Can rare earth elements be recovered from abandoned mine tailings by means of electrokinetic-assisted phytoextraction?

Given the high impact of traditional mining, the recovery of rare earth elements (REEs) from hazardous waste materials could become an option for the future in accordance with the principles of the circular economy. In this work, the technical feasibility of REEs recovery from metal mine tailings has been explored using electrokinetic-assisted phytoremediation with ryegrass (Lolium perenne L.). Phytoextraction combined with both AC current and DC current with reversal polarity was applied (1 V cm-1, 8 h day-1) to real mine tailings containing a total concentration of REEs (Sc, Y, La, Ce, Pr, and Nd) of around 146 mg kg-1. Changes in REEs geochemical fractionation and their concentrations in the soil pore water showed the mobilization of REEs caused by plants and electric current; REE availability was increased to a higher extent for combined electrokinetic-assisted phytoextraction treatments showing the relevant role of plants in the process. Our results demonstrated the initial hypothesis that it is feasible to recover REEs from real metal mining waste by phytoextraction and that the performance of this technology can be significantly improved by applying electric current, especially of the AC type, which increased REE accumulation in ryegrass in the range 57-68% as compared to that of the treatment without electric field application.

A new hyperaccumulator plant (Spergularia rubra) for the decontamination of mine tailings through electrokinetic-assisted phytoextraction.

The screening of new effective metal hyperaccumulators is essential for the development of profitable phytoremediation projects in highly degraded environments such as mining areas. The goal of this research was to analyze the phytoextraction potential of the native plant Spergularia rubra to decontaminate and eventually recover metals (phytomining) from the mine tailings (belonging to an abandoned Pb/Zn Spanish mine) in which it grows spontaneously. To do so, the ability of this plant species to accumulate metals was evaluated both under natural conditions and through simple and electrokinetically assisted phytoextraction tests using alternating current and different combinations of voltage gradient (1/2 V cm-1) and application time (6/12 h per day). The complete duration of the greenhouse trial was 64 days, although alternating current was applied only during the last 14 days. The results obtained demonstrated the exceptional effectiveness of S. rubra for metal hyperaccumulation and growth without affecting toxicity in highly contaminated mining waste. Zn was the metal accumulated to a higher extent in the shoots, reaching concentrations up to 17,800 mg kg-1; Pb was mainly accumulated in the roots reaching a maximum concentration of 8709 mg kg-1. Cu and Cd were accumulated to a lesser extent but the bioconcentration factors were much >1. It has been proved that S. rubra is a hyperaccumulator species for Zn and Cd both in natural and greenhouse conditions and, very probably, Pb in wild conditions. The application of AC current did not significantly increase metal concentrations in plant tissues but it was able to increase the aerial biomass of S. rubra by 49.8 %. As a result, the phytoextraction yields of all metals were significantly improved as compared to wild conditions (up to 86 % for Zn). It could open new expectations about the economic viability of recovering high-value metals from mine tailings.

A classical modelling of abandoned mine tailings' bioleaching by an autochthonous microbial culture.

The aim of this study was to study and model the bioleaching of abandoned mine tailings at different pulp densities 1-20% w/v by using an autochthonous mesophilic microbial culture. Because of the importance of the ferrous-iron oxidation as sub-process on the bioleaching of sulphide mineral ores, the ferrous-iron oxidation process by the autochthonous microbial culture was studied at different ferrous-iron concentrations. A mathematical model fitted to the experimental results and the main kinetic and stoichiometric parameters were determined, being the most relevant the maximum ferrous-iron oxidation rate 5.1 (mmol Fe2+/mmol C·h) and the biomass yield, 0.01 mmol C/mmol Fe2+, values very similar to that of mixed cultured dominated by Leptospirillum strains. This autochthonous culture was used in the bioleaching experiment carried out at different pulp densities, obtaining a maximum metal recovery in the tests carried out at 1% w/v, recovering a 90% of Cd, 60% of Zn, 30% of Cu, 25% Fe and 6% of Pb. Finally, the different leaching mechanisms were modelled by using the pyrite as ore model obtaining a bioleaching rate of 0.316 mmol Fe2+/(L·h) for the direct mechanisms and a bioleaching rate for the indirect and cooperative leaching mechanisms of 0.055 Fe2+/(L·h).

Scaling up the electrokinetic-assisted phytoremediation of atrazine-polluted soils using reversal of electrode polarity: A mesocosm study.

Electrokinetic-assisted phytoremediation (EKPR) has been recently proposed for the removal of pesticides from polluted soils. In this work, we report the results from an EKPR experiment that was carried out in a mesocosm mock-up of 0.386 m3 using ryegrass (Lolium perenne L.) and a low permeability soil spiked with atrazine. Plants were initially grown for 35 days; then, the soil was spiked with atrazine at a dose of 2 mg kg-1 soil. A DC electrical field of 0.6 V cm-1 was applied 24 h every day, switching polarity daily. Another identical mock-up with the same experimental conditions but without plants was used for comparison purposes. The duration of the EKPR test was 19 days during which some operational parameters were registered (electric current intensity, soil pH and temperature) and soil porewater samples were taken and analysed. Plant tissues and soil samples from the different sections in which the mock-ups were divided, were also collected and analysed at the end of the experiment. 3-D profiles of soil pH, water content and atrazine residues concentration in plants and soil were obtained and discussed. The results of this experiment were compared with others previously reported by us from a similar EKPR pot test. In spite of the difficulties to get an adequate geometric and operational similarity between setups of different scale, the main output parameters of the EKPR process (electric current, specific current charge, overall atrazine removal, specific atrazine removal efficiency, root biomass:soil weight ratio) were discussed. It was shown that, although the processes carried out are essentially the same in both scales, their extent may be quite different; it highlights the limitations of small-scale experiments to predict the results at field conditions.

Can electrochemistry enhance the removal of organic pollutants by phytoremediation?

An electrokinetic-assisted phytoremediation test using maize (Zea mays L.) was conducted in order to assess the role of the electric field on the enhancement of plant uptake and degradation of the moderate polar pesticide atrazine in spiked soils. Twelve different treatments, including two different initial atrazine soil doses (5 and 10 mg kg-1) and two different values of the electric field applied (2 and 4 V cm-1), together with the corresponding control treatments without plants and/or without electric current, were tested. The application of an electric field during a period of 4 h a day and with periodical polarity inversion (each 2 h) did not caused significant changes in soil pH; moreover, maize plants increased the buffering capacity of the soil. The application of an electric field of 2 V cm-1 led to a slight decrease on maize biomass while the accumulation of atrazine and its main metabolites in plant tissues was significantly enhanced. On the overall, the yield of atrazine removal by electrokinetic-assisted phytoremediation with maize was increased up to 36.5% with respect to the phytoremediation process without electricity. On our knowledge, this work is the first one specifically focused on the removal of organic pollutants from soils by using the combination of phytoremediation and electrokinetic remediation.

Assessing the phytoremediation potential of crop and grass plants for atrazine-spiked soils.

Pollution of soil and groundwater by atrazine has become an increasing environmental concern in the last decade. A phytoremediation test using plastic pots was conducted in order to assess the ability of several crops and grasses to remove atrazine from a soil of low permeability spiked with this herbicide. Four plant species were assessed for their ability to degrade or accumulate atrazine from soils: two grasses, i.e., ryegrass (Lolium perenne) and tall fescue (Festuca arundinacea), and two crops, i.e., barley (Hordeum vulgare) and maize (Zea mays). Three different doses of atrazine were used for the contamination of the pots: 2, 5 and 10 mg kg-1. 16 days after spiking, the initial amount of atrazine was reduced by 88.6-99.6% in planted pots, while a decrease of only 63.1-78.2% was found for the unplanted pots, thus showing the contribution of plants to soil decontamination. All the plant species were capable of accumulating atrazine and its N-dealkylated metabolites, i.e., deethylatrazine and deisopropylatrazine, in their tissues. Some toxic responses, such as biomass decreases and/or chlorosis, were observed in plants to a greater or lesser extent for initial soil doses of atrazine above 2 mg kg-1. Maize was the plant species with the highest ability to accumulate atrazine derivatives, reaching up to 38.4% of the initial atrazine added to the soil. Rhizosphere degradation/mineralization by microorganisms or plant enzymes, together with degradation inside the plants, have been proposed as the mechanisms that contributed to a higher extent than plant accumulation to explain the removal of atrazine from soils.

HPLC-DAD-ESI-MS/MS characterization of pyranoanthocyanins pigments formed in model wine.

Formation of wine pyranoanthocyanins in model wine was monitored by HPLC-DAD-ESI-MS/MS, using red grape skin extracts and wine fermentation metabolites (acetaldehyde, pyruvic and acetoacetic acids, and diacetyl) and also hydroxycinnamic acids (p-coumaric, caffeic, ferulic, and sinapic acids). Pyruvic acid and acetaldehyde reacted fast, the first reaching high product yield and the second inducing mainly pigment polymerization. In contrast, acetoacetic acid and diacetyl reacted slowly with poor product yields. Hydroxycinnamic acids progressively reacted without apparent formation of polymeric pigments, the reaction rate and yield increasing as the number of hydroxy/methoxy groups did. Substituent at C-10 strongly affected the visible maximum absorbance wavelength, whereas B-ring substitution pattern or sugar acylation exerted little effect. The 10-methylpyranoanthocyanins formed from acetoacetic acid were also found as side products in the formation of 10-carboxypyranoanthocyanins. Finally, we report for the first time on UV-vis and MS spectral data of 10-acetylpyranoanthocyanins formed from diacetyl, and their occurrence in commercial red wines is suggested.

Characteristic phenolic composition of single-cultivar red wines of the Canary Islands (Spain).

The detailed phenolic composition of five single-cultivar (Baboso Negro, Listán Negro, Negramoll, Tintilla, and Vijariego Negro) young and aged (vintages 2005-2009) red wines of the Canary Islands has been determined by HPLC-DAD-ESI-MS(n). Despite the total monomeric anthocyanin content decreasing for older wines in each set of single-cultivar wines, the corresponding anthocyanin profiles remained almost unchanged. Although all wine anthocyanin profiles were dominated by malvidin 3-glucoside, their differentiation by grape cultivar was possible, with the exception of Listán Negro. In contrast, the total content of non-anthocyanin phenolics did not appreciably change within vintages but polymerization, hydrolysis, and isomerization reactions greatly modified the phenolic profiles. Aglycone-type flavonol profiles offered the best results for differentiation of the wines according to grape cultivar (Listán Negro and Negramoll; Baboso Negro and Vijariego Negro; and Tintilla). Within flavan-3-ols, the B-ring trihydroxylated monomers ((-)-epigallocatechin and (-)-gallocatechin) and also (-)-epicatechin provided additional cultivar differentiation. Hydroxycinnamic acid derivatives and stilbene profiles were very heterogeneous with regard to both grape cultivar and vintage and did not significantly contribute to wine differentiation, even when structure-type profiles were obtained, with the exception of Tintilla, which always appeared as the most different single-cultivar wines. Finally, most Canary Islands wines showed characteristic high contents of stilbenes, especially trans-resveratrol.