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Investigation of Organic Matter Entrapped in Synthetic Carbonates—A Multimethod Approach

  • Emilie Chalmin (a1) (a2), Yves Perrette (a2), Bernard Fanget (a2) and Jean Susini (a1)

Abstract

Organic matter (OM) entrapped in calcite is regularly used for environmental studies; however, insertion mechanisms and types of interaction remain poorly understood. The present study used a new methodology to investigate interactions between OM and the calcite matrix during crystallization processes with humic acid (HA) entrapment. A multimethod approach confirmed that HA is both adsorbed onto the calcite surface and incorporated into the calcite lattice during crystallization. Our results also confirm the log-linear correlation between fluorescence intensity and calcite matrix HA concentration. Fourier transform infrared spectroscopy showed that HA in colloidal conformation is adsorbed onto the calcite surface as a result of the structure of the OH stretching band. We also developed a new method based on synchrotron analysis that uses sulfur as a tracer element for entrapped HA and that localizes the OM electrostatically adsorbed onto the calcite surface. Changes in the sulfur environment, determined using X-ray absorption near-edge structure spectroscopy, indicated more complex insertion mechanisms than simple adsorption of HA during calcite crystallization. Desorption experiments revealed the stability of the OM atomic structure and its layered nature. These results allowed us to draw up a general model of OM insertion in calcite.

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Corresponding author

* Corresponding author. E-mail: emilie.chalmin-aljanabi@univ-savoie.fr

References

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Abdel-Aal, N. & Sawada, K. (2003). Inhibition of adhesion and precipitation of CaCO3 by aminophosphonate. J Cryst Growth 256, 188200.
Amjad, Z. (1987). Kinetic study of the seeded growth of calcium carbonate in the presence of benzenepolycarboxylic acids. Langmuir 3, 224228.
Astilleros, J.M., Pina, C.M., Fernandez-Diaz, L. & Putnis, A. (2000). The effect of barium on calcite {1014} surfaces during growth. Geochim Cosmochim Acta 64, 29652972.
Avena, M.J. & Koopal, L.K. (1999). Kinetics of humic acid adsorption at solid-water interfaces. Environ Sci Technol 33, 27392744.
Baker, A., Barnes, W.L. & Smart, P.L. (1996). Speleothem luminescence intensity and spectral characteristics: Signal calibration and a record of palaeovegetation change. Chem Geol 130, 6576.
Baker, A., Caseldine, C.J., Gilmour, M.A., Charman, D., Proctor, C.J., Hawkesworth, C.J. & Phillips, N. (1999). Stalagmite luminescence and peat humification records of palaeomoisture for the last 2500 years. Earth Planet Sci Lett 165, 157162.
Blyth, A.J., Baker, A., Collins, M.J., Penkman, K.E.H., Gilmour, M.A., Moss, J.S., Genty, D. & Drysdale, R.N. (2008). Molecular organic matter in speleothems and its potential as an environmental proxy. Quat Sci Rev 27, 905921.
Bonnin-Mosbah, M., Métrich, N., Susini, J., Salomé, M., Massare, D. & Menez, B. (2002). Micro X-ray absorption near edge structure at the sulfur and iron K-edges in natural silicate glasses. Spectrochim Acta B 57, 711725.
Borsato, A., Frisia, S., Fairchild, I.J., Somogyi, A. & Susini, J. (2007). Trace element distribution in annual stalagmite laminae mapped by micrometer-resolution X-ray fluorescence: Implications for incorporation of environmentally significant species. Geochim Cosmochim Acta 71, 14941512.
Bostick, B.C., Theissen, K.M., Dunbar, R.B. & Vairavamurthy, M.A. (2005). Record of redox status in laminated sediments from Lake Titicaca: A sulfur K-edge X-ray absorption near edge structure (XANES) study. Chem Geol 219, 163174.
Braissant, O., Cailleau, G., Dupraz, C. & Verrecchia, E.P. (2003). Bacterially induced mineralization of calcium carbonate in terrestrial environments: The role of exopolysaccharides and amino acids. J Sedimentary Res 73, 485490.
Burdon, J. (2001). Are the traditional concepts of the structures of humic substances realistic? Soil Sci 166, 752769.
Clapp, C.E. & Hayes, M.H.B. (1999). Sizes and shapes of humic substances. Soil Sci 164, 777789.
Collectif (1999). Special Issue. Soil Sci 164, 777876.
Cusack, M., Dauphin, Y., Cuif, J.-P., Salomé, M., Freer, A. & Yin, H. (2008). Micro-XANES mapping of sulphur and its association with magnesium and phosphorus in the shell of the brachiopod, Terebratulina retusa. Chem Geol 253, 172179.
Dauphin, Y., Cuif, P., Doucet, J., Salomé, M., Susini, J. & Willams, C.T. (2003). In situ chemical speciation of sulfur in calcitic biominerals and the simple prism concept. J Struct Biol 142, 272280.
Davis, K.J., Dove, P.M., Wasylenki, L.E. & De Yoreo, J.J. (2004). Morphological consequences of differential Mg2+ incorporation at structurally distinct steps on calcite. Am Mineral 89, 714720.
Dreybrodt, W., Buhmann, D., Michaelis, J. & Usdowski, E. (1992). Geochemically controlled calcite precipitation by CO2 outgassing: Field measurements of precipitation rates in comparison to theoretical predictions. Chem Geol 97, 285294.
Fairchild, I.J. & Treble, P. (2009). Trace elements in speleothems as recorders of environmental change. Quaternary Sci Rev 28, 449468.
Fenter, P., Geissbuhler, P., DiMasi, E., Srajer, G., Sorensen, L.B. & Sturchio, N.C. (2000). Surface speciation of calcite observed in situ by high-resolution X-ray reflectivity. Geochim Cosmochim Acta 64, 12211228.
Frisia, S., Borsato, A., Fairchild, I.J. & Susini, J. (2005). Variations in atmospheric sulphate recorded in stalagmites by synchrotron micro-XRF and XANES analyses. Earth Planet Sci Lett 235, 729740.
Fukushima, M., Yamamoto, K., Ootsuka, K., Komai, T., Aramaki, T., Ueda, S. & Horiya, S. (2009). Effects of the maturity of wood waste compost on the structural features of humic acids. Bioresour Technol 100, 791797.
Genty, D., Baker, A. & Vokal, B. (2001). Intra- and inter-annual growth rate of modern stalagmites. Chem Geol 176, 191212.
Giguet-Covex, C., Arnaud, F., Poulenard, F., Enters, D., Reyss, J.-L., Millet, L., Lazzaroto, J. & Vidal, O. (2010). Sedimentological and geochemical records of past trophic state and hypolimnetic anoxia in large, hard-water Lake Bourget, French Alps. J Paleolimnol 43, 171190.
Godelitsas, A., Astilleros, J.M., Hallam, K., Harissopoulos, S. & Putnis, A. (2003). Interaction of calcium carbonates with lead in aqueous solutions. Environ Sci Technol 37, 33513360.
Gruzensky, P.M. (1967). Growth of calcite crystals. In Crystal Growth, Peiser, H.S. (Ed.), pp. 365367. Oxford, UK: Pergamon.
Hartland, A., Fairchild, I.J., Lead, J.R., Borsato, A., Baker, A., Frisia, S. & Baalousha, M. (2012). From soil to cave: Transport of trace metals by natural organic matter in cave dripwaters. Chem Geol 304305, 6882.
Henriksen, K., Stipp, S.L.S., Young, J.R. & Marsh, M.E. (2004). Biological control on calcite crystallization: AFM investigation of coccolith polysaccharide function. Am Mineral 89, 17091716.
Hoch, A.R., Reddy, M.M. & Aiken, G.R. (2000). Calcite crystal growth inhibition by humic substances with emphasis on hydrophobic acids from the Florida Everglades. Geochim Cosmochim Acta 64, 6172.
Hundal, L.S., Carmo, A.M., Bleam, W.L. & Thompson, M.L. (2000). Sulfur in biosolids-derived fulvic acid: Characterization by XANES spectroscopy and selective dissolution approaches. Environ Sci Technol 34, 51845188.
Jones, G. & Indig, G.L. (1996). Spectroscopic and chemical binding properties of humic acids in water. New J Chem 20, 221232.
Kameda, Y., Teshigawara, Y., Sughi, M., Amo, Y. & Usuki, T. (2007). Structure of amorphous NaCl-glucose system studied by X-ray diffraction and IR methods. J Non-Cryst Solids 353, 19901993.
Kelleher, B.P. & Simpson, A.J. (2006). Humic substances in soils: Are they really chemically distinct? Environ Sci Technol 40, 46054611.
Kitano, Y. & Hood, D.W. (1965). The influence of organic material on the polymorphic crystallization of calcium carbonate. Geochim Cosmochim Acta 29, 2941.
Kontrec, J., Kralj, D., Brecevic, L. & Falini, G. (2008). Influence of some polysaccharides on the production of calcium carbonate filler particles. J Cryst Growth 310, 45544560.
Lee, Y.J., Elzinga, E.J. & Reeder, R.J. (2005). Cu(II) adsorption at the calcite-water interface in the presence of natural organic matter: Kinetic studies and molecular-scale characterization. Geochim Cosmochim Acta 69, 4961.
Lee, Y.J. & Reeder, R.J. (2006). The role of citrate and phthalate during Co(II) coprecipitation with calcite. Geochim Cosmochim Acta 70, 22532263.
Lin, Y.-P., Singer, P.C. & Aiken, G.R. (2005). Inhibition of calcite precipitation by natural organic material: Kinetics, mechanism, and thermodynamics. Environ Sci Technol 39, 64206428.
Liu, Z., Zu, Y., Meng, R., Xing, Z., Tan, S., Zhao, L., Sun, T. & Zhou, Z. (2011). Adsorption of humic acid onto carbonaceous surfaces: Atomic force microscopy study. Microsc Microanal 17, 10151021.
Lu, Y. & Allen, H.E. (2002). Characterization of copper complexation with natural dissolved organic matter (DOM)—Link to acidic moieties of DOM and competition by Ca and Mg. Water Res 36, 50835101.
Maia, C., Piccolo, A. & Mangrich, A.S. (2008). Molecular size distribution of compost-derived humates as a function of concentration and different counterions. Chemosphere 73, 11621166.
Malkaj, P. & Dalas, E. (2004). Calcium carbonate crystallization in the presence of aspartic acid. Cryst Growth Des 4, 721723.
Maslen, E.N., Streltsov, V.A., Streltsova, N.R. & Ishizawa, N. (1995). Electron density and optical anisotropy in rhombohedral carbonates: 3. Synchrotron X-ray studies of CaCO3, MgCO3 and MnCO3 . Acta Crystallogr B-Struct Sci 51, 929939.
Morra, M.J., Fendorf, S.E. & Brown, P.D. (1997). Speciation of sulfur in humic and fulvic acids using X-ray absorption near-edge structure (XANES) spectroscopy. Geochim Cosmochim Acta 613, 683688.
Myneni, S.C.B., Brown, J.T., Martinez, G.A. & Meyer-Ilse, W. (1999). Imaging of humic substance macromolecular structures in water and soils. Science 286, 13351337.
Namjesnik-Dejanovic, K., Maurice, P.A., Aiken, G.R., Cabaniss, S., Chin, Y.-P. & Pullin, M.J. (2000). Adsorption and fractionation of a muck fulvic acid on kaolinite and goethite at pH 3.7, 6, and 8. Soil Sci 165, 545559.
Oelkers, E.H., Golubev, S.V., Pokrovsky, O.S. & Bénézeth, P. (2011). Do organic ligands affect calcite dissolution rates? Geochim Cosmochim Acta 75, 17991813.
Ogino, T., Suzuki, T. & Sawada, K. (1990). The rate and mechanism of polymorphic transformation of calcium carbonate in water. J Cryst Growth 100, 159167.
Orme, C.A., Noy, A., Wierzbicki, A., McBride, M.T., Grantham, M., Teng, H.H., Dove, P.M. & De Yoreo, J.J. (2001). Formation of chiral morphologies through selective binding of amino acids to calcite surface steps. Nature 411, 775779.
Paquette, J. & Reeder, R.J. (1995). Relationship between surface structure, growth mechanism, and trace element incorporation in calcite. Geochim Cosmochim Acta 59, 735749.
Perrette, Y., Delannoy, J.J., Desmet, M., Lignier, V. & Destombes, J.L. (2005). Speleothem organic matter content imaging. The use of a fluorescence index to characterise the maximum emission wavelength. Chem Geol 214, 193208.
Piccolo, A. (2001). The supramolecular structure of humic substances. Soil Sci 166, 810832.
Prietzel, J., Thieme, J., Herre, A., Salomé, M. & Eichert, D. (2008). Differentiation between adsorbed and precipitated sulphate in soils and at micro-sites of soil aggregates by sulphur K-edge XANES. Eur J Soil Sci 59, 730743.
Prietzel, J., Thieme, J., Salomé, M. & Knicker, H. (2007). Sulfur K-edge XANES spectroscopy reveals differences in sulfur speciation of bulk soils, humic acid, fulvic acid, and particle size separates. Soil Biol Biochem 39, 877890.
Ramseyer, K., Miano, T.M., D'Orazio, V., Wildberger, A., Wagner, T. & Geister, J. (1997). Nature and origin of organic matter in carbonates from speleothems, marine cements and coral skeletons. Org Geochem 26, 361378.
Reddy, M.M. & Hoch, A.R. (2001). Calcite crystal growth rate inhibition by polycarboxylic acids. J Colloid Interface Sci 235, 365370.
Reyhani, M.M., Oliveira, A., Parkinson, G.M., Jones, F., Rohl, A.L. & Ogden, M.I. (2002). In situ characterization of calcite growth and inhibition using atomic force microscopy. Int J Mod Phys B 16, 2533.
Rodriguez-Navarro, C., Jimenez-Lopez, C., Rodriguez-Navarro, A., Gonzalez-Munoz, M.T. & Rodriguez-Gallego, M. (2007). Bacterially mediated mineralization of vaterite. Geochim Cosmochim Acta 71, 11971213.
Ruiz-Agudo, E., Putnis, C.V., Rodriguez-Navarro, C. & Putnis, A. (2011). Effect of pH on calcite growth at constant ratio and supersaturation. Geochim Cosmochim Acta 75, 284296.
Shin, H.-S., Monsallier, J.M. & Choppin, G.R. (1999). Spectroscopic and chemical characterizations of molecular size fractionated humic acid. Talanta 50, 641647.
Siéliéchi, J.M., Lartiges, B.S., Kayem, G.J., Hupont, S., Frochot, C., Thieme, J., Ghanbaja, J., d'Espinose de la Caillerie, J.B., Barrès, O., Kamga, R., Levitz, P. & Michot, L.J. (2008). Changes in humic acid conformation during coagulation with ferric chloride: Implications for drinking water treatment. Water Res 42, 21112123.
Steeling, C. (2002). Investigating humic acids in soils. Anal Chem 74, 326A333A.
Suess, E. (1970). Interaction of organic compounds with calcium carbonate—I. Association phenomena and geochemical implications. Geochim Cosmochim Acta 34, 157168.
Sutton, R. & Sposito, G. (2005). Molecular structure in soil humic substances: The new view. Environ Sci Technol 39, 90099015.
Tourney, J. & Ngwenya, B.T. (2009). Bacterial extracellular polymeric substances (EPS) mediate CaCO3 morphology and polymorphism. Chem Geol 262, 138146.
Ueyama, N., Takahasi, K., Onoda, A., Okamura, T. & Yamamoto, H. (2002). Tight binding of poly(carboxylate) ligand of calcium carbonate with intramolecular NH-0 hydrogen bond. Macromol Symp 186, 129134.
Van Beynen, P., Ford, D. & Schwarcz, H. (2000). Seasonal variability in organic substances in surface and cave waters at marengo Cave, Indiana. Hydrol Processes 14, 11771197.
Vdovic, N. & Kralj, D. (2000). Electrokinetic properties of spontaneoulsy precipitated calcium carbonate polymorphs: The influence of organic substances. Colloids Surf A 161, 499505.
Verrecchia, E.P. & Verrecchia, K.E. (1994). Needle-fiber calcite; a critical review and a proposed classification. J Sediment Res A64, 650664.
Weiner, S. & Addadi, L. (1997). Design strategies in mineralized biological materials. J Mater Chem 7, 689702.
White, W. (2007). Paleoclimate records from speleothems in limestone caves. In Studies of Cave Sediments, 2nd ed., Sasowsky, I.D. & Mylorie, J. (Eds.), pp. 135175. Springer Netherlands.
Wynn, P.M., Fairchild, I.J., Frisia, S., Spötl, C., Baker, A. & Borsato, A. (2010). High-resolution sulphur isotope analysis of speleothem carbonate by secondary ionisation mass spectrometry. Chem Geol 271, 101107.
Zak, K., Urban, J., Cilek, V. & Hercman, H. (2004). Cryogenic cave calcite from several Central European caves: Age, carbon and oxygen isotopes and a genetic model. Chem Geol 206, 119136.

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