water Article Effect of Dissolved Silicon on the Removal of Heavy Metals from Aqueous Solution by Aquatic Macrophyte Eleocharis acicularis Ha T.H. Nguyen 1,* , Masayuki Sakakibara 2, Minh N. Nguyen 1, Nhuan T. Mai 1 and Vinh T. Nguyen 3 1 VNU University of Science, Vietnam National University, 334 Nguyen Trai, Ha Noi 10053, Vietnam; [email protected] (M.N.N.); [email protected] (N.T.M.) 2 Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577, Japan; [email protected] 3 Faculty of Engineering and Information Technology, University of Technology, Sydney (UTS), PO Box 123, Broadway, Sydney, NSW 2007, Australia; [email protected] * Correspondence: [email protected] or [email protected]; Tel.: +84-243-558-7060 Received: 5 April 2019; Accepted: 2 May 2019; Published: 4 May 2019 Abstract: Silicon (Si) has been recently reconsidered as a beneficial element due to its direct roles in stimulating the growth of many plant species and alleviating metal toxicity. This study aimed at validating the potential of an aquatic macrophyte Eleocharis acicularis for simultaneous removal of heavy metals from aqueous solutions under different dissolved Si. The laboratory experiments designed for determining the removal efficiencies of heavy metals were conducted in the absence or presence of Si on a time scale up to 21 days. Eleocharis acicularis was transplanted into the solutions 1 containing 0.5 mg L− of indium (In), gallium (Ga), silver (Ag), thallium (Tl), copper (Cu), zinc 1 (Zn), cadmium (Cd), and lead (Pb) with various Si concentrations from 0 to 4.0 mg L− . The results revealed that the increase of dissolved Si concentrations enhanced removal efficiencies of E. acicularis for Ga, Cu, Zn, Cd, and Pb, while this increase did not show a clear effect for In, Tl, and Ag. Our study presented a notable example of combining E. acicularis with dissolved Si for more efficient removals of Cu, Zn, Cd, Pb, and Ga from aqueous solutions. The findings are applicable to develop phytoremediation or phytomining strategy for contaminated environment. Keywords: aqueous solution; Eleocharis acicularis; heavy metals; removal; silicon 1. Introduction Silicon (Si) is the second most abundant element in soil after oxygen. Almost all terrestrial plants contain Si in their tissues, although the content of Si varies considerably across species, ranging from 0.1% to 10% Si on a dry weight (wt) basis [1]. Monocots usually accumulate more Si than dicots [2]. Silicon has recently been reconsidered as a beneficial element for higher plants [3], because of its roles in various bio-physio-mechanical functions [4,5]. Recent studies reported that the application of Si or fast-reacting silicates can not only enhance crop yield [6] but also stimulate the tolerance and accumulation of heavy metals [7–9]. This has encouraged more work on the combination of plant selection and Si application for more efficient heavy metal removal to develop phytoremediation or phytomining techniques. Phytoremediation and phytomining or agromining [10] have emerged as cost-effective, long-lasting, and environment-friendly technologies for the treatment of water contaminated with heavy metals [11,12] and for the economic exploitation of low-grade surface ores or mineralized soils that are too metal-poor for conventional mining [13,14], respectively. The economic return from heavy Water 2019, 11, 940; doi:10.3390/w11050940 www.mdpi.com/journal/water Water 2019, 11, 940 2 of 11 metal phytoextractions could turn out to be an additional source of finance for the phytoremediation process. Therefore, phytoremediation, in combination with phytomining, appears to be a strategy for ensuring the commercialization of these technologies. Previous studies have attempted to enhance these technologies in both laboratory and field trials [15–17]. However, while Si is one of the most common elements in soil solution, its presence in and impact on the effectiveness of phytoremediation and phytomining has not been systematically studied. Eleocharis is a member of the Cyperaceae family—monocots—which is widely known as an accumulator of Si [18]. The aquatic macrophyte Eleocharis acicularis (L.) Roem. et Schult. var. longiseta Svenson is an emergent herbaceous perennial with a worldwide distribution [19]. This species has been reported to accumulate multiple metals from mine drainage, water, and sediment, and shows a great potential for phytoremediation [12,20–26]. However, currently, there is no available information regarding the simultaneous accumulation of rare metals (i.e., gallium (Ga) and thallium (Tl)) in E. acicularis. Despite the fact that an application of materials containing easy-soluble Si together with E. acicularis showed great effects on increasing the accumulation of chromate (Cr), zinc (Zn), arsenic (As), and cadmium (Cd) [24,27], there have also been contrasting observations in which evidence on the relation between the concentration of dissolved Si in the solution and the removal of heavy metals by E. acicularis was not confirmed [25]. This suggests that more works on the accumulation of heavy metals in E. acicularis under the presence of different levels of Si are necessary. In this study, E. acicularis was planted in pot experiments, with various levels of Si concentrations. Heavy metals (i.e., indium (In), Ga, silver (Ag), Tl, copper (Cu), Zn, Cd, and lead (Pb)) were introduced together and their concentrations from aqueous solutions to plants were examined on a time scale of up to 21 days. We aimed to clarify the effects of dissolved Si on either favoring or inhibiting the accumulation of heavy metals by E. acicularis. The findings of this study can help to establish phytoremediation and phytomining practices based on the combined utilization of E. acicularis and dissolved Si to remediate contaminated environments. 2. Materials and Methods 2.1. Plant and Solution Preparation Nitrate salt solutions of In, Ag, Ga, Tl, Cu, Zn, Cd, and Pb (standard solutions for atomic absorption spectrometry; Kanto Chemical Co. Inc., Japan) were simultaneously added to the tanks until 1 1 a concentration of 0.5 mg L− of each solution was achieved. The desired level of metals (0.5 mg L− ) was selected based on our previous study on the possible capacity of E. acicularis to simultaneously remove heavy metals from solutions [12]. Silicon (standard solutions of (NH4)2SiF6; Merck Corporation) 1 was also added to these tanks until final concentrations of 0, 0.5, 1.0, or 4.0 mg L− were achieved. A minor amount of 1 M NaOH solution was added to adjust the pH of the final solutions to 5.5. Eleocharis acicularis, which were about 20 cm high, were collected from a clump in an agricultural irrigation ditch in Northwestern Shikoku, Japan for pot experiments. The plant was washed thoroughly with tap water followed by Milli-Q water and placed into 20 L experimental tanks (20 40 25 cm3) × × filled with 15 L of solutions. The plant (85 g of fresh weight) was transplanted in the tanks containing the desired levels of mixed heavy metals (In, Ag, Ga, Tl, Cu, Zn, Cd, and Pb) and Si and held at the bottom of the tank by hard plastic net fix-aided tools. The same amount of the plant was also grown in a tank, without the addition of heavy metals or Si as the plant control. For the metal control, the same Si and metal concentrations were generated, but no plant was transplanted. All experiments were conducted in duplicate. The tanks were placed in a greenhouse with a controlled ambient condition: 2 1 exposure of white fluorescent light was set up at 54 µmol m− s− for 16 h per day, and the ambient temperature was constantly kept at 24 1 C during the experiment. ± ◦ Water 2019, 11, 940 3 of 11 2.2. Sampling and Analysis To identify removal efficiencies of heavy metals from aqueous solutions to plants, from each pot experiment, 10 mL of aliquot was sampled after 8 h, 1 day, 2 days and 3 days, and then every 2 days until 21 days. To examine the chemical composition of the plant samples and accumulation of heavy metals, the original E. acicularis plant sample and those harvested from pot experiments after 21 days were separated into the root and shoot parts, well rinsed with deionized water by using an ultrasonic cleaner and dried in a ventilated oven at 80 ◦C for 48 h. The dried samples were ground into a fine powder using a mortar mill. Silicon concentrations in the plant were determined by particle-induced X-ray emission (PIXE) at the Cyclotron Research Center, Iwate Medical University, Japan. In addition, plant samples (50 mg) of each sample were digested with H2O2, HF, HNO3 mixture (2:5:10, v/v). Soluble heavy metals in water and plant were determined by ICP-MS (Varian 810/820–MS) at the Integrated Center for Sciences, Ehime University, Japan. Certified reference materials NIES CRM No. 1 provided by the National Institute for Environmental Studies (NIES) of Japan and SRM 1643e provided by the U.S. National Institute of Standards Technology were used for quality control of the analytical procedure of plant and water samples, respectively. The recoveries of elements ranged from 91% to 105% of the certified values. All analytical measurements were performed in at least triplicates and approximately 96% of the results fall within a 3% error margin. 2.3. Bioconcentration Factor Bioconcentration factor (BCF) is used to estimate the potential of a plant for phytoremediation and calculated with the following Equation: CWhole plant BCF = (1) CWater where, CWhole plant and CWater were the concentrations of heavy metals in the whole plant of E. acicularis and those of the growing solution, respectively. The concentrations of heavy metals in the solutions at the start of the experiment were used to calculate the CWater values.