Strategies for optimizing biovivianite production using dissimilatory Fe(III)-reducing bacteria.

Vivianite (Fe3(PO4)2·8H2O), a sink for phosphorus, is a key mineralization product formed during the microbial reduction of phosphate-containing Fe(III) minerals in natural systems, and also in wastewater treatment where Fe(III)-minerals are used to remove phosphate. As biovivianite is a potentially useful Fe and P fertiliser, there is much interest in harnessing microbial biovivianite synthesis for circular economy applications. In this study, we investigated the factors that influence the formation of microbially-synthesized vivianite (biovivianite) under laboratory batch systems including the presence and absence of phosphate and electron shuttle, the buffer system, pH, and the type of Fe(III)-reducing bacteria (comparing Geobacter sulfurreducens and Shewanella putrefaciens). The rate of Fe(II) production, and its interactions with the residual Fe(III) and other oxyanions (e.g., phosphate and carbonate) were the main factors that controlled the rate and extent of biovivianite formation. Higher concentrations of phosphate (e.g., P/Fe = 1) in the presence of an electron shuttle, at an initial pH between 6 and 7, were needed for optimal biovivianite formation. Green rust, a key intermediate in biovivianite production, could be detected as an endpoint alongside vivianite and metavivianite (Fe2+Fe3+2(PO4)2.(OH)2.6H2O), in treatments with G. sulfurreducens and S. putrefaciens. However, XRD indicated that vivianite abundance was higher in experiments containing G. sulfurreducens, where it dominated. This study, therefore, shows that vivianite formation can be controlled to optimize yield during microbial processing of phosphate-loaded Fe(III) materials generated from water treatment processes.

Bioproduction of cerium-bearing magnetite and application to improve carbon-black supported platinum catalysts.

BACKGROUND: Biogeochemical processing of metals including the fabrication of novel nanomaterials from metal contaminated waste streams by microbial cells is an area of intense interest in the environmental sciences. RESULTS: Here we focus on the fate of Ce during the microbial reduction of a suite of Ce-bearing ferrihydrites with between 0.2 and 4.2 mol% Ce. Cerium K-edge X-ray absorption near edge structure (XANES) analyses showed that trivalent and tetravalent cerium co-existed, with a higher proportion of tetravalent cerium observed with increasing Ce-bearing of the ferrihydrite. The subsurface metal-reducing bacterium Geobacter sulfurreducens was used to bioreduce Ce-bearing ferrihydrite, and with 0.2 mol% and 0.5 mol% Ce, an Fe(II)-bearing mineral, magnetite (Fe(II)(III)2O4), formed alongside a small amount of goethite (FeOOH). At higher Ce-doping (1.4 mol% and 4.2 mol%) Fe(III) bioreduction was inhibited and goethite dominated the final products. During microbial Fe(III) reduction Ce was not released to solution, suggesting Ce remained associated with the Fe minerals during redox cycling, even at high Ce loadings. In addition, Fe L2,3 X-ray magnetic circular dichroism (XMCD) analyses suggested that Ce partially incorporated into the Fe(III) crystallographic sites in the magnetite. The use of Ce-bearing biomagnetite prepared in this study was tested for hydrogen fuel cell catalyst applications. Platinum/carbon black electrodes were fabricated, containing 10% biomagnetite with 0.2 mol% Ce in the catalyst. The addition of bioreduced Ce-magnetite improved the electrode durability when compared to a normal Pt/CB catalyst. CONCLUSION: Different concentrations of Ce can inhibit the bioreduction of Fe(III) minerals, resulting in the formation of different bioreduction products. Bioprocessing of Fe-minerals to form Ce-containing magnetite (potentially from waste sources) offers a sustainable route to the production of fuel cell catalysts with improved performance.

Copper bioreduction and nanoparticle synthesis by an enrichment culture from a former copper mine.

Microorganisms can facilitate the reduction of Cu2+ , altering its speciation and mobility in environmental systems and producing Cu-based nanoparticles with useful catalytic properties. However, only a few model organisms have been studied in relation to Cu2+ bioreduction and little work has been carried out on microbes from Cu-contaminated environments. This study aimed to enrich for Cu-resistant microbes from a Cu-contaminated soil and explore their potential to facilitate Cu2+ reduction and biomineralisation from solution. We show that an enrichment grown in a Cu-amended medium, dominated by species closely related to Geothrix fermentans, Azospira restricta and Cellulomonas oligotrophica, can reduce Cu2+ with subsequent precipitation of Cu nanoparticles. Characterisation of the nanoparticles with (scanning) transmission electron microscopy, energy-dispersive x-ray spectroscopy and electron energy loss spectroscopy supports the presence of both metallic Cu(0) and S-rich Cu(I) nanoparticles. This study provides new insights into the diversity of microorganisms capable of facilitating copper reduction and highlights the potential for the formation of distinct nanoparticle phases resulting from bioreduction or biomineralisation reactions. The implications of these findings for the biogeochemical cycling of copper and the potential biotechnological synthesis of commercially useful copper nanoparticles are discussed.

Microbial Reduction of Antimony(V)-Bearing Ferrihydrite by Geobacter sulfurreducens.

The reduction of Sb(V)-bearing ferrihydrite by Geobacter sulfurreducens was studied to determine the fate of the metalloid in Fe-rich systems undergoing redox transformations. Sb(V) added at a range of concentrations adsorbed readily to ferrihydrite, and the loadings had a pronounced impact on the rate and extent of Fe(III) reduction and the products formed. Magnetite dominated at low (0.5 and 1 mol%) Sb(V) concentrations, with crystallite sizes decreasing at higher Sb loadings: 37-, 25-, and 17-nm particles for no-Sb, 0.5% Sb, and 1% Sb samples, respectively. In contrast, goethite was the dominant end product for samples with higher antimony loadings (2 and 5 mol%), with increased goethite grain size in the 5% Sb sample. Inductively coupled mass spectrometry (ICP-MS) analysis confirmed that Sb was not released to solution during the bioreduction process, and X-ray photoelectron spectroscopy (XPS) analyses showed that no Sb(III) was formed throughout the experiments, confirming that the Fe(III)-reducing bacterium Geobacter sulfurreducens cannot reduce Sb(V) enzymatically or via biogenic Fe(II). These findings suggest that Fe (bio)minerals have a potential role in limiting antimony pollution in the environment, even when undergoing redox transformations. IMPORTANCE Antimony is an emerging contaminant that shares chemical characteristics with arsenic. Metal-reducing bacteria (such as Geobacter sulfurreducens) can cause the mobilization of arsenic from Fe(III) minerals under anaerobic conditions, causing widespread contamination of aquifers worldwide. This research explores whether metal-reducing bacteria can drive the mobilization of antimony under similar conditions. In this study, we show that G. sulfurreducens cannot reduce Sb(V) directly or cause Sb release during the bioreduction of the Fe(III) mineral ferrihydrite [although the sorbed Sb(V) did alter the Fe(II) mineral end products formed]. Overall, this study highlights the tight associations between Fe and Sb in environmental systems, suggesting that the microbial reduction of Fe(III)/Sb mineral assemblages may not lead to Sb release (in stark contrast to the mobilization of As in iron-rich systems) and offers potential Fe-based remediation options for Sb-contaminated environments.

Biomineralization of Cu2S Nanoparticles by Geobacter sulfurreducens.

Biomineralization of Cu has been shown to control contaminant dynamics and transport in soils. However, very little is known about the role that subsurface microorganisms may play in the biogeochemical cycling of Cu. In this study, we investigate the bioreduction of Cu(II) by the subsurface metal-reducing bacterium Geobacter sulfurreducens Rapid removal of Cu from solution was observed in cell suspensions of G. sulfurreducens when Cu(II) was supplied, while transmission electron microscopy (TEM) analyses showed the formation of electron-dense nanoparticles associated with the cell surface. Energy-dispersive X-ray spectroscopy (EDX) point analysis and EDX spectrum image maps revealed that the nanoparticles are rich in both Cu and S. This finding was confirmed by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses, which identified the nanoparticles as Cu2S. Biomineralization of CuxS nanoparticles in soils has been reported to enhance the colloidal transport of a number of contaminants, including Pb, Cd, and Hg. However, formation of these CuxS nanoparticles has only been observed under sulfate-reducing conditions and could not be repeated using isolates of implicated organisms. As G. sulfurreducens is unable to respire sulfate, and no reducible sulfur was supplied to the cells, these data suggest a novel mechanism for the biomineralization of Cu2S under anoxic conditions. The implications of these findings for the biogeochemical cycling of Cu and other metals as well as the green production of Cu catalysts are discussed.IMPORTANCE Dissimilatory metal-reducing bacteria are ubiquitous in soils and aquifers and are known to utilize a wide range of metals as terminal electron acceptors. These transformations play an important role in the biogeochemical cycling of metals in pristine and contaminated environments and can be harnessed for bioremediation and metal bioprocessing purposes. However, relatively little is known about their interactions with Cu. As a trace element that becomes toxic in excess, Cu can adversely affect soil biota and fertility. In addition, biomineralization of Cu nanoparticles has been reported to enhance the mobilization of other toxic metals. Here, we demonstrate that when supplied with acetate under anoxic conditions, the model metal-reducing bacterium Geobacter sulfurreducens can transform soluble Cu(II) to Cu2S nanoparticles. This study provides new insights into Cu biomineralization by microorganisms and suggests that contaminant mobilization enhanced by Cu biomineralization could be facilitated by Geobacter species and related organisms.

Impact of the Diamond Light Source on research in Earth and environmental sciences: current work and future perspectives.

Diamond Light Source Ltd celebrated its 10th anniversary as a company in December 2012 and has now accepted user experiments for over 5 years. This paper describes the current facilities available at Diamond and future developments that enhance its capacities with respect to the Earth and environmental sciences. A review of relevant research conducted at Diamond thus far is provided. This highlights how synchrotron-based studies have brought about important advances in our understanding of the fundamental parameters controlling highly complex mineral-fluid-microbe interface reactions in the natural environment. This new knowledge not only enhances our understanding of global biogeochemical processes, but also provides the opportunity for interventions to be designed for environmental remediation and beneficial use.

Biogenic nano-magnetite and nano-zero valent iron treatment of alkaline Cr(VI) leachate and chromite ore processing residue.

Highly reactive nano-scale biogenic magnetite (BnM), synthesized by the Fe(III)-reducing bacterium Geobacter sulfurreducens, was tested for the potential to remediate alkaline Cr(VI) contaminated waters associated with chromite ore processing residue (COPR). The performance of this biomaterial, targeting aqueous Cr(VI) removal, was compared to a synthetic alternative, nano-scale zero valent iron (nZVI). Samples of highly contaminated alkaline groundwater and COPR solid waste were obtained from a contaminated site in Glasgow, UK. During batch reactivity tests, Cr(VI) removal from groundwater was inhibited by ∼25% (BnM) and ∼50% (nZVI) when compared to the treatment of less chemically complex model pH 12 Cr(VI) solutions. In both the model Cr(VI) solutions and contaminated groundwater experiments the surface of the nanoparticles became passivated, preventing complete coupling of their available electrons to Cr(VI) reduction. To investigate this process, the surfaces of the reacted samples were analyzed by TEM-EDX, XAS and XPS, confirming Cr(VI) reduction to the less soluble Cr(III) on the nanoparticle surface. In groundwater reacted samples the presence of Ca, Si and S was also noted on the surface of the nanoparticles, and is likely responsible for earlier onset of passivation. Treatment of the solid COPR material in contact with water, by addition of increasing weight % of the nanoparticles, resulted in a decrease in aqueous Cr(VI) concentrations to below detection limits, via the addition of ⩾5% w/w BnM or ⩾1% w/w nZVI. XANES analysis of the Cr K edge, showed that the % Cr(VI) in the COPR dropped from 26% to a minimum of 4-7% by the addition of 5% w/w BnM or 2% w/w nZVI, with higher additions unable to reduce the remaining Cr(VI). The treated materials exhibited minimal re-mobilization of soluble Cr(VI) by re-equilibration with atmospheric oxygen, with the bulk of the Cr remaining in the solid fraction. Both nanoparticles exhibited a considerable capacity for the remediation of COPR related Cr(VI) contamination, with the synthetic nZVI demonstrating greater reactivity than the BnM. However, the biosynthesized BnM was also capable of significant Cr(VI) reduction and demonstrated a greater efficiency for the coupling of its electrons towards Cr(VI) reduction than the nZVI.

Redox interactions between Cr(VI) and Fe(II) in bioreduced biotite and chlorite.

Contamination of the environment with Cr as chromate (Cr(VI)) from industrial activities is of significant concern as Cr(VI) is a known carcinogen, and is mobile in the subsurface. The capacity of Fe(II)-containing phyllosilicates including biotite and chlorite to alter the speciation, and thus the mobility, of redox-sensitive contaminants including Cr(VI) is of great interest since these minerals are common in soils and sediments. Here, the capacity of bacteria, ubiquitous in the surface and near-surface environment, to reduce Fe(III) in phyllosilicate minerals and, thus, alter their redox reactivity was investigated in two-step anaerobic batch experiments. The model Fe(III)-reducing bacterium Geobacter sulfurreducens was used to reduce Fe(III) in the minerals, leading to a significant transformation of structural Fe(III) to Fe(II) of 0.16 mmol/g (∼ 40%) in biotite and 0.15 mmol/g (∼ 20%) in chlorite. The unaltered minerals could not remove Cr(VI) from solution despite containing a larger excess of Fe(II) than would be required to reduce all the added Cr(VI), unless they were supplied in a very high concentration (a 1:10 solid to solution ratio). By contrast, even at very low concentrations, the addition of bioreduced biotite and chlorite caused removal of Cr(VI) from solution, and surface and near surface X-ray absorption spectroscopy confirmed that this immobilization was through reductive transformation to Cr(III). We provide empirical evidence that the amount of Fe(II) generated by microbial Fe(III) reduction is sufficient to reduce the Cr(VI) removed and, in the absence of reduction by the unaltered minerals, suggest that only the microbially reduced fraction of the iron in the minerals is redox-active against the Cr(VI).

The interplay between Cs and K in Pseudanabaena catenata; from microbial bloom control strategies to bioremediation options for radioactive waters.

Pseudanabaena dominates cyanobacterial blooms in the First-Generation Magnox Storage Pond (FGMSP) at a UK nuclear site. The fission product Cs is a radiologically significant radionuclide in the pond, and understanding the interactions between Cs and Pseudanabaena spp. is therefore important for determining facility management strategies, as well as improving understanding of microbiological responses to this non-essential chemical analogue of K. This study evaluated the fate of Cs following interactions with Pseudanabaena catenata, a laboratory strain most closely related to that dominating FGMSP blooms. Experiments showed that Cs (1 mM) exposure did not affect the growth of P. catenata, while a high concentration of K (5 mM) caused a significant reduction in cell yield. Scanning transmission X-ray microscopy elemental mapping identified Cs accumulation to discrete cytoplasmic locations within P. catenata cells, indicating a potential bioremediation option for Cs. Proteins related to stress responses and nutrient limitation (K, P) were stimulated by Cs treatment. Furthermore, selected K+ transport proteins were mis-regulated by Cs dosing, which indicates the importance of the K+ transport system for Cs accumulation. These findings enhance understanding of Cs fate and biological responses within Pseudanabaena blooms, and indicate that K exposure might provide a microbial bloom control strategy.

Engineering biogenic magnetite for sustained Cr(VI) remediation in flow-through systems.

In this work, we report a route to enhance the reactivity and longevity of biogenic magnetite in Cr(VI) remediation under continuous-flow conditions by combining functionalization of the biomagnetite surface with a precious metal catalyst, nanoscale palladium, and exposure to formate. Column influent conditions were varied to simulate oxic, anoxic, and nitrate cocontaminated environments. The addition of sodium formate as an electron donor for Pd-functionalized magnetite increased capacity and longevity allowing 80% removal of Cr(VI) after 300 h in anoxic conditions, whereas complete breakthrough occurred after 60 h in anoxic nonformate and nonfunctionalized systems. Removal of Cr(VI) was optimized under anoxic conditions, and the presence of oxidizing agents results in a modest loss in reductive capacity. Examination of reacted Pd-functionalized magnetite reveals close association of Fe with Cr, suggesting that Pd-coupled oxidation of formate serves to regenerate the reactive surface. XMCD studies revealed that Cr(III) is partially substituted for Fe in the magnetite structure, which serves to immobilize Cr. No evidence for a mechanistic interference by nitrate cocontamination was observed, suggesting that this novel system could provide robust, effective and sustained reduction of contaminants, even in the presence of common oxidizing cocontaminants, outperforming the reductive capacity of nonfunctionalized biogenic magnetite.

Microbial reduction of arsenic-doped schwertmannite by Geobacter sulfurreducens.

The fate of As(V) during microbial reduction by Geobacter sulfurreducens of Fe(III) in synthetic arsenic-bearing schwertmannites has been investigated. During incubation at pH7, the rate of biological Fe(III) reduction increased with increasing initial arsenic concentration. From schwertmannites with a relatively low arsenic content (<0.3 wt %), only magnetite was formed as a result of dissimilatory iron reduction. However, bioreduction of schwertmannites with higher initial arsenic concentrations (>0.79 wt %) resulted in the formation of goethite. At no stage during the bioreduction process did the concentration of arsenic in solution exceed 120 µgL(1), even for a schwertmannite with an initial arsenic content of 4.13 wt %. This suggests that the majority of the arsenic is retained in the biominerals or by sorption at the surfaces of newly formed nanoparticles. Subtle differences in the As K-edge XANES spectra obtained from biotransformation products are clearly related to the initial arsenic content of the schwertmannite starting materials. For products obtained from schwertmannites with higher initial As concentrations, one dominant population of As(V) species bonded to only two Fe atoms was evident. By contrast, schwertmannites with relatively low arsenic concentrations gave biotransformation products in which two distinctly different populations of As(V) persisted. The first is the dominant population described above, the second is a minority population characterized by As(V) bonded to four Fe atoms. Both XAS and XMCD evidence suggest that the latter form of arsenic is that taken into the tetrahedral sites of the magnetite. We conclude that the majority population of As(V) is sorbed to the surface of the biotransformation products, whereas the minority population comprises As(V) incorporated into the tetrahedral sites of the biomagnetite. This suggests that microbial reduction of highly bioavailable As(V)-bearing Fe(III) mineral does not necessarily result in the mobilization of the arsenic.

Adsorption of octahedral mono-molybdate and poly-molybdate onto hematite: A multi-technique approach.

Molybdenum (Mo) is a key trace element and a contaminant in many environments including mine tailings and acid mine drainage systems. Under oxic conditions Mo exists in a number of forms, including mono-molybdate (Mo(VI)O42-) and various poly-molybdate species (e.g. Mo(VI)7O246-) depending on the geochemical conditions (e.g. pH). The mobility and bioavailability of Mo is often controlled by sorption to mineral surfaces, including iron (oxyhydr)oxides e.g. hematite (Fe2O3). This study uses adsorption isotherms, PHREEQC geochemical modeling, Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR), and X-ray Absorption Spectroscopy (XAS) to holistically characterise the molecular scale adsorption of molybdate to hematite as a function of pH (3-12) and Mo(VI) concentration (0.01 × 10-4 - 2 × 10-3 M). PHREEQC and ATR-FTIR indicated both pH and Mo concentration are important variables when forming mono- vs. poly- molybdate and suggest low pH (≤ 4) and high Mo(VI) concentration (≥ 5 × 10-4 M) contribute to the formation of a poly-molybdate surface species on the hematite surface. XAS found Mo adsorbed to hematite via an inner-sphere corner-sharing bidentate binuclear complex with an octahedral mono-molybdate structure at a Mo concentration of 0.6 × 10-4 M across the pH range, and at a Mo(VI) concentration of 5 × 10-4 M and pH over 5. This is the first direct observation of octahedrally coordinated Mo(VI) adsorption species on hematite, and this information has broad implications for the mobility and transport of Mo as a contaminant in the environment.

Investigating different mechanisms for biogenic selenite transformations: Geobacter sulfurreducens, Shewanella oneidensis and Veillonella atypica.

The metal-reducing bacteria Geobacter sulfurreducens, Shewanella oneidensis and Veillonella atypica, use different mechanisms to transform toxic, bioavailable sodium selenite to less toxic, non-mobile elemental selenium and then to selenide in anaerobic environments, offering the potential for in situ and ex situ bioremediation of contaminated soils, sediments, industrial effluents, and agricultural drainage waters. The products of these reductive transformations depend on both the organism involved and the reduction conditions employed, in terms of electron donor and exogenous extracellular redox mediator. The intermediary phase involves the precipitation of elemental selenium nanospheres and the potential role of proteins in the formation of these structures is discussed. The bionanomineral phases produced during these transformations, including both elemental selenium nanospheres and metal selenide nanoparticles, have catalytic, semiconducting and light-emitting properties, which may have unique applications in the realm of nanophotonics. This research offers the potential to combine remediation of contaminants with the development of environmentally friendly manufacturing pathways for novel bionanominerals.

Optimising the transport properties and reactivity of microbially-synthesised magnetite for in situ remediation.

Engineered nanoparticles offer the potential for remediation of land and water that has been contaminated by organics and metals. Microbially synthesized nano-scale magnetite, prepared from Fe(III) oxides by subsurface Fe(III)-reducing bacteria, offers a scalable biosynthesis route to such a nano-scale remediation reagent. To underpin delivery of "bionanomagnetite" (BNM) nanomaterial during in situ treatment options, we conducted a range of batch and column experiments to assess and optimise the transport and reactivity of the particles in porous media. Collectively these experiments, which include state of the art gamma imaging of the transport of 99m Tc-labelled BNM in columns, showed that non-toxic, low cost coatings such as guar gum and salts of humic acid can be used to enhance the mobility of the nanomaterial, while maintaining reactivity against target contaminants. Furthermore, BNM reactivity can be enhanced by the addition of surface coatings of nano-Pd, extending the operational lifetime of the BNM, in the presence of a simple electron donor such as hydrogen or formate.

Effective treatment of alkaline Cr(VI) contaminated leachate using a novel Pd-bionanocatalyst: Impact of electron donor and aqueous geochemistry.

Palladium catalysts offer the potential for the effective treatment of a variety of priority reducible pollutants in natural waters. In this study, microbially synthesized magnetite nanoparticles were functionalized with Pd(0), creating a highly reactive, magnetically recoverable, nano-scale catalyst (Pd-BnM). This was then investigated for the treatment of model Cr(VI) contaminated solutions at a range of pH values, and also alkaline Cr(VI) contaminated leachates from chromite ore processing residue (COPR); a contaminant issue of global concern. The sample of COPR used in this study was obtained from a site in Glasgow, UK, where extensive Cr(VI) contamination has been reported. In initial experiments Pd-BnM was supplied with H2 gas or formate as electron donors, and Cr(VI) removal from model synthetic solutions was quantified at various pH values (2-12). Effective removal was noted at neutral to environmentally relevant alkaline (pH 12) pH values, while the use of formate as an electron donor resulted in loss of performance under acidic conditions (pH 2). Reaction kinetics were then assessed with increasing Pd-BnM loading in both model pH 12 Cr(VI) solutions and the COPR leachate. When formate was used as the electron donor for Pd-BnM, to treat COPR leachate, there was significant inhibition of Cr(VI) removal. In contrast, a promotion of reaction rate, was observed when H2 was employed. Upon sustained reaction with model Cr(VI) solutions, in the presence of excess electron donor (formate or H2), appreciable quantities of Cr(VI) were removed before eventual inactivation of the catalyst. Faster onset of inactivation was reported in the COPR leachates, removing 4% and 64% of Cr(VI) observed from model Cr(VI) solutions, when formate and H2 were used as electron donors, respectively. XAS, TEM-EDX and XPS analysis of the catalysts that had been inactivated in the model solution, showed that the surface had an extensive covering of reduced Cr(III), most likely as a CrOOH phase. COPR reacted catalysts recorded a lower abundance of Cr(III) alongside a high abundance of the leachate components Ca and Si, implicating these elements in the faster onset of inactivation.

Bacterially synthesized ferrite nanoparticles for magnetic hyperthermia applications.

Magnetic hyperthermia uses AC stimulation of magnetic nanoparticles to generate heat for cancer cell destruction. Whilst nanoparticles produced inside magnetotactic bacteria have shown amongst the highest reported heating to date, these particles are magnetically blocked so that strong heating occurs only for mobile particles, unless magnetic field parameters are far outside clinical limits. Here, nanoparticles extracellularly produced by the bacteria Geobacter sulfurreducens are investigated that contain Co or Zn dopants to tune the magnetic anisotropy, saturation magnetization and nanoparticle sizes, enabling heating within clinical field constraints. The heating mechanisms specific to either Co or Zn doping are determined from frequency dependent specific absorption rate (SAR) measurements and innovative AC susceptometry simulations that use a realistic model concerning clusters of polydisperse nanoparticles in suspension. Whilst both particle types undergo magnetization relaxation and show heating effects in water under low AC frequency and field, only Zn doped particles maintain relaxation combined with hysteresis losses even when immobilized. This magnetic heating process could prove important in the biological environment where nanoparticle mobility may not be possible. Obtained SARs are discussed regarding clinical conditions which, together with their enhanced MRI contrast, indicate that biogenic Zn doped particles are promising for combined diagnostics and cancer therapy.

Biotechnological synthesis of functional nanomaterials.

Biological systems, especially those using microorganisms, have the potential to offer cheap, scalable and highly tunable green synthetic routes for the production of the latest generation of nanomaterials. Recent advances in the biotechnological synthesis of functional nano-scale materials are described. These nanomaterials range from catalysts to novel inorganic antimicrobials, nanomagnets, remediation agents and quantum dots for electronic and optical devices. Where possible, the roles of key biological macromolecules in controlling production of the nanomaterials are highlighted, and also technological limitations that must be addressed for widespread implementation are discussed.

Microbial engineering of nanoheterostructures: biological synthesis of a magnetically recoverable palladium nanocatalyst.

Precious metals supported on ferrimagnetic particles have a diverse range of uses in catalysis. However, fabrication using synthetic methods results in potentially high environmental and economic costs. Here we show a novel biotechnological route for the synthesis of a heterogeneous catalyst consisting of reactive palladium nanoparticles arrayed on a nanoscale biomagnetite support. The magnetic support was synthesized at ambient temperature by the Fe(III)-reducing bacterium, Geobacter sulfurreducens , and facilitated ease of recovery of the catalyst with superior performance due to reduced agglomeration (versus conventional colloidal Pd nanoparticles). Surface arrays of palladium nanoparticles were deposited on the nanomagnetite using a simple one-step method without the need to modify the biomineral surface, most likely due to an organic coating priming the surface for Pd adsorption, which was produced by the bacterial culture during the formation of the nanoparticles. A combination of EXAFS and XPS showed the Pd nanoparticles on the magnetite to be predominantly metallic in nature. The Pd(0)-biomagnetite was tested for catalytic activity in the Heck reaction coupling iodobenzene to ethyl acrylate or styrene. Rates of reaction were equal to or superior to those obtained with an equimolar amount of a commercial colloidal palladium catalyst, and near complete conversion to ethyl cinnamate or stilbene was achieved within 90 and 180 min, respectively.

Optimizing Cr(VI) and Tc(VII) remediation through nanoscale biomineral engineering.

The influence of Fe(III) starting material on the ability of magnetically recoverable biogenic magnetites produced by Geobacter sulfurreducens to retain metal oxyanion contaminants has been investigated. The reduction/removal of aqueous Cr(VI) was used to probe the reactivity of the biomagnetites. Nanomagnetites produced by the bacterial reduction of schwertmannite powder were more efficient at reducing Cr(VI) than either ferrihydrite "gel"-derived biomagnetite or commercial nanoscale Fe(3)O(4). Examination of post-exposure magnetite surfaces indicated both Cr(III) and Cr(VI) were present. X-ray magnetic circular dichroism (XMCD) studies at the Fe L(2,3)-edge showed that the amount of Fe(III) "gained" by Cr(VI) reduction could not be entirely accounted for by "lost" Fe(II). Cr L(2,3)-edge XMCD spectra found Cr(III) replaced approximately 14%-20% of octahedral Fe in both biogenic magnetites, producing a layer resembling CrFe(2)O(4). However, schwertmannite-derived biomagnetite was associated with approximately twice as much Cr as ferrihydrite-derived magnetite. Column studies using a gamma-camera to image a (99)mTc(VII) radiotracer were performed to visualize the relative performances of biogenic magnetites at removing aqueous metal oxyanion contaminants. Again, schwertmannite-derived biomagnetite proved capable of retaining more (approximately 20%) (99)mTc(VII) than ferrihydrite-derived biomagnetite, confirming that the production of biomagnetite can be fine-tuned for efficient environmental remediation through careful selection of the Fe(III) mineral substrate supplied to Fe(III)-reducing bacteria.

Harnessing the extracellular bacterial production of nanoscale cobalt ferrite with exploitable magnetic properties.

Nanoscale ferrimagnetic particles have a diverse range of uses from directed cancer therapy and drug delivery systems to magnetic recording media and transducers. Such applications require the production of monodisperse nanoparticles with well-controlled size, composition, and magnetic properties. To fabricate these materials purely using synthetic methods is costly in both environmental and economical terms. However, metal-reducing microorganisms offer an untapped resource to produce these materials. Here, the Fe(III)-reducing bacterium Geobacter sulfurreducens is used to synthesize magnetic iron oxide nanoparticles. A combination of electron microscopy, soft X-ray spectroscopy, and magnetometry techniques was employed to show that this method of biosynthesis results in high yields of crystalline nanoparticles with a narrow size distribution and magnetic properties equal to the best chemically synthesized materials. In particular, it is demonstrated here that cobalt ferrite (CoFe(2)O(4)) nanoparticles with low temperature coercivity approaching 8 kOe and an effective anisotropy constant of ∼10(6) erg cm(-3) can be manufactured through this biotechnological route. The dramatic enhancement in the magnetic properties of the nanoparticles by the introduction of high quantities of Co into the spinel structure represents a significant advance over previous biomineralization studies in this area using magnetotactic bacteria. The successful production of nanoparticulate ferrites achieved in this study at high yields could open up the way for the scaled-up industrial manufacture of nanoparticles using environmentally benign methodologies.