Potentiometric Titrations to Characterize the Reactivity of Geomicrobial Surfaces

doi:10.1017/9781107707399.003

3 - Potentiometric Titrations to Characterize the Reactivity of Geomicrobial Surfaces

from Part II - Advanced Analytical Instrumentation

Published online by Cambridge University Press: 06 July 2019

Daniel S. Alessi ,

Shannon L. Flynn ,

Samrat Alam ,

Leslie J. Robbins and

Kurt O. Konhauser

Edited by

Janice P. L. Kenney ,

Harish Veeramani and

Daniel S. Alessi

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Janice P. L. Kenney: Affiliation:
MacEwan University, Edmonton
Harish Veeramani: Affiliation:
Carleton University, Ottawa
Daniel S. Alessi: Affiliation:
University of Alberta

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Summary

Potentiometric titrations are a widely used technique to quantify proton-active functional groups on microorganisms, their exudates, biominerals, and biofilms. In this chapter, we provide a step-by-step introduction to the preparation of microbial cells for the determination of proton buffering capacity using modern autotitration systems. Following a discussion of how to process titration data and plot titration curves, we review commonly used thermodynamic approaches to model titration curves in order to calculate cell wall functional group acidity constants and corresponding site concentrations. In geomicrobiology, protonation models are primarily used as a basis for the development of surface complexation models that can predict the adsorption of charged species such as metals to biomass. The case example that follows outlines the development of a surface complexation model for the adsorption of cadmium to a species of the marine cyanobacterium Synechococcus, using a protonation model developed from titration data as its basis. In the last section, we introduce the reader to other analytical tools that are complementary to titration results, and discuss a few common complications to the titration approach when it is applied to natural materials.

Type: Chapter
Information: Analytical Geomicrobiology
A Handbook of Instrumental Techniques
, pp. 79 - 92

DOI: https://doi.org/10.1017/9781107707399.003 [Opens in a new window]

Publisher: Cambridge University Press

Print publication year: 2019

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References

3.6 References

Alam, M. S., Gorman-Lewis, D., Chen, N., et al. (2018) Thermodynamic analysis of nickel(II) and zinc(II) adsorption to biochar. Environ. Sci. Technol. 52(11): 6246–6255.Google Scholar

Alessi, D. S., Fein, J. B. (2010) Cadmium adsorption to mixtures of soil components: Testing the component additivity approach. Chem. Geol. 270(1–4): 186–195.CrossRef Google Scholar

Alessi, D. S., Henderson, J. M., Fein, J. B. (2010) Experimental measurement of monovalent cation adsorption onto Bacillus subtilis cells. Geomicrobiol. J 27(5): 464–472.Google Scholar

Baker, M. G., Lalonde, S. V., Konhauser, K. O., Foght, J. M. (2010) Role of extracellular polymeric substances in the surface chemical reactivity of Hymenobacter aerophilus, a psychrotolerant bacterium. Appl. Environ. Microbiol. 76(1): 102–109.Google Scholar

Bethke, C. M., Brady, P. V. (2000) How the Kd approach undermines ground water cleanup. Ground Water 38(3): 435–443.Google Scholar

Beveridge, T. J., Murray, R. G. E. (1980) Sites of metal deposition in the cell wall of Bacillus subtilis. J. Bacteriol. 141(2): 876–887.Google Scholar

Borrok, D. M., Fein, J. B. (2005) The impact of ionic strength on the adsorption of protons, Pb, Cd, and Sr onto the surfaces of Gram negative bacteria: testing non-electrostatic, diffuse, and triple-layer models. J. Colloid Interface Sci. 286: 110–126.Google Scholar

Borrok, D. M., Fein, J. B., Kulpa, C. F. (2004) Proton and Cd adsorption onto natural bacterial consortia: testing universal adsorption behavior. Geochim. Cosmochim. Acta 68: 3231–3238.Google Scholar

Brassard, P., Kramer, J. R., Collins, P. V. (1990) Binding site analysis using linear programming. Environ. Sci. Technol. 24(2): 195–201.Google Scholar

Cox, J. S., Smith, D. S., Warren, L. A., Ferris, F. G. (1999) Characterizing heterogeneous bacterial surface functional groups using discrete affinity spectra for proton binding. Environ. Sci. Technol. 33(24): 4514–4521.Google Scholar

Davis, J.A., Kent, D. (1990) Surface complexation modeling in aqueous geochemistry. Rev. Mineral. Geochem. 23(1): 177–260.Google Scholar

Davis, J. A., Coston, J. A., Kent, D. B., Fuller, C. C. (1998) Application of the surface complexation modeling concept to complex mineral assemblages. Environ. Sci. Technol. 32(19): 2820–2828.CrossRef Google Scholar

Driver, S. J., Perdue, E. M. (2015) Acid-base chemistry of natural organic matter, hydrophobic acids, and transphilic acids from the Suwannee River, Georgia, as determined by direct potentiometric titration. Environ. Engineer. Sci. 32(1): 66–70.CrossRef Google Scholar

Duc, M., Gaboriaud, F., Thomas, F. (2005a) Sensitivity of the acid-base properties of clays to the method of preparation and measurement: 1. Literature review. J. Colloid Interface Sci. 289: 139–147.Google Scholar

Duc, M., Gaboriaud, F., Thomas, F. (2005b) Sensitivity of the acid-base properties of clays to the method of preparation and measurement: 2. Evidence from continuous potentiometric titrations. J. Colloid Interface Sci. 289: 139–147.CrossRef Google Scholar

Dzombak, D. A., Morel, F. M. M. (1990) Surface Complexation Modeling: Hydrous Ferric Oxide. Wiley-Interscience, New York, NY, 393 pp.Google Scholar

Fein, J. B. (2006) Thermodynamic modeling of metal adsorption onto bacterial cell walls: Current challenges. Adv. Agron. 90: 179–202.Google Scholar

Fein, J. B., Delea, D. E. (1999) Experimental study of the effect of EDTA on Cd adsorption by Bacillus subtilis: A test of the chemical equilibrium approach. Chem. Geol. 161: 375–383.Google Scholar

Fein, J. B., Daughney, C. J., Yee, N., Davis, T. A. (1997) A chemical equilibrium model for metal adsorption onto bacterial surfaces. Geochim. Cosmochim. Acta 61: 3319–3328.Google Scholar

Fein, J. B., Boily, J.-F., Yee, N., Gorman-Lewis, D., Turner, B. F. (2005) Potentiometric titrations of Bacillus subtilis cells to low pH and a comparison of modeling approaches. Geochim. Cosmochim. Acta 69: 1123–1132.CrossRef Google Scholar

Flynn, S. L., Gao, Q., Robbins, L. J., et al. (2017) Measurements of bacterial mat metal binding capacity in alkaline and carbonate-rich systems. Chem. Geol. 451: 17–24.CrossRef Google Scholar

Ginn, B. R., Szymanowski, J. S., Fein, J. B. (2008) Metal and proton binding onto the roots of Fescue rubra. Chem. Geol. 253: 130–135.Google Scholar

Gorgulho, H. F., Mesquita, J. P., Gonçalves, F., Pereira, M. F. R., Figueiredo, J. L. (2008) Characterization of the surface chemistry of carbon materials by potentiometric titrations and temperature-programmed desorption. Carbon 46(12): 1544–1555.Google Scholar

Gorman-Lewis, D., Fein, J. B., Jensen, M. P. (2006) Enthalpies and entropies of proton and cadmium adsorption onto Bacillus subtilis bacterial cells from calorimetric measurements. Geochim. Cosmochim. Acta 70: 4862–4873.CrossRef Google Scholar

Hao, W., Flynn, S. L., Alessi, D. S., Konhauser, K. O. (2018) Change of the point of zero net proton charge (pH_PZNPC) of clay minerals with ionic strength. Chem. Geol. 493: 458–467.Google Scholar

Herbelin, A. L., Westall, J. C. (1999) FITEQL: A Computer Program for Determination of Equilibrium Constants from Experimental Data. Department of Chemistry, Oregon State University, Corvallis, OR, Report 99–01.Google Scholar

Hetzer, A., Daughney, C. J., Morgan, H. W. (2006) Cadmium ion biosorption by the thermophilic bacteria Geobacillus stearothermophilus and G. thermocatenulatus. Appl. Environ. Microbiol, 72(6): 4020–4027.Google Scholar

Kenney, J. P. L., Fein, J. B. (2011) Importance of extracellular polysaccharides in proton and Cd binding to bacteria: A comparative study. Chem. Geol. 286(3–4): 109–117.Google Scholar

Koretsky, C. (2000) The significance of surface complexation reactions in hydrologic systems: A geochemist’s perspective. J. Hydrol. 230(3): 127–171.Google Scholar

Lalonde, S. V., Smith, D. S., Owttrim, G. W., Konhauser, K. O. (2008a) Acid-base properties of cyanobacterial cell surfaces. I: Influences of growth phase and nitrogen metabolism on cell surface reactivity. Geochim. Cosmochim. Acta 72: 1257–1268.Google Scholar

Lalonde, S. V., Smith, D. S., Owttrim, G. W., Konhauser, K. O. (2008b) Acid-base properties of cyanobacterial cell surfaces. II: Silica as a chemical stressor influencing cell surface reactivity. Geochim. Cosmochim. Acta 72: 1269–1280.Google Scholar

Lalonde, S. V., Dafoe, L., Pemberton, S. G., Gingras, M. K., Konhauser, K. O. (2010) Investigating the geochemical impact of burrowing animals: Proton and cadmium adsorption onto the mucus-lining of Terebellid polychaete worms. Chem. Geol. 271: 44–51.Google Scholar

Liu, Y., Alessi, D. S., Owttrim, G. W., et al. (2015) Cell surface reactivity of Synechococcus sp. PCC 7002: Implications for metal sorption from seawater. Geochim. Cosmochim. Acta 169: 30–44.Google Scholar

Liu, Y., Alessi, D. S., Owttrim, G. W., et al. (2016) Cell surface acid-base properties of cyanobacterium Synechococcus: Influences of nitrogen source, growth phase, and N:P ratios. Geochim. Cosmochim. Acta 187: 179–194.Google Scholar

Lützenkirchen, J., Preočanin, T., Kovačević, D., et al. (2012) Potentiometric titrations as a tool for surface charge determination. Croat. Chem. Acta 85(4): 391–417.CrossRef Google Scholar

Martinez, R. E., Ferris, F. G. (2001) Chemical equilibrium modeling techniques for the analysis of high-resolution bacterial metal sorption data. J. Colloid Interface Sci. 243: 73–80.Google Scholar

Martinez, R. E., Smith, D. S., Kulczycki, E., Ferris, F. G. (2002) Determination of intrinsic bacterial acidity constants using a Donnan shell model and a continuous pK_a distribution method. J. Colloid Interface Sci. 253(1): 130–139.Google Scholar

Ngwenya, B. T., Sutherland, I. W., Kennedy, L. (2003) Comparison of the acid-base behaviour and metal adsorption characteristics of a gram-negative bacterium with other strains. Appl. Geochem. 18(4): 527–538.Google Scholar

Pagnanelli, F., Bornoroni, L., Moscardini, E., Toro, L. (2006) Non-electrostatic surface complexation models for protons and lead(II) sorption onto single minerals and their admixtures. Chemosphere 63(7): 1063–1073.Google Scholar

Petrash, D. P., Raudsepp, M., Lalonde, S. V., and Konhauser, K. O. (2011a) Assessing the importance of matrix materials in biofilm chemical reactivity: Insights from proton and cadmium adsorption onto the commercially-available biopolymer alginate. Geomicrobiol. J. 28: 266–273.Google Scholar

Petrash, D. A., Lalonde, S. V., Gingras, M. K., and Konhauser, K. O. (2011b) A surrogate approach to studying the chemical reactivity of burrow mucus linings. Palaios 26: 595–602.Google Scholar

Turner, B. F., Fein, J. B. (2006) Protofit: A program for determining surface protonation constants from titration data. Comput. Geosci. 32: 1344–1356.CrossRef Google Scholar

Warchola, T., Flynn, S. L., Robbins, L. J., et al. (2017) Field- and lab-based potentiometric titrations of microbial mats from the Fairmont Hot Spring, Canada. Geomicrobiol. J. 34(10): 851–863.Google Scholar

Westall, J. C., Jones, J. D., Turner, G. D., Zachara, J. M. (1995) Models for association of metal ions with heterogeneous environmental sorbents. 1. Complexation of Co(II) by leonardite humic acid as a function of pH and NaClO₄ concentration. Environ. Sci. Technol. 29: 951–959.Google Scholar

Yee, N., Fein, J. (2001) Cd adsorption onto bacterial surfaces: A universal adsorption edge? Geochim. Cosmochim. Acta 65: 2037–2042.Google Scholar

Yu, Q., Fein, J. B. (2016) Sulfhydryl binding sites within bacterial extracellular polymeric substances. Environ. Sci. Technol. 50(11): 5498–5505.Google Scholar

Zhao, Z., Jia, Y., Xu, L., Zhao, S. (2011) Adsorption and heterogeneous oxidation of As(III) on ferrihydrite. Water Res. 45(19): 6496–6504.Google Scholar