Phytoremediation of heavy metals and study of the metal coordination by x-ray absorption spectroscopy

Spectroscopic approaches to plant and soil sciences have provided important information for several decades. However, many of these approaches suffered from a number of limitations and drawbacks especially in terms of spatial resolution and requirements for sample preparation. The advent of dedicated synchrotron facilities, that allow the exploitation of the particular qualities of synchrotron radiation as a research tool, has revolutionised the way we approach the investigation of nutrients and contaminants in environmental samples. Various synchrotron-based techniques are currently available that permit such investigations in situ and at the molecular level. The continuous development of these techniques is delivering substantial gains in terms of sensitivity and spatial resolution which allows analyses of diluted samples at the sub-micron scale. This paper aims at providing an introduction to synchrotron radiation and to the fundamentals of some widely used synchrotron-based techniques, in particular X-ray absorption, fluorescence and tomography. Furthermore, examples are provided regarding the applications of synchrotron-based techniques in the field of plant, soil and rhizosphere research. Finally, current limitations and future perspectives of synchrotron techniques are discussed.

Synchrotron-based techniques for plant and soil science: opportunities, challenges and future perspectives

Metal nanoparticles have many potential technological applications. Biological routes to the synthesis of these particles have been proposed including production by vascular plants, known as phytoextraction. While many studies have looked at metal uptake by plants, particularly with regard to phytoremediation and hyperaccumulation, few have distinguished between metal deposition and metal salt accumulation. This work describes the uptake of AgNO3, Na3Ag(S2O3)2, and Ag(NH3)2NO3 solutions by hydroponically grown Brassica juncea and the quantitative measurement of the conversion of these salts to silver metal nanoparticles. Using X-ray absorption near edge spectroscopy (XANES) to determine the metal speciation within the plants, combined with atomic absorption spectroscopy (AAS) for total Ag, the quantity of reduction of AgI to Ag0 is reported. Transmission electron microscopy (TEM) showed Ag particles of 2–35 nm. The factors controlling the amount of silver accumulated are revealed. It is found that there is a limit on the amount of metal nanoparticles that may be deposited, of about 0.35 wt.% Ag on a dry plant basis, and that higher levels of silver are obtained only by the concentration of metal salts within the plant, not by deposition of metal. The limit on metal nanoparticle accumulation, across a range of metals, is proposed to be controlled by the total reducing capacity of the plant for the reduction potential of the metal species and limited to reactions occurring at an electrochemical potential greater than 0 V (verses the standard hydrogen electrode).

The mechanism of metal nanoparticle formation in plants: limits on accumulation

Copper is an essential element in the cellular electron-transport chain, but as a free ion it can catalyze production of damaging radicals. Thus, all life forms attempt to prevent copper toxicity. Plants diminish excess copper in two structural regions: rare hyperaccumulators bind cationic copper to organic ligands in subaerial tissues, whereas widespread metal-tolerant plants segregate copper dominantly in roots by mechanisms thought to be analogous. Here we show using synchrotron microanalyses that common wetlands plants Phragmites australis and Iris pseudoacorus can transform copper into metallic nanoparticles in and near roots with evidence of assistance by endomycorrhizal fungi when grown in contaminated soil in the natural environment. Biomolecular responses to oxidative stress, similar to reactions used to abiotically synthesize Cu0 nanostructures of controlled size and shape, likely cause the transformation. This newly identified mode of copper biomineralization by plant roots under copper stress ...

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Formation of metallic copper nanoparticles at the soil-root interface.

Hyperaccumulators are being intensely investigated. They are not only interesting in scientific context due to their “strange” behaviour in terms of dealing with high concentrations of metals, but also because of their use in phytoremediation and phytomining, for which understanding the mechanisms of hyperaccumulation is crucial. Hyperaccumulators naturally use metal accumulation as a defence against herbivores and pathogens, and therefore deal with accumulated metals in very specific ways of complexation and compartmentation, different from non-hyperaccumulator plants and also non-hyperaccumulated metals. For example, in contrast to non-hyperaccumulators, in hyperaccumulators even the classical phytochelatin-inducing metal, cadmium, is predominantly not bound by such sulfur ligands, but only by weak oxygen ligands. This applies to all hyperaccumulated metals investigated so far, as well as hyperaccumulation of the metalloid arsenic. Stronger ligands, as they have been shown to complex metals in non-hyperaccumulators, are in hyperaccumulators used for transient binding during transport to the storage sites. This confirmed that enhanced active metal transport, and not metal complexation, is the key mechanism of hyperaccumulation. Hyperaccumulators tolerate the high amount of accumulated heavy metals by sequestering them into vacuoles, usually in large storage cells of the epidermis. This is mediated by strongly elevated expression of specific transport proteins in various tissues from metal uptake in the shoots up to the storage sites in the leaf epidermis. However, this mechanism seems to be very metal specific. Non-hyperaccumulated metals in hyperaccumulators seem to be dealt with like in non-hyperaccumulator plants, i.e. detoxified by binding to strong ligands such as metallothioneins.

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Jesus Arenas

Papers

XAS and microscopy studies of the uptake and bio-transformation of copper in Larrea tridentata (creosote bush)