Estudio de plomo isotópico del lingote depositado en el Museo Minero de Riotinto hallado en Masa Planes (Minas de Riotinto, Huelva - España)

Lead was a necessary element for Roman metallurgical work, so being able to determine its origin is very important to know the commercial circuits of commodities in the Roman world. On February 27th, 2015, a Roman lead ingot was found in Planes Lode (Riotinto Mines, Huelva, Spain), within the area of the Riotinto Project led by Atalaya Mining, we take the opportunity to thank this Company for supporting this Project. It`s the first lead ingot found in Riotinto with a known locationEl plomo fue un elemento necesario para los trabajos metalúrgicos romanos, por lo que poder determinar su origen es muy importante para conocer los circuitos comerciales de las materias primas en el mundo romano. El 27 de febrero de 2015 se encontró un lingote romano de plomo en Masa Planes (Minas de Riotinto, Huelva-España), dentro del área del Proyecto Riotinto liderado por Atalaya Mining, aprovechamos para agradecer a esta compañía el apoyo para este proyecto. Siendo el primer lingote de plomo hallado en Riotinto con una ubicación conocid

Elemental Fingerprinting Combined with Machine Learning Techniques as a Powerful Tool for Geographical Discrimination of Honeys from Nearby Regions

Discrimination of honey based on geographical origin is a common fraudulent practice and is one of the most investigated topics in honey authentication. This research aims to discriminate honeys according to their geographical origin by combining elemental fingerprinting with machinelearning techniques. In particular, the main objective of this study is to distinguish the origin of unifloral and multifloral honeys produced in neighboring regions, such as Sardinia (Italy) and Spain. The elemental compositions of 247 honeys were determined using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The origins of honey were differentiated using Principal Component Analysis (PCA), Linear Discriminant Analysis (LDA), and Random Forest (RF). Compared to LDA, RF demonstrated greater stability and better classification performance. The best classification was based on geographical origin, achieving 90% accuracy using Na, Mg, Mn, Sr, Zn, Ce, Nd, Eu, and Tb as predictor

Elemental fingerprinting combined with machine learning techniques as a powerful tool for geographical discrimination of honeys from nearby regions

Discrimination of honey based on geographical origin is a common fraudulent practice and is one of the most investigated topics in honey authentication. This research aims to discriminate honeys according to their geographical origin by combining elemental fingerprinting with machine-learning techniques. In particular, the main objective of this study is to distinguish the origin of unifloral and multifloral honeys produced in neighboring regions, such as Sardinia (Italy) and Spain. The elemental compositions of 247 honeys were determined using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The origins of honey were differentiated using Principal Component Analysis (PCA), Linear Discriminant Analysis (LDA), and Random Forest (RF). Compared to LDA, RF demonstrated greater stability and better classification performance. The best classification was based on geographical origin, achieving 90% accuracy using Na, Mg, Mn, Sr, Zn, Ce, Nd, Eu, and Tb as predictors

Study of isotopic lead in one ingot deposited in the mining museum of Riotinto found in planes lode (Rioting mines, Huelva - Spain)

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Toxic and trace elements in rice: analytical methods, bioconcentration, influence of irrigation techniques

The principal theme of this PhD thesis is focused on the effect that changes on the nature of the irrigation method of rice play on the bioaccumulation of some toxic elements (As, Cd, Cr, Sb, Hg, Pb, and Tl) or potentially toxic oligoelements (Al, Cu, Fe, Mn, Mo, Ni, Se, and Zn) in rice kernels. The bioaccumulation of harmful elements in rice grain is the most threatening reason of health concern for the strong consumers of this staple food for mankind. Three different irrigation methods have been considered (continuous flooding, periodical saturation, and sprinkler irrigation) as well as soils of different geopedological nature and pollution levels. Also, the effect has been evaluated on a large number of rice genotypes. The main goal reached is to find out the possibility that, working only on the nature of the irrigation method of the rice plant, it is possible to get environmentally friendly rice, characterized by both a smallest concentration of toxic elements and the highest level of food safety

Tuning of the Amount of Se in Rice (Oryza sativa) Grain by Varying the Nature of the Irrigation Method: Development of an ICP-MS Analytical Protocol, Validation and Application to 26 Different Rice Genotypes

The amount of specific trace elements like selenium (Se) may be of health concern for humans if contained in too high (or low) quantities in staple foods like rice. Among the attempts aimed to optimize the Se concentration in rice, only few studies have been focused on the use of irrigation methods other than continuous flooding. Since intermittent irriguous methods, like sprinkler and saturation, have found to be effective in modifying the bioaccumulation of arsenic and cadmium in rice kernels, the main goal of this study is to measure the amount of the total Se contained in grains of 26 rice genotypes cultivated for two consecutive agrarian vintages in the same open field and with the same water, but differently irrigated with continuous flooding, sprinkler or saturation. To do this, an original and validated ICP-MS method has been developed. The validation parameters accounted for a high sensitivity and accuracy. Sprinkler irrigation is able to reduce in the average of 90% the amount of total Se in kernels in comparison to values measured in rice irrigated with continuous flooding. In conclusion, different irrigation techniques and rice genotypes seem to be valuable tools in order to allow in the future the customized modulation of the Se concentration in rice grain according to the needs of the various populations

An Analytical Protocol for the Differentiation and the Potentiometric Determination of Fluorine-Containing Fractions in Bovine Milk

Free fluoride ions are effective in combating caries in children, and their supplementation in milk has been widely used worldwide for this purpose. Furthermore, it is known that ionic fluoride added to milk is distributed among its components, but little is known about their quantitative relationships. This is likely due to the absence of an analytical protocol aimed at differentiating and quantifying the most important forms of fluorine present in milk. For the first time, a comprehensive protocol made up of six potentiometric methods devoted to quantifying the most important fractions of fluorine in milk (i.e., the free inorganic fluoride, the inorganic bonded fluorine, the caseins-bonded fluorine, the whey-bonded fluorine, the lipid-bonded fluorine, and the total fluorine) has been developed and tested on real samples. Four of the six methods of the procedure are original, and all have been validated in terms of limit of detection and quantification, precision, and trueness. The data obtained show that 9% of all fluorine was in ionic form, while 66.3% of total fluorine was bound to proteins and lipids, therefore unavailable for human absorption. Beyond applications in dental research, this protocol could be extended also to other foods, or used in environmental monitoring

An Analytical Protocol for the Differentiation and the Potentiometric Determination of Fluorine-Containing Fractions in Bovine Milk

Free fluoride ions are effective in combating caries in children, and their supplementation in milk has been widely used worldwide for this purpose. Furthermore, it is known that ionic fluoride added to milk is distributed among its components, but little is known about their quantitative relationships. This is likely due to the absence of an analytical protocol aimed at differentiating and quantifying the most important forms of fluorine present in milk. For the first time, a comprehensive protocol made up of six potentiometric methods devoted to quantifying the most important fractions of fluorine in milk (i.e., the free inorganic fluoride, the inorganic bonded fluorine, the caseins-bonded fluorine, the whey-bonded fluorine, the lipid-bonded fluorine, and the total fluorine) has been developed and tested on real samples. Four of the six methods of the procedure are original, and all have been validated in terms of limit of detection and quantification, precision, and trueness. The data obtained show that 9% of all fluorine was in ionic form, while 66.3% of total fluorine was bound to proteins and lipids, therefore unavailable for human absorption. Beyond applications in dental research, this protocol could be extended also to other foods, or used in environmental monitoring

Chemical Characterization of Craft Filuferru Spirit from Sardinia, Italy

Traditional Filuferru is an ancient spirit from Sardinia, Italy, which is usually obtained from the distillation of wine or grape marc. In this contribution, the results of the first chemical characterization of a wide number of crafts Filuferru samples has been accomplished in terms of an evaluation of the alcoholic strength, qualitative and quantitative gas-chromatography–mass spectrometry (GC-MS) analysis of the volatile composition of the distillate, and its trace element composition by means an inductively coupled plasma–mass spectrometry (ICP-MS) method. Both instrumental methods have been validated and applied on 21 craft samples of Filuferru, whereas one sample of commercial distillate has been analyzed for comparison purposes. Alcoholic strength ranged between 41.0 and 62.4% (v/v). Sixty volatile compounds were identified and ten of them have been quantified. Analogies and differences with Grappa (i.e., the Italian distilled spirit closer to Filuferru) have been highlighted in the qualitative and quantitative profile of this matrix. Often meaningful amounts of acetaldehyde, ethyl acetate, dietyl acetal, and acetic acid were measured. Elemental analysis, performed on toxic, non-toxic elements, and oligoelements, 18 in total, revealed a wide variability of concentrations in both analytes and samples. High concentrations of Cu are sometimes evidenced, which are likely caused by losses from the distillation apparatus. The principal components analysis (PCA) allowed the differentiation of the ten volatile compounds quantified in two groups: the former, as described mainly by PC1, constituted by acetic acid, ethyl acetate, dietyl acetal, and acetaldehyde, and the second, described by PC2, constituted by 1-propanol, 2-methyl-1-propanol, the two coeluiting isomers 2-methyl-1-butanol and 3-methyl-1-butanol,1-hexanol, 2-phenylethanol, and 2,3-butanediol. Data obtained may be useful in order to establish a regulation for the production of high-quality traditional Filuferru from Sardinia

Elemental Fingerprinting of Pecorino Romano and Pecorino Sardo PDO: Characterization, Authentication and Nutritional Value

Sardinia, located in Italy, is a significant producer of Protected Designation of Origin (PDO) sheep cheeses. In response to the growing demand for high-quality, safe, and traceable food products, the elemental fingerprints of Pecorino Romano PDO and Pecorino Sardo PDO were determined on 200 samples of cheese using validated, inductively coupled plasma methods. The aim of this study was to collect data for food authentication studies, evaluate nutritional and safety aspects, and verify the influence of cheesemaking technology and seasonality on elemental fingerprints. According to European regulations, one 100 g serving of both cheeses provides over 30% of the recommended dietary allowance for calcium, sodium, zinc, selenium, and phosphorus, and over 15% of the recommended dietary intake for copper and magnesium. Toxic elements, such as Cd, As, Hg, and Pb, were frequently not quantified or measured at concentrations of toxicological interest. Linear discriminant analysis was used to discriminate between the two types of pecorino cheese with an accuracy of over 95%. The cheese-making process affects the elemental fingerprint, which can be used for authentication purposes. Seasonal variations in several elements have been observed and discussed