Fe II aq Fe III oxide electron transfer and Fe exchange: effect of organic carbon
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- Σίβύλ Παυλόπουλος
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1 Supplementary materials Fe II aq Fe III oxide electron transfer and Fe exchange: effect of organic carbon Timothy Pasakarnis, A Michael L. McCormick, B Gene F. Parkin, A Aaron Thompson C and Michelle M. Scherer A,D A Department of Civil and Environmental Engineering, The University of Iowa, Iowa City, IA 52242, USA. B Department of Biology, Hamilton College, Clinton, NY 13323, USA. C Department of Crop and Soil Sciences, University of Georgia, Athens, GA 30602, USA. D Corresponding author. michelle-scherer@uiowa.edu Page 1 of 6
2 Table S1. Selected physical and chemical characteristics of natural organic matter isolates used for electron transfer and Fe exchange experiments Elliott Soil Humic Acid data are from the International Humic Substances Society [1] and Thorn et al. [2] Suwannee River Fulvic Acid data are from the International Humic Substances Society [1] and Ravichandran et al. [3] n/a, not available Organic matter Elemental Composition (%) Avg molecular weight Aromatic C Carboxy groups Phenol Groups C H O N S Ash (Da) (% total C) (meq (g C) 1 ) Elliott Soil Humic Acid n/a Suwannee River Fulvic Acid Table S2. Recipes for growth media used to culture Shewanella oneidensis MR-1 for cell materials to use in electron transfer experiments Listed quantities are per litre of growth medium LB medium, Miller Composition Tryptone 10.0 g Yeast extract 5.0 g Sodium chloride 10 g Defined Shewanella medium Dipotassium phosphate g Monopotassium phosphate g Ammonium sulfate g Sodium chloride 0.46 g HEPES buffer 4.77 g Vitamin mix 5 ml Wolfe's mineral mix 5 ml 60 % D,L-lactate syrup 9.37 g Page 2 of 6
3 Table S3. Mass and Fe isotope data for enriched 57 Fe isotope tracer experiments between aqueous Fe II and goethite with various forms of organic carbon present f 57 Fe = ( 57 counts / counts), f 56 Fe = ( 56 counts / counts), f 54 Fe = ( 54 counts / counts); DOPA, 1,2-dioleoyl-sn-glycero-3-phosphate Time (days) Aqueous Fe II Residual solids Recovery (%) Fe II (μmoles) f 57 Fe f 56 Fe f 54 Fe Fe exchange (%) Fe II (μmoles) Total Fe (μmoles) f 57 Fe Fe II Fe III Total Fe Carbon free (0.5) (0.0.36) (0.035) (0.0023) (0.2) (13.6) (0.0005) (0.8) (0.010) (0.019) (0.0009) (7.4) (10.0) (0.001) (1.4) (0.010) (0.010) (0.0005) (0.0) (15.6) (0.004) (2.6) (0.018) (0.017) (0.001) (17.1) (9.8) (0.0008) (1.1) (0.019) (0.012) (0.001) (6.0) (30.3) (0.0004) (0.2) (0.013) (0.024) (0.0004) (3.5) (6.8) (0.002) Elliott Soil humic acid (0.1) (0.0043) (0.041) (0.0003) (0.2) (13.6) (0.0002) (0.9) (0.0008) (0.002) (0.0012) (11.4) (163.3) (0.0004) (3.0) (0.004) (0.003) (0.0038) (1.7) (16.3) (0.0011) Suwanee River fulvic acid (8 mg L 1 ) (0.1) (0.028) (0.027) (0.001) (0.2) (13.6) (0.0002) (1.7) (0.0066) (0.009) (0.0023) (0.6) (15.6) (0.0052) (0.3) (0.0066) (0.006) (0.0007) (1.4) (1.1) (0.0020) (0.8) (0.0148) (0.015) (0.0011) (0.1) (21.9) (0.0015) (1.1) (0.0019) (0.002) (0.0004) (1.0) (14.1) (0.0001) DOPA (0.1) (0.0013) (0.001) (0.0001) (0.2) (13.6) (0.0002) (0.2) (0.022) (0.021) (0.0005) (0.9) (2.1) (0.0005) (0.0) (0.009) (0.008) (0.0008) (1.1) (25.2) (0.0003) Page 3 of 6
4 Table S4. Mass and Fe isotope data for Fe isotope tracer experiments between aqueous Fe II and magnetite with various forms of organic carbon present f 57 Fe = ( 57 counts / counts), f 56 Fe = ( 56 counts / counts), f 54 Fe = ( 54 counts / counts); DOPA, 1,2-dioleoyl-sn-glycero-3-phosphate Time (days) Aqueous Fe II Residual solids Recovery (%) Fe II (μmoles) f 57 Fe f 56 Fe f 54 Fe Fe exchange (%) Fe II (μmoles) Total Fe (μmoles) f 57 Fe Fe II Fe III Total Fe Carbon free (0.1) (0.044) (0.041) (0.003) (19.9) (1.7) ( ) (0.4) (0.046) (0.045) (0.002) (28.9) (32.3) (0.0004) (0.2) (0.020) (0.019) (0.001) (10.2) (34.7) (0.001) (0.5) (0.032) (0.031) (0.002) (32.1) (119.3) (0.002) Elliot Soil humic acid (0.1) (0.044) (0.041) (0.003) (19.9) (1.7) ( ) (1.3) (0.102) (0.010) (0.005) (20.4) (46.6) (0.001) (1.5) (0.007) (0.007) (0.0007) (0.6) (1.5) (0.002) (1.2) (0.008) (0.008) (0.001) (9.8) (3.9) (0.0007) Suwanee River fulvic acid (8 mg L 1 ) (0.1) (0.044) (0.041) (0.003) (19.9) (1.7) ( ) (0.5) (0.033) (0.031) (0.003) (18.2) (63.1) (0.0016) (0.2) (0.015) (0.015) (0.001) (1.5) (111.4) (0.0002) (0.5) (0.028) (0.027) (0.002) (4.2) (4.3) (0.0002) (0.3) (0.019) (0.019) (0.001) (11.0) (12.9) (0.0003) DOPA (0.1) (0.001) (0.001) (0.0001) (19.9) (1.7) ( ) (0.5) (0.007) (0.007) (0.0006) (9.6) (4.8) (0.0005) (0.1) (0.016) (0.017) (0.0006) (62.6) (31.0) (0.0006) Page 4 of 6
5 A. Carbon Free B. Spent LB Medium Absorption Fe(II) C. Spent Defined Shewanella Medium T = 77 K Fig. S1. 57 Fe Mössbauer spectra of 1 mm 57 Fe II reacted with 56 Fe goethite and organic carbon in spent growth medium from Shewanella oneidensis MR-1 cultures. 56 Fe goethite was pre-equilibrated with (a) no carbon source, (b) a 1:10 dilution of spent Luria-Bertani medium, (c) a 1 : 10 dilution of spent defined medium. Samples were reacted with Fe II for 24 h before analysis. Page 5 of 6
6 References [1] Elemental Compositions and Stable Isotopic Ratios of IHSS Samples 2008 (International Humic Substances Society). Available at [Verified 20 October 2014]. [2] K. A. Thorn, D. W. Folan, P. MacCarthy, Characterization of the International Humic Substances Society Standard and Reference Fulvic and Humic Acids by Solution State Carbon-13 ( 13 C) and Hydrogen-1 ( 1 H) Nuclear Magnetic Resonance Spectrometry 1989 (US Geological Survey: Denver, CO, USA). [3] M. Ravichandran, G. R. Aiken, M. M. Reddy, J. N. Ryan, Enhanced dissolution of cinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades. Environ. Sci. Technol. 1998, 32, doi: /es Page 6 of 6
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