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Nickel hyperaccumulation in Blepharidium guatemalense Standl. (Rubiaceae) was found in the tropical forests of south-eastern Mexico. This study aimed to document the geographic extent of nickel hyperaccumulation in this species, to understand its process of hyperaccumulation and to explore nickel distribution within the tissues of this plant. To accomplish these objectives, a complete non-destructive elemental screening of herbarium specimens was performed with a hand-held X-ray fluorescence spectrometer. Besides, rhizosphere soils and plant tissues were collected in Mexico and analyzed for physical–chemical parameters. Finally, elemental distribution maps of nickel and other elements in plant tissues were obtained by X-ray fluorescence spectroscopy and microscopy. This study revealed that Blepharidium guatemalense is distributed throughout Chiapas, Tabasco and Campeche, reaching the maximum nickel concentration in leaves (4.3 wt%) followed by roots and seeds (2.0 wt%) and bark (1.8 wt%). Simultaneous hyperaccumulation of cobalt and nickel was found in 15% of the herbarium specimens. Blepharidium guatemalense has uncommon re-distribution mechanisms via phloem since this tissue is the highest nickel-enriched from all parts of the plant (from roots to leaves). A high total nickel (mean of 610 µg g−1) was found in rhizosphere soils even though no evidence of ophiolite emplacement in that area has been reported. Blepharidium guatemalense represents the first hypernickelophore (> 1 wt% Ni) to be reported as growing in soils that are neither ultramafic nor enriched by anthropogenic pollutants.

Background The fern Dicranopteris linearis is a hyperaccumulator of rare earth elements (REEs), aluminium (Al) and silicon (Si). However, the physiological mechanisms of tissue-level tolerance of high concentrations of REE and Al, and possible interactions with Si, are currently incompletely known. Methods A particle-induced X-ray emission (μPIXE) microprobe with the Maia detector, scanning electron microscopy with energy-dispersive spectroscopy and chemical speciation modelling were used to decipher the localization and biochemistry of REEs, Al and Si in D. linearis during uptake, translocation and sequestration processes. Results In the roots >80 % of REEs and Al were in apoplastic fractions, among which the REEs were most significantly co-localized with Si and phosphorus (P) in the epidermis. In the xylem sap, REEs were nearly 100 % present as REEH3SiO42+, without significant differences between the REEs, while 24–45 % of Al was present as Al-citrate and only 1.7–16 % Al was present as AlH3SiO42+. In the pinnules, REEs were mainly concentrated in necrotic lesions and in the epidermis, and REEs and Al were possibly co-deposited within phytoliths (SiO2). Different REEs had similar spatial localizations in the epidermis and exodermis of roots, the necrosis, veins and epidermis of pinnae of D. linearis. Conclusions We posit that Si plays a critical role in REE and Al tolerance within the root apoplast, transport within the vascular bundle and sequestration within the blade of D. linearis.

International audience; Background and Aims: In tropical ultramafic soils, potassium (K) is typically the most growth limiting nutrient. However, tropical nickel (Ni) hyperaccumulator plants, including Phyllanthus rufuschaneyi and Rinorea cf. bengalensis (which are ‘metal crops’ used in agromining) from Malaysia, have unusually high K shoot accumulation compared to other species, despite naturally growing on severely K-impoverished ultramafic soils. This study aimed to establish the response to soil K availability in relation to uptake of K and other elements in the roots and shoots of P. rufuschaneyi and R. cf. bengalensis.Methodology: We undertook an experiment in which soluble K was dosed to ultramafic soil in pots with P. rufuschaneyi and R. cf. bengalensis in Sabah (Malaysia).Results: The results show that root K concentrations increased markedly as the soil K availability increased by 35-fold, whilst the corresponding effect on K accumulation in the shoots of P. rufuschaneyi and R. cf. bengalensis was not significantly different in relation to soil K dosing. Observed divergent responses between root and shoot K accumulation in these species suggests a separate genetic control of K uptake and xylem loading in P. rufuschaneyi and R. cf. bengalensis.Conclusion: The tight control of root-to-shoot K translocation and constrained K accumulation in shoots under a soil K gradient is likely an adaptive mechanism to the evolution of these species to grow in highly nutrient-impoverished ultramafic soils. This study provides information that will be useful for better nutrient management of tropical Ni metal farms that use K-efficient Ni ‘metal crops’.

Background and Aims The aim of this study was to test the frequency distributions of foliar elements from a large dataset from Kinabalu Park (Sabah, Malaysia) for departure from unimodality, indicative of a distinct ecophysiological response associated with hyperaccumulation. Methods We collected foliar samples (n = 1533) comprising 90 families, 198 genera and 495 plant species from ultramafic soils, further foliar samples (n = 177) comprising 45 families, 80 genera and 120 species from non-ultramafic soils and corresponding soil samples (n = 393 from ultramafic soils and n = 66 from non-ultramafic soils) from Kinabalu Park (Sabah, Malaysia). The data were geographically (Kinabalu Park) and edaphically (ultramafic soils) constrained. The inclusion of a relatively high proportion (approx. 14 %) of samples from hyperaccumulator species [with foliar concentrations of aluminium and nickel (Ni) >1000 μg g–1, cobalt, copper, chromium and zinc >300 μg g–1 or manganese (Mn) >10 mg g–1] allowed for hypothesis testing. Key Results Frequency distribution graphs for most elements [calcium (Ca), magnesium (Mg) and phosphorus (P)] were unimodal, although some were skewed left (Mg and Mn). The Ni frequency distribution was bimodal and the separation point for the two modes was between 250 and 850 μg g–1. Conclusions Accounting for statistical probability, the established empirical threshold value (>1000 μg g–1) remains appropriate. The two discrete modes for Ni indicate ecophysiologically distinct behaviour in plants growing in similar soils. This response is in contrast to Mn, which forms the tail of a continuous (approximately log-normal) distribution, suggestive of an extension of normal physiological processes.

Background: Phytoextraction is an in situ technique that can be applied to minerals and mining wastes using hyperaccumulator plants to purposely bio-concentrate high levels of metals or metalloids into their shoots in order to remove them from the substrate, while achieving monetary gain. Phytoextraction can be applied to a limited number of elements depending on the existence of hyperaccumulator plants with suitable characteristics. Although phytoextraction has been trialled in experimental settings, it requires testing at field scale to assess commercial broad-scale potential. Scope: The novelty and purported environmental benefits of phytoextraction have attracted substantial scientific inquiry. The main limitation of phytoextraction with hyperaccumulators is the number of suitable plants with a high accumulation capacity for a target element. We outline the main considerations for applying phytoextraction using selected elemental case studies in which key characteristics of the element, hyperaccumulation and economic considerations are evaluated. Conclusions: The metals cobalt, cadmium, thallium and rhenium and the metalloids arsenic and selenium are present in many types of minerals wastes, especially base metal mining tailings, at concentrations amenable for economic phytoextraction. Phytoextraction should focus on the most toxic elements (arsenic, cadmium, and thallium) or especially valuable elements (selenium, cobalt, and rhenium). The value proposition is in the clean-up of contaminated land in the case of toxic elements, whereas it is in the ‘bio-ore’ generated by the process in the case of valuable elements.

The extend of biogeochemical cycling of nickel (Ni) by tropical hyperaccumulator plants in their native habitat is largely unknown, although these unusual plants are suspected to play a major role in the recycling of this element in ultramafic ecosystems. In this study, we have assessed the biogeochemical cycling of Ni (and other elements, including mineral nutrients) by a tropical Ni hyperaccumulator plant, i.e., Phyllanthus rufuschaneyi, which is one of the most promising species for tropical Ni agromining. The study site was a young secondary forest in Sabah (Malaysia) where Phyllanthus rufuschaneyi occurs as the dominant species on an ultramafic Cambisol. For 2 years, we monitored a 100-m2 plot and collected information on weather, biomass increase, soil fertility, water fluxes to the soil and litter fluxes for a wide range of elements, including Ni. The Ni cycle is mainly driven by internal fluxes, notably the degradation and recycling of Ni-rich litter. Over the period of investigation, the Ni litter flux corresponded to the total Ni stock of the litter (5.2 g m−2 year−1). The results further show that Ni turnover varies significantly with the accumulation properties of the plant cover. This points to the major influence of Ni hyperaccumulator plants in building up Ni available stocks in the topsoils, as has also been shown in temperate ultramafic systems. Litterfall and throughfall contribute substantially to the cycling of phosphorus, sulphur and potassium in this ecosystem, with throughfall contributing 2-, 220- and 20-fold higher to the respective nutrient fluxes relative to litterfall. The magnesium:calcium ratio far exceeded 1 in the soil, but was < 1 in the leaves of Phyllanthus rufuschaneyi. The insights from this study should be taken into account when designing tropical agromining operations; as Ni stocks could be more labile than initially thought. The removal of Ni- and nutrients-rich biomass will likely affect available Ni (and major nutrients) for the next cropping seasons, and requires sustainable fertilisation, to be utilized to replenish depleted major nutrients. These findings also have major ecological implications.

International audience; Aims: The agronomy of tropical ‘metal crops’ had not yet been tested until a recent pot trial was undertaken to test the growth and nickel (Ni) yield of two promising Ni ‘metal crops’ (Phyllanthus rufuschaneyi and Rinorea cf. bengalensis) from Sabah, Malaysia. The present study investigates the growth and Ni yield in P. rufuschaneyi in response to inorganic and organic fertilisation under field conditions.Methods: A two-year field experiment was undertaken on an ultramafic Cambisol in Sabah. Two experiments were set up with different types of fertilisers, either organic or inorganic. Ten 9-m2 plots were amended with either NPK (370 kg ha−1) or N (120 kg ha−1) fertilisation and were monitored during the first year. Another experiment with 25-m2 plots was set up to test three treatments of organic amendment (0, 1 or 2 kg m−2 of shredded P. rufuschaneyi biomass).Results: The results show that despite considerable variability, Ni concentration was generally lower in plant shoots amended with N only (i.e. urea). However, treatments showed no statistical effect on plant biomass and Ni yield in the short-term, even though organic treatments had a strong positive effect on the availability of Ni.Conclusion: The short-term effects of inorganic and organic treatments on Ni yield of the tropical ‘metal crop’ Phyllanthus rufuschaneyi were not apparent (75 kg Ni ha−1 yr−1). The field trials are ongoing to assess long-term effects. The preliminary results suggest that with appropriate agronomic systems and plant breeding, the Ni yield could be substantially increased.

Aims: Nickel hyperaccumulator plants require highly evolved mechanisms to avoid cellular-level toxicity to cope with the high prevailing concentrations of nickel in their seeds and seedlings. This study aimed to investigate tissue-level distribution and redistribution of Ni and other physiologically relevant elements during the germination of hyperaccumulator plants. Methods : Berkheya coddii Roessler (Asteraceae) and Odontarrhena muralis sensu latu (Waldst. & Kit.) Endl. (O. chalcidica), formerly Alyssum murale (Waldst. & Kit.) (Brassicaceae), were germinated for several days at room temperature before using synchrotron micro X-ray Fluorescence Spectroscopy (µXRF) to obtain high-sensitivity and high-resolution elemental images of live/hydrated plants at various stages of seed germination and seedling growth. Results: The results show that fruits and seeds of both species were highly enriched in nickel. In Berkheya coddii, nickel was located in the cotyledons, the micropylar area, the seed coat, and the point of attachment of the pappus with the cypsela body. In Odontarrhena muralis seeds, nickel occurred in the cotyledons and hypocotyl. The emergence of true leaves initiates nickel and calcium redistribution within seedlings in both species. Conclusions: The diversity in physiological responses to nickel in Berkheya coddii and Odontarrhena muralis does not only occur at the mature stage, but is inherent to both species as seed elemental storage and tolerance mechanisms during seedling development differ.

International audience; Ultramafic soils are usually marginal in macronutrients (nitrogen (N), phosphorus (P), potassium (K) and calcium (Ca)) for growth of crop plants. Commercial nickel (Ni) agromining is dependent on attaining high yield and high Ni concentration in harvestable biomass of Ni hyperaccumulator species. We previously reported on the biomass responses of two promising tropical ‘metal crops’ (Phyllanthus rufuschaneyi and Rinorea cf. bengalensis) to rates of N, P, and K fertilisers. Calcium, sulphur (S) and organic matter amendments have varied effects on the biomass production and Ni uptake in temperate Ni hyperaccumulator species used in agromining, but the trends in tropical ‘metal crops’ are not reported to-date. We investigated the effects of these amendments on the growth performance and the Ni (and other elements) uptake in P. rufuschaneyi and R. cf. bengalensis The experiments consisted of a large 12-month randomised growth trial in large pots in Sabah (Malaysia) using ultramafic soils under different treatment levels of soluble Ca and S, and organic matter amendments. We found that Ca and S additions had no significant effects on the growth of P. rufuschaneyi and R. cf. bengalensis. Organic matter amendments had strong positive effect on the growth of R. cf. bengalensis (p

International audience; Background and aims: Pioneer plants may improve the ecological restoration of degraded ultramafic areas by plant-soil interaction processes. In this study, we assess the effect of the pioneer actinorhizal tree C. terminale (Casuarinaceae) on the recovery of plant communities and soil functions on degraded tropical ultramafic sites.Methods: Soil and plant samples were collected along a tree-age gradient in two degraded ultramafic sites in Sabah (Northern Borneo, Malaysia): a Technosol and a Leptosol. Chemical composition of plants and soils, and biological activity of soils were assessed at both sites. Plant colonisation was assessed by plot vegetation surveys.Results: An improvement in soil fertility parameters (pH reduction from 8.5 to 6.8, an increase in the concentrations of several nutrients and enhanced soil enzyme activities) was observed along the C. terminale age gradient. However, plant cover and diversity was only improved around mature trees at the site that was not impacted by mining.Conclusion: C. terminale promotes the recovery of several soil functions, mainly related to the storage and recycling of N, P, K, S. Besides plant-soil feedback, other environmental factors (i.e. exposition to sunlight, drought) may play an important role on revegetation of ultramafic soils.

Ultramafic (i.e. serpentine) soils are widespread in the Balkans and particularly in Albania. They account for a large part of plant endemism in that region and host several hyperaccumulator species, which are characterized by leaf nickel concentrations frequently above 1%. This rich nickel hyperaccumulating flora could serve as candidate to be used in phytoextraction and agromining. Despite recent interest in metal hyperaccumulating plants and agromining, very few studies have investigated the bacterial diversity and the influence of environmental factors on microbial gene profiles in the rhizosphere of hyperaccumulator plants growing on ultramafic soils. Because rhizospheric bacteria could be crucial to the success of phytoremediation, we studied a total of 48 nickel-hyperaccumulating plants which were sampled from four species that are widespread in Albania: Noccaea ochroleuca, Odontarrhena smolikana, O. rigida and O. chalcidica. All samples were taken from the ultramafic regions of Librazhd and Pogradec in eastern Albania in October 2015. Our study shows that Proteobacteria, Actinobacteria and Acidobacteria dominated the soil bacterial communities. Of these three phyla, only Proteobacteria was relatively abundant. This study underlines the influence of soil Cation Exchange Capacity on the bacterial community's diversity and structure. Based on the predicted metagenomes, the genes belonging to amino acid, lipid and carbohydrate metabolisms were identified as major gene families. Our study sheds some light on our understanding of how bacterial communities are structured within and affect the rhizosphere of hyperaccumulator plants from ultramafic soils in Albania.

This article has been accepted for publication in Metalomics Published by Oxford University Press. DOI: 10.1093/mtomcs/mfab045; International audience; Plants have developed a diversity of strategies to take up and store essential metals in order to colonize various types of soils including mineralized soils. Yet, our knowledge of the capacity of plant species to accumulate metals is still fragmentary across the plant kingdom. In this study, we have used the X-Ray Fluorescence technology to analyze metal concentration in a wide diversity of species of the Neotropical flora that was not extensively investigated so far. In total, we screened more than 11 000 specimens representing about 5000 species from herbaria in Paris and Cuba. Our study provides a large overview of the accumulation of metals such as manganese, zinc and nickel in the Neotropical flora. We report 30 new nickel hyperaccumulating species from Cuba, including the first records in the families Connaraceae, Melastomataceae, Polygonaceae, Santalaceae and Urticaceae. We also identified the first species from this region of the world that can be considered as manganese hyperaccumulators in the genera Lomatia (Proteaceae), Calycogonium (Melastomataceae), Ilex (Aquifoliaceae), Morella (Myricaceae) and Pimenta (Myrtaceae). Finally, we report the first zinc hyperaccumulator, Rinorea multivenosa (Violaceae), from the Amazonas region. The identification of species able to accumulate high amounts of metals will become instrumental to support the development of phytotechnologies in order to limit the impact of soil metal pollution in this region of the world.

Aims Agromining aims to improve the fertility of naturally metal-rich soils by extracting metals, such as nickel (Ni), using hyperaccumulator plants. Ultramafic soils are characterized by low fertility levels, limiting hyperaccumulator yields. Here, we characterize the potential benefits for phytoextraction efficiency of cocropping a Ni-hyperaccumulator (Odontarrhena chalcidica) and a legume (Vicia sativa), following a two-year field experiment. Methods A two-year field experiment was set up in an ultramafic zone in North-West Spain. Three treatments were tested: co-cropping, fertilized control with ammonium nitrate and non-fertilized control. Results Over the 2 years, co-cropping increased O. chalcidica’s biomass by 24% and 403% compared to fertilized and non-fertilized controls, respectively. Moreover, co-cropping had higher Ni-yields for both years, while fertilization had a negative effect on soil parameters. A non-metric multidimensional scaling analysis of the operational taxonomic units showed that the soil bacterial diversity changed over time. Soil exchangeable Ni and organic carbon influenced the phyla’s relative abundance. Metabolic genes were dominant and their relative abundances increased over time with co-cropping. Conclus i o n Pluriannua l co-cropping of a hyperaccumulator with a legume improved both hyperaccumulator and Ni yields. In contrast, mineral fertilization was shown to be detrimental to some soil microbial parameters. Thus, ameliorating agromining by replacing mineral fertilizers would combine an eco-efficient strategy with sustainable metal recovery., This work was supported by French National Research Agency through the national “Investissements d’avenir” program, reference ANR-10-LABX- 21 - LABEX RESSOURCES21, through the “Agromine” project, reference ANR-14-CE04-0005, through the European ERA-net FACCE_SURPLUS project “AGRONICKEL: Developing Ni agromining on ultramafic land in Europe”, reference ANR-15- SUSF-0003-05, through the “Application of Nickel hyperaccumulating plants in phytomining processes” program, reference I-LINK0900 and the LIFE Environment and Resource Efficiency Programme (Life Agromine; LIFE15 ENV/FR/ 000512).

The rare phenomenon of plant manganese (Mn) hyperaccumulation within the Australian flora has previously been detected in the field, which suggested that the tree genus Gossia (Myrtaceae) might contain new Mn hyperaccumulators. We conducted the first growth experiment on Gossia using a multi-factorial dosing trial to assess Mn, cobalt (Co), and zinc (Zn) (hyper)accumulation patterns in selected Gossia species (G. fragrantissima and G. punctata) after a systematic assessment of elemental profiles on all holdings of the genus Gossia at the Queensland Herbarium using handheld X-ray fluorescence spectroscopy. We then conducted detailed in situ analyses of the elemental distribution of Mn, Co, Zn and other elements at the macro (organ) and micro (cellular) levels with laboratory- and synchrotron-based X-ray fluorescence microscopy (XFM). Gossia pubiflora and Gossia hillii were newly discovered to be Mn hyperaccumulator plants. In the dosing trial, G. fragrantissima accumulated 17 400 µg g−1 Mn, 545 µg g−1 Co, and 13 000 µg g−1 Zn, without signs of toxicity. The laboratory-based XFM revealed distinct patterns of accumulation of Co, Mn, and Zn in G. fragrantissima, while the synchrotron XFM showed their localization in foliar epidermal cells, and in the cortex and phloem cells of roots. This study combined novel analytical approaches with controlled experimentation to examine metal hyperaccumulation in slow-growing tropical woody species, thereby enabling insight into the phenomenon not possible through field studies.

Aims: The tropical nickel (Ni) hyperaccumulator plants, Rinorea cf. bengalensis and Phyllanthus rufuschaneyi, are locally common on ultramafic soils in the Malaysian state of Sabah on the island of Borneo. The aim of this study was to determine whether the structure and diversity of R. cf. bengalensis rhizosphere microbial communities were dependant on the Ni concentrations in the different rhizosphere soils studied. Methods: Rinorea cf. bengalensis and Phyllanthus rufuschaneyi were subjected to a randomized block design experiment in which four Ni dose levels were applied (0, 60, 240, 600 mg Ni kg−1) × 5 replicates per level for 12 months cultivation. At the end of the trial foliar elemental concentrations were measured. In addition, rhizosphere soils were collected for elemental and microbial analyses. The microbial analysis consisted of measuring microbial enzymatic activities and a diversity analysis based on Illumina sequencing. Results: The Illumina sequencing analysis yielded 2,649,138 sequences grouped under 2430 different Operational Taxonomic Units (OTUs) belonging to 25 phyla. No impact of the Ni amendments was shown for the four microbial enzymatic activities tested, even at the highest Ni dose level (600 mg Ni kg−1). Higher microbial enzymatic activities were found in the rhizosphere of R. cf. bengalensis relative to P. rufuschaneyi. Nickel concentrations appeared to have a high impact on the P. rufuschaneyi rhizosphere soils, whereas no effect was found for the rhizosphere bacterial community diversity of R. cf. bengalensis. Conclusions: There may be a significant role of rhizodeposits associated with R. cf. bengalensis that protect and preserve the microbial communities in the rhizosphere, regardless of the prevailing nickel concentrations.

The aim of this study was to assess the potential of the woody nickel hyperaccumulator species Blepharidium guatemalense (Standl.) Standl. for agromining in southeastern Mexico. Pot trials consisting of nickel dosing (0, 20, 50, 100, and 250 mg Ni kg−1), and synthetic and organic fertilization were conducted. Field trials were also undertaken with different harvesting regimes of B. guatemalense. Foliar nickel concentrations increased significantly with rising nickel additions, with a 300-fold increase at 250 mg Ni kg−1 treatment relative to the control. Synthetic fertilization strongly increased nickel uptake without any change in plant growth or biomass, whereas organic fertilization enhanced plant shoot biomass with a negligible effect on foliar nickel concentrations. A 5-year-old stand which was subsequently harvested twice per year produced the maximum nickel yield tree−1yr−1, with an estimated total nickel yield of 142 kg ha−1yr−1. Blepharidium guatemalense is a prime candidate for nickel agromining on account of its high foliar Ni concentrations, high bioconcentration (180) and translocation factors (3.3), fast growth rate and high shoot biomass production. Future studies are needed to test the outcomes of the pot trials in the field. Extensive geochemical studies are needed to identify potential viable agromining locations. Novelty Statement Our research team is a pioneer in the discovery of metal hyperaccumulator plants in Mesoamerica with at least 13 species discovered in the last 2 years. This study is the first to assess the potential of nickel agromining (phytomining) in Mexico (and in all the American continent), using one of the strongest nickel hyperaccumulators reported so far. The promising results of this study are the basis for optimal agricultural management of Blepharidium guatemalense.

International audience

International audience; The hyperaccumulator Pycnandra acuminata is a New Caledonian rainforest tree known to have the highest concentration of nickel in any living organism with 25 wt% in its latex. All trees (with diameter >10 cm) and soil profiles in a 0.25-hectare permanent plot were sampled to assess the biogeochemical compartmentalisation of nickel in a dense stand of Pycnandra acuminata trees. Nickel stable isotope analysis permitted insights into the cycling of nickel in this ecosystem. The total tree biomass of the plot was ~281 tonnes ha-1, approximately 0.44 kg of cobalt, 49.1 kg of manganese, 257 kg of nickel and 6.76 kg of zinc. Nickel stable isotope analysis identified the biotic origin of the nickel in the soil upper layers with P. acuminata shoots enriched in lighter nickel isotopes. The δ60Ni latex signature suggests that long-distance transport, radial xylem and phloem loading are at play in Pycnandra acuminata.

International audience; Background and aims: The genus Denhamia(Celastraceae) includes fifteen Australian species, many of which have a propensity for manganese (Mn) (hyper)accumulation. Among the key aims of this study were to: i) elucidate Mn accumulation in D. bilocularis, D. celastroides, D. pittosporoides and D. silvestris under controlled conditions; ii) examine the in situ distributions of Mn and other elements in tissues of i) above, and also in two other species growing in their natural habitat, i.e. D. silvestris and D. cunninghamii; iii) test numerous Denhamia herbarium specimens for Mn accumulation using portable X-ray fluorescence spectroscopy (XRF).Methods: Portable XRF and laboratory micro-XRF were used to examine Mn accumulation and foliar distribution patterns in several Australian Denhamia species. These techniques were variously applied to fresh field material and experimentally-raised plants treated with Mn (250 μg g−1, 500 μg g−1 and 1000 μg g−1) and dry herbarium material.Results: The findings revealed D. bilocularis as a new Mn hyperaccumulator, with foliar Mn concentrations of up to 15,300 μg g−1 in herbarium samples, and 13,700 μg g−1 in experimentally grown plants. Laboratory μXRF maps consistently showed that foliar Mn accumulation was localized at the extremities of wild D. cunninghamii and D. silvestris leaves; whereas it was found in the vasculature of experimentally grown D. bilocularis and D. pittosporoides leaves.Conclusions: This study presents evidence that Mn accumulation across the Australian Denhamia species is taxonomically variable, however further work is required.

International audience; 17 Aims. Rinorea cf. bengalensis is a Ni hyperaccumulator which occurs in Sabah (Malaysia), on Borneo Island, 18 that is able to accumulate considerable amounts of Ni and influences the Ni cycle in surface soil layers, both in 19 terms of Ni concentration and Ni isotopic composition. In this study, the biogeochemical processes underpinning 20 Ni isotopic fractionation in the soil-plant system and the mechanisms regulating Ni homeostasis in R. cf. 21 bengalensis plants were elucidated. 22 Methods. Two specimens of R. cf. bengalensis of different ages and associated surface soils were collected from 23 ultramafic soils in Sabah. Soil mineralogy, Ni concentrations, speciation and isotopic signatures were 24 subsequently determined in plant and soil samples. 25 Results. Nickel in R. cf. bengalensis leaves is mainly complexed with citrate. Soil Ni available fractions have 26 different δ 60 Ni values depending on the Ni bearing phases. Rinorea cf. bengalensis specimens take up lighter Ni 27 isotopes and a pronounced isotopic fractionation within the plant is observed, especially in the young specimen. 28 Conclusions. The results suggest that the observed fractionation in the young plant can be attributable to kinetic 29 effects (lighter isotopes move faster), which become less evident in the older specimen, as Ni is redistributed and 30 homogenized through phloem loading and unloading processes. 31 2

International audience; In Albania, ultramafic outcrops cover 11% of the surface and have the potential to support nickel phytomining. In a large-scale in-situ experiment on an ultramafic Vertisols in Pojske we are studying the influence of agronomical practices on Ni phytoextraction yield of Odontarrhena chalcidica (syn. Alyssum murale). Three cropping systems were compared in three plots in 2016-2017; POJ-1 Plot (0.3 ha) was established with plants that had germinated spontaneously without any treatments; POJ-2 plot (0.3 ha) was covered by plants that had germinated spontaneously and was treated with mineral fertilizer (N50P50K50 kg ha(-1)); and POJ-3 Plot (400 m(2)) was divided in four sub plots, where O. chalcidica was planted at a density of 4 plants m(-2) on which, we neither applied fertilizer, nor NPK fertilizer (N65P65K65), pig (FPM; N260:P105:K260 + 15 kg ha(-1)N, P, K) or chicken manure (FCHM; N260:P390:K260 +15 kg ha(-1) N, P, K. Irrigation and mechanical control of weeds was done on POJ-3. After 8 months, shoot Ni concentration, biomass, and Ni yields were higher in O. chalcidica treated with manure and the cost of biomass production was smaller. Nickel yield was more promising (145 kg ha(-1)) than in previous field trials. This study highlights that, using manure, the Ni yield increases Ni phytomining net values, thus agromining can become an economically justifiable agricultural cropping system.

International audience; Aim The identification and use of hyperaccumulator plants in mining projects has been recognized as an important component of mine planning at several sites around the world. The objective of this research was to provide information on relevant plant tissue chemistry and an indicative assessment of the potential for phytomining at Weda Bay Nickel (WBN), Halmahera. Methods The first stage was the identification of native nickel hyperaccumulator plants. In total, 280 plant tissue samples from 10 nickel accumulator species and 46 matching rhizosphere soil samples were collected. Chemical analyses of plant tissue samples were performed and physico-chemical parameters of the rhizosphere soils were also measured. Results A total of three species were considered as metal crops: Rinorea aff. bengalensis (up to 22,200 mg kg−1 dry weight at 2 m above ground level), Ficus trachypison (1060 mg kg−1) and Trichospermum morotaiense (5180 mg kg−1), but only R. aff. bengalensis has sufficiently high Ni concentrations in biomass to warrant field trials. Conclusions Utilising a successional planting strategy, F. trachypison and T. morotaiense could be used to facilitate site conditions, followed by the metal crop R. aff. bengalensis. Using this design, a nickel yield of 330 kg per hectare would be possible every 4 years. In addition to allowing the recovery of nickel, this approach could be an integrated mine site rehabilitation strategy to mitigate environmental impacts, improve soil quality and facilitate transition to other land-uses such as native forest.

Selenium (Se), a trace element essential for human and animal biological processes, is deficient in many agricultural soils. Some extremely rare plants can naturally accumulate extraordinarily high concentrations of Se. The native legume Neptunia amplexicaulis, endemic to a small area near Richmond and Hughenden in Central Queensland, Australia, is one of the strongest Se hyperaccumulators known on Earth, with foliar concentrations in excess of 4000 μg Se g−1 previously recorded. Here, we report on the Se distribution at a whole plant level using laboratory micro X-ray Fluorescence Microscopy (μXRF) and scanning electron microscopy (SEM-EDS), as well as on chemical forms of Se in various tissues using liquid chromatography-mass spectrometry (LC-MS) and synchrotron X-ray absorption spectroscopy (XAS). The results show that Se occurs in the forms of methyl-selenocysteine and seleno-methionine in the foliar tissues, with up to 13 600 μg Se g−1 total in young leaves. Selenium was found to accumulate primarily in the young leaves, flowers, pods and taproot, with lower concentrations present in the fine-roots and stem and the lowest present in the oldest leaves. Trichomes were not found to accumulate Se. We postulate that Se is (re)distributed in this plant via the phloem from older leaves to newer leaves, using the taproot as the main storage organ. High concentrations of Se in the nodes (pulvini) indicate this structure may play an important a role in Se (re)distribution. The overall pattern of Se distribution was similar in a non-Se tolerant closely related species (Neptunia gracilis), although the prevailing Se concentrations were substantially lower than in N. amplexicaulis.

Background and Aims Hybanthus austrocaledonicus (Violaceae) is a nickel (Ni) hyperaccumulator endemic to New Caledonia. One of the specimens stored at the local herbarium had a strip of bark with a remarkably green phloem tissue attached to the sheet containing over 4 wt% Ni. This study aimed to collect field samples from the original H. austrocaledonicus locality to confirm the nature of the green ‘nickel-rich phloem’ in this taxon and to systematically assess the occurrence of Ni hyperaccumulation in H. austrocaledonicus and Hybanthus caledonicus populations. Methods X-ray fluorescence spectroscopy scanning of all collections of the genus Hybanthus (236 specimens) was undertaken at the Herbarium of New Caledonia to reveal incidences of Ni accumulation in populations of H. austrocaledonicus and H. caledonicus. In parallel, micro-analytical investigations were performed via synchrotron X-ray fluorescence microscopy (XFM) and scanning electron microscopy with X-ray microanalysis (SEM-EDS). Key Results The extensive scanning demonstrated that Ni hyperaccumulation is not a characteristic common to all populations in the endemic Hybanthus species. Synchrotron XFM revealed that Ni was exclusively concentrated in the epidermal cells of the leaf blade and petiole, conforming with the majority of (tropical) Ni hyperaccumulator plants studied to date. SEM-EDS of freeze-dried and frozen-hydrated samples revealed the presence of dense solid deposits in the phloem bundles that contained >8 wt% nickel. Conclusions The occurrence of extremely Ni-rich green phloem tissues appears to be a characteristic feature of tropical Ni hyperaccumulator plants.

Nickel (Ni) is used in numerous industrial processes, with large amounts of Ni-rich industrial wastes produced, which are largely sent to landfill. Nickel recovery from waste materials that would otherwise be disposed is of particular interest. Nickel phytomining represents a new technology in which hyperaccumulator plants are cultivated on Ni-rich substrates for commercial metal recovery. The aim of this study was to investigate the possibility of Ni transfer from industrial waste into plant biomass, to support recovery processes from bio-ores. Different industrial galvanic sludges (containing 85–150 g kg−1 Ni) were converted into artificial substrates (i.e. technosols) and the Ni hyperaccumulator Odontarrhena chalcidica (formerly Alyssum murale) was cultivated on these Ni-rich matrices. A greenhouse pot experiment was conducted for three months including an ultramafic soil control and testing fertilized (NPK) and unfertilized replicates. The results showed that fertilization was effective in improving plant biomass for all the substrates and that O. chalcidica was capable of viably growing on technosols, producing a comparable biomass to O. chalcidica on the control (ultramafic soil). On all technosols, O. chalcidica achieved Ni shoot concentrations of more than >1000 mg Ni kg −1 and maximum Ni uptake was obtained from one of the technosols (26.8 g kg −1 Ni, unfertilized; 20.2 g kg −1 Ni, fertilized). Nickel accumulation from three of the technosols resulted to be comparable with the control ultramafic soil. This study demonstrated the feasibility of transferring Ni from toxic waste into the biomass of Odontarrhena chalcidica and that phytomining from galvanic sludge-derived technosols can provide similar Ni yields as from natural ultramafic soils.

New Caledonia is a global biodiversity hotspot known for its metal hyperaccumulator plants. X-ray fluorescence technology (XRF) has enabled non-destructive and quantitative determination of elemental concentrations in herbarium specimens from the ultramafic flora of the island. Specimens belonging to six major hyperaccumulator families (Cunoniaceae, Phyllanthaceae, Salicaceae, Sapotaceae, Oncothecaceae and Violaceae) and one to four specimens per species of the remaining ultramafic taxa in the herbarium were measured. XRF scanning included a total of c. 11 200 specimens from 35 orders, 96 families, 281 genera and 1484 species (1620 taxa) and covered 88.5% of the ultramafic flora. The study revealed the existence of 99 nickel hyperaccumulator taxa (65 known previously), 74 manganese hyperaccumulator taxa (11 known previously), eight cobalt hyperaccumulator taxa (two known previously) and four zinc hyperaccumulator taxa (none known previously). These results offer new insights into the phylogenetic diversity of hyperaccumulators in New Caledonia. The greatest diversity of nickel hyperaccumulators occur in a few major clades (Malphigiales and Oxalidales) and families (Phyllanthaceae, Salicaceae, Cunoniaceae). In contrast, manganese hyperaccumulation is phylogenetically scattered in the New Caledonian flora.

Albanian taxa and populations of the genus Odontarrhena are most promising candidates for research on metal tolerance and Ni-agromining, but their genetic structure remains unknown. We investigated phylogenetic relationships and genetic differentiation in relation to distribution and ploidy of the taxa, anthropic site disturbance, elevation, soil type, and trace metals at each population site. After performing DNA sequencing of selected accessions, we applied DNA-fingerprinting to analyze the genetic structure of 32 populations from ultramafic and non-ultramafic outcrops across Albania. Low sequence divergence resulted in poorly resolved phylograms, but supported affinity between the two diploid serpentine endemics O. moravensis and O. rigida. Analysis of molecular variance (AMOVA) revealed significant population differentiation, but no isolation by distance. Among-population variation was higher in polyploids than in diploids, in which genetic distances were lower. Genetic admixing at population and individual level occurred especially in the polyploids O. chalcidica, O. decipiens, and O. smolikana. Admixing increased with site disturbance. Outlier loci were higher in serpentine populations but decreased along altitude with lower drought and heat stress. Genetic variability gained by gene flow and hybridization at contact zones with &ldquo, resident&rdquo, species of primary ultramafic habitats promoted expansion of the tetraploid O. chalcidica across anthropogenic sites.

Plant and soil 457(1-2), 293 - 320 (2020). doi:10.1007/s11104-020-04714-x, AimsThis study aimed to establish elemental profiles and to spatially resolve the elemental distribution in five New Caledonian woody Ni hyperaccumulator plant species (Geissois pruinosa var. pruinosa, Homalium francii, Hybanthus austrocaledonicus, Psychotria gabriellae, and Pycnandra acuminata) originating from the Cunoniaceae, Salicaceae, Violaceae, Rubiaceae, and Sapotaceae families respectively.MethodsUsing synchrotron-based micro-X-ray Fluorescence (��XRF) imaging of different plant tissues, from the roots to the shoots and reproductive organs, this study aimed to clarify how distribution patterns of nickel, and other physiologically relevant elements, differ between these species.ResultsThe results show that the tissue-level and cellular-level distribution of nickel in P. gabriellae, H. austrocaledonicus, G. pruinosa var. pruinosa, and H. francii conform with the majority of studied Ni hyperaccumulator plant species globally, including (temperate) herbaceous species, with localization mainly in epidermal cells and phloem bundles. However, P. acuminata has nickel-rich laticifers, which constitute an independent network of cells that is parallel to the vascular bundles and are the main sink for nickel.ConclusionsSynchrotron-based micro-X-ray Fluorescence (��XRF) is a powerful method for investigating how metal hyperaccumulation influences acquisition and spatial distribution of a wide range of elements. This non-invasive method enables investigation into the in vivo distribution of multiple elements and the structure and organisation of cells (e.g. laticifers)., Published by Springer Science + Business Media B.V, Dordrecht [u.a.]

International audience; Hyperaccumulator plants have the ability to efficiently concentrate metallic elements, e.g. nickel, from low-grade sources into their living biomass. Although the majority of nickel hyperaccumulator plant species restrict cobalt uptake, some species are able to co-accumulate cobalt when growing in ultramafic soils. The asteraceous perennial herb Berkheya coddii from South Africa is one of the most promising agromining crops known globally. It may accumulate nickel in excess of 30 000 mg g À1 in dry leaves, while co-accumulating up to 600 mg g À1 cobalt. This study aimed to elucidate the interactions between nickel and cobalt for uptake by and translocation into B. coddii through a pot experiment including various cobalt/nickel treatment combinations in soil, after which uptake and localisation were recorded. Cobalt in the substrate limits nickel uptake by B. coddii plants and is mainly retained in the basal leaves in contrast to Ni that is rapidly transferred to the top of the plant. B. coddii was more tolerant to high Ni concentration, whether in the substrate or internally but remains a promising crop which could be used, with suitable agronomic measures and practices, for cobalt agromining in areas with high soil cobalt but low soil nickel. A yield of 77 kg ha À1 nickel and 16.5 kg ha À1 cobalt may be attainable under optimum conditions. Significance to metallomics The hyperaccumulator plant Berkheya coddii from South Africa is one of the most promising 'agromining crops' known globally. This article reports on the interactions between cobalt and nickel for uptake and translocation in this species. Cobalt in the substrate inhibits nickel uptake in plants, and while nickel is rapidly transferred to the top of the plant, cobalt is mainly retained in the basal leaves.

Plant and soil 455, 289 ��� 303 (2020). doi:10.1007/s11104-020-04629-7, $Aims$Knowledge on the ecophysiology of cobalt hyperaccumulator species is limited. The nickel hyperaccumulator Rinorea cf. bengalensis from Borneo can accumulate high concentrations of cobalt in nature. This study investigates the cobalt accumulation potential of Rinorea cf. bengalensis in relation to nickel concentrations in soils and the subsequent tissue and cellular-level distributions of cobalt, nickel and major cations.$Methods$Seedlings of Rinorea cf. bengalensis were grown in mixed treatments on ultramafic soil containing a high concentration of available nickel. Cobalt and nickel salts were then added to the soil to study their interactions. The tissue and cellular-level distributions of cobalt, calcium, nickel, and potassium were investigated using synchrotron-based X-ray fluorescence microscopy.$Results$The maximum foliar cobalt concentration reached 1200 ��g g$^{���1}$. Accumulation of cobalt competed with nickel accumulation although nickel seems to stimulate cobalt phloem translocation. Plants suffered toxicity in the treatment with the highest soil cobalt concentration. Cobalt and nickel have contrasting distribution patterns in the leaves of Rinorea cf. bengalensis, with cobalt mainly excreted on the surface of the leaves, whereas nickel is localised in foliar epidermal cells.$Conclusions$Rinorea cf. bengalensis can accumulate high concentrations of cobalt, but is intrinsically more tolerant to nickel. It does not rely on a similar sequestration mechanism for both metals, which could explain the lesser tolerance for cobalt. Nickel appears to be essential for the plant to tolerate high cobalt concentrations. Further studies intending to develop agronomic practices are needed to determine the viability of Rinorea cf. bengalensis for nickel-cobalt agromining., Published by Springer Science + Business Media B.V, Dordrecht [u.a.]

The fern Dicranopteris linearis (Gleicheniaceae) from China is a hyperaccumulator of rare earth element (REE), but little is known about the ecophysiology of REE in this species. This study aimed to clarify tissue-level and organ-level distribution of REEs via synchrotron-based X-ray fluorescence microscopy (XFM). The results show that REEs (La + Ce) are mainly colocalized with Mn in the pinnae and pinnules, with the highest concentrations in necrotic lesions and lower concentrations in veins. In the cross sections of the pinnules, midveins, rachis, and stolons, La + Ce and Mn are enriched in the epidermis, vascular bundles, and pericycle (midvein). In these tissues, Mn is localized mainly in the cortex and mesophyll. We hypothesize that the movement of REEs in the transpiration flow in the veins is initially restricted in the veins by the pericycle between vascular bundle and cortex, while excess REEs are transported by evaporation and cocompartmentalized with Mn in the necrotic lesions and epidermis in an immobile form, possibly a Si-coprecipitate. The results presented here provide insights on how D. linearis regulates high concentrations of REEs in vivo, and this knowledge is useful for developing phytotechnological applications (such as REE agromining) using this fern in REE-contaminated sites in China.

Aims Data on the variability of hyperaccumulation potential of the facultative serpentinophytes Noccaea kovatsii and N. praecox on different geological substrates are scarce. The aim of this study was to assess the accumulation potential of these two species from ultramafic and non-ultramafic substrates, with special emphasis on the hyperaccumulation of Ni, Zn and Cd. Methods Samples of plants and corresponding soils were collected from 16 sites covering a wide range of geochemistry. Elemental concentrations were determined in the roots, shoots and the rhizosphere soils. The pH, particle size distribution and content of organic matter were also determined in the soil samples. Results All ultramafic accessions of both species hyperaccumulated Ni with high intraspecific variability. Only one accession of N. kovatsii from a schist soil hyperaccumulated Zn, with also a high Cd accumulation. Accumulation and translocation of Ni in both species were much higher in the ultramafic accessions, whereas Zn accumulation and translocation was found in both ultramafic and non-ultramafic accessions. Conclusions Ni accumulation and translocation was restricted to ultramafic populations of both species, whereas it is a species-wide trait for Zn. This study provides new and comprehensive information on the natural variation of hyperaccumulation of Ni, Zn and Cd in N. kovatsii and N. praecox.

International audience; Gold mining generates trace elements in the environment that are often associated with adverse effects on human health. This study determines trace elements levels in water, soil and plants (Datura inoxia and Calotropis procera) in Komabangou area, the main artisanal gold mining site in Niger. The collected samples were pre-treated before trace element analysis by inductively coupled plasma mass spectrometry (ICP-MS) for soils samples and by inductively coupled plasma optical emission spectroscopy (ICP-OES) for waters and plants samples. For soils, concentrations reached up to 555 mg kg(-1) and 468 mg kg(-1) for As and Zn, respectively. In waters, highest levels were observed for Zn (540 mg L-1), followed in decreasing order by Cu (7.4 mg L-1) and Al (4.27 mg L-1). As and Zn concentrations were 134 mg kg(-1) and 388 mg kg(-1); 49 mg kg(-1) and 46 mg kg(-1) respectively in leaves of Datura inoxia and Calotropis procera from gold site, whereas As and Zn, represented only 0.56 mg kg(-1) and 0.48 mg kg(-1); 6.40 mg kg(-1) and 46 mg kg(-1) respectively in leaves of control species. In fact, results obtained revealed both contaminations by trace elements of soil and water for the majority of samples taken in gold zone with an exceeding of limit values recommended by WHO in particular for As, Cr, Ni, Pb and Zn. Therefore, the establishment of a monitoring and treatment program for polluted soils and waters in this gold zone would be necessary to preserve human health.

International audience; AimsThis study investigated the physico-geochemical properties of three types of ultramafic substrates in Sabah (Malaysia) and further characterised their influence on nickel (Ni) accumulation in two selected tropical ‘metal crops’ (Phyllanthus rufuschaneyi and Rinorea cf. bengalensis).MethodsThree experiments, consisting of a randomised block growth trial in large pots over 12 months in Sabah, were conducted: i) soil ratio experiment (Cambisol:Ferralsol:Leptosol), ii) soluble Ni dosing experiment with added 0, 60, 240, 600 mg Ni kg−1, and iii) soil pH adjustments (pH 5.2, 5.8 and 6.4) experiment.ResultsThe results show that the low pH status of Ferralsol did not result in increased extractable Ni concentrations, indicating that Ni-bearing phases and mineralogy play a major role in Ni extractability in these substrates. The increasing order of extractable Ni concentrations was Ferralsol < Leptosol < Cambisol. The selected ‘metal crops’ had remarkable shoot biomass (~40 g pot−1) and foliar Ni concentrations (>15 g kg−1 in P. rufuschaneyi) in the Cambisol, >5-fold higher relative to that recorded in Leptosol and Ferralsol. Mixing the Cambisol with the other substrates significantly improved Ni yield in both species relative to the individual substrates. The effect of Ni addition on the selected ‘metal crops’ was species-dependent, whereas reduction of soil pH in Cambisol significantly reduced Ni yield in both species.ConclusionsNickel accumulation patterns in ‘metal crops’ in response to the diverse ultramafic soils in the tropics are influenced by the physico-geochemical characteristics of the soil types. Soil Ni extractability in these soils is more dependent on the Ni-bearing phases and mineralogy rather than the pH status. This study provides useful information on plant-soil interactions required for identifying suitable substrates for implementing tropical Ni agromining.

International audience; PremiseHyperaccumulation of heavy metals in plants has never been documented from Central America or Mexico. Psychotria grandis, P. costivenia, and P. glomerata (Rubiaceae) have been reported to hyperaccumulate nickel in the Greater Antilles, but they also occur widely across the neotropics. The goals of this research were to investigate the geographic distribution of hyperaccumulation in these species and explore the phylogenetic distribution of hyperaccumulation in this clade by testing related species.MethodsPortable x‐ray fluorescence (XRF) spectroscopy was used to analyze 565 specimens representing eight species of Psychotria from the Missouri Botanical Garden herbarium.ResultsNickel hyperaccumulation was found in specimens of Psychotria costivenia ranging from Mexico to Costa Rica and in specimens of P. grandis from Guatemala to Ecuador and Venezuela. Among related species, nickel hyperaccumulation is reported for the first time in P. lorenciana and P. papantlensis, but no evidence of hyperaccumulation was found in P. clivorum, P. flava, or P. pleuropoda. Previous reports of hyperaccumulation in P. glomerata appear to be erroneous, resulting from taxonomic synonymy and specimen misidentification.ConclusionsHyperaccumulation of nickel by Psychotria is now known to occur widely from southern Mexico through Central America to northwestern South America, including some areas not known to have ultramafic soils. Novel aspects of this research include the successful prediction of new hyperaccumulator species based on molecular phylogeny, use of XRF technology to nondestructively obtain elemental data from herbarium specimens, and documentation of previously unknown areas of ultramafic or nickel‐rich soil based on such data.

Sabah (Malaysia) on the Island of Borneo has a high plant diversity (>8000 species) occurring on a wide range of soils, including ultramafic soils which are known to host hyperaccumulator plants. In this study a new approach (“Herbarium X-ray Fluorescence Ionomics”) was used to obtain elemental data from herbarium specimens using non-destructive X-ray Fluorescence spectroscopy analysis. In total ~7300 specimens were thus analysed for nickel, cobalt, and manganese concentrations at the Herbarium of the Forest Research Centre (FRC) in Sepilok, Sabah. The measurements led to recording a total of 759 specimens (originating from 17 families in 30 genera and 74 species) as trace element hyperaccumulators, including 28 nickel hyperaccumulator species (in 10 families, 17 genera), 12 cobalt hyperaccumulator species (in 3 families, 7 genera), and 51 manganese hyperaccumulator species (in 12 families, 24 genera). The outcomes of this research demonstrate that X-ray Fluorescence scanning is highly useful approach for hyperaccumulator plant discovery in herbarium collections that has the potential to add vast numbers of hyperaccumulating taxa to the global inventory.

Cette etude s’inscrit dans un projet de recherche portant sur l’evaluation des impacts environnementaux et sanitaires de l’orpaillage dans la zone de Komabangou au Niger. L’objectif est de determiner les niveaux de contamination des elements traces dans les sols et d'analyser leur distribution spatiale. Des echantillons des sols ont ete preleves en 2016 dans 27 localites dont 24 sur differents sites de la zone aurifere de Komabangou et 3 sur sites temoins. Les concentrations en elements traces (As, Cd, Co, Cr, Cu, Ni, Pb et Zn) dans les sols ont ete determinees par spectrometrie de masse avec plasma a couplage inductif (ICP-MS). La pollution des sols a ete evaluee en calculant les index de pollution (IP) des sols. Les resultats montrent que les concentrations en elements traces metalliques (ETM) dans les sols different en fonction du site et du metal considere. Les cartes de repartition spatiale montrent une importante concentration des elements traces tels que As, Cd, Pb et Zn au centre de la zone aurifere. Plusieurs de ces teneurs en ETM sont superieures aux seuils reglementaires. Aussi sur les 27 sites etudies, 12 ont des valeurs d’IP superieures a 1 revelant ainsi une contamination des sols par plusieurs elements. Ces resultats montrent une accumulation des metaux dans les sols qui peuvent persister dans l’environnement. Cela peut poser de serieux risques sanitaires pour l’Homme. Pour prevenir tout risque, un plan de surveillance de la contamination des sols devrait etre mis en place et il faudrait envisager de traiter les sites pollues. © 2019 International Formulae Group. All rights reserved. Mots cles : Orpaillage, sols, contamination, elements traces metalliques, valeurs limites, Komabangou, Niger. English Title : Spatial distribution of metallic trace elements in soils of Komabangou gold zone in Niger This study is part of research project on environmental and health impacts of gold mining in Komabangou area of Niger. The objective is to determine pollution levels of trace elements in soils and to analyze their spatial distribution. Soil samples were collected in 2016 at 27 localities, including 24 at different sites in Komabangou gold zone and 3 at control sites. Concentrations of trace elements (As, Cd, Co, Cr, Cu, Ni, Pb and Zn) in soils were determined by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Soil pollution was assessed by calculating soil pollution index (PI). The results show that metal trace element concentrations in soils differ depending to the site and the metal. Spatial distribution maps show a high concentration of trace elements such as As, Cd, Pb and Zn in the center of the gold zone. Many concentrations of trace elements in soils are above regulatory thresholds. Also, of the 27 sites studied, 12 have PI values greater than 1, revealing soil contamination by several elements. These results show an accumulation of metals in soils, which can persist in the environment. This can pose serious health risks for humans. To prevent any risk, soil contamination monitoring plan should be put in place and consideration should be given to treating polluted sites. Keywords : Gold panning, soils, contamination, trace elements, limit values, Komabangou, Niger.

Low soil fertility in ultramafic soils limits the efficiency of nickel phytoextraction. Developing more efficient cropping systems for agromining can be achieved by the association of a hyperaccumulator with a legume by enhancing soil fertility. However, legume crops can result sensitive to ultramafic soil conditions, including nickel Ni availability. We assessed here whether Lens culinaris is adapted to ultramafic environments by growing on soils displaying a wide range of Ni concentrations and consequently producing functional nodules. The soil was enriched with different Ni concentrations ([Ni]) (0–90 mg Ni kg 1). Natural 15N abundance was used to assess N2 fixation (%Ndfa). Biotic parameters were investigated (nodule number, Ni, carbon and nitrogen concentrations, plant biomass . . . ). Soil parameters were investigated (total [Ni], DTPA-extractable Ni, C and N concentrations . . . ). Most of the physicochemical and biological parameters were significantly affected by the increased soil [Ni]. Nodule numbers per plant was lower under high [Ni] than control (soil without Ni). Nodules lost their capacities to fix N2 under high Ni addition (90 mg Ni kg 1). For many parameters, there were no significant differences between control and treatments up to 60 mg of Ni kg 1 added to the soil. Lentil is able to grow on a soil containing amounts of Ni-DTPA similar to those generally found in serpentine soils. It could be used in association with a hyperaccumulator plant as a nitrogen provider in order to optimize Ni agromining.

On the basis of our previous field survey, we postulate that the pattern and degree of zinc (Zn) isotope fractionation in the Zn hyperaccumulator Noccaea caerulescens (J. & C. Presl) F. K. Mey may reflect a relationship between Zn bioavailability and plant uptake strategies. Here, we investigated Zn isotope discrimination during Zn uptake and translocation in N. caerulescens and in a nonaccumulator Thlaspi arvense L. with a contrasting Zn accumulation ability in response to low (Zn-L) and high (Zn-H) Zn supplies. The average isotope fractionations of the N. caerulescens plant as a whole, relative to solution (Δ(66)Znplant-solution), were -0.06 and -0.12‰ at Zn-L-C and Zn-H-C, respectively, indicative of the predominance of a high-affinity (e.g., ZIP transporter proteins) transport across the root cell membrane. For T. arvense, plants were more enriched in light isotopes under Zn-H-A (Δ(66)Znplant-solution = -0.26‰) than under Zn-L-A and N. caerulescens plants, implying that a low-affinity (e.g., ion channel) transport might begin to function in the nonaccumulating plants when external Zn supply increases. Within the root tissues of both species, the apoplast fractions retained up to 30% of Zn mass under Zn-H. Moreover, the highest δ(66)Zn (0.75‰-0.86‰) was found in tightly bound apoplastic Zn, pointing to the strong sequestration in roots (e.g., binding to high-affinity ligands/precipitation with phosphate) when plants suffer from high Zn stress. During translocation, the magnitude of isotope fractionation was significantly greater at Zn-H (Δ(66)Znroot-shoot = 0.79‰) than at Zn-L, indicating that fractionation mechanisms associated with root-shoot translocation might be identical to the two plant species. Hence, we clearly demonstrated that Zn isotope fractionation could provide insight into the internal sequestration mechanisms of roots when plants respond to low and high Zn supplies.

Phytomining, now called agromining, consists of growing hyperaccumulator plants in orderto farm metals and recover them from the biomass. This technology enables us to extractmetals from secondary resources (e.g. metal containing-soils, mineral wastes, polluted soils)and manufacture high-value products. It has proved feasible for nickel, since more than 400hyperaccumulators have been identified worldwide, able to accumulate at least 1% Ni intheir tissues. Moreover, Ni is a target metal with a relatively high economic value.We have recently designed and patented a method for the synthesis of a nickel salt,ammonium nickel sulfate hexahydrate (ANSH: Ni(NH4)2(SO4)2·6H2O), from the biomass ofthe hyperaccumulator plant Alyssum murale, grown in the Balkans. In this contribution, theprocess has been improved in order to save water, energy and chemicals, while producinga high purity salt. The biomass is dried and ashed, potassium is removed by washing ashwith pure water following a cross-current pathway, nickel is extracted by acid leaching (2 MH2SO4, 95◦C, 2 h, mass fraction of 10%). The leachate is neutralized by Ca(OH)2to reach a pHof 4–5 and magnesium is removed by precipitating MgF2after addition of NaF. Then volumeis reduced by evaporation and ANSH crystallization is run at 2◦C for 4 h. The crystals are dis-solved and a second crystallization is run. The final ANSH was characterized by combinedtechniques (ICP-AES, XRD and gravimetric analysis), and the purity was 99.1 ± 0.2%.

Nickel hyperaccumulators are a group of particular plant species which possess high efficient Ni uptake transport systems in their roots, the mechanisms of which however are far from being understood. Study on the interactions between nickel and other trace metals during root absorption process can provide insights into the Ni uptake patterns. Therefore, this work used model hyperaccumulator species Noccaea caerulescens to comprehensively assess the interaction between Ni and other trace metals (Zn, Fe, Mn, Cu and Co) during the root uptake process. Plants were grown in nutrient solutions containing different concentrations of Ni, Zn, Fe and Co, and the metal concentrations in roots and shoots were determined. Furthermore, the gene expression levels of Zn and Fe transporters were determined by quantitative real-time reverse transcriptase PCR. Results showed that Ni uptake could be severely suppressed by the presence of Zn or Co, while greatly stimulated by Zn or Fe deficiency. Iron uptake could be also stimulated by Ni exposure. In addition, the expression levels of the Zn transporter ZIP10 and the Fe transporter IRT1 were increased after Ni exposure. It could be concluded that the great competition between Ni and the non-essential element Co indicates that Ni uptake is mainly controlled by non-specific transporters. Nickel may be mainly taken up via Zn transporters, while Fe transporters also play a role for Ni absorption.

Agromining is the chain of processes of phytoextraction of economically valuable elements by selected hyperaccumulator plants, and subsequent processing of biomass to produce targeted metals or commercial compounds of high value. Although substantial unrealized opportunities exist for developing economic nickel (Ni) agromining in the tropics, this technology has remained relatively unexplored. This study investigated the soil chemistry of a newly established tropical ‘metal farm’ and elucidated the performance of a prospective ‘metal crop’ species (Phyllanthus rufuschaneyi) to be used in a large-scale tropical Ni agromining program on ultramafic soils in Sabah (Malaysia). We found that a major portion of the site (>90%) had high total Ni concentrations (>2000 μg g−1) in the soil (shallow Eutric Cambisol Magnesic). This study also recorded high phytoavailable soil Ni concentrations in the field site, which is a desired property of soils intended for Ni agromining. Moreover, the average soil pH of the field (pH 6.4) is ideal for maximum Ni uptake in the local candidate species. We recorded low concentrations of Ca, K and P, suggesting the need for a fertilizer regime in the farm. The extraordinary shoot Ni concentrations (>2 wt%), coupled with the high purity of the ‘bio-ore’ derived from Phyllanthus rufuschaneyi, confirm its high potential for economic Ni agromining. The success of our first field trial is critical to provide ‘real-life’ evidence of the value of large-scale tropical ‘metal farming’. Research priorities include the need to intensify the search for candidate species, determine their agronomy, develop mass propagation methods, and to test technologies to process the biomass to recover valuable products.

The fern Pteris vittata has been the subject of numerous studies because of its extreme arsenic hyperaccumulation characteristics. However, information on the arsenic chemical speciation and distribution across cell types within intact frozen-hydrated Pteris vittata fronds is necessary to better understand the arsenic biotransformation pathways in this unusual fern. While 2D X-ray absorption spectroscopy imaging studies show that different chemical forms of arsenic, As(III) and As(V), occur across the plant organs, depth-resolved information on arsenic distribution and chemical speciation in different cell types within tissues of Pteris vittata have not been reported. By using a combination of planar and confocal μ-X-ray fluorescence imaging and fluorescence computed μ-tomography, we reveal, in this study, the localization of arsenic in the endodermis and pericycle surrounding the vascular bundles in the rachis and the pinnules of the fern. Arsenic is also accumulated in the vascular bundles connecting into each sporangium, and in some mature sori. The use of 2D X-ray absorption near edge structure imaging allows for deciphering arsenic speciation across the tissues, revealing arsenate in the vascular bundles and arsenite in the endodermis and pericycle. This study demonstrates how different advanced synchrotron X-ray microscopy techniques can be complementary in revealing, at tissue and cellular levels, elemental distribution and chemical speciation in hyperaccumulator plants.

International audience; Surface mining or other disturbing operations on ultramafic outcrops degrade soil conditions and decrease major ecosystem functions in those habitats. Human disturbances exacerbate the harsh conditions of some ultramafic soils, making recovery more difficult. Recovery of ecosystem functions of disturbed areas may vary from passive to active reclamation measures, depending on the starting situation, available resources and expected outcomes. In this study, three treatments (topsoil application, topsoil + non-compacted, and topsoil + non-compacted + organic amendment), representing a gradient of increasing reclamation effort, were tested for the reclamation of a tropical ultramafic Spolic Technosol in Sabah (Malaysia). Soil treatments were tested at the mesocosm-scale for 12 months, and drainage water fluxes, evolution of soil physicochemical parameters, soil microbial activities and spontaneous plant colonisation, diversity and growth were monitored along the duration of the experiment. The results show that application of topsoil improved the plant biomass and water filtration functions in the non-reclaimed sites, with no additional benefit from lesser compaction. The most intensive treatment (topsoil + non-compacted + organic amendment) gave the best improvements in nutrient cycling and biomass production functions, but with a reduction of water filtration function, due to an increase in soluble concentrations and cumulative fluxes of nickel. Introduced species were dominant in the vegetation colonising the mesocosms, and therefore planting of selected native species will be necessary to create habitats for native biodiversity. This information will be useful to select a strategy for the recovery of degraded tropical serpentinite quarries and dump sites.

Soils derived from ultramafic bedrock are known for hosting distinct vegetation types as a consequence of atypical soil chemistries consisting of high trace elements concentrations (Ni, Cr, Co) and exchangeable cation imbalances (high Mg:Ca quotients); the high Mg:Ca ratio causes Ca infertility in plant species not adapted to ultramafic soils. Ecological studies use a range of single-stage extraction methods for chemical characterization of such soils in order to be able to interpret plant response, and ultimately to explain plant community composition. Few studies to date have compared different soil extraction methods in relation to tropical ultramafic soils. This study compares eight commonly used extraction methods on a large number of ultramafic soil samples collected from Kinabalu Park (Malaysia). The tested methods were: for trace elements: NH4Ac, DTPA, CaCl2, Sr(NO3)2 and Mehlich-3, for exchangeable cations: NH4Ac and silverthiorea, and for plant-available phosphorus: Mehlich-3 and Olsen-P. These single-stage extraction methods were compared and evaluated for predictive power for chemically characterizing soils, interrelatedness and ecological application. The methods were also contrasted with a sequential extraction scheme. Finally, several operational parameters including molar ratio (0.01 and 0.1 M CaCl2, Sr(NO3)2) and pH buffering (DTPA-TEA) were also evaluated. The majority of single-stage extraction methods are highly inter-correlated and predictive power could be improved by including independent soil parameters (pH, CEC, pseudo-total element concentration) in the multivariate regression equation. Ecological interpretation remains difficult because of lack of experimental studies in relation to plant uptake response and potential phytotoxicity effects on tropical native plants from ultramafic soils.

In Galicia (NW Spain), ultramafic outcrops represent approximately 5% of the land surface and several mining and quarrying activities take place in these areas. Resulting mine-soils present physical, chemical and biological properties which limit plant growth and soil functioning. Nickel phytomining, an eco-friendly strategy for metal recovery, could potentially be applied to these areas. A one-year field experiment was carried out in a serpentine quarry to evaluate the performance of four Ni hyperaccumulating plant species, comparing the Mediterranean spp. Bornmuellera emarginata and Odontarrhena muralis with the native populations of Noccaea caerulescens and Odontarrhena serpyllifolia. Field plots were established and amended with inorganic NPK fertilisers or composted sewage sludge. Three replicate plots (4 m2) were planted for each plant species and fertilisation regime. Amending with compost reduced pH from 7.8 to 6.6, and increased soil cation exchange capacity (CEC), nutrient concentrations and Ni availability. Moreover, compost-amended mine-soil presented higher microbial density and activity, parameters which were further stimulated by plant growth. Plant biomass production of all plant species was significantly higher in compost-amended soils than that after NPK fertilisation, being most pronounced for O. muralis and B. emarginata. Despite the reduction in shoot Ni concentrations observed in plants (except O. muralis) grown in compost-amended plots, the increased biomass production led to significantly higher Ni yields (in kg ha−1) in B. emarginata (2.9), N. caerulescens (1.9) and O. muralis (2.3). All plant species were able to establish and grow in the mine-soil (with the Mediterranean species showing a higher capacity for adaptation) and to generate moderate Ni yields. Nonetheless, the results highlight the need for further optimisation in order to enhance the Ni phytoextraction efficiency. Finally, the improvement in soil quality after compost amendment and plant growth support the idea that phytomining systems can be effective approaches for the rehabilitation of soils affected by quarrying operations after mine closure.

International audience; Ultramafic derived soils are characterized by low nutrient soils, a low Ca:Mg ratio, and high metal contents such as Ni, Co and Cr. The vegetation growing on these soils is highly adapted and includes both Ni hyperaccumulator and accumulator species. Today, approximately 530 Ni hyperaccumulator species are listed worldwide and the Ni concentration can be extremely high, e.g. up to 25% in latex from Pycnandra acuminata (Sapotaceae), a tree found in New Caledonia. The aim of this study is to identify the potential role of Ni hyperaccumulator plants in the Ni biogeochemical cycle at the soil surface by using Ni isotopes. A set of Ni hyperaccumulator and Ni accumulator plants as well as topsoils were sampled on the Barro Alto and Niquelândia ultramafic complexes (Goiás State, Brazil). Three Ni hyperaccumulator plants were collected: Justicia lanstyakii, Heliotropium aff. salicoides, Cnidoscolus aff. urens, as well as one Ni accumulator plant, Manihot sp. The isotopic compositions of the whole plants were determined and compared to those of the bulk topsoils and DTPA-extractable Ni. The topsoils exhibited δ60Ni values ranging from −0.30 ± 0.06‰ to 0.16 ± 0.05‰. The DTPA-extractable Ni in the topsoils ranged from 94 to 623 mg kg−1, i.e. 0.9–4.9% of the total soil Ni and was found to be isotopically heavier than the corresponding topsoil (from −0.30 ± 0.05‰ to 0.34 ± 0.08‰). The δ60Ni values for the Ni accumulator plants showed an enrichment in heavy Ni isotopes in the aerial parts of the plant compared to the roots, whereas similar δ60Ni values for the roots, stems and aerial parts suggested that no significant fractionation results from Ni uptake and translocation in Ni hyperaccumulator plants. Moreover, the aerial parts (i.e. leaves and flowers) from all of the plants analyzed showed the highest Ni concentrations and the heaviest δ60Ni values up to 1.21 ± 0.05‰. The enrichment in heavy Ni isotopes in the leaves (0.09 ± 0.06‰

International audience; Lateritic topsoils, which are usually removed and stored apart before mining operations take place, play an essential role in the success of post-mining restoration. They contain elements to recover chemical (organic matter, nutrients) and biological (seed and bud banks, microorganisms) fertility of the soil. Conserving topsoil fertility during storage time is essential for a successful use of topsoil during restoration. In this study, different chemico-mineralogical properties of a lateritic topsoil from the Goro nickel mine (New Caledonia) were monitored from its original in situ emplacement on the soil profile, immediately after its stockpiling and after 24 months of storage. Our analyses show that topsoil experienced noticeable changes immediately after storage, mostly produced by mixing of different soil profiles. Cation Exchange Capacities and concentrations of most elements did not vary even after 24 months of storage. However, a slight reduction of Ni, Cr, K, Na and of the C:N ratio, and an increase of Ca have been observed. Stockpiling has not affected negatively the chemical fertility of the topsoil, although biological parameters should be considered to have a complete view of stockpiling sustainability.

International audience; Ultramafic soils are typically enriched in nickel (Ni), chromium (Cr), and cobalt (Co) and deficient in essential nutrients, making them unattractive for traditional agriculture. Implementing agromining systems in ultramafic agricultural soils represent an ecological option for the sustainable management and re-valorisation of these low-productivity landscapes. These novel agroecosystems cultivate Ni-hyperaccumulating plants which are able to bioaccumulate this metal in their aerial plant parts; harvested biomass can be incinerated to produce Ni-enriched ash or “bio-ore” from which Ni metal, Ni ecocatalysts or pure Ni salts can be recovered. Nickel hyperaccumulation has been documented in ∼450 species, and in temperate latitudes these mainly belong to the family Brassicaceae and particularly to the genus Odontarrhena (syn. Alyssum pro parte). Agromining allows for sustainable metal recovery without causing the environmental impacts associated with conventional mining activities, and at the same time, can improve soil fertility and quality and provide essential ecosystem services. Parallel reductions in Ni phytotoxicity over time would also permit cultivation of conventional agricultural crops. Field studies in Europe have been restricted to Mediterranean areas and these only evaluated the Ni-hyperaccumulator Odontarrhena muralis s.l. Two recent EU projects (Agronickel and LIFE-Agromine) have established a network of agromining field sites in ultramafic regions with different edapho-climatic characteristics across Albania, Austria, Greece and Spain. Soil and crop management practices are being developed so as to Kidd et al. Sustainable Agromining Systems for Nickel Recovery optimize the Ni agromining process; field studies are evaluating the potential benefits of fertilization regimes, crop selection and cropping patterns, and bioaugmentation with plant-associated microorganisms. Hydrometallurgical processes are being up-scaled to produce nickel compounds and energy from hyperaccumulator biomass. Exploratory techno-economic assessment of Ni metal recovery by pyrometallurgical conversion of O. muralis s.l. shows promising results under the condition that heat released during incineration can be valorized in the vicinity of the processing facility.