A multi-analytical approach to studying the chemical composition of typical carbon sink samples.

Peatlands in southern South America (Tierra del Fuego region, TdF) play a key role in the ecological dynamics of Patagonia. It is, therefore, necessary to increase our knowledge and awareness of their scientific and ecological value to ensure their conservation. This study aimed to assess the differences in the distribution and accumulation of elements in peat deposits and Sphagnum moss from the TdF. Chemical and morphological characterization of the samples was carried out using various analytical techniques, and total levels of 53 elements were determined. Furthermore, a chemometric differentiation based on the elemental content of peat and moss samples was performed. Some elements (Cs, Hf, K, Li, Mn, Na, Pb, Rb, Si, Sn, Ti and Zn) showed significantly higher contents in moss samples than in peat samples. In contrast, only Mo, S and Zr were significantly higher in peat samples than in moss samples. The results obtained highlight the ability of moss to accumulate elements and to act as a means to facilitate the entry of elements into peat samples. The valuable data obtained in this multi-methodological baseline survey can be used for more effective conservation of biodiversity and preservation of the ecosystem services of the TdF.

Applying the monitoring breakdown structure model to trace metal content in edible biomonitors: An eight-year survey in the Beagle Channel (southern Patagonia).

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.

Baseline trace metals in gastropod mollusks from the Beagle Channel, Tierra del Fuego (Patagonia, Argentina).

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.

Baseline trace metals in bivalve molluscs from the Beagle Channel, Patagonia (Argentina).

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.

Evaluation of performance of three different hybrid mesoporous solids based on silica for preconcentration purposes in analytical chemistry: From the study of sorption features to the determination of elements of group IB.

Several studies involving the physicochemical interaction of three silica based hybrid mesoporous materials with metal ions of the group IB have been performed in order to employ them for preconcentration purposes in the determination of traces of Cu(II), Ag(I) and Au(III). The three solids were obtained from mesoporous silica functionalized with 3-aminopropyl (APS), 3-mercaptopropyl (MPS) and N-[2-aminoethyl]-3-aminopropyl (NN) groups, respectively. Adsorption capacities for Au, Cu and Ag were calculated using Langmuir's isotherm model and then, the optimal values for the retention of each element onto each one of the solids were found. Physicochemical data obtained under thermodynamic equilibrium and under kinetic conditions - imposed by flow through experiments - allowed the design of simple analytical methodologies where the solids were employed as fillings of microcolumns held in continuous systems coupled on-line to an atomic absorption spectrometry. In order to control the interaction between the filling and the analyte at short times (flow through conditions) and thus, its effect on the analytical signal and the presence of interferences, the initial adsorption velocities were calculated using the pseudo second order model. All these experiments allowed the comparison of the solids in terms of their analytical behaviour at the moment of facing the determination of the three elements. Under optimized conditions mainly given by the features of the filling, the analytical methodologies developed in this work showed excellent performances with limits of detection of 0.14, 0.02 and 0.025 microg L(-1) and RSD % values of 3.4, 2.7 and 3.1 for Au, Cu and Ag, respectively. A full discussion of the main findings on the interaction metal ions/fillings will be provided. The analytical results for the determination of the three metals will be also presented.

Non-chromatographic determination of ultratraces of V(V) and V(IV) based on a double column solid phase extraction flow injection system coupled to electrothermal atomic absorption spectrometry.

In this work, a non-chromatographic procedure for the on-line determination of ultratraces of V(V) and V(IV) is presented. The method involves a solid phase extraction-flow injection system coupled to electrothermal atomic absorption spectrometry (SPE-FI-ETAAS). The system holds two microcolumns (MC) set in parallel and filled with lab-made mesoporous silica functionalized with 3-aminopropyltriethoxy silane (APS) and mesoporous silica MCM-41, respectively. The pre-concentration of V(V) is performed by sorption onto the first MC (C1) filled with APS at pH 3, whilst that of V(IV) is performed by sorption onto the second column (C2) filled with mesoporous silica MCM-41 at pH 5. Aqueous samples containing both analytes are loaded and, after pre-concentration (pre-concentration factor PCF=10, sorption flow rate=1 mL min(-1), sorption time=10 min), they are eluted in separate vessels with hydroxylammonium chloride (HC) 0.1 mol L(-1) in HCl 0.5 mol L(-1) (elution volume=1 mL, elution flow rate=0.5 mL min(-1)). Afterwards, both analytes are determined through ETAAS with graphite furnace. Under optimized conditions, the main analytical figures of merit for V(V) and V(IV) are, respectively: detection limits (3s): 0.5 and 0.6 microg L(-1), linear range: 2-100 microg L(-1) (both analytes), sensitivity: 0.015 and 0.013 microg(-1)L and sample throughput: 6h(-1) (both analytes). Recoveries of both species were assayed in different water samples. Validation was performed through certified reference materials for ultratraces of total vanadium in river water.

Characterization of Italian honeys (Marche Region) on the basis of their mineral content and some typical quality parameters.

BACKGROUND: The characterization of three types of Marche (Italy) honeys (Acacia, Multifloral, Honeydew) was carried out on the basis of the their quality parameters (pH, sugar content, humidity) and mineral content (Na, K, Ca, Mg, Cu, Fe, and Mn). Pattern recognition methods such as principal components analysis (PCA) and linear discriminant analysis (LDA) were performed in order to classify honey samples whose botanical origins were different, and identify the most discriminant parameters. Lastly, using ANOVA and correlations for all parameters, significant differences between diverse types of honey were examined. RESULTS: Most of the samples' water content showed good maturity (98%) whilst pH values were in the range 3.50 - 4.21 confirming the good quality of the honeys analysed. Potassium was quantitatively the most relevant mineral (mean = 643 ppm), accounting for 79% of the total mineral content. The Ca, Na and Mg contents account for 14, 3 and 3% of the total mineral content respectively, while other minerals (Cu, Mn, Fe) were present at very low levels. PCA explained 75% or more of the variance with the first two PC variables. The variables with higher discrimination power according to the multivariate statistical procedure were Mg and pH. On the other hand, all samples of acacia and honeydew, and more than 90% of samples of multifloral type have been correctly classified using the LDA. ANOVA shows significant differences between diverse floral origins for all variables except sugar, moisture and Fe. CONCLUSION: In general, the analytical results obtained for the Marche honeys indicate the products' high quality. The determination of physicochemical parameters and mineral content in combination with modern statistical techniques can be a useful tool for honey classification.