Desferrioxamine B Research Articles

Investigating a siderophore-based approach for the recovery of critical metals from waste streams and leach solutions using microorganisms

As technological advancements progress and unsustainable consumerism of electrical devices rapidly increases, the demand for critical metals continues to rise. The limited supply of these metals, driven by the depletion of non-renewable natural resources, calls for the recycling of waste materials and the development of sustainable and cost-effective extraction methods. Conventional methods of leaching such as pyrometallurgy pose threats to the environment by creating slags and releasing toxic secondary materials. Biohydrometallurgy emerges as an environmentally friendly method to extract metals from low-grade ores and waste material. Siderophores are secondary metabolites secreted by microorganisms that have the ability to selectively chelate certain metals. By immobilizing these siderophores for subsequent bioleaching, target metals can be extracted from multielement solutions. This research focuses on optimizing the immobilization efficiency of the siderophore desferrioxamine B (DFOB) in sodium alginate using physical entrapment for the removal of gallium. Four parameters were varied to find optimal conditions: sodium alginate concentration (1 – 4 % w/v), calcium chloride concentration (1 – 10% w/v), agitation time (0.25 – 10 hours), and DFOB concentration (1 – 4 mM). Using UV-Vis spectroscopy, free siderophore concentration could be determined. After 30 runs, the highest immobilization yield of 80.05% was determined at 2.5% sodium alginate, 10% calcium chloride—the highest concentration tested—after 5.13 hours with a concentration of 2.25 mM DFOB. Design Expert-13 software was used to analyze all experimental results. 2D graphs support that DFOB immobilization depends on responsive parameters, CaCl2 demonstrating the largest impact.

Efficient density functional theory directed identification of siderophores with increased selectivity towards indium and germanium

Siderophores are promising ligands for application in novel recycling and bioremediation technologies, as they can selectively complex a variety of metals. However, with over 250 known siderophores, the selection of suiting complexants in the wet lab is impractical. Thus, this study established a density functional theory (DFT) based approach to efficiently identify siderophores with increased selectivity towards target metals on the example of germanium and indium. Considering 239 structures, chemically similar siderophores were clustered, and their complexation reactions modeled utilizing DFT. The calculations revealed siderophores with, compared to the reference siderophore desferrioxamine B (DFOB), up to 128 % or 48 % higher selectivity for indium or germanium, respectively. Experimental validation of the method was conducted with fimsbactin A and agrobactin, demonstrating up to 40 % more selective indium binding and at least sevenfold better germanium binding than DFOB, respectively. The results generated in this study open the door for the utilization of siderophores in eco-friendly technologies for the recovery of many different critical metals from various industry waters and leachates or bioremediation approaches. This endeavor is greatly facilitated by applying the herein-created database of geometry-optimized siderophore structures as de novo modeling of the molecules can be omitted.

Synthesis and antibacterial properties under blue LED light of conjugates between the siderophore desferrioxamine B (DFOB) and an Iridium(III) complex

The decline of antibiotics efficacy worldwide has recently reached a critical point urging for the development of new strategies to regain upper hand on multidrug resistant bacterial strains. In this context, the raise of photodynamic therapy (PDT), initially based on organic photosensitizers (PS) and more recently on organometallic PS, offers promising perspectives. Many PS exert their biological effects through the generation of reactive oxygen species (ROS) able to freely diffuse into and to kill surrounding bacteria. Hijacking of the bacterial iron-uptake systems with siderophore-PS conjugates would specifically target pathogens. Here, we report the synthesis of unprecedented conjugates between the siderophore desferrioxamine B (DFOB) and an antibacterial iridium(III) PS. Redox properties of the new conjugates have been determined at excited states and compared to that of an antibacterial iridium PS previously reported by our groups. Tested on nosocomial pathogen Pseudomonas aeruginosa and other bacteria, these conjugates demonstrated significant inhibitory activity when activated with blue LED light. Ir(III) conjugate and iridium free DFOB-2,2′-dipyridylamine ligands were crystallized in complex with FoxA, the outer membrane transporter involved in DFOB uptake in P. aeruginosa and revealed details of the binding mode of these unprecedented conjugates.

Organic Ligand-Mediated Dissolution and Fractionation of Rare-Earth Elements (REEs) from Carbonate and Phosphate Minerals.

Global efforts to build a net-zero economy and the irreplaceable roles of rare-earth elements (REEs) in low-carbon technologies urge the understanding of REE occurrence in natural deposits, discovery of alternative REE resources, and development of green extraction technologies. Advancement in these directions requires comprehensive knowledge on geochemical behaviors of REEs in the presence of naturally prevalent organic ligands, yet much remains unknown about organic ligand-mediated REE mobilization/fractionation and related mechanisms. Herein, we investigated REE mobilization from representative host minerals induced by three representative organic ligands: oxalate, citrate, and the siderophore desferrioxamine B (DFOB). Reaction pH conditions were selected to isolate the ligand-complexation effect versus proton dissolution. The presence of these organic ligands displayed varied impacts, with REE dissolution remarkably enhanced by citrate, mildly promoted by DFOB, and showing divergent effects in the presence of oxalate, depending on the mineral type and reaction pH. Thermodynamic modeling indicates the dominant presence of REE-ligand complexes under studied conditions and suggests ligand-promoted REE dissolution to be the dominant mechanism, consistent with experimental data. In addition, REE dissolution mediated by these ligands exhibited a distinct fractionation toward heavy REE (HREE) enrichment in the solution phase, which can be mainly attributed to the formation of thermodynamically predicted more stable HREE-ligand complexes. The combined thermodynamic modeling and experimental approach provides a framework for the systematic investigation of REE mobilization, distribution, and fractionation in the presence of organic ligands in natural systems and for the design of green extraction technologies.

Chelating Effect of Siderophore Desferrioxamine-B on Uranyl Biomineralization Mediated by Shewanella putrefaciens.

In contaminated water and soil, little is known about the role and mechanism of the biometabolic molecule siderophore desferrioxamine-B (DFO) in the biogeochemical cycle of uranium due to complicated coordination and reaction networks. Here, a joint experimental and quantum chemical investigation is carried out to probe the biomineralization of uranyl (UO22+, referred to as U(VI) hereafter) induced by Shewanella putrefaciens (abbreviated as S. putrefaciens) in the presence of DFO and Fe3+ ion. The results show that the production of mineralized solids {hydrogen-uranium mica [H2(UO2)2(PO4)2·8H2O]} via S. putrefaciens binding with UO22+ is inhibited by DFO, which can both chelate preferentially UO22+ to form a U(VI)-DFO complex in solution and seize it from U(VI)-biominerals upon solvation. However, with Fe3+ ion introduced, the strong specificity of DFO binding with Fe3+ causes re-emergence of biomineralization of UO22+ {bassetite [Fe(UO2)2(PO4)2·8(H2O)]} by S. putrefaciens, owing to competitive complexation between Fe3+ and UO22+ for DFO. As DFO possesses three hydroxamic functional groups, it forms hexadentate coordination with Fe3+ and UO22+ ions via these functional groups. The stability of the Fe3+-DFO complex is much higher than that of U(VI)-DFO, resulting in some DFO-released UO22+ to be remobilized by S. putrefaciens. Our finding not only adds to the understanding of the fate of toxic U(VI)-containing substances in the environment and biogeochemical cycles in the future but also suggests the promising potential of utilizing functionalized DFO ligands for uranium processing.

Inactivation of siderophore iron-chelating moieties by the fungal wheat root symbiont Pyrenophora biseptata.

We investigated the ability of four plant and soil-associated fungi to modify or degrade siderophore structures leading to reduced siderophore iron-affinity in iron-limited and iron-replete cultures. Pyrenophora biseptata, a melanized fungus from wheat roots, was effective in inactivating siderophore iron-chelating moieties. In the supernatant solution, the tris-hydroxamate siderophore desferrioxamine B (DFOB) underwent a stepwise reduction of the three hydroxamate groups in DFOB to amides leading to a progressive loss in iron affinity. A mechanism is suggested based on the formation of transient ferrous iron followed by reduction of the siderophore hydroxamate groups during fungal high-affinity reductive iron uptake. P. biseptata also produced its own tris-hydroxamate siderophores (neocoprogen I and II, coprogen and dimerum acid) in iron-limited media and we observed loss of hydroxamate chelating groups during incubation in a manner analogous to DFOB. A redox-based reaction was also involved with the tris-catecholate siderophore protochelin in which oxidation of the catechol groups to quinones was observed. The new siderophore inactivating activity of the wheat symbiont P. biseptata is potentially widespread among fungi with implications for the availability of iron to plants and the surrounding microbiome in siderophore-rich environments.

Oxidation of Biogenic U(IV) in the Presence of Bioreduced Clay Minerals and Organic Ligands.

Bioreduction of soluble U(VI) to sparingly soluble U(IV) is proposed as an effective approach to remediating uranium contamination. However, the stability of biogenic U(IV) in natural environments remains unclear. We conducted U(IV) reoxidation experiments following U(VI) bioreduction in the presence of ubiquitous clay minerals and organic ligands. Bioreduced Fe-rich nontronite (rNAu-2) and Fe-poor montmorillonite (rSWy-2) enhanced U(IV) oxidation through shuttling electrons between oxygen and U(IV). Ethylenediaminetetraacetic acid (EDTA), citrate, and siderophore desferrioxamine B (DFOB) promoted U(IV) oxidation via complexation with U(IV). In the presence of both rNAu-2 and EDTA, the rate of U(IV) oxidation was between those in the presence of rNAu-2 and EDTA, due to a clay/ligand-induced change of U(IV) speciation. However, the rate of U(IV) oxidation in other combinations of reduced clay and ligands was higher than their individual ones because both promoted U(IV) oxidation. Unexpectedly, the copresence of rNAu-2/rSWy-2 and DFOB inhibited U(IV) oxidation, possibly due to (1) blockage of the electron transport pathway by DFOB, (2) inability of DFOB-complexed Fe(III) to oxidize U(IV), and (3) stability of the U(IV)-DFOB complex in the clay interlayers. These findings provide novel insights into the stability of U(IV) in the environment and have important implications for the remediation of uranium contamination.

Effects of iron concentration and DFB (Desferrioxamine-B) on transcriptional profiles of an ecologically relevant marine bacterium

Research into marine iron cycles and biogeochemistry has commonly relied on the use of chelators (including siderophores) to manipulate iron bioavailability. To test whether a commonly used chelator, desferrioxamine B (DFB) caused effects beyond changing the iron-status of cells, cultures of the environmentally relevant marine heterotrophic bacterium, Ruegeria pomeroyii, were grown in media with different concentrations of iron and/or DFB, resulting in a gradient of iron availability. To determine how cells responded, transcriptomes were generated for cells from the different treatments and analyzed to determine how cells reacted to these to perturbations. Analyses were also performed to look for cellular responses specific to the presence of DFB in the culture medium. As expected, cells experiencing different levels of iron availability had different transcriptomic profiles. While many genes related to iron acquisition were differentially expressed between treatments, there were many other genes that were also differentially expressed between different sample types, including those related to the uptake and metabolism of other metals as well as genes related to metabolism of other types of molecules like amino acids and carbohydrates. We conclude that while DFB certainly altered iron availability to cells, it also appears to have had a general effect on the homeostasis of other metals as well as influenced metabolic processes outside of metal acquisition.

Ligand exchange provides new insight into the role of humic substances in the marine iron cycle

Organic complexation of iron plays a crucial role in preventing its precipitation, facilitating its transport, and modulating its reactivity and bioavailability in natural waters. Although humic substances (HS) complexes serve as the primary source of terrestrial iron reaching ocean waters, the transition from Fe-HS species to other forms of organic complexation with ocean autochthonous ligands has not yet been properly described. Taking advantage of the electrolability of Fe-HS complexes, we monitored the ligand exchange of iron-saturated Suwannee River fulvic and humic acids (SRFA and SRHA) after the addition of desferrioxamine B (DFOB) and other ligands for comparison. We observed that Fe-HS concentrations gradually decreased until reaching an apparent steady state, typical of a reversible reaction within 1 to 15 h. The dissociation kinetics and species partitioning of Fe-SRHS complexes at the equilibrium showed some features contrary to the current paradigm of HS iron complexation. The affinity of SRFA to bind iron is close to that of DFOB and for SRHA is even higher. The heterogeneity of the HS iron binding groups was confirmed, although experiments in NaCl solutions revealed that in seawater it is substantially caused by the interaction of major divalent ions. The different dissociation kinetics of Fe-SRHS complexes obtained with different competing ligands and the absence of Fe-DFOB dissociation in the presence of iron-free SRFA indicate an intimate associative mechanism of ligand exchange, with the presence of a ternary complex (SRHS-Fe-DFOB) that does not form if the departing complex is Fe-DFOB. We hypothesize that at the concentrations of HS and siderophores found in the open ocean, iron ligand exchange is limited and organic iron speciation will be close to being regulated on a “first come, first served” basis. Experiments conducted under saturation of all iron complexes support the formation of a permanent concentration of a ternary complex. Our findings show the real complexity of cation-ligand interactions in seawater, with implications for the interpretation of recent chromatographic and electrochemical measurements and for the understanding of iron partitioning in the presence of ubiquitous HS.

A Preliminary Sorption Study of Uranium on MnO2 (Pyrolusite) in the Presence of Siderophore Desferrioxamine B—The Mechanism of a Ternary System

Manganese oxides have influential sorptive properties to efficiently sequester metals, such as uranium. Sorption can become complicated by metal chelating siderophores, which create a ternary system that is capable of multiple feasible mechanisms. This study analyzes the sorption behavior of desferrioxamine B (DFOB) and desferrioxamine D (DFOD) onto pyrolusite, β-MnO2, in the presence of U(VI) at pHs 6 and 8. The electrostatic adsorption performance is shown to have a 23% difference between the DFOB and DFOD surface sorption at pH 6. Inner-sphere coordination was identified through hydrolysis products of succinate and acetate. Together, these behaviors indicate a ternary complex system where both metals and ligands interact with the surface. Therefore, uranium in the environment can be attenuated by the conditions of a complex configuration involving multiple species and functional groups. This mechanism needs to be considered for any future modeling or strategies involving radionuclide remediation.

Reversible Covalent Binding of Desferrioxamine B (DFOB) to Polystyrene Microspheres for the Chelation of Aqueous Iron Citrate

Reversible Covalent Binding of Desferrioxamine B (DFOB) to Polystyrene Microspheres for the Chelation of Aqueous Iron Citrate

Trace metal dissolution kinetics of East Asian size-fractionated aerosols in seawater: The effect of a model siderophore

Aerosol soluble metals are considered bioavailable to marine phytoplankton and may influence phytoplankton growth, their community structure, and material cycling in the ocean. The dissolution is controlled by the physical and chemical properties of aerosols and various atmospheric, physical, and biogeochemical processes before and after depositing in the surface water. Among these complicated processes, the interaction of aerosol metals with organic ligands in seawater is one of the major factors. In this study, we systematically investigated the dissolution kinetics of trace metals from fine (0.45–0.95 μm) and coarse (>7.2 μm) aerosols in seawater for 30 days under conditions with or without adding a model Fe organic ligand, siderophore desferrioxamine B (DFB). We found that most of the soluble metals in the fine aerosols were leached rapidly within the first hour. In terms of the coarse aerosols, with DFB addition, the fractional solubility of Fe increased substantially from 0.1 to 10%, and the solubilities of most other metals generally increased by about 2-fold within 30 days. Without DFB addition, we found that most soluble metals were still gradually released over time in coarse aerosols, except particle-reactive metals, Fe and Pb. We further observed strong linear correlations between dissolved metals (Al, Fe, Mn, Co, Ni, and Zn) and silicate concentrations for DFB addition with coarse aerosols, with metal to silicate ratios comparable to those of typical aluminosilicates. Quantitatively, the aluminosilicate-associated dissolved metals accounted for >85% of total dissolved Fe, Al, and Co, and 40–60% for total dissolved Mn and Ni with the addition of DFB for 30 days. By comparing dissolved metal to Al ratios with lithogenic ratios, the metals leached in the first hour for both coarse and fine aerosols originated from anthropogenic sources, and lithogenic aerosols gradually became the dominant soluble metal source for coarse aerosols after 1 h, extending to 720 h. The findings of this study exhibit the importance of the time-dependent interaction of lithogenic aerosols with organic ligands in seawater. The residence time of aerosol particles and the concentrations of available organic ligands in the euphotic zone are key factors affecting aerosol dissolved metal availability to marine phytoplankton in the surface ocean.

Synthesis of Modular Desferrioxamine Analogues and Evaluation of Zwitterionic Derivatives for Zirconium Complexation.

The natural siderophore desferrioxamine B (DFOB) has been used for targeted PET imaging with 89 Zr before. However, Zr-DFOB has a limited stability and a number of derivatives have been developed with improved chelation properties for zirconium. We describe the synthesis of pseudopeptidic analogues of DFOB with azido side chains. These are termed AZA-DFO (hexadentate) and AZA-DFO* (octadentate) and are assembled via a modular synthesis from Orn-β-Ala and Lys-β-Ala. Nine different chelators have been conjugated to zwitterionic moieties by copper-catalyzed azide-alkyne cycloaddition (CuAAC). The resulting water-soluble chelators form Zr complexes under mild conditions (room temperature for 90 min). Transchelation assays with 1000-fold excess of EDTA and 300-fold excess of DFOB revealed that a short spacing of hydroxamates in (Orn-β-Ala)3-4 leads to improved complex stability compared to a longer spacing in (Lys-β-Ala)3-4 . We found that the alignment of amide groups in the pseudopeptide backbone and the presence of zwitterionic sidechains did not compromise the stability of the Zr-complexes with our chelators. We believe that the octadentate derivative AZA-DFO* is particularly valuable for the preparation of new Zr-chelators for targeted imaging which combine tunable pharmacokinetic properties with high complex stability and fast Zr-complexation kinetics.

Siderophore-Mediated Mobilization of Manganese Limits Iron Solubility in Mixed Mineral Systems.

Recent laboratory and field studies show the need to consider the formation of aqueous Mn(III)-siderophore complexes in manganese (Mn) and iron (Fe) geochemical cycling, a shift from the historical view that aqueous Mn(III) species are unstable and thus unimportant. In this study, we quantified Mn and Fe mobilization by desferrioxamine B (DFOB), a terrestrial bacterial siderophore, in single (Mn or Fe) and mixed (Mn and Fe) mineral systems. We selected manganite (γ-MnOOH), δ-MnO2, lepidocrocite (γ-FeOOH), and 2-line ferrihydrite (Fe2O3·0.5H2O) as relevant mineral phases. We found that DFOB mobilized Mn(III) as Mn(III)-DFOB complexes to varying extents from both Mn(III,IV) oxyhydroxides but reduction of Mn(IV) to Mn(III) was required for the mobilization of Mn(III) from δ-MnO2. The initial rates of Mn(III)-DFOB mobilization from manganite and δ-MnO2 were not affected by the presence of lepidocrocite but decreased by a factor of 5 and 10 for manganite and δ-MnO2, respectively, in the presence of 2-line ferrihydrite. Additionally, the decomposition of Mn(III)-DFOB complexes through Mn-for-Fe ligand exchange and/or ligand oxidation led to Mn(II) mobilization and Mn(III) precipitation in the mixed-mineral systems (∼10% (mol Mn/mol Fe)). As a result, the concentration of Fe(III) mobilized as Fe(III)-DFOB decreased by up to 50% and 80% in the presence of manganite and δ-MnO2, respectively, compared to the single mineral systems. Our results demonstrate that siderophores, through their complexation of Mn(III), reduction of Mn(III,IV), and mobilization of Mn(II), can redistribute Mn to other soil minerals and limit the bioavailability of Fe in natural systems.

Desferrioxamine B: Investigating the Efficacy of Hydrogels and Ethanol Gels for Removing Akaganeite and Maghemite from Dry Wooden Substrates

Cultural heritage (CH) wooden artifacts are often stained by iron oxides/hydroxy-oxides, which may have detrimental effects on wood. Their removal is a common conservation practice, and it is usually achieved with non-eco-friendly chelators, such as ethylene diamine tetra acetic acid (EDTA) and diethylene triamine penta acetic acid (DTPA). Siderophores are green materials that have been recently explored as chelators, given the currently growing environmental concerns. This work investigated desferrioxamine B (DFO-B), a promising siderophore that has not been adequately studied for its potential in removing ferric oxides/hydroxy-oxides from dry CH wooden substrates. Mock-ups of maple (Acer platanoides L.) were artificially stained with akaganeite and maghemite, and DFO-B was employed via hydrogels (pH: 6.5 and 8.6) and ethanol gels. The chelator efficacy was assessed using Energy-Dispersive Spectroscopy (EDS), Attenuated Total Reflection–Fourier Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (SEM) and colorimetry. The hydrogels’ impact on the wood was also assessed using ATR-FTIR and colorimetry. The obtained results demonstrate that the most effective DFO-B formulation was the alkaline hydrogel (pH 8.6), followed by the acidic (pH 6.5) hydrogel and the DFO-B ethanol gel. No differences in wood chemistry or color were recorded when using pH 6.5 or 8.6. The DFO-B ethanol gels were also proven to be potential alternatives to hydrogels for use with water-sensitive CH substrates.

Reduction-cleavable desferrioxamine B pulldown system enriches Ni(ii)-superoxide dismutase from a Streptomyces proteome.

Two resins with the hydroxamic acid siderophore desferrioxamine B (DFOB) immobilised as a free ligand or its Fe(iii) complex were prepared to screen the Streptomyces pilosus proteome for proteins involved in siderophore-mediated Fe(iii) uptake. The resin design included a disulfide bond to enable the release of bound proteins under mild reducing conditions. Proteomics analysis of the bound fractions did not identify proteins associated with siderophore-mediated Fe(iii) uptake, but identified nickel superoxide dismutase (NiSOD), which was enriched on the apo-DFOB-resin but not the Fe(iii)-DFOB-resin or the control resin. While DFOB is unable to sequester Fe(iii) from sites deeply buried in metalloproteins, the coordinatively unsaturated Ni(ii) ion in NiSOD is present in a surface-exposed loop region at the N-terminus, which might enable partial chelation. The results were consistent with the notion that the apo-DFOB-resin formed a ternary complex with NiSOD, which was not possible for either the coordinatively saturated Fe(iii)-DFOB-resin or the non-coordinating control resin systems. In support, ESI-TOF-MS measurements from a solution of a model Ni(ii)-SOD peptide and DFOB showed signals that correlated with a ternary Ni(ii)-SOD peptide-DFOB complex. Although any biological implications of a DFOB-NiSOD complex are unclear, the work shows that the metal coordination properties of siderophores might influence an array of metal-dependent biological processes beyond those established in iron uptake.

Cr(VI) Reduction by Siderophore Alone and in Combination with Reduced Clay Minerals.

Siderophores and iron-containing clays are known to influence the transformation of chromium in the environment. The role of clays in hexavalent chromium [Cr(VI)] reduction has been reported extensively. However, the mechanisms of Cr(VI) reduction by siderophores and their combination with iron-bearing clays are poorly known. Herein, we report the kinetics and products of Cr(VI) reduction by a siderophore alone or in combination with reduced clays. Results showed that Cr(VI) reduction by a tri-hydroxamate siderophore─desferrioxamine B (DFOB)─at a pH of 6 was achieved by one-electron transfer via the formation of Cr(V) intermediate. The formed Cr(V) was further reduced to organically complexed Cr(III). The Cr(VI) reduction rate and extent in the presence of both DFOB and reduced clays unexpectedly decreased relative to that with reduced clays alone, despite both serving as Cr(VI) reductants. The interaction between DFOB and clays (e.g., adsorption/intercalation, dissolution, and/or oxidation) was primarily responsible for Cr(VI) reduction inhibition. The extent of inhibition increased at higher DFOB concentrations in the presence of iron-rich nontronite but decreased in the presence of iron-poor montmorillonite, which may be related to their different Cr(VI) reduction mechanisms. This study highlights the importance of siderophores in chromium transformation and its impact on the reactivity of iron-bearing clays toward heavy metal reduction in the environment.

Impact of biogenic exudates on the dissolution and browning of stained glass windows

The browning phenomenon is a pathology affecting Mn-bearing medieval stained-glass-windows in potash-lime-silicate glass system. In order to unravel the potential implication of microorganisms in the appearance of this pathology, three model glasses respectively containing no MnO, 1 wt% and 2 wt% MnO were altered at circumneutral pH, with and without organic exudates (oxalic acid (OA) 1000 μM and siderophore desferrioxamine B (DFOB) 50–1000 μM) likely to be produced by bacteria and fungi. In the absence of exudates, the dissolution rates are inversely dependent on the Mn content of the glasses (0.8, 0.5 and 0.4 g m−2d−1 respectively for no MnO, 1 wt% and 2 wt% MnO glasses). In contact with exudates, an opposite trend is observed. The prevalent mechanisms are interpreted as a strong ligand-promoted dissolution for DFOB (dissolution rate increase up to 270%) and a dominant proton-promoted dissolution for OA (dissolution rate increase up to 60%). When DFOB and OA are added together, the effect of DFOB on the dissolution rate is prevailing, while OA effect is tangible on the stoichiometry of the dissolution of the alteration. These results suggest that an indirect biological activity could be involved in the mobilization of Mn from a Mn-bearing glass, thus playing a role in the appearance of the browning phenomenon.

Ligand-Induced U Mobilization from Chemogenic Uraninite and Biogenic Noncrystalline U(IV) under Anoxic Conditions.

Microbial reduction of soluble hexavalent uranium (U(VI)) to sparingly soluble tetravalent uranium (U(IV)) has been explored as an in situ strategy to immobilize U. Organic ligands might pose a potential hindrance to the success of such remediation efforts. In the current study, a set of structurally diverse organic ligands were shown to enhance the dissolution of crystalline uraninite (UO2) for a wide range of ligand concentrations under anoxic conditions at pH 7.0. Comparisons were made to ligand-induced U mobilization from noncrystalline U(IV). For both U phases, aqueous U concentrations remained low in the absence of organic ligands (<25 nM for UO2; 300 nM for noncrystalline U(IV)). The tested organic ligands (2,6-pyridinedicarboxylic acid (DPA), desferrioxamine B (DFOB), N,N′-di(2-hydroxybenzyl)ethylene-diamine-N,N′-diacetic acid (HBED), and citrate) enhanced U mobilization to varying extents. Over 45 days, the ligands mobilized only up to 0.3% of the 370 μM UO2, while a much larger extent of the 300 μM of biomass-bound noncrystalline U(IV) was mobilized (up to 57%) within only 2 days (>500 times more U mobilization). This work shows the potential of numerous organic ligands present in the environment to mobilize both recalcitrant and labile U forms under anoxic conditions to hazardous levels and, in doing so, undermine the stability of immobilized U(IV) sources.

Contrasting effects of siderophores pyoverdine and desferrioxamine B on the mobility of iron, aluminum, and copper in Cu-contaminated soils

Siderophores are biogenic metallophores that can play significant roles in the dynamics of a range of metals, including Cu, in the soil. Understanding the impact of siderophores on the mobility and the availability of metals in soil is required to optimize the efficiency of soil remediation processes such as phytoextraction. This study compared the ability of siderophores desferrioxamine B (DFOB) and pyoverdine (Pvd) to mobilize metals in a series of Cu-contaminated soils, and investigated the extent their metal mobilization efficiency changed over time and with the level of Cu contamination of the soil. Siderophores were supplied (or not) to Cu-contaminated soils and metal mobility was assessed through their total concentration in 0.005 M CaCl2 extract. DFOB selectively mobilized Fe and Al while Pvd also mobilized Cu and Ni, Co, V and As but to a lesser degree. The 1:1 relationship between DFOB in the CaCl2 extract and Fe + Al mobilized from the solid phase suggests that DFOB mobilized metals by ligand-controlled dissolution. The accumulation of Cu in soil enhanced the adsorption of DFOB and Pvd at the surface of soil constituents and the mobilization of Fe to the detriment of Al by the two siderophores. The metal mobilization efficiency of DFOB and to a lesser extent of Pvd decreased over 22 days. According to 15N-Pvd analyses, Pvd degradation at least partly contributed to the progressive reduction in the metal mobilization efficiency of Pvd. The processes behind these results and the relevance of these results for manipulating the availability of Cu (and Fe) in soil are discussed.