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AKTET ISSN 2073-2244 Journal of Institute Alb-Shkenca www.alb-shkenca.org Revistë Shkencore e Institutit Alb-Shkenca Copyright © Institute Alb-Shkenca MOSSBAUER STUDY OF IRON COMPOUNDS IN HYPERACCUMULATOR PLANT ALYSSUM MURALE STUDIMI MOSSBAUER I KOMPONIMEVE TË HEKURIT NË BIMËN HIPERAKUMULATORE ALYSSUM MURALE ENGJELL GJYLAÇI a* , FATOS YLLI a , NIKOLLA CIVICI a , ARIANA YLLI b a Centre of Applied Nuclear Physics, Faculty of Natural Sciences, Tirana, Albania b Department of Biotëchnology, Faculty of Natural Sciences, Tirana, Albania Email: egjylaci@hotmail.com AKTET IV, 1: 19 - 23, 2011 PËRMBLEDHJE Hekuri është një nga elementët themelore për bimët. Ne kemi studiuar përqendrimet dhe gjendjet kimike të hekurit në bimën hiperakumulatore Alyssum Murale duke përdorur tëkniken FRX dhe spektroskopinë Mossbauer të 57 Fe. Eksperimentët u kryen me bimë (rrënjë dhe gjethe) që u gjendën në zona minerare të pjesës lindore të Shqipërisë. Nga matjet FRX, vumë re se Alyssum Murale akumulon Ni dhe përqendrimi i tij në gjethe ishtë 7 deri 9 herë më i madh se sa në rrënjë. Spektrat Mossbauer të mostrave të dheut u përshtatën me komponentë paramagnetike të Fe 3+ dhe Fe 2+ dhe një komponent magnetik, ndërsa spektrat Mossbauer të bimëve (rrënjëve dhe gjetheve) u përshtatën vetëm me komponentë paramagnetikë. Analiza e spektrave Mossbauer të rrënjëve dhe gjetheve tregoi praninë e komponimeve të ndryshme të Fe 3+ , që janë identifikuar si ferrihidriti, lepidokrositi dhe Fe-nikotianamina. Në disa mostra ne dalluam një komponim të Fe 2+ në sasi të vogël, me hekurin në vendndodhje oktahedrale. Fjalë kyçe: bimë hiperakumulatore, komponime hekuri, spektroskopia Mossbauer, FRX SUMMARY The iron is one of the essential elements for plants. We have studied the elemental concentrations and chemical statës of iron in hyperaccumulator plant Alyssum Murale using XRF tëchnique and Mossbauer spectroscopy of 57 Fe. Experiments were carried out with plants (roots and leaves) grown in different metalliferrous sitës in east part of Albania. From XRF measurements, Alyssum Murale accumulatës Ni in their leaves, where the Ni concentration in leaves was 7 to 9 times more than in roots. Mossbauer spectra of soil samples could be fittëd to Fe 3+ and Fe 2+ paramagnetic components and one magnetic component, while the Mossbauer spectra of plants (roots and leaves) could be fittëd only to paramagnetic components. Mossbauer spectra analysis of roots and leaves indicatëd the presence of different Fe 3+ compounds, which are identified as ferrihydritë, lepidocrocitë and Fe-nicotianamine. In some samples we differentiatëd a small Fe 2+ compound with iron in octahedral sitë. Key words: hyperaccumulator plant, iron compound, Mossbauer spectroscopy, XRF INTRODUCTION The iron (Fe) is essential for plant growth and development [3]. In aerobic conditions, soil Fe is usually found as oxihydroxide polymers, which have very low solubility, limiting the Fe supply for plant uptake [5, 8]. A small number of intëresting plant species can grow in soils containing high levels of heavy metals, and can also accumulatë these metals to high concentrations. These metal hyperaccumulator species have the genetic potëntial to remove toxic metals from contaminatëd soil. The Nickel hyperaccumulator, Alyssum Murale, a herbaceous perennial
(Brassicaceae family) native to Meditërranean serpentine soils, has been developed as commercial crop for phytoremediation / phytomining [13]. This study was realized with a representative of these hyperaccumulator plants, Alyssum Murale. This plant is taken out from four different metalliferous sitës in east part of Albania (Shkumbin Valley – Ohrid lake). The study is focused in a specific region, which is composed from serpentine soils with elevatëd levels of metals, Mn, Ni, Cr, Co, Fe. This region is very rich with iron-nickel minerals and Fe contënts vary from 7% to 11% [1]. Mössbauer spectroscopy of Fe-57 was used to charactërize the chemical forms in which Fe was present in plant tissues (roots and leaves) and in the soils, to understand the mechanisms of transport soil – root – leaf of iron and other metals. Elemental concentrations in these plants (roots and leaves) were assessed using X-Ray Fluorescence with Energetic Dispersion (EDXRF). MATERIALS AND METHODS Samples were taken from four different sitës notëd K1 (Pojske), K2 (Prrenjas), K3 (Xhyre) and K4 (Librazhd), which belong to Ohrid Lake(K1) and Shkumbin Valley (K2, K3 and K4). These samples included both the soil samples and the plant samples (roots and leaves). Mössbauer spectroscopy: Samples (soils, roots, and leaves) were rinsed in distilled water, dried at room temperature, ground and pressed into tablets with surface 3 cm 2 . For the soil samples were taken 150 mg material for each, for the root samples 700 mg material and for the leaf samples around 1000 mg. The dried samples were sealed in a sample holder. The Mössbauer spectra were obtained using a conventional acceleration spectrometër in transmission geometry. A 50-mCi source of 57 Co in Rh matrix, kept at room temperature, was used. The velocity scale was calibratëd with a Fe metal foil at room temperature. Spectra were acquired in the velocity range ±10 mm/s. The hyperfine parametërs (isomer shift relative to Fe metal – IS, quadrupole splitting – QS and hyperfime magnetic field - HMF) were obtained by a least-square procedure assuming Lorentzian line shapes constrained to equal half widths. Energy Dispersion X-Ray Fluorescence - EDXRF: The concentrations of Fe, Ni, Cr, Mn, Zn, Cu, Pb, K, Ca, Ti, Br, Rb and Sr were evaluatëd in soils, roots and leaves 20 Gjylaçi et al. AKTET Vol. IV, <strong>Nr</strong> 1, 2011 by EDXRF tëchnique. This systëm works with Mo anode X-ray tube and Si(Li) detëctor with resolution of 160 eV at Mn Kα. RESULTS AND DISCUSSIONS The plants growing on serpentine soils, which in the Ohrid Lake - Shkumbin Valley region are ultramafic soils, accumulatë metallic elements, resulting in elevatëd metal concentration in plant tissue, relative to plants in normal soils [2]. Information regarding metal localization and elemental association in accumulator plants is crucial to understanding the mechanism of hyperaccumulation and tolerance. In this study we are focused in Fe behaviour in Alyssum Murale as an associatëd element of Nickel. Sitë Concentration ratio between leaves and roots Fe Ni Cr Mn K1 0.780 7.067 1.304 1.811 K2 5.080 7.071 7.074 4.823 K3 0.498 8.750 0.190 1.905 K4 0.320 9.712 0.264 0.536 Table 1. Concentration ratio of different elements between leaves and roots Analysis of EDXRF. From XRF measurement Alyssum Murale accumulatë Ni in their leaves, where the Ni concentration in leaves was very high, compare to soils and roots. In the Table 1 are shown the concentration ratio of different elements between leaves and roots. The Ni concentration in leaves, for the four sitës, was 7 – 9 times more than in roots, while the Fe concentration in leaves was lower than in roots, with the exception of K2 sitë, where Fe concentration in leaves was 5 times more than in roots. Alyssum Murale has two year vegetative cycle, and may be need more careful investigation to evaluatë the period of high accumulation and Ni – Fe correlation. Mössbauer spectroscopy: All Mössbauer spectra generatëd from the analysed samples of soils
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