Supporting Information Electron Transfer Between Sorbed Fe(II) and Structural Fe(III) in Smectites and its Effects on Nitrate-Dependent Iron Oxidation by Pseudogulbenkiania sp. strain 2002 Li Zhang 1 , Hailiang Dong 1,2* , Ravi K. Kukkadapu 3* , Qusheng Jin 4 , and Libor Kovarik 3 1 Department of Geology and Environmental Earth Science Miami University, Oxford, OH 45056, USA 2 State Key Laboratory of Biogeology and Environmental Geology China University of Geosciences, Beijing 100083, China 3 EMSL, Pacific Northwest National Laboratory, Richland, WA 99352, USA 4 Department of Earth Sciences, University of Oregon, Eugene, OR 97403 S1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
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Supporting Information
Electron Transfer Between Sorbed Fe(II) and Structural Fe(III) in Smectites and its Effects
on Nitrate-Dependent Iron Oxidation by Pseudogulbenkiania sp. strain 2002
Li Zhang1, Hailiang Dong1,2*, Ravi K. Kukkadapu3*, Qusheng Jin4, and Libor Kovarik3
1Department of Geology and Environmental Earth Science
Miami University, Oxford, OH 45056, USA
2State Key Laboratory of Biogeology and Environmental Geology
China University of Geosciences, Beijing 100083, China
3EMSL, Pacific Northwest National Laboratory, Richland, WA 99352, USA
4Department of Earth Sciences, University of Oregon, Eugene, OR 97403
1center shift; 2quadrupole splitting (QS); 3QS standard deviation;4 quadrupole splitting parameter; 5magnetic hyperfine field (HFD);6HFD standard deviation; 7relative contribution (assuming identical recoilless fractions for all the species);8goodness of fit; 9Chemical method can only determine total Fe(II) and Fe(III) contents, not contents of individual Fe species.
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Table S3 Summary of electron balance calculations following Fe2+ sorption
Clay pH [Fe(II)initially sorbed]
(wt.% in clay or
mmol/g)
[Fe(II)Initially sorbed]/Total Fein clay1
(%)
[Structural Fe(II)]/Total Fe
in clay after IET2
(%)
Structural Fe(II) after IET
Initial clay structural
Fe(II) 7
(wt.% in clay or
mmol/g)
Newly produced clay structural Fe(II)
from IET
Residual fraction of the sorbed Fe(II)
after IET
5(wt.% in clay or mmol/g)
6(% of total Fe)
8(wt.% in clay or mmol/g)
9(% in total Fe)
10(wt.% in clay or mmol/g)
11(% in total Fe)
NAu-2 8.0 2.93 (0.525)
12.6 ~12.63 2.93 (0.525)
11.5 0.583 (0.104)
2.35 (0.421)
9.23 0.580 (0.104)
2.27
SWy-2 6.0 1.43 (0.256)
46.4 ~46.44 1.43 (0.256)
32.1 0.202 (0.036)
1.23 (0.220)
27.6 0.200 (0.036)
4.48
8.0 4.66
(0.835)
151 ~704 2.16
(0.387)
28.4 0.202
(0.036)
1.96
(0.351)
25.8 2.70
(0.484)
35.5
Fe(II) in clay is expressed in both wt% and mmol/g (in parenthesis). Fe(II) relative to total Fe is in % only. 1Calculted using data in Table 1 as sorbed Fe(II) divided by total Fe in pre-sorption clay;2 This column of data is obtained based on references on stoichiometric electron transfer between sorbed Fe(II) and structural Fe(III).3 based on data in Schaefer et al., for pH 7.5 (their Fig. 4)(Schaefer et al., 2011); 4Latta et al. (their Fig. 8)(Latta et al., 2017); 5Calculated by multiplying [structural Fe(II)]/Total Fe in clay (column 5) by Total Fe in pre-sorption clay (Table 1, last column); 6Calculated by dividing structural Fe(II) by total Fe in clay (with Fe2+ sorption); 7Initial Fe(II) in each clay (Table 1); 8Calculated by the difference between the total Fe(II) and initial amount of Fe(II); 9Calculated by dividing Fe(II)8 by total Fe in clay (with Fe2+ sorption); 10Calculated by the difference between the total amount of sorbed Fe(II) and the amount used to reduce structural Fe(III)8; 11Calculated by dividing Fe(II)10 by total Fe in clay (with Fe2+ sorption).
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Fig. S1. Nitrate reduction during the growth of strain 2002 in the presence of either acetate or
aqueous Fe2+ (10 mM) as electron donor.
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342
343
344
Fig. S2. Nitrate reduction by strain 2002 cells at pH 6 & 8. Electron donor is inferred to be from
Fig. S3. Negligible amounts of abiotic nitrite reduction by clay-associated Fe(II) at pH 6 and pH
8.
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350
351
352
Fig. S4 Time-course change of aqueous Fe2+ concentration in the supernatant of bio-oxidation
experiments with clay-associated Fe(II). Total Fe(II) concentration is shown in Fig. 1A, D, and
G.
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354
355
356
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358
0 2 4 6Time (d)
0.0
0.2
0.4
0.6
Bio
mas
s (m
gkg
1)
B
0
5
10
Fe2+
(mM
)
1
2
3
4
Nitr
ate
(mM
)
A
Fe2+
Nitrate
Fig. S5. Variations in the concentrations of Fe(II) and nitrate (A), and biomass (B) during the
growth of strain 2002 in laboratory batch reactors. Data points are from a previous study (Weber
et al., 2006) and lines are the modeling results.
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360
361
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363
364
Fig. S6 TEM images for SWy-2 at pH 8 after Fe(II) sorption (A) and after bio-oxidation (B): A)
before oxidation, amorphous nanoparticles are located on the edge of clay; B) after bio-
oxidation, goethite are still present with a bundle-shaped morphology, but the nanoparticles are
absent.
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369
370
Fig. S7 Room temperature (RT, A) and 150 K (B-E) Mössbauer spectra of pristine, Fe(II)-
sorbed, and Fe(II)-sorbed, bio-oxidized NAu-2 samples at pH 6 and pH 8.
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Fig. S8 150-K Mössbauer spectra of pristine (A), Fe(II)-sorbed (B), and Fe(II)-sorbed, bio-
oxidized SWy-2 (C) samples at pH 6. At pH 8, Mössbauer spectra for the latter two samples are
shown (D and E, respectively).
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References
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Jaisi D. P., Liu C., Dong H., Blake R. E. and Fein J. B. (2008) Fe2+ sorption onto nontronite (NAu-2). Geochim. Cosmochim. Acta 72, 5361–5371.
Latta D. E., Neumann A., Premaratne W. A. P. J. and Scherer M. M. (2017) Fe(II)–Fe(III) Electron Transfer in a Clay Mineral with Low Fe Content. ACS Earth Space Chem. 1, 197–208.
Neumann A., Olson T. L. and Scherer M. M. (2013) Spectroscopic Evidence for Fe(II)–Fe(III) Electron Transfer at Clay Mineral Edge and Basal Sites. Environ. Sci. Technol. 47, 6969–6977.
Neumann A., Wu L., Li W., Beard B. L., Johnson C. M., Rosso K. M., Frierdich A. J. and Scherer M. M. (2015) Atom Exchange between Aqueous Fe(II) and Structural Fe in Clay Minerals. Environ. Sci. Technol. 49, 2786–2795.
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Weber K. A., Picardal F. W. and Roden E. E. (2001) Microbially Catalyzed Nitrate-Dependent Oxidation of Biogenic Solid-Phase Fe(II) Compounds. Environ. Sci. Technol. 35, 1644–1650.
Weber K. A., Pollock J., Cole K. A., O’Connor S. M., Achenbach L. A. and Coates J. D. (2006) Anaerobic Nitrate-Dependent Iron(II) Bio-Oxidation by a Novel Lithoautotrophic Betaproteobacterium, Strain 2002. Appl. Environ. Microbiol. 72, 686–694.
Zhao L., Dong H., Edelmann R. E., Zeng Q. and Agrawal A. (2017) Coupling of Fe(II) oxidation in illite with nitrate reduction and its role in clay mineral transformation. Geochim. Cosmochim. Acta 200, 353–366.
Zhao L., Dong H., Kukkadapu R., Agrawal A., Liu D., Zhang J. and Edelmann R. E. (2013) Biological oxidation of Fe(II) in reduced nontronite coupled with nitrate reduction by Pseudogulbenkiania sp. Strain 2002. Geochim. Cosmochim. Acta 119, 231–247.