Ravi Kukkadapu's Publications

2009

Smith SC, M Douglas, DA Moore, RK Kukkadapu, and BW Arey. 2009. "Uranium Extraction From Laboratory Synthesized, Uranium-Doped Hydrous Ferric Oxides ." Environmental Science & Technology 43:2341-2347. Abstract The extractability of uranium (U) from synthetic hydrous ferric oxides has been shown to decrease as a function of mineral ripening, consistent with the hypothesis that the ripening process decrease contaminant lability. To evaluate this process, three hydrous ferric oxide (HFO) suspensions were co-precipitated with uranyl (UO22+) and maintained at pH 7.0 ± 0.1. Uranyl was added to the HFO post-precipitation in a fourth suspension. Two suspensions also contained either co-precipitated silicate (Si-U-HFO) or phosphate (P-U-HFO). After precipitation of the HFOs, at time intervals of one week, one month, six months, one year, and 2 years, aliquots of the suspensions were contacted with five solutions for a range of time. The extracts were analyzed for U and iron (Fe). The results are consistent with the hypothesis that U and Fe extractability will decrease as the mineral phase ripens. All extracting solutions exhibited some degree of selectivity for U, as the proportional extraction of U exceeded that for congruent dissolution. Micro X-ray diffraction analysis indicates the transformation from an amorphous phase to a material containing substantial proportions of crystalline goethite and hematite, except the P-U-HFO which remained primarily amorphous. Further analysis of the co-precipitates by the Mössbauer technique and scanning electron microscopy (SEM) provides further evidence of mineralogic ripening
Wiatrowski HA, S Das, RK Kukkadapu, ES Ilton, T Barkay, and N Yee. 2009. "Reduction of Hg(II) to Hg(0) by Magnetite." Environmental Science & Technology 43(14):5307-5313. doi:10.1021/es9003608 Abstract Mercury (Hg) is a highly toxic element, and its contamination of groundwater presents a significant threat to terrestrial ecosystems. Understanding the geochemical processes that mediate mercury transformations in the subsurface is necessary to predict its fate and transport. In this study, we investigated the redox transformation of mercuric Hg (Hg[II]) in the presence of the Fe(II)/Fe(III) mixed valence iron oxide mineral magnetite. Kinetic and spectroscopic experiments were performed to elucidate reaction rates and mechanisms. The experimental data demonstrated that reaction of Hg(II) with magnetite results in the loss of Hg(II) and the formation of volatile elemental Hg (Hg[0]). Kinetic experiments showed that Hg(II) reduction occurred within minutes, with reaction rates increasing with increasing magnetite suspension density (0.05 to 0.2 g/L) and solution pH (4.8 to 6.7), and decreasing with increasing chloride concentration (10-6 to 10-2 mol/L). Mössbauer spectroscopic analysis of reacted magnetite samples revealed a decrease in Fe(II) content, corresponding the oxidation of Fe(II) to Fe(III) in the magnetite structure. X-ray photoelectron spectroscopy detected the presence of Hg(II) on magnetite surfaces, suggesting that adsorption is involved in the electron transfer process. These results suggest that Hg(II) reaction with solid-phase Fe(II) is a kinetically favorable pathway for Hg(II) reduction in magnetite-bearing environmental systems.
Zhang G, H Dong, H Jiang, RK Kukkadapu, J Kim, DD Eberl, and Z Xu. 2009. "Biomineralization Associated with Microbial Reduction of Fe3+ and Oxidation of Fe2+ in Solid Minerals ." American Mineralogist 94(7):1049-1058. Abstract Iron- reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so they play an important role in geochemical cycling of iron in a wide range of environments. This study was undertaken to investigate iron redox cycling in the deep subsurface by taking an advantage of the Chinese Continental Scientific Deep Drilling project. A fluid sample from 2450 m was collected and Fe(III)-reducing microorganisms were enriched using specific media (pH 6.2). Nontronite, an Fe(III)-rich clay mineral, was used in initial enrichments with lactate and acetate as electron donors under strictly anaerobic condition at the in-situ temperature of the fluid sample (65oC). Instead of a monotonic increase in Fe(II) concentration with time as would have been expected if Fe(III) bioreduction was the sole process, Fe(II) concentration initially increased, reached a peak, but then decreased to a minimum level. Continued incubation revealed an iron cycling with a cycling period of five to ten days. These initial results suggested that there might be Fe(III) reducers and Fe(II) oxidizers in the enrichment culture. Subsequently, multiple transfers were made with an attempt to isolate individual Fe(III) reducers and Fe(II) oxidizers. However, iron cycling persisted after multiple transfers. Additional experiments were conducted to ensure that iron reduction and oxidation was indeed biological. Biological Fe(II) oxidation was further confirmed in a series of roll tubes (with a pH gradient) where FeS and siderite were used as the sole electron donor. The oxidation of FeS occurred only at pH 10, and goethite, lepidocrocite, and ferrihydrite formed as oxidation products. Although molecular evidence (16S rRNA gene analysis) collectively suggested that only a single organism (a strain of Thermoanaerobacter ethanolicus) might be responsible for both Fe(III) reduction and Fe(II) oxidation, we could not rule out the possibility that Fe(III) reduction and Fe(II) oxidation may be accomplished by a consortia of organisms. Nonetheless, our data were definitive in showing that iron redox cycling exists in the deep subsurface.

2008

Bank TL, RK Kukkadapu, AS Madden, ME Baldwin, and PM Jardine. 2008. "Effects of gamma-sterilization on the physico-chemical properties of natural sediments." Chemical Geology 251(1-4):1-7. doi:10.1016/j.chemgeo.2008.01.003 Abstract A series of experiments were completed to determine the effects of soil sterilization on various soil chemical properties including U(VI) sorption, soil pH, natural organic matter (NOM), cation exchange capacity (CEC), and iron oxidation state. Soils under investigation were a saprolitic sequence of interbedded weathered shale and limestone collected from the Oak Ridge Reservation (ORR). Sediments were sterilized by either steam sterilization at 121oC or by γ-irradiation using a cobalt-60 source. Subsamples of sediments were pretreated with dithionate-citrate-bicarbonate (DCB) and/or H2O2 to remove reducible Fe(III) oxides and NOM. Results from aerobic U(VI) sorption experiments indicated that γ-sterilized sediments sorbed more U(VI) compared to non-sterile sediments. Results from sorption experiments completed using DCB and H2O2-treated samples indicated that the iron oxide and NOM fractions of the sediment accounted for the majority of U(VI) sorption and that γ-irradiation of these phases resulted in increased sorption of U(VI). Mössbauer spectra of γ-sterilized sedimentsdisplayed a decrease in the amount of ferric iron associated with goethite and a small increase in the amount of reduced iron in silicate minerals compared to spectra from non-sterile samples. Our results suggest that sterilization by γ-irradiation induced iron reduction that may have increased sorption of U(VI) on these sediments.
Komlos J, Jr., A Peacock, RK Kukkadapu, and PR Jaffe. 2008. "Long-Term Dynamics of Uranium Reduction/Reoxidation under Low Sulfate Conditions." Geochimica et Cosmochimica Acta 72(15):3603-3615. doi:10.1016/j.gca.2008.05.040 Abstract The biological reduction and precipitation of uranium has shown potential to prevent uranium migration from contaminated areas. Although previous research has shown that uranium bioremediation is maximized during iron reducing conditions, little research has been performed to understand how long iron/uranium reducing conditions can be maintained. Similarly, questions remain about the stability of the bioreduced uranium and that of the uranium-reducing microbial population after iron/uranium biostimulation conditions are terminated and an oxidant (i.e. oxygen) is introduced into the previously reduced zone. To gain further insights into these processes, columns, packed with sediment containing iron as Fe-oxides (mainly Al-goethite) and silicate Fe (Fe-containing clays), were operated in the laboratory under field-relevant flow conditions to measure the long-term (> 200 d) removal efficiency of uranium from a simulated groundwater during biostimulation with acetate under low sulfate conditions. The biostimulation experiments were then followed by reoxidation of the reduced sediments with oxygen. During biostimulation, Fe(III) reduction occurred simultaneously with U(VI) reduction. Both Fe-oxides and silicate Fe(III) were partly reduced, and silicate Fe(III) reduction was detected only during the first half of the biostimulation phase while Fe-oxide reduction occurred throughout the whole biostimulation period. Mössbauer measurements indicated that the biogenic Fe(II) precipitate resulting from Fe-oxide reduction was neither siderite nor FeS0.09 (mackinawite). U(VI) reduction efficiency increased throughout the bioreduction period, while the Fe(III) reduction gradually decreased with time. Effluent Fe(II) concentrations decreased linearly by 30% over the final 100 days of biostimulation, indicating that bioreducible Fe(III) in the sediment was not exhausted at the termination of the experiment. Even though Fe(III) reduction did not change substantially with time, microorganisms not typically associated with Fe(III) and U(VI) reduction (including methanogens) became a significant fraction of the total microbial population during long-term biostimulation, meaning that most acetate was utilized for other biological processes than Fe(III) and U(VI) reduction. Selected columns were reoxidized after 209 days by discontinuing acetate addition and purging the influent media with a gas containing 20% oxygen. Uranium reoxidation occurred rapidly with 61% of the precipitated uranium resolubilized and transported out of the column after 21 days and virtually all of the uranium being removed by day 122. During the first 21 days of reoxidation, the Fe(III) and U(VI) reducing microbial population remained at pre-oxidation levels (even though the methanogen population decreased by 99%) indicating that short-term disruptions in biostimulation (equipment failure, etc.) would not negatively affect the uranium reducing microbial population.
Mohanty SR, B Kollah, DB Hedrick, AD Peacock, RK Kukkadapu, and EE Roden. 2008. "Biogeochemical Processes In Ethanol Stimulated Uranium Contaminated Subsurface Sediments." Environmental Science & Technology 42(12):4384-4390. Abstract A laboratory incubation experiment was conducted with uranium contaminated subsurface sediment to assess the geochemical and microbial community response to ethanol amendment. A classical sequence of TEAPs was observed in ethanol-amended slurries, with NO3- reduction, Fe(III) reduction, SO4 2- reduction, and CH4 production proceeding in sequence until all of the added 13C-ethanol (9 mM) was consumed. Approximately 60% of the U(VI) content of the sediment was reduced during the period of Fe(III) reduction. No additional U(VI) reduction took place during the sulfate-reducing and methanogenic phases of the experiment. Only gradual reduction of NO3 -, and no reduction of U(VI), took place in ethanol-free slurries. Stimulation of additional Fe(III) or SO4 2- reduction in the ethanol-amended slurries failed to promote further U(VI) reduction. Reverse transcribed 16S rRNA clone libraries revealed major increases in the abundance of organisms related to Dechloromonas, Geobacter, and Oxalobacter in the ethanolamended slurries. PLFAs indicative of Geobacter showed a distinct increase in the amended slurries, and analysis of PLFA 13C/12C ratios confirmed the incorporation of ethanol into these PLFAs. A increase in the abundance of 13C-labeled PLFAs indicative of Desulfobacter, Desulfotomaculum, and Desulfovibrio took place during the brief period of sulfate reduction which followed the Fe(III) reduction phase. Our results show that major redox processes in ethanol-amended sediments can be reliably interpreted in terms of standard conceptual models of TEAPs in sediments. However, the redox speciation of uranium is complex and cannot be explained based on simplified thermodynamic considerations.
Peretyazhko T, JM Zachara, SM Heald, BH Jeon, RK Kukkadapu, C Liu, DA Moore, and CT Resch. 2008. "Heterogeneous Reduction of Tc(VII) by Fe(II) at the Solid-Water Interface." Geochimica et Cosmochimica Acta 72(6):1521-1539. doi:10.1016/j.gca.2008.01.004 Abstract Technetium-99 is a byproduct of uranium fission. It exists in two stable valence states (IV/VII) and exhibits a half-cell potential of intermediate value (Eo = 0.748 V). The oxidized form of 99Tc [pertechnetate, TcO4-] is an oxyanion that sorbs poorly to amphoteric surfaces and forms few solid phases with geochemically relevant cations. It is consequently highly mobile in oxic water-rock systems. The reduced valence state [Tc(IV)] is relatively insoluble (<10-8 mol L-1), and, hence immobile as an oxyhydroxide precipitate [TcO2•nH2O(s)]. In spite of favorable thermodynamics, Tc(VII) reacts slowly with Fe2+(aq) under anoxic conditions. Experiments were performed herein to investigate the rates and products of heterogeneous reduction of Tc(VII) by Fe(II) sorbed to hematite and goethite, and by structural Fe(II) in a dithionite-citrate-bicarbonate (DCB) reduced natural phyllosilicate mixture containing vermiculite, illite, and muscovite. The heterogeneous reduction of Tc(VII) by Fe(II) sorbed to the Fe(III) oxides increased with increasing pH and was coincident with a second event of Fe2+(aq) adsorption. The reaction was almost instantaneous above pH 7. In contrast, the reduction rates of Tc(VII) by structural Fe(II) in the DCB-reduced phyllollsilicates, were not sensitive to pH or the concentration of ion-exchangeable Fe(II), and were orders of magnitude slower than observed for the Fe(III) oxides. Tc-EXAFS spectroscopy revealed that the reduction products were virtually identical on hematite and goethite that were comprised primarily of sorbed octahedral TcO2 monomers and dimers with significant Fe(III) in the second coordination shell. The nature of heterogeneous Fe(III) resulting from the redox reaction was ambiguous as probed by Tc-EXAFS spectroscopy, although Mössbauer spectroscopy applied to an experiment with 56Fe-goethite with adsorbed 57Fe(II) implied that redox product Fe(III) was goethite-like. The Tc(IV) reduction product formed on the DCB-reduced phyllosilicates was different from the Fe(III) oxides, and was more similar to Tc(IV) oxyhydroxide in its second coordination shell. The heterogeneous reduction of Tc(VII) to less soluble forms by sorbed and structural Fe(II) in anoxic environments may be a very important geochemical process that will proceed at very different rates and that will yield different surface species depending subsurface pH and mineralogy.
Peretyazhko T, JM Zachara, SM Heald, RK Kukkadapu, C Liu, AE Plymale, and CT Resch. 2008. "Reduction of Tc(VII) by Fe(II) Sorbed on Al (hydr)oxides." Environmental Science & Technology 42(15):5499-5506. doi:10.1021/es8003156 Abstract Technetium speciation, solubility and sorption behavior is strongly dependent on its valence state. Under oxic conditions, Tc exists as the soluble, weakly-sorbing pertechnetate [TcO4-] anion. The reduced form of technetium, Tc(IV), is stable in anoxic environments and is sparingly soluble as TcO2·xH2O(s). Here we investigate the heterogeneous reduction of Tc(VII) by Fe(II) sorbed on Al (hydr)oxides [diaspore (α-AlOOH) and corundum (α-Al2O3)]. Experiments were performed to study the kinetics of Tc(VII) reduction, examine changes in Fe surface speciation during Tc(VII) reduction (Mössbauer spectroscopy), and identify the nature of Tc(IV)-containing reaction products (X-ray absorption spectroscopy). We found that Tc(VII) was completely reduced by adsorbed Fe(II) within 11d (diaspore suspension) and 4d (corundum suspension). Mössbauer measurements revealed that the Fe(II) signal became less intense with Tc(VII) reduction, and was accompanied by increase in Fe(III) doublet and magnetically-ordered Fe(III) sextet signals, with latter parameters close to those for hematite. Formation of magnetically ordered Fe(III) did not depend on the oxidant nature, as both Tc(VII) or O2 lead to the formation of a virtually identical hematite-like phase. The Fe(II) doublet displayed no differences in Mössbauer parameters before and after Tc(VII) reduction, likely due to Fe(II) adsorption to similar sites and no Fe(II) sorption to or precipitation within solid phases formed. Tc-EXAFS spectroscopy revealed that the final heterogeneous redox product on corundum was similar to Tc(IV) oxyhydroxide, TcO2·xH2O. The formation of precursor polymeric TcnOy (4n-2y)+ chains prior to TcO2⋅xH2O precipitation might explain the formation of the separate TcO2-like phase on corundum without coprecipitated Fe.

2007

Borch T, Y Masue, RK Kukkadapu, and S Fendorf. 2007. "Phosphate Imposed Limitations on Biological Reduction and Alteration of Ferrihydrite Mineralization." Environmental Science & Technology 41(1):166-172. Abstract Biogeochemical transformation (inclusive of dissolution) of iron (hydr)oxides resulting from dissimilatory reduction has a pronounced impact on the fate and transport of nutrients and contaminants in subsurface environments. Despite the reactivity noted for pristine (unreacted) minerals, iron (hydr)oxides within native environments will likely have a different reactivity owing in part to changes in surface composition. Accordingly, here we explore the impact of surface modifications induced by phosphate adsorption on ferrihydrite reduction by Shewanella putrefaciens under static and advective flow conditions. Alterations in surface reactivity induced by phosphate adsorption change the extent, nearly linearly, and pathway of iron biomineralization. Magnetite is the most appreciable mineralization product while minor amounts of vivianite and green rust-like phases are formed in systems having high aqueous concentrations of phosphate, ferrous iron, and biogenic bicarbonate. Goethite and lepidocrocite, characteristic biomineralization products at low ferrous-iron concentrations, are inhibited in the presence of adsorbed phosphate. Considering deviations in reactivity of iron (hydr)oxides with changes in surface composition is important for deciphering mineralization pathways under native conditions and predicting reactive characteristics.
Komlos J, Jr., RK Kukkadapu, JM Zachara, and PR Jaffe. 2007. "Biostimulation of Iron Reduction and Subsequent Oxidation of Sediment Containing Fe-silicates and Fe-oxides: Effect of Redox Cycling on Fe(III) Bioreduction." Water Research 41(13):2996-3004. doi:10.1016/j.watres.2007.03.019 Abstract Microbial reduction of iron has been shown to be important in the transformation and remediation of contaminated sediments. Re-oxidation of microbially reduced iron may occur in sediments that experience oxidation-reduction cycling and can thus impact the extent of contaminant remediation. The purpose of this research was to quantify iron oxidation in a flow-through column filled with biologically-reduced sediment and to compare the iron phases in the re-oxidized sediment to both the pristine and biologically-reduced sediment. The sediment contained both Fe(III)-oxides (primarily goethite) and silicate Fe (illite/vermiculite) and was biologically reduced in phosphate buffered (PB) medium during a 497 day column experiment with acetate supplied as the electron donor. Long-term iron reduction resulted in partial reduction of silicate Fe(III) without any goethite reduction, based on Mössbauer spectroscopy measurements. This reduced sediment was treated with an oxygenated PB solution in a flow-through column resulting in the oxidation of 38% of the biogenic Fe(II). Additional batch experiments showed that the Fe(III) in the oxidized sediment was more quickly reduced compared to the pristine sediment, indicating that oxidation of the sediment not only regenerated Fe(III) but also enhanced iron reduction compared to the pristine sediment. Oxidation-reduction cycling may be a viable method to extend iron-reducing conditions during in-situ bioremediation.

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