Abstract
Humic substances (HS), including humic and fulvic acids, play a significant role in the fate of metals in soils. The interaction of metal cations with HS occurs predominantly through the ionized (anionic) acidic functions. In the context of the effect of HS on transport of radioactive cesium isotopes in soils, a study of the interaction between the cesium cation and model carboxylic acids was undertaken. Structure and energetics of the adducts formed between Cs+ and cesium carboxylate salts [Cs+RCOO−] were studied by the kinetic method and density functional theory (DFT). Clusters generated by electrospray ionization mass spectrometry from mixtures of a cesium salt (nitrate, iodide, trifluoroacetate) and carboxylic acids were quantitatively studied by CID. By combining the results of the kinetic method and the energetic data from DFT calculations, a scale of cesium cation affinity, CsCA, was built for 33 cesium carboxylates representing the first scale of cation affinity of molecular salts. The structural effects on the CsCA values are discussed.
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Unterweger, M. P.; Hoppes, D. D.; Schima, F. J. New and Revised Half-Life Measurements Results. Nucl. Instrum. Methods Phys. Res. A. 1992, 312, 349–352;
Unterweger, M. P. Radionuclide Half-Life Measurements (version 3. 0, April 2003). Available online: http://physics.nist.gov/Halflife.National Institute of Standards and Technology: Gaithersburg, MD, USA.
Pourcelot, L.; Louvat, D.; Gauthier-Lafaye, F.; Stille, P. Formation of Radioactivity Enriched Soils in Mountain Areas. J. Environ. Radioact. 2003, 68, 215–233.
Zhiyanski, M.; Sokolovska, M.; Lucot, E.; Badot, P.-M. Cs-137 Contamination in Forest Ecosystems in Southwest Rila Mountain, Bulgaria. Environ. Chem. Lett. 2005, 3, 49–52.
Rezzoug, S.; Michel, H.; Fernex, F.; Barci-Funel, G.; Barci, V. Evaluation of 137Cs Fallout from the Chernobyl Accident in a Forest Soil and its Impact on Alpine Lake Sediments, Mercantour Massif, S. E. France. J. Environ. Radioact. 2006, 85, 369–379.
Garaudée, S.; Elhabiri, M.; Kalny, D.; Robiolle, C.; Trendel, J.-M.; Hueber, R.; Van Dorsselaer, A.; Albrecht, P.; Albrecht-Gary, A.-M. Allosteric Effects in Norbadione A: A Clue for the Accumulation Process of 137Cs in Mushrooms? Chem. Commun. 45, 944–945;
Desage-El Murr, M.; Nowaczyk, S.; Le Gall, T.; Mioskowski, C.; Amekraz, B.; Moulin, C.; Norbadione, A. Synthetic Approach to the Bis(pulvinic acid) Moiety and Cesium Complexation Studies. Angew. Chem. Int. Ed. 2003, 45, 1289–1293;
Giovani, C.; Garavaglia, M.; Scruzzi, E. Radiocaesium in Mushrooms from Northeast Italy, 1986–2002. Radiat. Prot. Dosimetry 2004, 111, 377–383;
Tadaaki Ban-nai, T.; Yoshida, S.; Muramatsu, Y.; Akira Suzuki, A. Uptake of Radiocesium by Hypha of Basidiomycetes-Radiotracer Experiments. J. Nucl. Radiochem. Sci. 2005, 6, 111–113;
Karadeniz, O.; Yaprak, G. Dynamic Equilibrium of Radiocesium with Stable Cesium Within the Soil-Mushroom System in Turkish Pine Forest. Environ. Pollut. 2007, 148, 316–324.
Su, Y.; Maruthi Sridhar, B. B.; Han, F. X.; Diehl, S. V.; Monts, D. L. Effect of Bioaccumulation of Cs and Sr Natural Isotopes on Foliar Structure and Plant Spectral Reflectance of Indian Mustard (Brassica Juncea). Water Air Soil. Pollut. 2007, 180, 65–74.
Paller, M. H.; Jannik, G. T.; Fledderman, P. D. Changes in 137Cs Concentrations in Soil and Vegetation on the Floodplain of the Savannah River over a 30 Year Period. J. Environ. Radioact. 2008, 99, 1302–1310.
Hurel, C.; Marmier, N.; Séby, F.; Giffaut, E.; Bourg, A. C. M.; Fromage, F. Sorption Behavior of Caesium on a Bentonite Sample. Radiochim. Acta. 2002, 90, 695–698;
Hurel, C.; Marmier, N.; Bourg, A. C. M.; Fromage, F. Sorption of Cs and Rb on Purified and Crude MX-80 Bentonite in Various Electrolytes. J. Radioanal. Nucl. Chem. 2009, 279, 113–119.
Dumat, C.; Staunton, S. Reduced Adsorption of Caesium on Clay Minerals Caused by Various Humic Substances. J. Environ. Radioact. 1999, 46, 187–200.
Staunton, S.; Dumat, C.; Zsolnay, A. Possible Role of Organic Matter in Radiocaesium Adsorption in Soils. J. Environ. Radioact. 2002, 58, 163–173.
Nakamaru, Y.; Ishikawa, N.; Tagami, K.; Uchida, S. Role of Soil Organic Matter in the Mobility of Radiocesium in Agricultural Soils Common in Japan. Colloids Surf. A Physicochem. Eng. Asp. 2007, 306, 111–117.
Sutton, R.; Sposito, G. Molecular Structure in Soil Humic Substances: The New View. Environ. Sci. Technol. 2005, 39, 9009–9015.
McCarthy, P. The Principles of Humic Substances. Soil Sci. 2001, 166, 738–751.
Albers, C. N.; Banta, G. T.; Jacobsen, O. S.; Hansen, P. E. Characterization and Structural Modeling of Humic Substances in Field Soil Displaying Significant Differences from Previously Proposed Structures. Eur. J. Soil. Sci. 2008, 59, 693–705.
Tipping, E. Cation Binding by Humic Substances, 1st ed. In Cambridge Environmental Chemistry, Vol. XII, Chap. 8; Cambridge University Press: Cambridge, UK, 2002.
Cardoza, L. A.; Korir, A. K.; Otto, W. H.; Wurrey, C. J.; Larive, C. K. Application of NMR Spectroscopy in Environmental Science. Prog. Nucl. Magn. Reson. Spectrosc. 2004, 45, 209–238.
Christl, I.; Milne, C. J.; Kinniburgh, D. G.; Kretzschmar, R. Relating Ion Binding by Fulvic and Humic Acids to Chemical Composition and Molecular Size: II. Metal Binding. Environ. Sci. Technol. 2001, 35, 2512–2517.
Leenheer, J. A.; Brown, G. K.; MacCarthy, P.; Cabaniss, S. E. Models of Metal Binding Structures in Fulvic Acid from the Suwannee River, Georgia. Environ. Sci. Technol. 1998, 32, 2410–2416.
Baziramakenga, R.; Simard, R. R.; Leroux, G. D. Determination of Organic Acids in Soil Extracts by Ion Chromatography. Soil. Biol. Biochem. 1995, 27, 349–356.
Strobel, B. W. Influence of Vegetation on Low-Molecular-Weight Carboxylic Acids in Soil—a Review. Geoderma. 2001, 99, 169–198.
Ehlken, S.; Kirchner, G. Environmental Processes Affecting Plant Root Uptake of Radioactive Trace Elements and Variability of Transfer Factor Data: A Review. J. Environ. Radioact. 2002, 58, 97–112;
Degryse, F.; Verma, V. K.; Smolders, E. Mobilization of Cu and Zn by Root Exudates of Dicotyledonous Plants in Resin-Buffered Solutions and in Soil. Plant Soil 2008, 306, 69–84.
Krivacsy, Z.; Kiss, G.; Varga, B.; Galambos, I.; Sarvari, Z.; Gelencser, A.; Molnar, A.; Fuzzi, S.; Facchini, M. C.; Zappoli, S.; Andracchio, A.; Alsberg, T.; Hansson, H. C.; Persson, L. Study of Humic-Like Substances in Fog and Interstitial Aerosol by Size-Exclusion Chromatography and Capillary Electrophoresis. Atm. Environ. 2000, 34, 4273–4281;
Kiss, G.; Varga, B.; Gelencser, A.; Krivacsy, Z.; Molnar, A.; Alsberg, T.; Persson, L.; Hansson, H.-C.; Facchini, M. C. Characterization of Polar Organic Compounds in Fog Water. Atm. Environ. 2001, 35, 2193–2200.
Kippenberger, M.; Winterhalter, R.; Moortgat, G. K. Determination of Higher Carboxylic Acids in Snow Samples Using Solid-Phase Extraction and LC/MS-TOF. Anal. Bioanal. Chem. 2008, 392, 1459–1470.
Smith, J. N.; Rathbone, G. J. Carboxylic Acid Characterization in Nanoparticles by Thermal Desorption Chemical Ionization Mass Spectrometry. Int. J. Mass Spectrom. 2008, 274, 8–13.
Gal, J.-F.; Maria, P.-C.; Massi, L.; Mayeux, C.; Burk, P.; Tammiku-Taul, J. Cesium Cation Affinities and Basicities. Int. J. Mass Spectrom. 2007, 267, 7–23.
Maria, P.-C.; Gal, J.-F.; Massi, L.; Burk, P.; Tammiku-Taul, J.; Tamp, S. Investigation of Cluster Ions Formed Between Cesium Cations and Benzoic, Salicylic and Phthalic Acids by Electrospray Mass Spectrometry and Density-Functional Theory Calculations: Toward a Modeling of the Interaction of Cs+ with Humic Substances. Rapid Commun. Mass Spectrom. 2005, 19, 568–573.
Maria, P.-C.; Massi, L.; Sindreu Box, N.; Gal, J.-F.; Burk, P.; Tammiku-Taul, J.; Kutsar, M. Bonding Energetics in Clusters Formed by Cesium Salts: A Study by Collision-Induced Dissociation and Density Functional Theory. Rapid Commun. Mass Spectrom. 2006, 20, 2057–2062.
Mayeux, C.; Massi, L.; Gal, J.-F.; Maria, P.-C.; Tammiku-Taul, J.; Lohu, E.-L.; Burk, P. Bonding Between Cesium Cation and Substituted Benzoic Acids or their Anions in the Gas Phase: Density Functional Theory and Mass Spectrometry Study. Collect. Czech. Chem. Commun. 2009, 74, 167–188.
Cooks, R. G.; Kruger, T. L. Intrinsic Basicity Determination Using Metastable Ions. J. Am. Chem. Soc. 1977, 99, 1279–1281;
Cooks, R. G.; Patrick, J. S.; Kotiaho, T.; McLuckey, S. A. Thermochemical Determinations by the Kinetic Method. Mass Spectrom. Rev. 1994, 13, 287–339;
Cooks, R. G.; Wong, P. S. H. Kinetic Method of Making Thermochemical Determinations: Advances and Applications. Acc. Chem. Res. 1998, 31, 379–386.
Chen, G.; Cooks, R. G. Estimation of Heterolytic Bond Dissociation Energies by the Kinetic Method. J. Mass Spectrom. 1997, 32, 1258–1261;
Wu, L.; Denault, J. W.; Cooks, R. G.; Drahos, L.; Vékey, K. Alkali Chloride Cluster Ion Dissociation Examined by Kinetic Method: Heterolytic Bond Dissociation Energies, Effective Temperatures, and Entropic Effects. J. Am. Soc. Mass Spectrom. 2002, 13, 1388–1395.
McIntyre, C.; McRae, C. Proposed Guidelines for Sample Preparation and ESI-MS Analysis of Humic Substances to Avoid Self-Esterification. Org. Geochem. 2005, 36, 543–553.
McIntyre, C.; McRae, C.; Jardine, D.; Batts, B. D. Self-Esterification of Fulvic Acid Model Compounds in Methanolic Solvents as Observed by Electrospray Ionization Mass Spectrometry. Rapid Commun. Mass Spectrom. 2002, 16, 785–789.
McClellan, J. E.; Phy, J.; Mulholland, J. J.; Yost, R. A. Effects of Fragile Ions on Mass Resolution and on Isolation for Tandem Mass Spectrometry in the Quadrupole Ion Trap Mass Spectrometer. Anal. Chem. 2002, 74, 402–412.
Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A. Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision C. 01 Gaussian Inc.: Pittsburgh, PA, 2003.
Becke, A. D. Density-Functional Thermochemistry: III. The Role of Exact Exchange. J. Chem. Phys. 1993, 98, 5648–5652;
Lee, C.; Yang, W.; Parr, R. G. Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density. Phys. Rev. B 1988, 37, 785–789;
Vosko, S. H.; Wilk, L.; Nusair, M. Accurate Spin-Dependent Electron Liquid Correlation Energies for Local Spin Density Calculations: A Critical Analysis. Can. J. Phys. 1980, 58, 1200–1211;
Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force-Fields. J. Phys. Chem. 1994, 98, 11623–11627.
Dunning T. H. Jr. Gaussian Basis Functions for Use in Molecular Calculations: I. Contraction of (9s5p) Atomic Basis Sets for the First-Row Atoms. J. Chem. Phys. 1970, 53, 2823–2833;
Dunning, T. H., Jr.; Hay, P. J. Gaussian Basis Set for Molecular Calculations. In: Modern Theoretical Chemistry, Vol. III, Chap. 1: Methods of Electronic Structure Theory, Schaefer, H.F. III, Ed.; Plenum Press: New York, 1977.
Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; von Schleyer, P. R. Efficient Diffuse Function-Augmented Basis Set for Anion Calculations: III. The 3–21+G Basis Set for the First-Row Elements, Lithium to Fluorine. J. Comp. Chem. 1983, 4, 294–301.
Bergner, A.; Dolg, M.; Kuechle, W.; Stoll, H.; Preuss, H. Ab Initio Energy-Adjusted Pseudopotentials for Elements of Groups 13–17. Mol. Phys. 1983, 80, 1431–1441;
Dolg, M.; Stoll, H.; Preuss, H.; Pitzer, R. M. Relativistic and Correlation Effects for Element 105 (hahnium, Ha): A Comparative Study of M and MO (M=Nb, Ta, Ha) Using Energy-Adjusted Ab Initio Pseudopotentials. J. Phys. Chem. 1993, 97, 5852–5859.
Glendening, E. D.; Feller, D.; Thompson, M. A. An Ab Initio Investigation of the Structure and Alkali Metal Cation Selectivity of 18-Crown-6. J. Am. Chem. Soc. 1994, 116, 10657–10659.
Weigend, F.; Ahlrichs, R. Balanced Basis Sets of Split Valence, Triple Zeta Valence and Quadruple Zeta Valence. Phys. Chem. Chem. Phys. 2005, 7, 3297–3305;
Schaefer, A.; Huber, C.; Ahlrichs, R. Fully Optimized Contracted Gaussian Basis Set of Triple Zeta Valence. J. Chem. Phys. 1994, 100, 5829–5835.
Feller, D. The Role of Databases in Support of Computational Chemistry Calculations. J. Comp. Chem. 1996, 17, 1571–1586;
Schuchardt, K. L.; Didier, B. T.; Elsethagen, T.; Sun, L.; Gurumoorthi, V.; Chase, J.; Li, J.; Windus, T. L. Basis Set Exchange: A Community Database for Computational Sciences. J. Chem. Inf. Model 2007, 47, 1045–1052.
Leininger, T.; Nicklass, A.; Kuechle, W.; Stoll, H.; Dolg, M.; Bergner, A. The Accuracy of the Pseudopotential Approximation: Non-Frozen-Core Effects for Spectroscopic Constant of Alkali Fluorides XF (X=K, Rb, Cs). Chem. Phys. Lett. 1996, 255, 274–280.
Peterson, K. A.; Figgen, D.; Goll, E.; Stoll, H.; Dolg, M. Systematically Convergent Basis Set with Relativistic Pseudopotentials: II Small-Core Pseudopotentials and Correlation Consistent Basis Set for the Post-d Group 16–18 Elements. J. Chem. Phys. 2003, 119, 11113–11123.
Armentrout, P. B. Is the Kinetic Method a Thermodynamic Method? J. Mass Spectrom. 1999, 34, 74–78;
Drahos, L.; Vékey, K. How Closely Related are the Effective and the Real Temperature. J. Mass Spectrom. 1999, 34, 79–84;
Cooks, R. J.; Koskinen, J. T.; Thomas, P. D. The Kinetic Method of Making Thermochemical Determinations. J. Mass Spectrom. 1999, 34, 85–92.
Ma, J. C.; Dougherty, D. A. The Cation/π Interaction. Chem. Rev. 1997, 97, 1303–1324.
Gal, J. F.; Maria, P. C.; Decouzon, M.; Mo, O.; Yanez, M. Gas-Phase Lithium-Cation Basicities of Some Benzene Derivatives: An Experimental and Theoretical Study. Int. J. Mass Spectrom. Ion Processes. 2002, 219, 445–456.
Amunugama, R.; Rodgers, M. T. Influence of Substituents on Cation/π Interactions: I. Absolute Binding Energies of Alkali Metal Cation-Toluene Complexes Determined by Threshold Collision-Induced Dissociation and Theoretical Studies. J. Phys. Chem. A. 2002, 106, 5529–5539;
Amunugama, R.; Rodgers, M. T. Influence of Substituents on Cation/π Interactions: II. Absolute Binding Energies of Alkali Metal Cation-Fluorobenzene Complexes Determined by Threshold Collision-Induced Dissociation and Theoretical Studies. J. Phys. Chem. A. 2002, 106, 9092–9103;
Amunugama, R.; Rodgers, M. T. The Influence of Substituents on Cation/π Interactions: IV. Absolute Binding Energies of Alkali Metal Cation-Phenol Complexes Determined by Threshold Collision-Induced Dissociation and Theoretical Studies. J. Phys. Chem. A. 2002, 106, 9718–9728;
Amunugama, R.; Rodgers, M. T. Influence of Substituents on Cation/π Interactions: III. Absolute Binding Energies of Alkali Metal Cation-Aniline Complexes Determined by Threshold Collision-Induced Dissociation and Theoretical Studies. Int. J. Mass Spectrom. Ion Processes 2003, 227, 339–360;
Amunugama, R.; Rodgers, M. T. Influence of Substituents on Cation/π Interactions: V. Absolute Binding Energies of Alkali Metal Cation-Anisole Complexes Determined by Threshold Collision-Induced Dissociation and Theoretical Studies. Int. J. Mass Spectrom. Ion Processes 2003, 222, 431–450.
McMahon, T. B.; Kebarle, P. Intrinsic Acidities of Substituted Phenols and Benzoic Acids Determined by Gas-Phase Proton-Transfer Equilibria. J. Am. Chem. Soc. 1977, 99, 2222–2230.
Leo, H. A.; Taft, R. W. A Survey of Hammett Substituent Constants and Resonance and Field Parameters. Chem. Rev. 1991, 91, 165–195.
Drahos, L.; Vekey, K. Entropy Evaluation Using the Kinetic Method: Is it Feasible? J. Mass Spectrom. 2003, 38, 1025–1042;
Kish, M. M.; Wesdemiotis, G.; Ohanessian, G. The Sodium Ion Affinity of Glycylglycine. J. Phys. Chem. B 2004, 108, 3086–3091;
Bouchoux, G. Evaluation of the Protonation Thermochemistry Obtained by the Extended Kinetic Method. J. Mass Spectrom. 2006, 41, 1006–1013.
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Mayeux, C., Tammiku-Taul, J., Massi, L. et al. Interaction of the cesium cation with mono-, di-, and tricarboxylic acids in the gas phase. A Cs+ affinity scale for cesium carboxylates ion pairs. J Am Soc Mass Spectrom 20, 1912–1924 (2009). https://doi.org/10.1016/j.jasms.2009.07.003
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DOI: https://doi.org/10.1016/j.jasms.2009.07.003