Relationships between the trace-elements (TE) content of plants and associated soil have been widely investigated especially to understand the ecology of TE hyperaccumulating species to develop applications using TE phytoextraction. Many studies have focused on the possibility of quantifying the soil TE fraction available to plants, and used bioconcentration (BC) as a measure of the plants ability to absorb TE. However, BC only offers a static view of the dynamic phenomenon of TE accumulation. Accumulation kinetics are required to fully account for TE distributions in plants. They are also crucial to design applications where maximum TE concentrations in plant leaves are needed. This paper provides a review of studies of BC (i.e. soil-plant relationships) and leaf-age in relation to TE hyperaccumulation. The paper focuses of Ni and Mn accumulators and hyperaccumulators from New Caledonia who were previously overlooked until recent Ecocatalysis applications emerged for such species. Updated data on Mn hyperaccumulators and accumulators from New Caledonia are also presented and advocate further investigation of the hyperaccumulation of this element. Results show that leaf-age should be considered in the design of sample collection and allowed the reclassification of Grevillea meisneri known previously as a Mn accumulator to a Mn hyperaccumulator.

Among the phytotechnologies used for the reclamation of degraded mining sites, phytoextraction aims to diminish the concentration of polluting elements in contaminated soils. However, the biomass resulting from the phytoextraction processes (highly enriched in polluting elements) is too often considered as a problematic waste. The manganese-enriched biomass derived from native Mn-hyperaccumulating plants of New Caledonia was presented here as a valuable source of metallic elements of high interest in chemical catalysis. The preparation of the catalyst Eco-Mn₁and reagent Eco-Mn₂derived from Grevillea exul exul and Grevillea exul rubiginosa was investigated. Their unusual polymetallic compositions allowed to explore new reactivity of low oxidative state of manganese—Mn(II) for Eco-Mn₁and Mn(IV) for Eco-Mn₂. Eco-Mn₁was used as a Lewis acid to catalyze the acetalization/elimination of aldehydes into enol ethers with high yields; a new green and stereoselective synthesis of (−)-isopulegol via the carbonyl-ene cyclization of (+)-citronellal was also performed with Eco-Mn₁. Eco-Mn₂was used as a mild oxidative reagent and controlled the oxidation of aliphatic alcohols into aldehydes with quantitative yields. Oxidative cleavage was interestingly noticed when Eco-Mn₂was used in the presence of a polyol. Eco-Mn₂allowed direct oxidative iodination of ketones without using iodine, which is strongly discouraged by new environmental legislations. Finally, the combination of the properties in the Eco-Mn catalysts and reagents gave them an unprecedented potential to perform sequential tandem oxidation processes through new green syntheses of p-cymene from (−)-isopulegol and (+)-citronellal; and a new green synthesis of functionalized pyridines by in situ oxidation of 1,4-dihydropyridines.

Increasing pressure on mineral resources has drawn research efforts into innovative supply and recycling. Metal-rich biomass produced in phytoextraction recently proved an interesting starting material for green chemistry. It allows the production of new catalysts, referred to as ecocatalysts. Ecocatalysts provide increased yields in chemical production and increased regio- and chemo-selectivity, which result in high added value. This new approach to using metal-rich biomass could spur the development of phytoextraction, a technique considered promising for long, yet without credible economic outlets. In this regard, metallophyte biodiversity hotspots, such as New Caledonia, are of particular interest for biomass supply. Potential phytoextraction from mine spoils using two species endemic to New Caledonia is discussed here. Geissois pruinosa, a hypernickelophore, and Grevillea exul, a Mn accumulator, were selected for these original experiments. The results presented here 20 months after plantation of young trees from a nursery show the interest of the approach. Mean Ni concentrations of up to 1513 mg kg⁻¹are reported in G. pruinosa, as well as 2000 mg kg⁻¹Mn in G. exul. Concentrations of Ni and Mn in the leaves of each species appear to be correlated with leaf age. Plantation of these species may also ensure mine reclamation, and experiments were conducted with the principles of ecological restoration in mind adding a further dimension to the approach.