Phytoaccumulation potential of nine plant species for selected nutrients, rare earth elements (REEs), germanium (Ge), and potentially toxic elements (PTEs) in soil.

Given the possible benefits of phytoextraction, this study evaluated the potential of nine plant species for phytoaccumulation/co-accumulation of selected nutrients, rare earth elements, germanium, and potentially toxic elements. Plants were grown on 2 kg potted soils for 12 weeks in a greenhouse, followed by a measurement of dry shoot biomass. Subsequently, elemental concentrations were determined using inductively coupled mass spectrometry, followed by the determination of amounts of each element accumulated by the plant species. Results show varying accumulation behavior among plants for the different elements. Fagopyrum esculentum and Cannabis sativa were better accumulators of most elements investigated except for chromium, germanium, and silicon that were better accumulated by Zea mays, the only grass species. F. esculentum accumulated 9, 24, and 10% of Copper, Chromium, and Rare Earth Elements in the mobile/exchangeable element fraction of the soils while Z. mays and C. sativa accumulated amounts of Cr and Ge ∼58 and 17% (for Z. mays) and 20 and 9% (for C. sativa) of the mobile/exchangeable element fraction of the soils. Results revealed co-accumulation potential for some elements e.g., (1) Si, Ge, and Cr, (2) Cu and Pb, (3) P, Ca, Co, and REEs based on chemical similarities/sources of origin.

This is a novel study because it focuses on evaluating plant species not only the accumulation behavior but the possibilities of co-accumulation of elements comprising selected nutrients, PTEs and CRMs (Ge and REEs) by plants. It provides new information on the biomass production and accumulation behavior of some plant species for some elements, some of which have not been previously studied. It also provides information on the possibility of predicting species accumulation behavior for some elements based on similarities in the source of origin, chemical similarities, or antagonism.

Effects of citric acid and the siderophore desferrioxamine B (DFO-B) on the mobility of germanium and rare earth elements in soil and uptake in Phalaris arundinacea.

Effects of citric acid and desferrioxamine B (DFO-B) on the availability of Ge and selected rare earth elements (REEs) (La, Nd, Gd, Er) to Phalaris arundinacea were investigated. A soil dissolution experiment was conducted to elucidate the effect of citric acid and DFO-B at different concentrations (1 and 10 mmol L-1 citric acid) on the release of Ge and REEs from soil. In a greenhouse, plants of P. arundinacea were cultivated on soil and on sand cultures to investigate the effects of citric acid and DFO-B on the uptake of Ge and REEs by the plants. Addition of 10 mmol L-1 citric acid significantly enhanced desorption of Ge and REEs from soil and uptake into soil-grown plants. Applying DFO-B enhanced the dissolution and the uptake of REEs, while no effect on Ge was observed. In sand cultures, the presence of citric acid and DFO-B significantly decreased the uptake of Ge and REEs, indicating a discrimination of the formed complexes during uptake. This study clearly indicates that citric acid and the microbial siderophore DFO-B may enhance phytoextraction of Ge and REEs due to the formation of soluble complexes that increase the migration of elements in the rhizosphere.

Effects of intercropping of oat (Avena sativa L.) with white lupin (Lupinus albus L.) on the mobility of target elements for phytoremediation and phytomining in soil solution.

This study aims to investigate how intercropping of oat (Avena sativa L.) with white lupin (Lupinus albus L.) affects the mobile fractions of trace metals (Fe, Mn, Pb, Cd, Th, U, Sc, La, Nd, Ge) in soil solution. Oat and white lupin were cultivated in monocultures and mixed cultures with differing oat/white lupin ratios (11% and 33% lupin, respectively). Temporal variation of soil solution chemistry was compared with the mobilization of elements in the rhizosphere of white lupin and concentrations in plant tissues. Relative to the monocrops, intercropping of oat with 11% white lupin significantly increased the concentrations of Fe, Pb, Th, La and Nd in soil solution as well as the concentrations of Fe, Pb, Th, Sc, La and Nd in tissues of oat. Enhanced mobility of the mentioned elements corresponded to a depletion of elements in the rhizosphere soil of white lupin. In mixed cultures with 33% lupin, concentrations in soil solution only slightly increased. We conclude that intercropping with 11% white lupin might be a promising tool for phytoremediation and phytomining research enhancing mobility of essential trace metals as well as elements with relevance for phytoremediation (Pb, Th) and phytomining (La, Nd, Sc) in soil.

Selenium Species and Fractions in the Rock-Soil-Plant Interface of Maize (Zea mays L.) Grown in a Natural Ultra-Rich Se Environment.

Selenium (Se) enrichments or deficiency in maize (Zea mays L.), one of the world's most important staple foods and livestock feeds, can significantly affect many people's diets, as Se is essential though harmful in excess. In particular, Se-rich maize seems to have been one of the factors that led to an outbreak of selenosis in the 1980s in Naore Valley in Ziyang County, China. Thus, this region's geological and pedological enrichment offers some insight into the behavior of Se in naturally Se-rich crops. This study examined total Se and Se species in the grains, leaves, stalks, and roots of 11 maize plant samples, Se fractions of soils around the rhizosphere, and representative parent rock materials from Naore Valley. The results showed that total Se concentrations in the collected samples were observed in descending order of soil > leaf > root > grain > stalk. The predominant Se species detected in maize plants was SeMet. Inorganic Se forms, mainly Se(VI), decreased from root to grain, and were possibly assimilated into organic forms. Se(IV) was barely present. The natural increases of Se concentration in soils mainly affected leaf and root dry-weight biomasses of maize. In addition, Se distribution in soils markedly correlated with the weathered Se-rich bedrocks. The analyzed soils had lower Se bioavailability than rocks, with Se accumulated predominantly as recalcitrant residual Se. Thus, the maize plants grown in these natural Se-rich soils may uptake Se mainly from the oxidation and leaching of the remaining organic-sulfide-bound Se fractions. A viewpoint shift from natural Se-rich soils as menaces to possibilities for growing Se-rich agricultural products is also discussed in this study.

Effect of substrate properties and phosphorus supply on facilitating the uptake of rare earth elements (REE) in mixed culture cropping systems of Hordeum vulgare, Lupinus albus and Lupinus angustifolius.

This study presents how phosphate (P) availability and intercropping may influence the migration of rare earth elements (REEs) in legume-grass associations. In a replacement model, Hordeum vulgare was intercropped with 11% Lupinus albus and 11% Lupinus angustifolius. They were cultivated on two substrates, A (pH = 7.8) and B (pH = 6.6), and treated with 1.5 g P m-2 or 3 g P m-2. Simultaneously, a greenhouse experiment was conducted to quantify carboxylate release. There, one group of L. albus and L. angustifolius was supplied with either 200 µmol L-1 P or 20 µmol L-1 P. L. albus released higher amounts of carboxylates at low P supply than L. angustifolius, while L. angustifolius showed the opposite response. Plants cultivated on substrate B accumulated substantially higher amounts of nutrients and REE, compared to substrate A. Higher P supply did not influence the leaf and stem P concentrations of H. vulgare. Addition of P decreased REE accumulation in barley monocultures on alkaline soil A. However, when H. vulgare was cultivated in mixed culture with L. angustifolius on alkaline substrate A with high P supply, the accumulation of REE in H. vulgare significantly increased. Conversely, on acidic substrate B, intercropping with L. albus decreased REE accumulation in H. vulgare. Our findings suggest a predominant effect of soil properties on the soil-plant transfer of REEs. However, in plant communities and within a certain soil environment, interspecific root interactions determined by species-specific strategies related to P acquisition in concert with the plant's nutrient supply impact REE fluxes between neighbouring plants.

Impact of Soil Inoculation with Bacillus amyloliquefaciens FZB42 on the Phytoaccumulation of Germanium, Rare Earth Elements, and Potentially Toxic Elements.

Bioaugmentation promises benefits for agricultural production as well as for remediation and phytomining approaches. Thus, this study investigated the effect of soil inoculation with the commercially available product RhizoVital®42, which contains Bacillus amyloliquefaciens FZB42, on nutrient uptake and plant biomass production as well as on the phytoaccumulation of potentially toxic elements, germanium, and rare earth elements (REEs). Zea mays and Fagopyrum esculentum were selected as model plants, and after harvest, the element uptake was compared between plants grown on inoculated versus reference soil. The results indicate an enrichment of B. amyloliquefaciens in inoculated soils as well as no significant impact on the inherent bacterial community composition. For F. esculentum, inoculation increased the accumulation of most nutrients and As, Cu, Pb, Co, and REEs (significant for Ca, Cu, and Co with 40%, 2042%, and 383%, respectively), while it slightly decreased the uptake of Ge, Cr, and Fe. For Z. mays, soil inoculation decreased the accumulation of Cr, Pb, Co, Ge, and REEs (significant for Co with 57%) but showed an insignificant increased uptake of Cu, As, and nutrient elements. Summarily, the results suggest that bioaugmentation with B. amyloliquefaciens is safe and has the potential to enhance/reduce the phytoaccumulation of some elements and the effects of inoculation are plant specific.

Secondary metabolites released by the rhizosphere bacteria Arthrobacter oxydans and Kocuria rosea enhance plant availability and soil-plant transfer of germanium (Ge) and rare earth elements (REEs).

Here, we explore effects of metallophore-producing rhizobacteria on the plant availability of germanium (Ge) and rare earth elements (REEs). Five isolates of the four species Rhodococcus erythropolis, Arthrobacter oxydans, Kocuria rosea and Chryseobacterium koreense were characterized regarding their production of element-chelators using genome-mining, LC-MS/MS analysis and solid CAS-assay. Additionally, a soil elution experiment was conducted in order to identify isolates that increase solubility of Ge and REEs in soil solution. A. oxydans ATW2 and K. rosea ATW4 released desferrioxamine-, bacillibactin- and surfactin-like compounds that mobilized Ge and REEs as well as P, Fe, Si and Ca in soil. Subsequently, oat, rapeseed and reed canary grass were cultivated on soil and sand and treated with cells and iron depleted culture supernatants of A. oxydans ATW2 and K. rosea ATW4. Inoculation increased plant yield and shoot phosphorus (P), manganese (Mn), Ge and REE concentrations. However, effects of the inoculation varied substantially between the growth substrates and plant species. On sand, A. oxydans ATW2 increased accumulation of REEs in all plant species and root-shoot translocation in rapeseed, while K. rosea ATW4 enhanced REE accumulation in rapeseed only, without effects on other plant species. Sand-cultured oat plants showed increased Ge accumulation and root-shoot translocation in presence of A. oxydans ATW2 cells and K. rosea ATW4 supernatant; however, there was no effect on other plant species, irrespective the growth substrate used. In contrast, soil-cultured rapeseed showed enhanced REE accumulation in presence of cells of A. oxydans ATW2 while there were no effects on other plant species and Ge. The processes involved are not yet fully understood. Nevertheless, we demonstrated that chemical microbe-soil-plant relationships influence plant availability of nutrients together with Ge and REEs, which has major implications on our understanding of biogeochemical element cycling and development of sustainable bioremediation and biomining technologies.

Open Access publishing practice in geochemistry: overview of current state and look to the future.

Open Access (OA) describes the free, unrestricted access to and re-use of research articles. Recently, a new wave of interest, debate, and practice surrounding OA publishing has emerged. In this paper, we provide a simple overview of the trends in OA practice in the broad field of geochemistry. Characteristics of the approach such as whether or not an article processing charge (APC) exists, what embargo periods or restrictions on self-archiving' policies are in place, and whether or not the sharing of preprints is permitted are described. The majority of journals have self-archiving policies that allow authors to share their peer reviewed work via green OA without charge. There is no clear relationship between journal impact and APC. The journals with the highest APC are typically those of the major commercial publishers, rather than the geochemistry community themselves. The rise in OA publishing has potential impacts on the profiles of researchers and tends to devolve costs from organizations to individuals. Until the geochemistry community makes the decision to move away from journal-based evaluation criteria, it is likely that such high costs will continue to impose financial inequities upon research community. However, geochemists could more widely choose legal self-archiving as an equitable and sustainable way to disseminate their research.

Cultivation dependent formation of siderophores by Gordonia rubripertincta CWB2.

Herein we demonstrate cultivation-dependent siderophore production by the actinomycete Gordonia rubripertincta CWB2. The strain produces mostly citrate, but also desferrioxamine E (DFOE) and new hydroxamate-type siderophores. The production of hydroxamate-like siderophores is influenced by cultivation conditions, for example available carbon sources or presence of metals, such as the rare earth erbium or the heavy metal lead. By cultivation with succinate and extraction with an adsorbing resin (XAD) we purified the G. rubripertincta CWB2 siderophores (yield up to 178 mg L-1). The respective workflow comprises genome mining, cultivation, and overproduction strategies, a rapid screening procedure, as well as traditional structure enrichment and structure elucidation methods. This combination of methods allows the discovery of new natural products with metal complexation capacity, also for lanthanides of commercial value. G. rubripertincta CWB2 carries a desferrioxamine-like biosynthetic gene cluster. Its transcription was proven by a transcriptomic approach comparing expression levels of the selected gene cluster during cultivation in iron-depleted and repleted media. Further investigation of the siderophores of this desferrioxamine producing Actinobacterium could lead to new structures.

Data on metal-chelating, -immobilisation and biosorption properties by Gordonia rubripertincta CWB2 in dependency on rare earth adaptation.

Recent studies have shown that the metal adaptation of Actinobacteria offers a rich source of metal inducible environmentally relevant bio-compounds and molecules. These interact through biosorption towards the unique cell walls or via metal chelating activity of metallophors with trace elements, heavy metals and even with lanthanides to overcome limitations and toxic concentrations. Herein, the purpose is to investigate the adaptation potential of Gordonia rubripertincta CWB2 in dependence of the rare earths and to determine if we can utilize promising metallophore metal affinities for metal separation from aquatic solutions. For details on data interpretation and applicability of siderophores we refer to the related article entitled "Cultivation dependent formation of siderophores by Gordonia rubripertincta CWB2" [1]. The respective workflow comprises a metal adaptation method to demonstrate effects on bacterial growth, pH, metallophore production, and metabolic change. All this was evaluated by LC-MS/MS and effects on biosorption of rare earths was verified by ICP-MS. Furthermore, we were able to carry out batch metal adsorption and desorption studies of metallophores entrapped in inorganic polymers of tetramethoxysilane (TMOS) to determine metal chelating capacities and selective enrichment effects from model solutions. The adaptation potential of strain CWB2 at increased erbium and manganese concentrations was verified by increased chelating activity on agar plates, in liquid assays and demonstrated by the successful enrichment of erbium by metallophore-functionalized TMOS-polymers from an aquatic model solution. Furthermore, the number of detected compounds in dependency of rare earths differ in spectral counts and diversity compared to the wild type. Finally, the biosorption of rare earths for the selected adaptation was increased significantly up to 2-fold compared to the wild-type. Overall a holistic approach to metal stress was utilised, integrating a bacterial erbium adaptation, metal chelating, biosorption of lanthanides and immobilization as well as enrichment of metals using metallophore functionalized inorganic TMOS polymers for separation of metals from aquatic model solutions.

Germanium in the soil-plant system-a review.

Germanium (Ge) is widespread in the Earth's crust. As a cognate element to silicon (Si), Ge shows very similar chemical characteristics. Recent use of Ge/Si to trace Si cycles and changes in weathering over time, growing demand for Ge as raw material, and consequently an increasing interest in Ge phytomining have contributed to a growing interest in this previously rather scarcely considered element in geochemical studies. This review deals with the distribution of Ge in primary minerals and surface soils as well as the factors influencing the mobility of Ge in soils including the sequestration of Ge in secondary mineral phases and soil organic matter. Furthermore, the uptake and accumulation of Ge in plants and effects of plant-soil relationships on the availability of Ge in soils and the biogeochemical cycling of Ge are discussed. The formation of secondary soil minerals and soil organic matter are of particular importance for the concentration of Ge in plant-available forms. The transfer from soil to plant is usually low and shows clear differences between species belonging to the functional groups of grasses and forbs. Possible uptake mechanisms in the rhizosphere are discussed. However, the processes that are involved in the formation of plant-available Ge pools in soils and consequently its biogeochemical cycling are not yet well understood. There is, therefore, a need for future studies on the uptake mechanisms and stoichiometry of Ge uptake under field conditions and plant-soil-microbe interactions in the rhizosphere as well as the chemical speciation in different plant parts.

Analysis of desferrioxamine-like siderophores and their capability to selectively bind metals and metalloids: development of a robust analytical RP-HPLC method.

The Actinobacterium Gordonia rubripertincta CWB2 (DSM 46758) produces hydroxamate-type siderophores (188 mg L-1) under iron limitation. Analytical reversed-phase HPLC allowed determining a single peak of ferric iron chelating compounds from culture broth which was confirmed by the Fe-CAS assay. Elution profile and its absorbance spectrum were similar to those of commercial (des)ferrioxamine B which was used as reference compound. This confirms previously made assumptions and shows for the first time that the genus Gordonia produces desferrioxamine-like siderophores. The reversed-phase HPLC protocol was optimized to separate metal-free and -loaded oxamines. This allowed to determine siderophore concentrations in solutions as well as metal affinity. The metal loading of oxamines was confirmed by ICP-MS. As a result, it was demonstrated that desferrioxamine prefers trivalent metal ions (Fe3+ > Ga3+ > V3+ > Al3+) over divalent ones. In addition, we aimed to show the applicability of the newly established reversed-phase HPLC protocol and to increase the re-usability of desferrioxamines as metal chelators by immobilization on mesocellular silica foam carriers. The siderophores obtained from strain CWB2 and commercial desferrioxamine B were successfully linked to the carrier with a high yield (up to 95%) which was verified by the HPLC method. Metal binding studies demonstrated that metals can be bound to non-immobilized and to the covalently linked desferrioxamines, but also to the carrier material itself. The latter was found to be unspecific and, therefore, the effect of the carrier material remains a field of future research. By means of a reversed CAS assay for various elements (Nd, Gd, La, Er, Al, Ga, V, Au, Fe, As) it was possible to demonstrate improved Ga3+- and Nd3+-binding to desferrioxamine loaded mesoporous silica carriers. The combination of the robust reversed-phase HPLC method and various CAS assays provides new avenues to screen for siderophore producing strains, and to control purification and immobilization of siderophores.