Jeffrey P. Fitts

Virus disinfection in water by biogenic silver immobilized in polyvinylidene fluoride membranes

The development of innovative water disinfection strategies is of utmost importance to prevent outbreaks of waterborne diseases related to poor treatment of (drinking) water. Recently, the association of silver nanoparticles with the bacterial cell surface of Lactobacillus fermentum (referred to as biogenic silver or bio-Ag(0)) has been reported to exhibit antiviral properties. The microscale bacterial carrier matrix serves as a scaffold for Ag(0) particles, preventing aggregation during encapsulation. In this study, bio-Ag(0) was immobilized in different microporous PVDF membranes using two different pre-treatments of bio-Ag(0) and the immersion-precipitation method. Inactivation of UZ1 bacteriophages using these membranes was successfully demonstrated and was most probably related to the slow release of Ag(+) from the membranes. At least a 3.4 log decrease of viruses was achieved by application of a membrane containing 2500 mg bio-Ag(0)(powder) m(-2) in a submerged plate membrane reactor operated at a flux of 3.1 L m(-2) h(-1). Upon startup, the silver concentration in the effluent initially increased to 271 μg L(-1) but after filtration of 31 L m(-2), the concentration approached the drinking water limit ( = 100 μg L(-1)). A virus decline of more than 3 log was achieved at a membrane flux of 75 L m(-2) h(-1), showing the potential of this membrane technology for water disinfection on small scale.

Concomitant microbial generation of palladium nanoparticles and hydrogen to immobilize chromate

The catalytic properties of various metal nanoparticles have led to their use in environmental remediation. Our aim is to develop and apply an efficient bioremediation method based on in situ biosynthesis of bio-Pd nanoparticles and hydrogen. C. pasteurianum BC1 was used to reduce Pd(II) ions to form Pd nanoparticles (bio-Pd) that primarily precipitated on the cell wall and in the cytoplasm. C. pasteurianum BC1 cells, loaded with bio-Pd nanoparticle in the presence of glucose, were subsequently used to fermentatively produce hydrogen and to effectively catalyze the removal of soluble Cr(VI) via reductive transformation to insoluble Cr(III) species. Batch and aquifer microcosm experiments using C. pasteurianum BC1 cells loaded with bio-Pd showed efficient reductive Cr(VI) removal, while in control experiments with killed or viable but Pd-free bacterial cultures no reductive Cr(VI) removal was observed. Our results suggest a novel process where the in situ microbial production of hydrogen is directly coupled to the catalytic bio-Pd mediated reduction of chromate. This process offers significant advantages over the current groundwater treatment technologies that rely on introducing preformed catalytic nanoparticles into groundwater treatment zones and the costly addition of molecular hydrogen to above ground pump and treat systems.

Biosupported bimetallic Pd-Au nanocatalysts for dechlorination of environmental contaminants

Biologically produced monometallic palladium nanoparticles (bio-Pd) have been shown to catalyze the dehalogenation of environmental contaminants, but fail to efficiently catalyze the degradation of other important recalcitrant halogenated compounds. This study represents the first report of biologically produced bimetallic Pd/Au nanoparticle catalysts. The obtained catalysts were tested for the dechlorination of diclofenac and trichlorethylene. When aqueous bivalent Pd(II) and trivalent Au(III) ions were both added to concentrations of 50 mg L(-1) and reduced simultaneously by Shewanella oneidensis in the presence of H(2), the resulting cell-associated bimetallic nanoparticles (bio-Pd/Au) were able to dehalogenate 78% of the initially added diclofenac after 24 h; in comparison, no dehalogenation was observed using monometallic bio-Pd or bio-Au. Other catalyst-synthesis strategies did not show improved dehalogenation of TCE and diclofenac compared with bio-Pd. Synchrotron-based X-ray diffraction, (scanning) transmission electron microscopy and energy dispersive X-ray spectroscopy indicated that the simultaneous reduction of Pd and Au supported on cells of S. oneidensis resulted in the formation of a unique bimetallic crystalline structure. This study demonstrates that the catalytic activity and functionality of possibly environmentally more benign biosupported Pd-catalysts can be improved by coprecipitation with Au.

Arsenic fractionation in mine spoils 10 years after aided phytostabilization

Aided phytostabilization using a combination of compost, zerovalent iron grit and coal fly ash (CZA) amendments and revegetation effectively promoted the biological recovery of mining spoils generated at a gold mine in Portugal. Selective dissolution of spoil samples in combination with solid phase characterization using microbeam X-ray absorption near edge structure (μXANES) spectroscopy and microbeam X-ray fluorescence (μXRF) mapping were used to assess As associations in spoils ten years after CZA treatment. The results show that As preferentially associates with poorly crystalline Fe-oxyhydroxides as opposed to crystalline Fe-(oxyhydr)oxide phases. The crystalline Fe(III)-phases dominated in the treated spoil and exceeded those of the untreated spoil three-fold, but only 2.6-6.8% of total As was associated with this fraction. Correlation maps of As:Fe reveal that As in the CZA-treated spoils is primarily contained in surface coatings as precipitates and sorbates. Arsenic binding with poorly crystalline Fe-oxyhydroxides did not inhibit As uptake by plants.

Recovery of critical metals using biometallurgy

The increased development of green low-carbon energy technologies that require platinum group metals (PGMs) and rare earth elements (REEs), together with the geopolitical challenges to sourcing these metals, has spawned major governmental and industrial efforts to rectify current supply insecurities. As a result of the increasing critical importance of PGMs and REEs, environmentally sustainable approaches to recover these metals from primary ores and secondary streams are needed. In this review, we define the sources and waste streams from which PGMs and REEs can potentially be sustainably recovered using microorganisms, and discuss the metal-microbe interactions most likely to form the basis of different environmentally friendly recovery processes. Finally, we highlight the research needed to address challenges to applying the necessary microbiology for metal recovery given the physical and chemical complexities of specific streams.

Chromium(III) oxidation by three poorly-crystalline manganese(IV) oxides. 1. Chromium(III)-oxidizing capacity.

The Cr(III)-oxidizing capacity of three layered poorly crystalline Mn(IV)O(2) phases, i.e. δ-MnO(2), Random Stacked Birnessite (RSB), and Acid Birnessite (AB), was determined in real-time and in situ, using Quick X-ray Absorption Fine Structure Spectroscopy (Q-XAFS). The results obtained with this technique, which allows the measurement of the total amount of Cr(VI) produced in the system, indicated that the Cr(III) oxidation reaction had ceased between 30 min and 1 h under most experimental conditions. However, this cessation was not observed with a traditional batch technique, which only allows the measurement of Cr(VI) present in solution and thus neglects the amount of Cr(VI) that may be sorbed to Mn(IV)O(2). This study also demonstrated that the Mn(IV)O(2) phase oxidizing the highest amount of Cr(III), which is positively charged in solution, was the mineral featuring the most negatively charged surface. Also, the results indicated that the presence of Mn(II) and/or Mn(III) impurities inside the Mn(IV)O(2) structure could enhance the minerals capacity to oxidize Cr(III). The information provided in this study will be useful in predicting the capabilities of naturally occurring Mn oxide minerals, which are similar to the three synthetic Mn(IV)O(2) investigated, to oxidize Cr(III) to toxic and mobile Cr(VI) in the soil of contaminated sites.

Alterations of Fractures in Carbonate Rocks by CO2-Acidified Brines

Fractures in geological formations may enable migration of environmentally relevant fluids, as in leakage of CO2 through caprocks in geologic carbon sequestration. We investigated geochemically induced alterations of fracture geometry in Indiana Limestone specimens. Experiments were the first of their kind, with periodic high-resolution imaging using X-ray computed tomography (xCT) scanning while maintaining high pore pressure (100 bar). We studied two CO2-acidified brines having the same pH (3.3) and comparable thermodynamic disequilibrium but different equilibrated pressures of CO2 (PCO2 values of 12 and 77 bar). High-PCO2 brine has a faster calcite dissolution kinetic rate because of the accelerating effect of carbonic acid. Contrary to expectations, dissolution extents were comparable in the two experiments. However, progressive xCT images revealed extensive channelization for high PCO2, explained by strong positive feedback between ongoing flow and reaction. The pronounced channel increasingly directed flow to a small region of the fracture, which explains why the overall dissolution was lower than expected. Despite this, flow simulations revealed large increases in permeability in the high-PCO2 experiment. This study shows that the permeability evolution of dissolving fractures will be larger for faster-reacting fluids. The overall mechanism is not because more rock dissolves, as would be commonly assumed, but because of accelerated fracture channelization.

Assessment of Aided Phytostabilization of Copper-Contaminated Soil by X-ray Absorption Spectroscopy and Chemical Extractions

Field plots were established at a timber treatment site to evaluate remediation of Cu contaminated topsoils with aided phytostabilization. Soil containing 2600 mg kg⁻¹ Cu was amended with a combination of 5 wt% compost and 2 wt% iron grit, and vegetated. Sequential extraction was combined with extended X-ray absorption fine structure (EXAFS) spectroscopy to correlate changes in Cu distribution across five fractions with changes in the predominant Cu compounds two years after treatment in parallel treated and untreated field plots. Exchangeable Cu dominated untreated soil, most likely as Cu(II) species non-specifically bound to natural organic matter. The EXAFS spectroscopic results are consistent with the sequential extraction results, which show a major shift in Cu distribution as a result of soil treatment to the fraction bound to poorly crystalline Fe oxyhydroxides forming binuclear inner-sphere complexes.

Chromium(III) oxidation by three poorly crystalline manganese(IV) oxides. 2. Solid phase analyses.

Layered, poorly crystalline Mn(IV)O(2) phases are abundant in the environment. These mineral phases may rapidly oxidize Cr(III) to more mobile and toxic Cr(VI) in soils. There is still, however, little knowledge of how Cr(III) oxidation by Mn(IV)O(2) proceeds at the microscopic and molecular levels. Therefore, the sorption mechanisms of Cr(III) and Cr(VI) on Random Stacked Birnessite (RSB), δ-MnO(2), and Acid Birnessite (AB) were determined by Extended X-ray Absorption Fine Structure Spectroscopy (EXAFS). These three synthetic Mn(IV)O(2), which are poorly crystalline phases and have layered structures, were reacted with 50 mM Cr(III) at pH 2.5, 3, and 3.5 before being analyzed by EXAFS. The results indicated that Cr(VI) was loosely sorbed as an outer-sphere complex on Mn(IV)O(2), while Cr(III) was tightly sorbed as an inner-sphere complex. Further research is needed to understand why Cr(III) stopped being significantly oxidized by Mn(IV)O(2) after 30 min. This study, however, demonstrated that the formation of a Cr surface precipitate is not necessarily responsible for the cessation in Cr(III) oxidation. Indeed, no Cr surface precipitate was detected at the microscopic and molecular levels on Mn(IV)O(2) surfaces reacted with Cr(III) for 1 h, although the Cr(III) oxidation ceased before 1 h of reaction at most employed experimental conditions.

Virus Removal by Biogenic Cerium

The rare earth element cerium has been known to exert antifungal and antibacterial properties in the oxidation states +III and +IV. This study reports on an innovative strategy for virus removal in drinking water by the combination of Ce(III) on a bacterial carrier matrix. The biogenic cerium (bio-Ce) was produced by addition of aqueous Ce(III) to actively growing cultures of either freshwater manganese-oxidizing bacteria (MOB) Leptothrix discophora or Pseudomonas putida MnB29. X-ray absorption spectroscopy results indicated that Ce remained in its trivalent state on the bacterial surface. The spectra were consistent with Ce(III) ions associated with the phosphoryl groups of the bacterial cell wall. In disinfection assays using a bacteriophage as model, it was demonstrated that bio-Ce exhibited antiviral properties. A 4.4 log decrease of the phage was observed after 2 h of contact with 50 mg L(-1) bio-Ce. Given the fact that virus removal with 50 mg L(-1) Ce(III) as CeNO(3) was lower, the presence of the bacterial carrier matrix in bio-Ce significantly enhanced virus removal.