Effects of microbial iron reduction and oxidation on the immobilization and mobilization of copper in synthesized Fe(III) minerals and Fe-rich soils.

The effects of microbial iron reduction and oxidation on the immobilization and mobilization of copper were investigated in a high concentration of sulfate with synthesized Fe(III) minerals and red earth soils rich in amorphous Fe (hydr)oxides. Batch microcosm experiments showed that red earth soil inoculated with subsurface sediments had a faster Fe(III) bioreduction rate than pure amorphous Fe(III) minerals and resulted in quicker immobilization of Cu in the aqueous fraction. Coinciding with the decrease of aqueous Cu, SO4(2-) in the inoculated red earth soil decreased acutely after incubation. The shift in the microbial community composite in the inoculated soil was analyzed through denaturing gradient gel electrophoresis. Results revealed the potential cooperative effect of microbial Fe(III) reduction and sulfate reduction on copper immobilization. After exposure to air for 144 h, more than 50% of the immobilized Cu was remobilized from the anaerobic matrices; aqueous sulfate increased significantly. Sequential extraction analysis demonstrated that the organic matter/sulfide-bound Cu increased by 52% after anaerobic incubation relative to the abiotic treatment but decreased by 32% after oxidation, indicating the generation and oxidation of Cu-sulfide coprecipitates in the inoculated red earth soil. These findings suggest that the immobilization of copper could be enhanced by mediating microbial Fe(III) reduction with sulfate reduction under anaerobic conditions. The findings have an important implication for bioremediation in Cucontaminated and Fe-rich soils, especially in acid-mine-drainage-affected sites.

Anaerobic digestion of municipal solid waste composed of food waste, wastepaper, and plastic in a single-stage system: performance and microbial community structure characterization.

The performance of municipal organic solid waste anaerobic digestion was investigated using a single-stage bioreactor, and the microbial community structures were characterized during the digestion. The results showed that the biogas and methane production rates were 592.4 and 370.1L/kg with volatile solid added at the ratio of 2:1:1 for food waste, wastepaper, and plastic based on dry weight. The methane volume concentration fluctuated between 44.3% and 75.4% at steady stage. Acetic acid, propionic acid, and butyric acid were the major volatile fatty acids produced during the digestion process. The anaerobic process was not inhibited by the accumulation of ammonia and free ammonia. The bacterial community was found to consist of at least 21 bands of bacteria and 12 bands of archaea at the steady state. All of the results indicated that the mixture of food waste, wastepaper, and plastic could be efficiently co-digested using the anaerobic digestion system.

Prediction of aluminum, uranium, and co-contaminants precipitation and adsorption during titration of acidic sediments.

Batch and column recirculation titration tests were performed with contaminated acidic sediments. A generic geochemical model was developed combining precipitation, cation exchange, and surface complexation reactions to describe the observed pH and metal ion concentrations in experiments with or without the presence of CO2. Experimental results showed a slow pH increase due to strong buffering by Al hydrolysis and precipitation and CO2 uptake. The cation concentrations generally decreased at higher pH than those observed in previous tests without CO2. Using amorphous Al(OH)3 and basaluminite precipitation reactions and a cation exchange selectivity coefficient K(Na\Al) of 0.3, the model approximately described the observed (1) pH titration curve, (2) Ca, Mg, and Mn concentration by cation exchange, and (3) U concentrations by surface complexation with Fe hydroxides at pH < 5 and with liebigite (Ca2UO2(CO3)3·10H2O) precipitation at pH > 5. The model indicated that the formation of aqueous carbonate complexes and competition with carbonate for surface sites could inhibit U and Ni adsorption and precipitation. Our results suggested that the uncertainty in basaluminite solubility is an important source of prediction uncertainty and ignoring labile solid phase Al underestimates the base requirement in titration of acidic sediments.

Biochars prepared from anaerobic digestion residue, palm bark, and eucalyptus for adsorption of cationic methylene blue dye: characterization, equilibrium, and kinetic studies.

Biochars prepared from anaerobic digestion residue (BC-R), palm bark (BC-PB) and eucalyptus (BC-E) were used as sorbents for removal of cationic methylene blue dye (MB). The FE-SEM images indicated that the biochars have a well-developed pore structure, and the Brunauer-Emmett-Teller surface areas of BC-R, BC-PB, and BC-E were 7.60, 2.46, and 10.35 m(2)g(-1), respectively. The efficiencies of MB removal in the samples with initial concentrations of 5 mg L(-1) at pH 7.0 and 40°C by BC-R, BC-PB, and BC-E after 2h were 99.5%, 99.3%, and 86.1%, respectively. Pseudo-second-order kinetics was the most suitable model for describing the adsorption of MB onto the biochars. The experimental data were best described by the Langmuir isotherm model, with a maximum monolayer adsorption capacity of 9.50 mg g(-1) at 40°C for BC-R. The biochars produced from the three types of solid waste showed considerable potential for adsorption.

Interaction of plant secondary metabolites and organic carbon substrates affected on biodegradation of polychlorinated biphenyl.

Using plant secondary metabolites (PSM) as an inducer to stimulate biodegradation of polychlorinated biphenyl (PCB) is considered a promising strategy to remove PCB from the environment. In this study, the effects of PSM including naringin, salicylic acid or biphenyl on PCB biodegradation using soil isolates were tested in mineral salt medium using either soil organic carbon (MSMS) or glucose (MSMG). In addition, the effects of surfactant hydroxypropyl-beta-cyclodextrin (HP-beta-CD) were examined. The results indicated that PCB removal was higher in medium with glucose as carbon substrate than in medium with SOC, and further enhanced with biphenyl amendment. However, interactions between salicylic acid and glucose limited PCB removal in treatments using both chemicals as carbon substrate while PCB removal was sustained in treatment using salicylic acid and SOC. Removal of tetra-chlorinated PCB was improved by adding HP-beta-CD, suggesting increased bioavailability due to surfactant. These results suggest that interaction of organic carbon substrates could influence PCB degradation in contaminated environments.

Innovative mathematical modeling in environmental remediation.

There are two different ways to model reactive transport: ad hoc and innovative reaction-based approaches. The former, such as the Kd simplification of adsorption, has been widely employed by practitioners, while the latter has been mainly used in scientific communities for elucidating mechanisms of biogeochemical transport processes. It is believed that innovative mechanistic-based models could serve as protocols for environmental remediation as well. This paper reviews the development of a mechanistically coupled fluid flow, thermal transport, hydrologic transport, and reactive biogeochemical model and example-applications to environmental remediation problems. Theoretical bases are sufficiently described. Four example problems previously carried out are used to demonstrate how numerical experimentation can be used to evaluate the feasibility of different remediation approaches. The first one involved the application of a 56-species uranium tailing problem to the Melton Branch Subwatershed at Oak Ridge National Laboratory (ORNL) using the parallel version of the model. Simulations were made to demonstrate the potential mobilization of uranium and other chelating agents in the proposed waste disposal site. The second problem simulated laboratory-scale system to investigate the role of natural attenuation in potential off-site migration of uranium from uranium mill tailings after restoration. It showed inadequacy of using a single Kd even for a homogeneous medium. The third example simulated laboratory experiments involving extremely high concentrations of uranium, technetium, aluminum, nitrate, and toxic metals (e.g., Ni, Cr, Co). The fourth example modeled microbially-mediated immobilization of uranium in an unconfined aquifer using acetate amendment in a field-scale experiment. The purposes of these modeling studies were to simulate various mechanisms of mobilization and immobilization of radioactive wastes and to illustrate how to apply reactive transport models for environmental remediation.

Modeling uranium transport in acidic contaminated groundwater with base addition.

This study investigates reactive transport modeling in a column of uranium(VI)-contaminated sediments with base additions in the circulating influent. The groundwater and sediment exhibit oxic conditions with low pH, high concentrations of NO(3)(-), SO(4)(2-), U and various metal cations. Preliminary batch experiments indicate that additions of strong base induce rapid immobilization of U for this material. In the column experiment that is the focus of the present study, effluent groundwater was titrated with NaOH solution in an inflow reservoir before reinjection to gradually increase the solution pH in the column. An equilibrium hydrolysis, precipitation and ion exchange reaction model developed through simulation of the preliminary batch titration experiments predicted faster reduction of aqueous Al than observed in the column experiment. The model was therefore modified to consider reaction kinetics for the precipitation and dissolution processes which are the major mechanism for Al immobilization. The combined kinetic and equilibrium reaction model adequately described variations in pH, aqueous concentrations of metal cations (Al, Ca, Mg, Sr, Mn, Ni, Co), sulfate and U(VI). The experimental and modeling results indicate that U(VI) can be effectively sequestered with controlled base addition due to sorption by slowly precipitated Al with pH-dependent surface charge. The model may prove useful to predict field-scale U(VI) sequestration and remediation effectiveness.

Dissolution of uranium-bearing minerals and mobilization of uranium by organic ligands in a biologically reduced sediment.

The stability and mobility of uranium (U) is a concern following its reductive precipitation or immobilization by techniques such as bioremediation at contaminated sites. In this study, the influences of complexing organic ligands such as citrate and ethylenediaminetetraacetate (EDTA) on the mobilization of U were investigated in both batch and column flow systems using a contaminated and bioreduced sediment. Results indicate that both reduced U(IV) and oxidized U(VI) in the sediment can be effectively mobilized with the addition of EDTA or citrate under anaerobic conditions. The dissolution and mobilization of U appear to be correlated to the dissolution of iron (Fe)- or aluminum (Al)-bearing minerals, with EDTA being more effective (with R2≥0.89) than citrate (R2<0.60) in dissolving these minerals. The column flow experiments confirm that U, Fe, and Al can be mobilized by these ligands under anoxic conditions, although the cumulative amounts of U removal constituted ∼0.1% of total U present in this sediment following a limited period of leaching. This study concludes that the presence of complexing organic ligands may pose a long-term concern by slowly dissolving U-bearing minerals and mobilizing U even under a strict anaerobic environment.

Sequestering uranium and technetium through co-precipitation with aluminum in a contaminated acidic environment.

This research evaluated a method of controlled base addition for immobilizing uranium (U) and technetium (Tc) through coprecipitation with aluminum (Al) and other metal ions which coexist in a highly contaminated acidic environment. The batch and column experiments indicate that the addition of strong base (NaOH) provided a rapid yet effective means of sequestering U, Tc, and toxic metal ions such as nickel (Ni2+) and cobalt (Co2+) in the sediment and groundwater. Greater than 94% of soluble U (as UO2(2+)) and > 83% of Tc (as TcO4-) can be immobilized at pH above 4.5 by co-precipitation with Al-oxyhydroxides. The presence of sediment minerals appeared to facilitate co-precipitation of these contaminants at lower pH values than those in the absence of sediments. The immobilized U and Tc were found to be stable against dissolution in Ca(NO3)2 solution (up to 50 mM) because of the formation of strong surface complexes between U or Tc and Al-oxyhydroxides. This research concludes that as long as a relatively high pH (> 5) and a low carbonate concentration are maintained, both U and Tc can be effectively immobilized under given site-specific conditions.

Dissolution and mobilization of uranium in a reduced sediment by natural humic substances under anaerobic conditions.

Biological reduction and precipitation of uranium (U) has been proposed as a remedial option for immobilizing uranium at contaminated sites, but the long-term stability and mobility of uranium remain a concern because the uranium is neither removed nor destroyed. In this study, the dissolution and mobilization of reduced and oxidized forms of uranium [U(IV) and U(VI)] by natural humic substances were investigated in batch and column-flow systems using a bioreduced sediment containing both U(IV) and U(VI). The addition of humic substances significantly increased the dissolution of U(IV) under anaerobic conditions. Humic acid (HA) was found to be more effective than fulvic acid (FA) in dissolving U(IV) in 1 mM KCl or KHCO3 background solution. However, more U(VI) was dissolved in 1 mM KHCO3 than in 1 mM KCl background electrolyte. HA also was found to be more effective than FA in mobilizing uranium under reducing and column-flow conditions, although the cumulative amount of eluted U(VI) and U(IV) was relatively low (<60 microg) after leaching with approximately 97 pore volumes of the humic solution in 1 mM KHCO3. These observations suggestthat natural humic substances could potentially influence the long-term stability of bioreduced U(IV) even under strongly reducing environments.

Geochemical modeling of reactions and partitioning of trace metals and radionuclides during titration of contaminated acidic sediments.

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This studywas undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cation exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/ dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO4(2-) for contaminated sediments indicated close agreement suggesting that the model could potentially be used to predictthe acid-base behavior of the sediment-solution system under variable pH conditions.

Organic carbon effects on aerobic polychlorinated biphenyl removal and bacterial community composition in soils and sediments.

Certain organic compounds, including biphenyl and salicylic acid, stimulate polychlorinated biphenyl (PCB) degradation by microorganisms in some environments. However, the usefulness of these amendments for improving PCB removal by microorganisms from diverse habitats has not been extensively explored. This study evaluated the effects of biphenyl, salicylic acid, and glucose on changes in aerobic PCB removal and bacterial communities from an agricultural soil, a wetland peat soil, a river sediment, and a mixture of these samples. PCB removal patterns were significantly different between soils and sediments amended with carbon compounds: (i) terrestrial soil microorganisms removed more PCBs than river sediment microorganisms, particularly with regard to PCBs with >4 chlorine substituents, (ii) glucose-supplemented, agricultural soil microorganisms removed more hexachlorobiphenyl than unsupplemented samples, (iii) biphenyl-supplemented, river sediment microorganisms removed more di- and tri-chlorobiphenyls than unamended samples. Carbon amendments also caused unique shifts in soil and sediment bacterial communities, as determined by specific changes in bacterial 16S rRNA denaturing gradient gel electrophoresis banding patterns. These results indicate that organic carbon amendments had site-specific effects on bacterial populations and PCB removal. Further work is needed to more accurately characterize PCB degrading communities and functional gene expression in diverse types of environments to better understand how they respond to bioremediation treatments.

Surface-enhanced Raman spectroscopy for uranium detection and analysis in environmental samples.

Techniques for rapid screening of uranium in environmental samples are needed, and this study entails the development of surface-enhanced Raman scattering (SERS) for analyzing uranium in aqueous media with improved sensitivity and reproducibility. A new SERS substrate based on (aminomethyl)phosphonic acid (APA)-modified gold nanoparticles was found to give greater than three orders of magnitude SERS enhancement compared with unmodified bare gold nanoparticles. Intensities of uranyl band at about 830 cm(-1) were proportional to the concentrations of uranium in solution, especially at relatively low concentrations (<10(-5) M). A detection limit of approximately 8x10(-7) M was achieved with a good reproducibility since the measurement was performed directly in dispersed aqueous suspension. Without pretreatment, the technique was successfully employed for detecting uranium in a highly contaminated groundwater with a low pH, high dissolved salts (e.g., nitrate, sulfate, calcium and aluminum) and total organic carbon.

Influence of bicarbonate, sulfate, and electron donors on biological reduction of uranium and microbial community composition.

A microcosm study was performed to investigate the effect of ethanol and acetate on uranium(VI) biological reduction and microbial community changes under various geochemical conditions. Each microcosm contained an uranium-contaminated sediment (up to 2.8 g U/kg) suspended in buffer with bicarbonate at concentrations of either 1 or 40 mM and sulfate at either 1.1 or 3.2 mM. Ethanol or acetate was used as an electron donor. Results indicate that ethanol yielded in significantly higher U(VI) reduction rates than acetate. A low bicarbonate concentration (1 mM) was favored for U(VI) bioreduction to occur in sediments, but high concentrations of bicarbonate (40 mM) and sulfate (3.2 mM) decreased the reduction rates of U(VI). Microbial communities were dominated by species from the Geothrix genus and Proteobacteria phylum in all microcosms. However, species in the Geobacteraceae family capable of reducing U(VI) were significantly enriched by ethanol and acetate in low-bicarbonate buffer. Ethanol increased the population of unclassified Desulfuromonales, while acetate increased the population of Desulfovibrio. Additionally, species in the Geobacteraceae family were not enriched in high-bicarbonate buffer, but the Geothrix and the unclassified Betaproteobacteria species were enriched. This study concludes that ethanol could be a better electron donor than acetate for reducing U(VI) under given experimental conditions, and electron donor and groundwater geochemistry alter microbial communities responsible for U(VI) reduction.

In situ bioreduction of uranium (VI) to submicromolar levels and reoxidation by dissolved oxygen.

Groundwater within Area 3 of the U.S. Department of Energy (DOE) Environmental Remediation Sciences Program (ERSP) Field Research Center at Oak Ridge, TN (ORFRC) contains up to 135 microM uranium as U(VI). Through a series of experiments at a pilot scale test facility, we explored the lower limits of groundwater U(VI) that can be achieved by in-situ biostimulation and the effects of dissolved oxygen on immobilized uranium. Weekly 2 day additions of ethanol over a 2-year period stimulated growth of denitrifying, Fe(III)-reducing, and sulfate-reducing bacteria, and immobilization of uranium as U(IV), with dissolved uranium concentrations decreasing to low levels. Following sulfite addition to remove dissolved oxygen, aqueous U(VI) concentrations fell below the U.S. Environmental Protection Agengy maximum contaminant limit (MCL) for drinking water (< 30/microg L(-1) or 0.126 microM). Under anaerobic conditions, these low concentrations were stable, even in the absence of added ethanol. However, when sulfite additions stopped, and dissolved oxygen (4.0-5.5 mg L(-1)) entered the injection well, spatially variable changes in aqueous U(VI) occurred over a 60 day period, with concentrations increasing rapidly from < 0.13 to 2.0 microM at a multilevel sampling (MLS) well located close to the injection well, but changing little at an MLS well located further away. Resumption of ethanol addition restored reduction of Fe(III), sulfate, and U(VI) within 36 h. After 2 years of ethanol addition, X-ray absorption near-edge structure spectroscopy (XANES) analyses indicated that U(IV) comprised 60-80% of the total uranium in sediment samples. Atthe completion of the project (day 1260), U concentrations in MLS wells were less than 0.1 microM. The microbial community at MLS wells with low U(VI) contained bacteria that are known to reduce uranium, including Desulfovibrio spp. and Geobacter spp., in both sediment and groundwater. The dominant Fe(III)-reducing species were Geothrix spp.