Potentially Toxic Elements (Ptes) in Soils and Bulbs of Elephant Garlic

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Potentially Toxic Elements (Ptes) in Soils and Bulbs of Elephant Garlic applied sciences Article Potentially Toxic Elements (PTEs) in Soils and Bulbs of Elephant Garlic (Allium ampeloprasum L.) Grown in Valdichiana, a Traditional Cultivation Area of Tuscany, Italy Andrea Vannini 1 , Martina Grattacaso 1, Giulia Canali 1, Francesco Nannoni 2, Luigi Antonello Di Lella 2, Giuseppe Protano 2 , Stefano Biagiotti 3 and Stefano Loppi 1,4,* 1 Department of Life Science, University of Siena, 53100 Siena, Italy; [email protected] (A.V.); [email protected] (M.G.); [email protected] (G.C.) 2 Department of Physical, Earth and Environmental Sciences, University of Siena, 53100 Siena, Italy; [email protected] (F.N.); [email protected] (L.A.D.L.); [email protected] (G.P.) 3 Pegaso Online University, 53045 Montepulciano, Italy; [email protected] 4 BAT Center-Interuniversity Center for Studies on Bioinspired Agro-Environmental Technology, University of Naples ‘Federico II’, 80138 Napoli, Italy * Correspondence: [email protected] Featured Application: Evaluation of the ecological and health risk associated with the cultivation and consumption of the typical product “Aglione della Valdichiana” (elephant garlic). Abstract: The aim of this study was to provide, for the first time, data on the concentration of potentially toxic elements (PTEs) in soils and bulbs of elephant garlic (Allium ampeloprasum L.) Citation: Vannini, A.; Grattacaso, M.; cultivated in Valdichiana, a traditional agricultural area of Tuscany, Italy. Bulbs of elephant garlic Canali, G.; Nannoni, F.; Di Lella, L.A.; and soil samples were collected in four cultivation fields and analyzed by inductively coupled Protano, G.; Biagiotti, S.; Loppi, S. Potentially Toxic Elements (PTEs) in plasma-mass spectrometry (ICP-MS) to determine the concentrations of As, Cd, Co, Cr, Cu, Ni, Pb, Soils and Bulbs of Elephant Garlic Sb, Tl, U, V, Zn. The concentrations of these PTEs in bulbs and cultivation soils were used to calculate (Allium ampeloprasum L.) Grown in geochemical, ecological and health risk indices. The results of this study suggest that, although Valdichiana, a Traditional Cultivation bulbs of elephant garlic from the Valdichiana area may present slightly high concentrations of Cd, Area of Tuscany, Italy. Appl. Sci. 2021, Ni and Pb, the associated health risk based on the daily intake is absolutely negligible. Cultivation 11, 7023. https://doi.org/10.3390/ soils had somewhat high Cu concentrations probably due to the diffuse use of Cu-based products in app11157023 agriculture, but showed overall a very low ecological risk. Academic Editor: Chiara Cavaliere Keywords: Allium ampeloprasum; elephant garlic; environmental risk; health risk; heavy metals Received: 15 July 2021 Accepted: 27 July 2021 Published: 29 July 2021 1. Introduction Publisher’s Note: MDPI stays neutral Tuscany is home to some of the most typical Italian food products [1], which are with regard to jurisdictional claims in particularly appreciated for their gastronomic quality. Among them is elephant garlic published maps and institutional affil- (Allium ampeloprasum L.) cultivated in the Valdichiana area, locally known as “Aglione iations. della Valdichiana” (hereafter, AdV). The AdV is currently deeply investigated with the aim of promoting its particular nutraceutical features [2], which are quite different from those of common garlic (Allium sativum L.) [3]. The most important feature of elephant garlic is a much lower content of fibers and alliin, the sulfur-containing compound responsible for the aggressive taste of garlic, giving to this plant a greater digestibility and a much more Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. delicate taste. This article is an open access article Bulbs of common garlic are known to accumulate potentially toxic elements (PTEs) distributed under the terms and such as Cd, Cu, Ni, Pb [4–7]; therefore, this plant is of questionable edibility when cultivated conditions of the Creative Commons in contaminated soils with uncertain safety [8,9]. Allicin, an organosulfur compound Attribution (CC BY) license (https:// originated from alliin, has been suggested to be involved in the accumulation process of creativecommons.org/licenses/by/ PTEs in common garlic as a metal-binding molecule [10]. Due to its lower alliin content 4.0/). compared to common garlic, elephant garlic may show a lower capacity to accumulate Appl. Sci. 2021, 11, 7023. https://doi.org/10.3390/app11157023 https://www.mdpi.com/journal/applsci Appl. Sci. 2021, 11, 7023 2 of 11 PTEs in the bulbs [11], thus ensuring greater safety for its consumption. Nevertheless, to the best of our knowledge, data on the concentration of PTEs in the Tuscan traditional product AdV are completely missing, and there is thus the need of a quick investigation of this chemical feature of AdV, especially as its notoriety is increasing and it is being preferred over common garlic in many traditional recipes. Similarly, data on the concentration of PTEs in soils where AdV is cultivated are also missing. From an environmental point of view, soils of the Valdichiana area are generally not at risk of contamination from polluted air and waters since their main use is as arable land and industrial activities are only marginally present. However, this area is classified as vulnerable to nitrates [12], and agricultural practices could alter the geochemical profile of Valdichiana soils, due to the release of chemical elements from fertilizers and pesticides which can affect soil quality as well as crop edibility [13–15]. In this view, the concentrations of several PTEs (namely As, Cd, Co, Cr, Cu, Ni, Pb, Sb, Tl, U, V, Zn) were determined in bulbs of AdV and soils from cultivation fields in the Valdichiana area. The aim of this study is to fill the gap of knowledge about the inorganic chemical composition of AdV, by providing, for the first time, data on the concentration of PTEs in bulbs and cultivation soils, with the final purpose to assess the uptake and accumulation of these chemicals in bulbs and the potential risk associated with AdV consumption. 2. Materials and Methods 2.1. Study Area Valdichiana (the Chiana plain) is an almost flat geographic area of ca. 2000 km2 located in SE Tuscany. From the geological point of view, Valdichiana is a NW–SE oriented tectonic basin filled by marine, lacustrine and continental deposits (Miocene-Pleistocene) mainly consisting of sandy, silty-clayey and clayey sediments. The climate is sub-Mediterranean, with rainfall in the range of 700–900 mm/year and mean temperatures from 5.4 ◦C in January to 23.5 ◦C in July–August. The local economy is based on agriculture, and in- dustrial activities are scanty [16]. The Valdichiana area is crossed by important routes of communication such as the highway 1, the main highway of Italy, and the important railway line connecting Rome with Florence. 2.2. Experimental Design and Sample Treatment To realize this study, four cultivation fields in the Valdichiana area were selected among the farms producing the AdV, members of the local “Association for the Protection and Promotion of the “Aglione della Valdichiana”. From each cultivation field, 50 cloves of AdV used as seeds and 10 surface soil samples (0–20 cm) were randomly collected during October 2019 at the time of sowing. AdV cloves derived from the harvesting campaign of June 2019. In the laboratory, 10 cloves from each cultivation field were randomly selected, coupled two by two, and divided in five separated stocks. Then, the cloves were peeled, cut in pieces of ca. 1 cm3, freeze-dried for 12 h, then powdered using a ceramic mortar. Soil samples were air dried at room temperature and then processed as follows. Five soil samples were randomly selected from each cultivation field, and dried for two days at 40 ◦C in a ventilated oven; the dried soil samples were then crushed using a rubber hammer and sieved at 2 mm. The soil fraction < 2 mm was homogenized by quartering and pulverization using an agate mortar and a mechanical pulverizer for 40 min. 2.3. Chemical Analysis The AdV samples were solubilized by the following procedure: 3 mL of nitric acid (HNO3) and 1 mL of hydrogen peroxide (H2O2) (ultrapure reagents) were added to about 250 mg of powdered AdV sample. Soil samples were solubilized by acid digestion adding 2 mL of HNO3, 2 mL of hydrofluoric acid (HF) and 1 mL H2O2 (ultrapure reagents) to 250 mg of pulverized soil sample. Digestion of AdV and soil samples was carried out in Teflon Appl. Sci. 2021, 11, 7023 3 of 11 bombs in a Milestone Ethos 900 microwave lab station. Concentrations of PTEs in AdV and soil samples were determined by inductively coupled plasma-mass spectrometry (ICP- MS) using a Perkin Elmer NexION 350 spectrometer. Analytical accuracy was evaluated analyzing the standard reference materials GBW 07604 (Poplar Leaves) and SRM 2709 (San Joaquin Soil; see Table S1 of “Supplementary Files”). Recoveries ranged from 91% (Cr) to 114% (Cd) for GBW 07604, and from 90.4% (Ni) to 105.5% (Cu) for SRM 2709 (see Table S1 of “Supplementary Files” for details). 2.4. Data Analysis Since concentrations of each analyzed PTE in AdV and soil samples approached normal distribution (Shapiro–Wilk test, p < 0.05), their descriptive statistics are given as min, max, mean, standard deviation and coefficients of variation. To appreciate selective uptake of PTEs by AdV from the soil, a soil–plant rank-ordered plot of these chemical elements was arranged. Soil contamination, ecological risk and health risk were evaluated using the following specific indices. 2.4.1. Health Risk The risk associated with the consumption of the AdV bulbs was evaluated by means of the Health Risk Index (HRI) as the ratio between the Daily Intake of PTE (DIPTE) and its reference dose (Rfd), expressed as mg/kg/day: Health Risk Index (HRI) = DIPTE/Rfd, The DIPTE for the inhabitants of the Valdichiana area was calculated following the formula proposed by Khan et al.
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