Mechanistic investigation and modeling of Cd immobilization by iron (hydr)oxide-humic acid coprecipitates.

A molecular-scale understanding of aqueous metal adsorption onto humic acid-iron (hydr)oxide coprecipitates, and our ability to model these interactions, are lacking. Here, the molecular-scale mechanisms for Cd binding onto iron (hydr)oxide-humic acid (HA) composites were probed using X-ray absorption fine structure (XAFS) spectroscopy and surface complexation modeling (SCM). The immobilization of Cd in (hydr)oxide precipitation systems occurs predominantly through adsorption onto the freshly-formed (hydr)oxide nanoparticles, and SCM calculations suggest a specific surface area of 2400 m2/g available for Cd. The solution and XAFS measurements indicate that HA promotes the precipitation of both Fe clusters and Fe-Cd associations mainly through ligand exchange reactions. Site masking reactions result in a dramatic blockage of functional sites on HA and ~45% migration of the adsorbed Cd to iron (hydr)oxide binding sites at high HA:Fe mass ratios. A composite model that accounts for both site masking between Fe ions and HA and the increase of Fe hydroxyl sites simulate the distribution of Cd in the composites reasonably well. Overall, this study demonstrates that the Fe clusters play an overriding role for heavy metal stabilization in coprecipitation systems, while HA promotes the immobilization of Cd by facilitating the flocculation and dispersion of Fe clusters.

Tellurite Adsorption onto Bacterial Surfaces.

Tellurium (Te) is an emerging contaminant and its chemical transformation in the environment is strongly influenced by microbial processes. In this study, we investigated the adsorption of tellurite [Te(IV), TeO32-] onto the common soil bacterium Bacillus subtilis. Thiol-blocking experiments were carried out to investigate the role of cell surface sulfhydryl sites in tellurite binding, and extended X-ray absorption fine structure (EXAFS) spectroscopy was performed to determine the chemical speciation of the adsorbed tellurite. The results indicate that tellurite reacts with sulfhydryl functional groups in the extracellular polymeric substances (EPS) produced by B. subtilis. Upon binding to sulfhydryl sites in the EPS, the Te changes from Te-O bonds to Te-S coordination. Further analysis of the surface-associated molecules shows that the EPS of B. subtilis contain proteins. Removal of the proteinaceous EPS dramatically decreases tellurite adsorption and the sulfhydryl surface site concentration. These findings indicate that sulfhydryl binding in EPS plays a key role in tellurite adsorption on bacterial surfaces.

Glyphosate adsorption onto kaolinite and kaolinite-humic acid composites: Experimental and molecular dynamics studies.

Glyphosate (PMG) has been the most widely used herbicide in the world, and its environmental mobility and fate are mainly controlled by interactions with mineral surfaces. In soil systems, kaolinite is typically associated with humic acids (HAs) in the form of mineral-HA complexes, and hence it is crucial to characterize the molecular-scale interactions that occur between PMG and kaolinite and kaolinite-HA complexes. Batch experiments, Fourier transform infrared spectrum (FTIR) and X-ray photoelectron spectroscopy (XPS), isothermal titration calorimetry (ITC), and molecular dynamics (MD) simulations were performed to decipher the molecular interactions between PMG and kaolinite and kaolinite-HA composites. Our results reveal that kaolinite-HA composites adsorb higher concentrations of PMG than does kaolinite alone, likely due to more adsorption sites existed on kaolinite-HA than on kaolinite. FTIR and XPS analysis reveal that the carboxyl, phosphonyl and amino groups of PMG interacted with kaolinite and kaolinite-humic acid via Hydrogen bonds. The ITC results and interaction energy calculations indicate that the adsorption of PMG onto the kaolinite-HA is more energetically favorable relative to that onto kaolinite. MD simulations suggest that the PMG molecule adsorbs parallel to the surface of kaolinite and the composites through hydrogen bonding. Humic acid increases the adsorption of PMG through the creation of H-bond networks between PMG, the kaolinite surface, and humic acid. The results from this study improve our molecular-level understanding of the interactions between PMG and two important components of soil systems, and hence yield valuable information for characterizing the fate and behavior of PMG in soil environments.

Quantitative analysis of the surficial and adhesion properties of the Gram-negative bacterial species Comamonas testosteroni modulated by c-di-GMP.

Cyclic diguanylate monophosphate (c-di-GMP) is a ubiquitous intracellular secondary messenger which governs the transition from a bacterial cell's planktonic state to biofilm formation by stimulating the production of a variety of exopolysaccharide material by the bacterial cell. A range of genes involved in c-di-GMP signaling in the Gram-negative species Comamonas testosteroni have been identified previously, yet the physical-chemical properties of the produced extracellular polymeric substances (EPS) and the bacterial adhesion characteristics regulated by c-di-GMP are not well understood. Here, we modulated the in vivo c-di-GMP levels of Comamonas testosteroni WDL7 through diguanylate cyclase (YedQ) and phosphodiesterase (YhjH) gene editing. The strains and their adhesion properties were characterized by Fourier-transform infrared and two-dimensional correlation spectroscopy analysis (FTIR-2D CoS), contact angle and zeta potential measurements, atomic force microscopy (AFM) and extended-Derjaguin-Landau-Verwey-Overbeek (ExDLVO) analysis. Our results show that high c-di-GMP levels promoted the secretion of long-chain hydrophobic and electroneutral extracellular polysaccharides and proteins. The protein molecules on WDL7/pYedQ2 promoted the bacterial self-aggregation and adhesion onto negatively charged surfaces. In contrast, the reduction of intracellular c-di-GMP concentrations resulted in a nearly 80 % decrease in the adhesion of bacterial cells, although little change in the surface hydrophobicity or surface charge properties were observed for these cells relative to the wild type. These results indicate that the reduced adsorption of WDL7/YhjH that we observed may be caused by the flagellum-accelerated mobility at low c-di-GMP concentrations. Taken together, these results improve our mechanistic understanding of the effects of c-di-GMP in controlling bacterial physical-chemical properties and initial biofilm development.

The role of interfacial reactions in controlling the distribution of Cd within goethite-humic acid-bacteria composites.

Mineral-organic interfacial reactions strongly influence the adsorption, distribution and bioavailability of metal cations in soil systems. The molecular binding mechanisms and distribution of Cd onto goethite, humic acid, Pseudomonas putida cells, and their composites at different mass ratios were studied through the combination of bulk adsorption coupled with EXAFS, ITC and SCM. In binary and ternary composites, the energetics of the overall adsorption of Cd was dominated by the entropy of Cd adsorption onto the organic fraction. The formation of a type-B HA bridging complex >FeOH-HACOOCdOH enhanced Cd adsorption by 10-30% at low Cd concentrations, and more than 93.5% of the adsorbed Cd was bound onto HA fraction. In ternary systems, the component additivity over-estimated Cd adsorption onto bacteria by ~21.8%, likely due to site blocking effects. Models involving the masking of phosphoryl sites and HA bridging reactions can simulate the distribution of Cd in the composites. Our modelling suggests that HA is the main scavenger of Cd under a range of environmental conditions, and that bacteria become important in affecting the distribution of Cd under lower pH settings. This study demonstrates the impact of iron oxide-HA-bacteria interactions on the fate and distribution of Cd in soils and associated environments.

Role of bacterial cell surface sulfhydryl sites in cadmium detoxification by Pseudomonas putida.

Understanding bacterial metal detoxification systems is crucial for determining the environmental impacts of metal pollution and for developing advanced bioremediation and water disinfection strategies. Here, we explore the role of cell surface sulfhydryl sites in bacterial detoxification of Cd, using Pseudomonas putida with surface sulfhydryl sites mostly on its EPS molecules as a model organism. Our results show that 5 and 20 ppm Cd in LB growth medium affects the lag phase of P. putida, but not the overall extent of cell growth at stationary phase, indicating that P. putida can detoxify Cd at these concentrations. EXAFS analysis of Cd bound to biomass from the different growth stages indicates that Cd binds to both sulfhydryl and non-sulfhydryl sites, but that the importance of Cd-sulfhydryl binding increases from early exponential to stationary phase. Cell growth is positively correlated to the measured sulfhydryl concentration on different biomass samples, but is independent of the measured non-sulfhydryl binding site concentration on the cell surfaces. Taken together, our results demonstrate that the sulfhydryl binding sites on EPS molecules can play an important role in binding and detoxifying toxic metals, significantly decreasing the bioavailability of the metal by sequestering it away from the bacterial cells.

Role of interfacial reactions in biodegradation: A case study in a montmorillonite, Pseudomonas sp. Z1 and methyl parathion ternary system.

Organophosphate pesticides are currently the most commonly used pesticides, but the mechanisms of biodegradation of these compounds are often unknown. In this study, we constructed a ternary biodegradation system containing methyl parathion (MP), a bacterial strain of Pseudomonas sp. Z1 with capability of degrading MP and montmorillonite, which is a common clay mineral in soils. The role of interfacial reactions between montmorillonite and the MP degrader on the biodegradation of MP was investigated by batch adsorption as well as through semi-permeable membrane experiments. The contact between degrader and montmorillonite in biodegradation was also dynamically examined using in situ attenuated total reflectance Fourier transform infrared spectroscopy. The metabolic activity of the degrading bacteria was also assessed using an isothermal microcalorimetric technique. The results indicate that sorption of bacterial cells onto montmorillonite enhances the metabolic activity of the bacteria and hence the biodegradation of MP by the bacteria, and that an amide group on a bacterial surface protein is responsible for the bacterial adhesion onto the montmorillonite. This stimulated effect ceased when the bacteria were physically separated from the surface of the clay by a membrane, demonstrating the importance of sorption of both the bacteria and the MP in the biodegradation process.

Testing the component additivity approach to surface complexation modeling using a novel cadmium-specific fluorescent probe technique.

Over the past 40 years, laboratory experiments involving single metal-single sorbent systems have been conducted in order to determine thermodynamic stability constants for metal-bacteria and metal-mineral surface complexes. The component additivity (CA) approach to surface complexation modeling (SCM) represents one method for using these experimentally-derived stability constants to predict the extent of metal adsorption in complex, multi-sorbent systems. However, quantitative tests of the CA approach are rare due to difficulties in determining the distribution of metals in complex multi-sorbent systems. In this study, we use a novel technique that couples the use of a cadmium(Cd)-specific fluorescent probe with confocal scanning laser microscopy to quantify Cd adsorption to bacteria in fully hydrated multi-sorbent samples that contain different ratios of Bacillus subtilis bacterial cells, the clay mineral kaolinite, and the aqueous chelating ligand EDTA. In this approach, we directly determine the distribution of Cd by measuring the total concentration of adsorbed Cd and the concentration of Cd that is adsorbed to bacterial cells, and by difference we calculate the concentration of Cd that is adsorbed to kaolinite. We compare these experimental measurements to the extent of Cd adsorption that is calculated using a CA approach to predict the distribution of Cd under our experimental conditions. In general, the CA predictions of the distribution of Cd between the aqueous phase and the two sorbents agree within uncertainties with the measured concentrations of Cd in each reservoir in both the EDTA-free and the EDTA-bearing experimental systems. This study demonstrates that the Cd-fluorescent probe technique is a suitable, and relatively simple, option for quantitatively testing CA surface complexation models. Our results suggest that although the CA approach can yield reasonable predictions of the distribution of Cd in mixed sorbent systems, the accuracy of the predictions depends directly on the accuracy of the measurements of stability constants for both the aqueous and surface metal-ligand complexes that occur in a system of interest.

Adsorption of Methylmercury onto Geobacter bemidijensis Bem.

The anaerobic bacterium Geobacter bemidijensis Bem has the unique ability to both produce and degrade methylmercury (MeHg). While the adsorption of MeHg onto bacterial surfaces can affect the release of MeHg into aquatic environments as well as the uptake of MeHg for demethylation, the binding of MeHg to the bacterial envelope remains poorly understood. In this study, we quantified the adsorption of MeHg onto G. bemidijensis and applied X-ray absorption spectroscopy (XAS) to elucidate the mechanism of MeHg binding. The results showed MeHg adsorption onto G. bemidijensis cell surfaces was rapid and occurred via complexation to sulfhydryl functional groups. Titration experiments yielded cell surface sulfhydryl concentrations of 3.8 ± 0.2 µmol/g (wet cells). A one-site adsorption model with MeHg binding onto sulfhydryl sites provided excellent fits to adsorption isotherms conducted at different cell densities. The log K binding constant of MeHg onto the sulfhydryl sites was determined to be 10.5 ± 0.4. These findings provide a quantitative framework to describe MeHg binding onto bacterial cell surfaces and elucidate the importance of bacterial cells as possible carriers of adsorbed MeHg in natural aquatic systems.

Adsorption of Selenite onto Bacillus subtilis: The Overlooked Role of Cell Envelope Sulfhydryl Sites in the Microbial Conversion of Se(IV).

Microbial activities play a central role in the global cycling of selenium. Microorganisms can reduce, methylate, and assimilate Se, controlling the transport and fate of Se in the environment. However, the mechanisms controlling these microbial activities are still poorly understood. In particular, it is unknown how the negatively charged Se(IV) and Se(VI) oxyanions that dominate the aqueous Se speciation in oxidizing environments bind to negatively charged microbial cell surfaces in order to become bioavailable. Here, we show that the adsorption of selenite onto Bacillus subtilis bacterial cells is controlled by cell envelope sulfhydryl sites. Once adsorbed onto the bacteria, selenite is reduced and forms reduced organo-Se compounds (e.g., R1S-Se-SR2). Because sulfhydryl sites are present within cell envelopes of a wide range of bacterial species, sulfhydryl-controlled adsorption of selenite likely represents a general mechanism adopted by bacteria to make selenite bioavailable. Therefore, sulfhydryl binding of selenite likely occurs in a wide range of oxidized Se-bearing environments, and because it is followed by microbial conversion of selenite to other Se species, the process represents a crucial step in the global cycling of Se.

Enhanced Removal of Dissolved Hg(II), Cd(II), and Au(III) from Water by Bacillus subtilis Bacterial Biomass Containing an Elevated Concentration of Sulfhydryl Sites.

In this study, the sorption of Hg(II), Cd(II), and Au(III) onto Bacillus subtilis biomass with an elevated concentration of sulfhydryl sites, induced by adding excess glucose to the growth medium (termed 'High Sulfhydryl Bacillus subtilis' or HSBS) was compared to that onto B. subtilis biomass with a low concentration of sulfhydryl sites (termed 'Low Sulfhydryl Bacillus subtilis' or LSBS) and to sorption onto a commercially available cation exchange resin. Our results show that HSBS exhibits sorption capacities for the three studied metals that are two to five times greater than the sorption capacities of LSBS for these metals. After blocking the bacterial cell envelope sulfhydryl sites using a qBBr treatment, the sorption of the metals onto HSBS was significantly inhibited, indicating that the enhanced sorption onto HSBS was mainly due to the elevated concentration of sulfhydryl sites on the bacteria. A direct comparison of the removal capacity of the HSBS and that of the cation exchange resin for the three metals demonstrates that HSBS, compared to this commercially available resin, exhibits superior sorption capacity and selectivity for the removal of Hg(II), Cd(II), and Au(III), especially in systems with dilute metal concentrations. These results suggest that bacterial sulfhydryl sites control the sorption behavior of these three metals, and therefore biomass with induced high concentrations of sulfhydryl sites represents a promising and low cost biosorbent for the effective removal and recovery of chalcophile heavy metals from aqueous media.

An X-ray absorption fine structure spectroscopy study of metal sorption to graphene oxide.

Remediation and prevention of environmental contamination by toxic metals is an ongoing issue. Additionally, improving water filtration systems is necessary to prevent toxic metals from circulating through the water supply. Graphene oxide (GO) is a highly sorptive material for a variety of heavy metals under different ionic strength conditions over a wide pH range, making it a promising candidate for use in metal adsorption from contaminated sites or in filtration systems. We present X-ray absorption fine structure (XAFS) spectroscopy results investigating the binding environment of Cd (II), U(VI) and Pb(II) ions onto multi-layered graphene oxide (MLGO). This study shows that the binding environment of each metal onto the MLGO is unique, with different behaviors governing the sorption as a function of pH. For Cd sorption to MLGO, the same mechanism of electrostatic attraction between the MLGO and the Cd+2 ions surrounded by water molecules prevails over the entire pH range studied. The U(VI), present in solution as the uranyl ion, shows only subtle changes as a function of pH, likely due to the varied speciation of uranium in solution. The adsorption of the U to the MLGO is through a covalent, inner-sphere bond. The only metal from this study where the dominant adsorption mechanism to the MLGO changes with pH is Pb. In this case, under lower pH conditions, Pb is bound onto the MLGO through dominantly outer-sphere, electrostatic adsorption, while under higher pH conditions, the bonding changes to be dominated by inner-sphere, covalent adsorption. Since each of the metals in this study show unique binding properties, it is possible that MLGO could be engineered to effectively adsorb specific metal ions from solution and optimize environmental remediation or filtration for each metal.

Experimental Measurements and Surface Complexation Modeling of U(VI) Adsorption onto Multilayered Graphene Oxide: The Importance of Adsorbate-Adsorbent Ratios.

Surface complexation models use experimental adsorption measurements to calculate stability constants that quantify the thermodynamic stability of adsorbed species. However, these constants are often poorly constrained due to nearly complete removal of the solute from solution and/or because the tested adsorbate:adsorbent ratios are not varied sufficiently. Using data sets that quantify the adsorption of U(VI) to multilayered graphene oxide (MLGO), we tested whether three different U(VI):MLGO ratios (3 ppm U; 20-210 mg L-1 MLGO) affect the ability of nonelectrostatic and diffuse layer models to predict U(VI) adsorption behaviors across a range of ionic strength (1-100 mM) and pH (2-9.5) conditions. Model formulations assumed interactions between discrete MLGO surfaces sites and the most abundant aqueous U(VI) complex(es) within a given pH range. We determined that the observed extents of U(VI) binding require adsorption of more than one U(VI) species (UO22+ and uranyl hydroxide(s) and/or carbonate(s)) and calculated the respective stability constants for the important U(VI)-MLGO surface complexes. The results also unequivocally illustrated that models using adsorption data from treatments with higher U(VI):MLGO ratios provide better fits throughout the tested range of experimental conditions, meaning that the U(VI)-MLGO stability constants calculated herein can be confidently applied to a range of natural or engineered systems.

Controls on Bacterial Cell Envelope Sulfhydryl Site Concentrations: The Effect of Glucose Concentration During Growth.

Bacterial sulfhydryl sites can form strong complexes with chalcophilic metals such as Hg and Cd, thereby affecting the fate, transport, and bioavailability of these metals in both natural and engineered systems. In this study, five bacterial species were cultured in M9 minimal media containing a range of glucose concentrations as carbon source and in a high-nutrient TSB medium enriched with 50 g/L of glucose, and the sulfhydryl site concentrations of the obtained biomass samples were determined through selective sulfhydryl site-blocking, potentiometric titrations, and surface complexation modeling. The experimental results show that the glucose concentration in the M9 minimal media strongly affects the concentration of sulfhydryl sites that are present on the bacteria, with higher glucose concentrations yielding higher bacterial sulfhydryl site concentrations for each species studied. In contrast, although adding 50 g/L of glucose to the TSB medium significantly increases the sulfhydryl site concentrations for the three Bacillus species studied, the elevated glucose concentration does not significantly affect sulfhydryl site concentrations for S. oneidensis and P. putida samples when grown in the TSB medium. Our results suggest that bacterial sulfhydryl site concentrations in natural systems are likely affected by the composition of the bacterial community and by the available nutrients, and that these factors must be considered in order to determine and model the effects of bacterial cells on metal cycling and metal bioavailability in the environment.

Sulfhydryl Binding Sites within Bacterial Extracellular Polymeric Substances.

In this study, the concentration of sulfhydryl sites on bacterial biomass samples with and without extracellular polymeric substances (EPS) was measured in order to determine the distribution of sulfhydryl sites on bacteria. Three different approaches were employed for EPS removal from Pseudomonas putida, and the measured sulfhydryl concentrations on bacterial EPS molecules are independent of the EPS removal protocols used. Prior to EPS removal, the measured sulfhydryl sites within P. putida samples was 34.9 ± 9.5 µmol/g, and no sulfhydryl sites were detected after EPS removal, indicating that virtually all of the sulfhydryl sites are located on the EPS molecules produced by P. putida. In contrast, the sulfhydryl sites within the S. oneidensis samples increased from 32.6 ± 3.6 µmol/g to 51.9 ± 7.2 µmol/g after EPS removal, indicating that the EPS produced by S. oneidensis contained fewer sulfhydryl sites than those present on the untreated cells. This study suggests that the sulfhydryl concentrations on EPS molecules may vary significantly from one bacterial species to another, thus it is crucial to quantify the concentration of sulfhydryl sites on EPS molecules of other bacterial species in order to determine the effect of bacterial EPS on metal cycling in the environment.

Atomic force microscopy measurements of bacterial adhesion and biofilm formation onto clay-sized particles.

Bacterial adhesion onto mineral surfaces and subsequent biofilm formation play key roles in aggregate stability, mineral weathering, and the fate of contaminants in soils. However, the mechanisms of bacteria-mineral interactions are not fully understood. Atomic force microscopy (AFM) was used to determine the adhesion forces between bacteria and goethite in water and to gain insight into the nanoscale surface morphology of the bacteria-mineral aggregates and biofilms formed on clay-sized minerals. This study yields direct evidence of a range of different association mechanisms between bacteria and minerals. All strains studied adhered predominantly to the edge surfaces of kaolinite rather than to the basal surfaces. Bacteria rarely formed aggregates with montmorillonite, but were more tightly adsorbed onto goethite surfaces. This study reports the first measured interaction force between bacteria and a clay surface, and the approach curves exhibited jump-in events with attractive forces of 97 ± 34 pN between E. coli and goethite. Bond strengthening between them occurred within 4 s to the maximum adhesion forces and energies of -3.0 ± 0.4 nN and -330 ± 43 aJ (10(-18) J), respectively. Under the conditions studied, bacteria tended to form more extensive biofilms on minerals under low rather than high nutrient conditions.

Uranium reduction by Shewanella oneidensis MR-1 as a function of NaHCO3 concentration: surface complexation control of reduction kinetics.

It is crucial to determine the controls on the kinetics of U(VI) bioreduction in order to understand and model the fate and mobility of U in groundwater systems and also to enhance the effectiveness of U bioremediation strategies. In this study, we measured the rate of U(VI) reduction by Shewanella oneidensis strain MR-1 as function of NaHCO3 concentration. The experiments demonstrate that increasing concentrations of NaHCO3 in the system lead to slower U(VI) reduction kinetics. The NaHCO3 concentration also strongly affects the speciation of U(VI) on the bacterial cell envelope. We used a thermodynamic surface complexation modeling approach to determine the speciation and concentration of U(VI) adsorbed onto the bacteria as a function of the NaHCO3 concentration in the experimental systems. We observed a strong positive correlation between the measured U(VI) reduction rates and the calculated total concentration of U(VI) surface complexes formed on the bacterial cell envelope. This positive correlation indicates that the speciation and concentration of U(VI) adsorbed on the bacterial cell envelope control the kinetics of U(VI) bioreduction under the experimental conditions. The results of this study serve as a basis for developing speciation-based kinetic rate laws for enzymatic reduction of U(VI) by bacteria.

Bioreduction of hydrogen uranyl phosphate: mechanisms and U(IV) products.

The mobility of uranium (U) in subsurface environments is controlled by interrelated adsorption, redox, and precipitation reactions. Previous work demonstrated the formation of nanometer-sized hydrogen uranyl phosphate (abbreviated as HUP) crystals on the cell walls of Bacillus subtilis, a non-U(VI)-reducing, Gram-positive bacterium. The current study examined the reduction of this biogenic, cell-associated HUP mineral by three dissimilatory metal-reducing bacteria, Anaeromyxobacter dehalogenans strain K, Geobacter sulfurreducens strain PCA, and Shewanella putrefaciens strain CN-32, and compared it to the bioreduction of abiotically formed and freely suspended HUP of larger particle size. Uranium speciation in the solid phase was followed over a 10- to 20-day reaction period by X-ray absorption fine structure spectroscopy (XANES and EXAFS) and showed varying extents of U(VI) reduction to U(IV). The reduction extent of the same mass of HUP to U(IV) was consistently greater with the biogenic than with the abiotic material under the same experimental conditions. A greater extent of HUP reduction was observed in the presence of bicarbonate in solution, whereas a decreased extent of HUP reduction was observed with the addition of dissolved phosphate. These results indicate that the extent of U(VI) reduction is controlled by dissolution of the HUP phase, suggesting that the metal-reducing bacteria transfer electrons to the dissolved or bacterially adsorbed U(VI) species formed after HUP dissolution, rather than to solid-phase U(VI) in the HUP mineral. Interestingly, the bioreduced U(IV) atoms were not immediately coordinated to other U(IV) atoms (as in uraninite, UO2) but were similar in structure to the phosphate-complexed U(IV) species found in ningyoite [CaU(PO4)2·H2O]. This indicates a strong control by phosphate on the speciation of bioreduced U(IV), expressed as inhibition of the typical formation of uraninite under phosphate-free conditions.

Cell wall reactivity of acidophilic and alkaliphilic bacteria determined by potentiometric titrations and Cd adsorption experiments.

In this study, we used potentiometric titrations and Cd adsorption experiments to determine the binding capacities of two acidophilic (A. cryptum and A. acidophilum) and two alkaliphilic (B. pseudofirmus and B. circulans) bacterial species in order to determine if any consistent trends could be observed relating bacterial growth environment to proton and Cd binding properties and to compare those binding behaviors to those of neutrophilic bacteria. All of the bacterial species studied exhibited significant proton buffering over the pH range in this study, with the alkaliphiles exhibiting significantly higher acidity constants than the acidophiles as well as the neutrophilic bacterial consortia. The calculated average site concentrations for each of the bacteria in this study are within 2σ experimental error of each other, with the exception of A. cryptum, which has a significantly higher Site 2 concentration than the other species. Despite differing acidity constants between the acidophiles and alkaliphiles, all bacteria except A. cryptum exhibited remarkably similar Cd adsorption behavior to each other, and the observed extent of adsorption was also similar to that predicted from a generalized model derived using neutrophilic bacterial consortia. This study demonstrates that bacteria that grow under extreme conditions exhibit similar proton and metal adsorption behavior to that of previously studied neutrophilic species and that a single set of proton and metal binding constants can be used to model the behavior of bacterial adsorption under a wide range of environmental conditions.

Thermodynamic properties of autunite, uranyl hydrogen phosphate, and uranyl orthophosphate from solubility and calorimetric measurements.

In this study, we use solubility and drop-solution calorimetry measurements to determine the thermodynamic properties of the uranyl phosphate phases autunite, uranyl hydrogen phosphate, and uranyl orthophosphate. Conducting the solubility measurements from both supersaturated and undersaturated conditions and under different pH conditions rigorously demonstrates attainment of equilibrium and yields well-constrained solubility product values. We use the solubility data and the calorimetry data, respectively, to calculate standard-state Gibbs free energies of formation and standard-state enthalpies of formation for these uranyl phosphate phases. Combining these results allows us also to calculate the standard-state entropy of formation for each mineral phase. The results from this study are part of a combined effort to develop reliable and internally consistent thermodynamic data for environmentally relevant uranyl minerals. Data such as these are required to optimize and quantitatively assess the effect of phosphate amendment remediation technologies for uranium contaminated systems.