The reduction of Pd(II) to Pd(0) was accelerated by using the sulfate-reducing bacterium Desulfovibrio desulfuricans NCIMB 8307 at the expense of formate or H(2) as electron donors at pH 2-7. With formate no reduction occurred at pH 2, but with H(2) 50% of the activity was retained at pH 2, with the maximum rate (1.3-1.4 micromol min(-1) mg dry cells(-1)) seen at pH 3-7, which was similar to the rate with formate at neutral pH. Excess nitrate was inhibitory to Pd(II) reduction using formate, but not H(2). Chloride ion was inhibitory as low as 100 mM using formate but with H(2) only ca. 25% inhibition was observed at 500 mM Cl(-) and H(2) was concluded to be the electron donor of choice for the potential remediation of industrial wastes. Deposited Pd was visible on the cells using transmission and scanning electron microscopy and analysis by energy dispersive X-ray microanalysis (EDAX) identified the deposit as Pd, confirmed as Pd(0) by X-ray powder diffraction analysis (XRD). The crystal size of the biodeposited Pd(0) was determined to be only 50% of the size of Pd(0) crystals manufactured chemically from Pd(II) at the expense of H(2) and, unlike the chemically manufactured material, the biocrystal size was independent of the pH. The "biological" Pd(0) functioned as a superior chemical catalyst in a test reaction which liberated hydrogen from hypophosphite. Pd, and also Pt and Rh, could be recovered by resting cell suspensions under H(2) from an industrial processing wastewater, suggesting a possible future application of bioprocessing technology for precious metals.

Worldwide usage of platinum group metals is increasing, prompting new recovery technologies. Resting cells of Desulfovibrio desulfuricans reduced soluble Pd2+ to elemental, cell-bound Pd0 supported by pyruvate, formate, or H2 as the electron donor without biochemical cofactors. Pd reduction was O2 insensitive, opening the way for recycling and recovery of Pd under oxic conditions.

A Citrobacter sp. accumulated uranyl ion (UO 2M2 ) via precipitation with phosphate ligand liberated by phosphatase activity. The onset and rate of uranyl phosphate deposition were promoted by NH M 4 , forming NH 4 UO 2 PO 4 , which has a lower solubility product than NaUO 2 PO 4 . This acceleration decoupled the rate-limiting chemical crystallization process from the biochemical phosphate ligand generation. This provided a novel approach to monitor the cell-surface-associated changes using atomic-force microscopy in conjunction with transmission electron microscopy and electron-probe X-ray microanalysis, to visualize deposition of uranyl phosphate at the cell surface. Analysis of extracted surface materials by 31

The complete and continuous reduction of 1 mM Cr(VI) to Cr(III) was achieved in a flow-through reactor using a novel bioinorganic catalyst ("MM-bio-Pd(0)"), which was produced by single-step reduction of platinum group metals (PGM) from industrial waste solution onto biomass of Desulfovibrio desulfuricans ATCC 29577. Two flow-through reactor systems were compared using both "MM-bioPd(0)" and chemically reduced Pd(0). Reactors containing the latter removed Cr(VI) for 1 week only at the expense of formate as the electron donor, whereas the former gave complete Cr(VI) removal for 3 months of continuous operation. Mass balance analysis showed 100% reduction of Cr(VI) to soluble Cr(III) in the bioreactor exit solution. With the use of electron paramagnetic resonance (EPR) no intermediate Cr(V) species could be detected. Pd(0) was biodeposited similarly using Escherichia coliMC4100 and "bio-Pd(0)". The latter was used to recover Pd(II) from two acidic industrial waste leachates to generate two types of "MM-bio-Pd(0)": "SI-bio-Pd(0)" and "SII-bio-Pd(0)", respectively. The biomaterial composition was comparable in both cases, and the catalytic activity was related inversely to the amount of chloride in the waste leachate from which it was derived.

Palladium uptake by resting cell suspensions of Desulfovibrio desulfuricans NCIMB 8307 was studied without or with electron donor (formate), which gave metal uptake attributable to biosorption of Pd(II) and bioreduction of Pd(II) to Pd(0), respectively. The maximum biosorption capacity of palladium (at pH 2) was up to 196 mg Pd g À1 dry cells (1.85 mmol g À1 ; approx 20% of the dry weight). Biosorption was to 85% of the maximum in less than 10 min and the biomass was saturated within 30 min. Biosorption of Pd(II) was greater from the chloro-than the ammine complex and was inhibited in the presence of excess chloride ion. Bioreductive accumulation of Pd(II) from Pd(NH 3 ) 4 2 was achieved in the presence of electron donor (formate) but was also inhibited by excess Cl À . Up to 100% of Pd(II) reduction to Pd(0) was achieved within 5 min anaerobically at pH 7 and 30 min at pH 3. Pd(0) was localized on the biomass surface using electron microscopy and was characterized using energy dispersive X-ray microanalysis (EDAX) and X-ray diffraction analysis (XRD). Biosorption was Pd-speci®c with respect to Pt and Rh using test solutions and acid (aqua regia) leachates from spent automotive catalysts. The total Pd removed from the latter was only 15%, attributable to the inhibitory effect of residual chloride ion from the acidic extractant. Pd biorecovery is limited by the need for an improved extraction technology to minimize the formation of PdCl 4 2À in solution rather than by constraints of the Pd-accumulating biomass.

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Platinum group metals are routinely used in automotive catalysts but recycle technology lags behind demand. There is no available 'dean technology' and leach solutions (e.g. aqua regia) to solubilise the metals from scrap are highly aggressive. A microwave-assisted leaching method was developed which gave 80% metals recovery, with the leach time reduced from 2 h to 15 min using 50% (aq.) diluted aqua regia to give potentially a more biocompatible leachate. Desulfovibrio desulfuricans reduces soluble platinum group metals to cell-bound insoluble base metals (e.g. Pd(II) --> Pd(0)). For use, biofilm was immobilised on a Pd-23% Ag solid alloy membrane which delivered H. to the cells via an electrochemical chamber at the back-side. The biomass-coated Pd-Ag alloy electrode was used in a flow-through reactor for recovery of Pd, Pt and Rh from aqua regia leachates (pH 2.5) of spent automotive catalysts with up to 90% efficiency at a flow residence time of 15 minutes. Free cells did not reduce platinum group metals from the leachates but the electrobioreactor did so using biofilm-cells pre-loaded with Pd(0). Reactors lacking biomass or reactors with heat-killed biofilm removed less platinum group metals, via electrochemically-synthesised H. reductant alone. The use of an active biofilm layer in a flow-through electrobioreactor provides a simple, dean and rapid potential recycle technology.

The majority of the radionuclides generated by the nuclear fuel cycle can be removed during established remediation processes. However among the long-lived, α-emitting actinides neptunium(V) is recalcitrant to removal from solution by physicochemical or biotechnological methods. The latter include a biocrystallization process, based on the enzymatic liberation of phosphate as a precipitating ligand by a Citrobacter sp., which was previously shown to precipitate tetravalent actinides such as Th(IV) and Pu(IV) as their corresponding phosphates. Np(V) was reduced to a lower valence (probably Np(IV)) by ascorbic acid or biologically, using the reductive capability of Shewanella putrefaciens, but reduction alone did not desolubilize Np. However Np(V) was removed by the two organisms, S. putrefaciens and Citrobacter sp. in concert; bioreduction to Np(IV) by S. putrefaciens, together with phosphate liberation by the Citrobacter sp., permitted bioprecipitative removal of 237Np as well as its daughter 233protactinium. Tests were made possible by a novel technique permitting actinide separation by paper chromatography followed by quantification of the radioactive species using a phosphorImager. This study has implications for the development of methods to remove Np(V) from solution, by the simple combination of two biotechnological methods, which can succeed where chemical treatments are ineffective.