampling sites and periods. Obtained results will be shown and the bioaccumulation ability of M. chilensis will be evaluated by comparison with results obtained for Mytilus species in different geographical marine areas. A fully discussion on the possibility of employing the results as background levels for comparative purposes in other marine waters of the world will be provided. The possible harm derived from human consumption of these mollusks will be also assessed.

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Lichen samples of Usnea barbata were used as possible biomonitors of the atmospheric background level of iridium (Ir), platinum (Pt) and rhodium (Rh) in the remote region of Tierra del Fuego (South Patagonia, Argentina). Lichens were collected in 2006 at 53 sites covering 7 different areas of the region (24 transplanted lichens of the northern region and 29 native lichen samples of the central-southern region). A microwave acidic digestion procedure was used to mineralize the samples and a sector field inductively coupled plasma mass spectrometry method was developed to quantify the elements. The study of the influence of interferences on analyte signals and a quality control procedure were carried out. The analytical protocol was further applied to evaluate Ir, Pt and Rh bioaccumulation in lichens. The detection limits obtained were 0.010 ng g⁻¹, 0.013 ng g⁻¹ and 0.030 ng g⁻¹ for Ir, Pt and Rh, respectively. Recoveries at different fortification levels were between 96.3% and 106% and precision was 3.3% on average. The metals concentration (as dry weight) spanned the following ranges: Ir, <0.010-1.011 ng g⁻¹; Pt, 0.016-2.734 ng g⁻¹; and Rh, 0.063-1.298 ng g⁻¹. Data on 7 areas were similar suggesting that no specific source, for example traffic or anthropogenic activity, influenced directly the metal concentrations in Tierra del Fuego. Values detected are more likely influenced by the long-range atmospheric transport of these pollutants and, in comparison with densely populated areas in the world, they can represent the baseline for low impacted areas.

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Lichen Usnea barbata was tested as a possible biomonitor of atmospheric deposition in a supposedly pristine environment Tierra del Fuego (Argentina). Lichen samples were collected in 2005 and again in 2006 in 71 sites covering almost the entire region. The aim of the study was to evaluate the bioaccumulation of 26 elements in order to define the background levels in the region. The quantification was carried out by the sector field inductively coupled plasma mass spectrometry. No relevant temporal accumulation patterns between 2005 and 2006 sampling campaigns were observed. Then, the results were submitted to multivariate statistical analysis (cluster and principal component analyses). Cluster analysis produced a dendrogram where the 71 sites were divided into four clusters at (Dlink/Dmax)100<30. The areas and the elements were correlated according to the element concentrations by principal component analysis. Four significant components that accounted for 67% were obtained. Cluster 1 was mainly composed of sites of Ushuaia-Road 3 (E area) and it was characterized by high levels of Cd, Co, Ni, Pb, Sb, and W in lichens. The present study has revealed the good capacity of U. barbata to reflect the baseline levels of elements in the environment at a regional scale level. The presence of certain level of elements in lichens agrees with the hypothesis that Tierra del Fuego is not a relatively pristine environment as occasionally supposed. However, when comparing our results with other countries, Tierra del Fuego lichens have a very low content of the measured elements.

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