Rapid mobilization of noncrystalline U(IV) coupled with FeS oxidation

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1 Rapid mobilization of noncrystalline U(IV) coupled with FeS oxidation Yuqiang Bi 1, Malgorzata Stylo 2, Rizlan Bernier-Latmani 2, Kim F. Hayes *1 1 Civil and Environmental Engineering, University of Michigan 2 Environmental Microbiology Laboratory, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland * Corresponding author: ford@umich.edu, Tel. (734) , Fax. (734) This Supporting Information covers 12 pages, including 8 figures, 3 tables. Prepared October 20, 2015 S1

2 Appendix Supplemental Data Table S1. Basal media compositions of Widdle Low Phosphate (WLP) used for U(VI) reduction by Shewanella oneidensis strain MR-1. Chemicals Conc. (mm) CaCl 2 2H 2 O 0.68 KCl 6.71 KH 2 PO MgCl 2 6H 2 O 2.46 NaCl NH 4 Cl 4.67 NaHCO 3 30 PIPES 20 Yeast Extract 0.05% Conc. (ml/l) Trace elements* 1 Vitamin B12* 1 Selenium Tunstate* 1 Vitamin mix* 1 Thiamine* 1 ph 7.3 * The stock concentration can be found in Bernier-Latmani et al. (2010) S2

3 Table S2. Comparison of the influent solution recipe for flow-through experiments under varied ph and DIC concentrations. Experimental design ph 7.0 high DIC ph 7.0, medium DIC ph 7.0, no DIC ph 5.4 ph 9.0 NaHCO 3 (mm) KCl (mm) CaCl 2 (mm) Gas mixture (O 2 /CO 2 /N 2 ) % MOPS buffer (mm) 4/5/91 4/0.5/95.5 4/0/96 4/5/91 4/0/96 \ \ 10 \ \ DIC * (mm) * Concentration calculated from MINEQL+ 4.6 at equilibrium with the customized gas mixture. Table S3. Binding energy (BE), full width at half maximum (FWHM), and percent peak areas for Fe 2p 3/2 XPS spectra of samples collected from selected flow-through experiments containing biomass-associated noncrystalline U(IV). Reaction time (t/τ) BE of Fe-S(II) peak (ev)* FWHM Fe(II)-S (%) Fe(II)-O (%) Fe(III)-S (%) Fe(III)-O (%) Experiment No. 1 with 10.8 mm DIC and 4.8 mm FeS *Binding energy (BE) of Fe-S(II) component is characteristic of mackinawite. Full width at half maximum (FWHM) of fitted U components on Fe 2p 3/2 XPS spectra. All three U components are constrained to have the same FWHM in a spectrum. S3

Fourier Transform Magnitude 3 3 U-O shell U-U shell 2 2 1 A. B. C. 1 0.2 μm 0 0 2 4 6 R + dr (Å) Figure S1.

bright-field (TEM) image of noncrystalline U(IV) prepared in the same manner; and (C) U L III -edge Fourier transforms of EXAFS

4 Fourier Transform Magnitude 3 3 U-O shell U-U shell A. B. C μm R + dr (Å) Figure S1. (A) Biogenic noncrystalline U(IV) materials produced by Shewanella oneidensis strain MR-1 for this study; (B) An example of bright-field (TEM) image of noncrystalline U(IV) prepared in the same manner; and (C) U L III -edge Fourier transforms of EXAFS showing the lack of U-U pair coordination. The final U(IV) species used for this study was characterized to contain less than 10% UO 2 precipitates. S4

5 Figure S2. Schematic of the flow-through reactor system used for the oxidation of noncrystalline U(IV) in the presence and absence of FeS. S5

6 Cumulative U release (μmol) a (10.8 mm DIC) 1b (10.8 mm DIC) Normalized Time (t/τ) Figure S3. The cumulative release of dissolved U in the flow-through experiments calculated based on the noncrystalline U(IV) oxidation profiles (Experiments # 1a, 1b). The slopes of the linear portion were then calculated using linear regression to derive the dissolution rate. The dash line represents the total amount of noncrystalline U(IV) in the flow-through reactor. S6

7 Effluent U conc. (μm) Effluent U conc. (μm) w/ 7 (10.8 FeS mm DIC) no 8 (10.8 FeS mm DIC) Normalized Time (t/τ) Normalized Time (t/τ) Figure S4. Release of dissolved U from flow-through experiments under anoxic conditions in the presence and absence of 4.8 mm FeS (Experiments # 7 and 8). Influent composition: 0.4 mm KCl, 2.0 mm CaCl 2, and 10.8 mm DIC. The solution was equilibrated with 0% P O2, 5% P CO2 gas mixture, ph 7.0. S7

Figure S5. Solid suspensions of final oxidation products collected at ~80 residence times from flow-through experiments at different solution ph with ~0.47 mm noncrystalline U(IV) and 4.8 mm FeS.

8 Figure S5. Solid suspensions of final oxidation products collected at ~80 residence times from flow-through experiments at different solution ph with ~0.47 mm noncrystalline U(IV) and 4.8 mm FeS. By the time of collection, complete FeS oxidation by dissolved oxygen has occurred. Due to substantial dissolution, the majority of Fe(II) was released into effluent at ph 5.4. The orange colored suspensions at neutral and basic ph are mixtures of goethite, lepidocrocite, and elemental sulfur. S8

9 Effluent DO Conc. (mg/l) Effluent Fe(II) Conc. (μm) Effluent U Conc. (μm) Effluent U Conc. (μm) Mono 9 (ph U(IV) = 5.4) ph5 Mono 1a (ph U(IV) = 7.0) ph 7 Mono 1 b (ph U(IV) = 7.0) 7 rep Mono 10 (ph U(IV) = 9.0) ph Normalized Time (t/τ) Figure S6. Profiles of dissolved U (A), Fe(II) (B), and, DO (C) concentrations in flow-through experiments at ph 5.4, 7.0, and 9.0 during the oxidative mobilization of ~0.47 mm noncrystalline U(IV) in the presence of 4.8 mm FeS (Experiments # 1a, 1b, 9, and 10). Replicates are represented by the filled vs open symbols. S9

10 Effluent Effluent U concentration concentration (μm) (μm) Ferrihydrite 13 (w/ ferrihydrite) & monou Crys. 12 (w/ Fe(III) aged & goethite) mono U No 4 Fe(III)_mono ( control) U Normalized Time (t/τ) Normalized Time (t/τ) Figure S7. Release of dissolved U from flow-through experiments in the presence of 4.4 mm aged Fe(III) products and 5.1 mm 2-line ferrihydrite solids (Experiments # 12, 13 and 4, respectively). Influent composition: 0.4 mm KCl, 2.0 mm CaCl 2, and 10.8 mm DIC. The influent solutions were equilibrated with 4% PO 2, 5% P CO2 gas mixture, ph 7.0. S10

11 Data U(IV) U(V) U(VI) fit N 1s a. b. c Binding Energy (ev) Figure S8. Narrow scans of U 4f XPS spectra of solid samples collected from selected flowthrough experiments (a) 6 τ oxidized noncrystalline U(IV) in control experiment (#4); (b) 5 τ oxidized noncrystalline U(IV) in the presence of FeS without DIC (experiment #6); and (c) 15 τ oxidized noncrystalline U(IV) in the presence of FeS without DIC (experiment #6). All experiments were carried out under influent DO of 1.8 mg/l artificial groundwater conditions. The dots and colored solid lines are the experimental data and the corresponding fits, respectively. S11

12 References: Bernier-Latmani, R., Veeramani, H., Vecchia, E. D., Junier, P., Lezama-Pacheco, J. S., Suvorova, E. I., Sharp, J. O., Wigginton, N. S., and Bargar, J. R., Non-uraninite products of microbial U(VI) reduction. Environ. Sci. Technol. 44, S12

Stimulation of Fe(II) oxidation, biogenic lepidocrocite formation and arsenic. immobilization by Pseudogulbenkiania sp.

1 2 Stimulation of Fe(II) oxidation, biogenic lepidocrocite formation and arsenic immobilization by Pseudogulbenkiania sp. strain 2002 3 4 5 Wei Xiu 1, 2, Huaming Guo 1, 2, *, Jiaxing Shen 2, Shuai Liu