Eu ³⁺ Sequestration by Biogenic Nano-Hydroxyapatite Synthesized at Neutral and Alkaline pH

<p>Biogenic hydroxyapatite (bio-HA) has the potential for radionuclide capture and remediation of metal-contaminated environments. Biosynthesis of bio-HA was achieved via the phosphatase activity of a <i>Serratia sp</i>. supplemented with various concentrations of CaCl₂ and glycerol 2-phosphate (G2P) provided at pH 7.0 or 8.6. Presence of hydroxyapatite (HA) was confirmed in the samples by X-ray powder diffraction analysis. When provided with limiting (1 mM) G2P and excess (5 mM) Ca²⁺ at pH 8.6, monohydrocalcite was found. This, and bio-HA with less (1 mM) Ca²⁺ accumulated Eu(III) to ∼31% and 20% of the biomineral mass, respectively, as compared to 50% of the mineral mass accumulated by commercial HA. Optimally, with bio-HA made at initial pH 7.0 from 2 mM Ca²⁺ and 5 mM G2P, Eu(III) accumulated to ∼74% of the weight of bio-HA, which was equal to the mass of the HA mineral component of the biomaterial. The implications with respect to potential bio-HA-barrier development in situ or as a remediation strategy are discussed.</p

Biotechnology Processes for Scalable, Selective Rare Earth Element Recovery

Biorecovery of rare earth elements (REE) from wastes and ores is achieved by bacteria using biogenic phosphates. One approach uses an enzyme that biomineralises REE phosphate crystals into the extracellular polymeric matrix (EPM). The enzyme, co-localised in the EPM, provides a continuous phosphate feed into biomineralisation. The bacteria can be immobilised in a column, allowing continuous metal removal. Metals biocrystallise at different rates. By choosing suitable conditions and column flow rates selective recovery of REE against uranium and thorium can potentially overcome a bottleneck in recovery of REE from mine tailings and ore leachates co-contaminated with these radionuclides. Another approach to REE recovery first lays down calcium phosphate as hydroxyapatite (Bio-HA) using the enzymatic process. Bio-HA then captures REE, loading REE of up to 84% of the HA-mass. REE3+ first localises at the grain boundaries of the small bio-crystallites and then substitutes for Ca2+ stoichiometrically within the HA. After REE capture the bio-HA/REE hybrid can be separated magnetically. A wider concept: using a ‘priming’ deposit of one mineral to facilitate the capture of REEs, has been shown, potentially providing a basis for selective REE recovery which would provide advantages over the > 100 steps currently used in commercial REE refining

Influence of pH, competing ions, and salinity on the sorption of strontium and cobalt onto biogenic hydroxyapatite

Anthropogenic radionuclides contaminate a range of environments as a result of nuclear activities, for example, leakage from waste storage tanks/ponds (e.g. Hanford, USA or Sellafield sites, UK) or as a result of large scale nuclear accidents (e.g. Chernobyl, Ukraine or Fukushima, Japan). One of the most widely applied remediation techniques for contaminated waters is the use of sorbent materials (e.g. zeolites and apatites). However, a key problem at nuclear contaminated sites is the remediation of radionuclides from complex chemical environments. In this study, biogenic hydroxyapatite (BHAP) produced by Serratia sp. bacteria was investigated for its potential to remediate surrogate radionuclides (Sr2+ and Co2+) from environmentally relevant waters by varying pH, salinity and the type and concentration of cations present. The sorption capacity of the BHAP for both Sr2+ and Co2+ was higher than for a synthetically produced hydroxyapatite (HAP) in the solutions tested. BHAP also compared favorably against a natural zeolite (as used in industrial decontamination) for Sr 2+ and Co 2+ uptake from saline waters. Results confirm that hydroxyapatite minerals of high surface area and amorphous calcium phosphate content, typical for biogenic sources, are suitable restoration or reactive barrier materials for the remediation of complex contaminated environments or wastewaters

Enhanced hydrogenation catalyst synthesized by Desulfovibrio desulfuricans exposed to a radio frequency magnetic field

EPSRC (EP/I007806/1; EP/D05768X/1), BBSRC (BB/ C516128/1), NERC (NE/L014076/1), The Royal Society (Industrial Fellowship) and Spanish Government Sistema Nacional de Garantia Juvenil grant PEJ-2014-P-00391.This work was supported by EPSRC (grants No EP/ I007806/1 and EP/D05768X/1), BBSRC (grant No BB/ C516128/1), NERC (grant NE/L014076/1) and by a Royal Society Industrial Fellowship to LEM for secondment into C-Tech Innovation Ltd., who provided the bespoke apparatus used in this work. We acknowledge the invaluable contributions of the late Dr Ruth Wroe of C-Tech Innovation Ltd. into useful discussions and the kind permission of Drs S. Megit, C. Berry and A. Morby (University of Cardiff, UK) to show their unpublished work in Supplementary Information. This work was partially supported by the Spanish Government Sistema Nacional de Garantia Juvenil Grant PEJ-2014-P- 00391 (Promocion de Empleo Joven e Implantacion de la Garantia Juvenil 2014, MINECO) with a scholarship to JGB. We also thank the EM Centre at U. Granada for access to high-resolution electron microscopy (in Fig. S2 and S3). All authors declare no competing interests.Desulfovibrio desulfuricans reduces Pd(II) to Pd(0)-nanoparticles (Pd-NPs) which are catalytically active in 2-pentyne hydrogenation. To make Pd-NPs, resting cells are challenged with Pd(II) ions (uptake), followed by addition of electron donor to promote bioreduction of cell-bound Pd(II) to Pd(0) (bio-Pd). Application of radiofrequency (RF) radiation to prepared 5 wt% bio-Pd catalyst (60 W power, 60 min) increased the hydrogenation rate by 70% with no adverse impact on selectivity to cis-2-pentene. Such treatment of a 5 wt% Pd/carbon commercial catalyst did not affect the conversion rate but reduced the selectivity. Lower-dose RF radiation (2-8 W power, 20 min) was applied to the bacteria at various stages before and during synthesis of the bio-scaffolded Pd-NPs. The reaction rate (mu mol 2-pentyne converted s(-1)) was increased by similar to threefold by treatment during bacterial catalyst synthesis. Application of RF radiation (2 or 4 W power) to resting cells prior to Pd(II) exposure affected the catalyst made subsequently, increasing the reaction rate by 50% as compared to untreated cells, while nearly doubling selectivity for cis 2-pentene. The results are discussed with respect to published and related work which shows altered dispersion of the Pd-NPs made following or during RF exposure.UK Research & Innovation (UKRI) Engineering & Physical Sciences Research Council (EPSRC) EP/I007806/1 EP/D05768X/1UK Research & Innovation (UKRI) Biotechnology and Biological Sciences Research Council (BBSRC) BB/C516128/1UK Research & Innovation (UKRI)Natural Environment Research Council (NERC) NE/L014076/1Royal Society of London European CommissionSpanish Government Sistema Nacional de Garantia Juvenil grant PEJ-2014-P-0039

Electro-extractive fermentation for efficient biohydrogen production

Electrodialysis, an electrochemical membrane technique, was found to prolong and enhance the production of biohydrogen and purified organic acids via the anaerobic fermentation of glucose by Escherichia coli. Through the design of a model electrodialysis medium using cationic buffer, pH was precisely controlled electrokinetically, i.e. by the regulated extraction of acidic products with coulombic efficiencies of organic acid recovery in the range 50–70% maintained over continuous 30-day experiments. Contrary to\ud previous reports, E. coli produced H2 after aerobic growth in minimal medium without inducers and with a mixture of organic acids dominated by butyrate. The selective separation of organic acids from fermentation provides a potential nitrogen-free carbon source for further biohydrogen production in a parallel photofermentation. A parallel study incorporated this fermentation system into an integrated biohydrogen refinery (IBR) for the conversion of organic waste to hydrogen and energy

Biosynthesis of zinc sulfide quantum dots using waste off-gas from a metal bioremediation process

Waste H2S biogas from a mine-water remediation bioprocess is used to make zinc sulfide quantum dots which are identical to ZnS QDs made by chemical methods.</p