Hostname: page-component-586b7cd67f-t8hqh Total loading time: 0 Render date: 2024-11-24T03:08:15.014Z Has data issue: false hasContentIssue false

Electron and Force Microscopy Characterization of Particle Size Effects and Surface Phenomena Associated with Individual Natural Organic Matter Fractions

Published online by Cambridge University Press:  26 February 2014

Lee W. Hoffman*
Affiliation:
Department of Chemistry & Biochemistry, South Dakota State University, Box 2202, Brookings, SD 57007-0896, USA
Gabriela Chilom
Affiliation:
Department of Chemistry & Biochemistry, South Dakota State University, Box 2202, Brookings, SD 57007-0896, USA
Swaminathan Venkatesan
Affiliation:
Department of Electrical Engineering and Computer Science, South Dakota State University, Box 2202, Brookings, SD 57007-0896, USA
James A. Rice
Affiliation:
Department of Chemistry & Biochemistry, South Dakota State University, Box 2202, Brookings, SD 57007-0896, USA
*
*Corresponding author. [email protected]
Get access

Abstract

Natural organic matter (NOM) generically refers to organic substances found in soils, waters, and sediments. It is the brown-to-black, heterogeneous organic material produced through the diagenetic alteration of plant tissue and microbial biomass via a myriad of biotic and abiotic reactions. Since NOM is the primary source of organic carbon in the earth’s surficial environment, understanding the processes by which NOM is produced is integral to understanding carbon sequestration, contaminant fate and transport, and other earth surface processes. NOM samples (HA0) consist of nonamphiphilic (HA1), lipid-like (L0 and L1), and strongly amphiphilic (HA2) components. Here we present the structure and morphology of self-assembled NOM components based on scanning electron microscopy (SEM), atomic force microscopy (AFM), and electrostatic force microscopy (EFM) characterizations. Effects of surface charge and hydrophobicity/hydrophilicity of the amphiphile on the interaction and resulting structures were investigated using SEM, AFM, and EFM. Data shows that the component’s amphiphilic nature plays a key role in the formation of NOM. SEM data show that aggregates form while AFM/EFM analysis verifies the existence of hydrophobic/hydrophilic moieties in different fractions of HA0. Subsequently, the amphiphilic nature of HA2 will have a substantial effect on interfacial interactions and subsequent self-assembly of HA0’s components.

Type
Biological Applications
Copyright
© Microscopy Society of America 2014 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Alber, F., Dokudovskaya, S., Veenhoff, L.M., Wenzhu, Z., Kipper, J., Devos, D., Suprapto, A., Karni-Schmidt, O., Williams, R., Chait, B.T., Rout, M.P. & Sali, A. (2007). Determining the architectures of macromolecular assemblies. Nature 450(7170), 683694.CrossRefGoogle ScholarPubMed
Alexandridis, P. & Lindman, B. Eds. (2000). Amphiphilic Block Copolymers: Self-Assembly and Applications. Amsterdam, The Netherlands: Elsevier Science B.V. Google Scholar
Balazs, A.C., Ginzburg, V.V., Qiu, F., Peng, G. & Jasnow, D. (2000). Multi-scale model for binary mixtures containing nanoscopic particles. J Phys Chem B 104(15), 34113422.Google Scholar
Brown, F.L.H. (2008). Elastic modeling of biomembranes and lipid bilayers. Annu Rev Phys Chem 59(1), 685712.CrossRefGoogle ScholarPubMed
Chen, Y. & Schnitzer, M. (1976). Scanning electron microscopy of a humic acid and a fulvic acid and its metal and clay complexes. Soil Sci Soc Am J 40, 682686.CrossRefGoogle Scholar
Chilom, G., Bruns, A.S. & Rice, J.A. (2009). Aggregation of humic acid in solution: Contributions of different fractions. Organic Geochem 40(4), 455460.CrossRefGoogle Scholar
Chilom, G. & Rice, J.A. (2005). Glass transition and crystallite melting in natural organic matter. Organic Geochem 36(10), 13391346.CrossRefGoogle Scholar
Chilom, G. & Rice, J.A. (2009). Structural organization of humic acid in the solid state. Langmuir 25(16), 90129015.Google Scholar
Dekanski, A.B. (1997). Material surface characterization by electronic techniques. II. Electron microscopy. Hem Ind 51, 403410.Google Scholar
Dougan, L., Crain, J., Finney, J.L. & Soper, A.K. (2010). Molecular self-assembly in a model amphiphile system. Phys Chem Chem Phys 12(35), 1022110229.Google Scholar
Gross, L. (2011). Recent advances in submolecular resolution with scanning probe microscopy. Nat Chem 3, 273278.Google Scholar
Guetzloff, T.F. & Rice, J.A. (1994). Does humic acid form a micelle? Sci Total Environ 152(1), 3135.Google Scholar
Guetzloff, T.F. & Rice, J.A. (1996). Micellar Nature of Humic Colloids. In Humic and Fulvic Acids, Gaffney, J.S., Marley, N.A. & Clark, S.B. (Eds.), pp. 1825. Washington, DC: American Chemical Society.Google Scholar
Ikai, A. (1997). STM and AFM of bio/organic molecules and structures. Surf Sci Rep 26, 261332.Google Scholar
Israelachvili, J.N., Mitchell, D.J. & Ninham, B.W. (1976). Theory of self-assembly of hydrocarbon amphiphiles into micelles and bilayers. J Chem Soc, Faraday Trans. 2(72), 1525.Google Scholar
Kikunaga, K., Toosaka, K., Kamohara, T., Sakai, K. & Nonaka, K. (2011). A study of electrostatic charge on insulating film by electrostatic force microscopy. J Phys 301(1), 012043.Google Scholar
Kohl, S. (1999). Role of Lipids in the Sorption and Binding of Nonpolar Anthropogenic Organic Compounds to Soil Organic Matter. (PhD Dissertation), South Dakota State University.Google Scholar
Kononova, M.M. (1966). Soil Organic Matter. Oxford: Pergamon.Google Scholar
Krafft, M.P. (2012). Large organized surface domains self-assembled from nonpolar amphiphiles. Acc Chem Res 45, 514524.Google Scholar
Langford, C.H. & Melton, J.R. (2005). When should humic substances be treated as dynamic combinatorial systems? In Humic substances, Ghabbour, E.A. & Davies, G.R. (Eds.), pp. 6578. New York, NY: Taylor & Francis.Google Scholar
Leng, Y. & Williams, C.C. (1993). Molecular charge mapping with the electrostatic force microscope. Proc SPIE-Int Soc Opt Eng 1855, 3539.Google Scholar
MacCarthy, P. (2001 a). The principles of humic substances. Soil Sci 166(11), 738751.Google Scholar
MacCarthy, P. (2001 b). The principles of humic substances: An introduction to the first principle. Spec Publ – R Soc Chem 273, 1930.Google Scholar
MacCarthy, P. & Rice, J.A. (1991). An ecological rationale for the heterogeneous nature of humic substances. In Scientists on Gaia Schneider, S.H. & Boston, P.J. (Eds.), pp. 339345. Cambridge, MA: MIT Press.Google Scholar
Mao, J.D., Hu, W.G., Schmidt-Rohr, K., Davies, G., Ghabbour, E.A. & Xing, B. (2000). Quantitative characterization of humic substances by solid-state carbon-13 nuclear magnetic resonance. Soil Science Society of America Journal 64, 873884.Google Scholar
Mayes, M., Jagadamma, S., Ambaye, H., Petridis, L. & Lauter, V. (2013). Neutron reflectometry reveals the internal structure of organic compounds deposited on aluminum oxide. Geoderma 192(0), 182188.Google Scholar
Mertig, M., Klemm, D., Zänker, H. & Pompe, W. (2002). Scanning force microscopy of two-dimensional structure formation in thin humic acid films. Surf Interface Anal 33(2), 113117.Google Scholar
Moore, R. (1986). Soil survey of the Pike and San Isabel National Forest, Northern Part, Soil Survey No. 8657. Pueblo, Co.: US Forest Service.Google Scholar
Nambu, K., van Hees, P.A.W., Essén, S.A. & Lundström, U.S. (2005). Assessing centrifugation technique for obtaining soil solution with respect to leaching of low molecular mass organic acids from pine roots. Geoderma 127(3–4), 263269.Google Scholar
Nečas, D. & Klapetek, P. (2012). Gwyddion: An open-source software for SPM data analysis. Centr Eur J Phys 10(1), 181188.Google Scholar
Nielsen, S.O., Srinivas, G., Lopez, C.F. & Klein, M.L. (2005). Modeling surfactant adsorption on hydrophobic surfaces. Phys Rev Lett 94(22), 228301.Google Scholar
Nikiforov, M.P. & Bonnell, D.A. (2007). Scanning Probe Microscopy in Materials Science, pp. 929968. New York: Springer.Google Scholar
Nogues, C. & Wanunu, M. (2004). A rapid approach to reproducible, atomically flat gold films on mica. Surface Sci 573(3), L383L389.CrossRefGoogle Scholar
Orlov, D.S. (1985). Humus Acids of Soils . New Delhi: Amerind Publishing.Google Scholar
Paananen, A. (2007). On the Interactions and Interfacial Behaviour of Biopolymers. An AFM Study, vol. 637. VTT Publ, A101A102.Google Scholar
Park, C., Lee, J. & Kim, C. (2011). Functional supramolecular assemblies derived from dendritic building blocks. Chemical Communications 47(44), 1204212056.Google Scholar
Piccolo, A. (2001). The supramolecular structure of humic substances. Soil Sci 166(11), 810832.Google Scholar
Piccolo, A. (2002). The supramolecular structure of humic substances: A novel understanding of humus chemistry and implications in soil science. In Advances in Agronomy, Sparks, D. (Ed.), pp. 57134. San Diego, CA: Academic Press.Google Scholar
Qi, Y. (2011). Investigation of organic films by atomic force microscopy: Structural, nanotribological and electrical properties. Surf Sci Rep 66, 379393.CrossRefGoogle Scholar
Rice, J.A. & MacCarthy, P. (1991). Composition of humin in stream sediments and peat. In Organic Substances and Sediments in Water, Vol. 1: Humics and Soils, Baker, R.A. (Ed.), pp. 3546. Chelsea, MI: Lewis Publications.Google Scholar
Rice, J.A. & MacCarthy, P. (1992). Disaggregation and characterization of humin. Sci Total Environ 117–118(0), 8388.Google Scholar
Sarid, D. (1991). Oxford Series on Optical Sciences, Vol. 2: Scanning Force Microscopy with Applications to Electric, Magnetic, and Atomic Forces. New York, NY: Oxford University Press.Google Scholar
Schneider, C.A., Rasband, W.S. & Eliceiri, K.W. (2012). NIH Image to ImageJ: 25 years of image analysis. Nat Meth 9(7), 671675.Google Scholar
Senesi, N., Rizzi, F.R., Dellino, P. & Acquafredda, P. (1997). Fractal humic acids in aqueous suspensions at various concentrations, ionic strengths, and pH values. Colloids Surf A 127(1–3), 5768.Google Scholar
Six, J. & Jastrow, J.D. (2006). Organic matter turnover. In Encyclopedia of Soil Science Lal, R. (Ed.), pp. 936942. Boca Raton, FL: Taylor & Francis.Google Scholar
Stevenson, F.J. (1994). Humus Chemistry: Genesis, Composition, Reactions. Hoboken, NJ: Wiley.Google Scholar
Swift, D.L. (1985). Fractionation of soil humic substances. In Humic Substances in Soil, Sediment, and Water: Geochemistry, Isolation, and Characterization, Aiken, G.R., McKnight, D.M., Wershaw, R.L. & MacCarthy, P. (Eds.), pp. 387408. New York: John Wiley and Sons.Google Scholar
Takano, H., Wong, S.-S., Harnisch, J.A. & Porter, M.D. (2000). Mapping the subsurface composition of organic films by electric force microscopy. Langmuir 16(12), 52315233.Google Scholar
Tan, K.H. (1985). Scanning electron microscopy of humic matter as influenced by methods of preparation. Soil Sci Soc Am J 49, 11851191.Google Scholar
Thurman, E.M. (1985). Organic Geochemistry of Natural Waters. Dordrecht; Boston; Hingham, MA, USA: M. Nijhoff; Distributors for the US and Canada, Kluwer Academic.Google Scholar
Valdre, G. (1999). Correlative microscopy and probing in materials science. NATO Sci Ser, Ser E 364, 455472.Google Scholar
Wang, C., Wang, Z. & Zhang, X. (2012). Amphiphilic building blocks for self-assembly: From amphiphiles to supra-amphiphiles. Acc Chem Res 45(4), 608618.Google Scholar
Wang, Y., Xu, H. & Zhang, X. (2009). Tuning the amphiphilicity of building blocks: Controlled self-assembly and disassembly for functional supramolecular materials. Adv Mater 21(28), 28492864.Google Scholar
Wershaw, R. (1993). Model for humus in soils and sediments. Environ Sci Technol 27(5), 814816.Google Scholar
Wershaw, R. (2004). Evaluation of conceptual models of natural organic matter (humus) from a consideration of the chemical and biochemical processes of humification. Scientific Investigations Report 2004–5121, pp. 49. Reston, VA: USGS.Google Scholar
Wu, Q., Schleuss, U. & Blume, H.-P. (1995). Investigation on soil lipid extraction with different organic solvents. Zeitschrift für Pflanzenernährung und Bodenkunde 158(4), 347350.Google Scholar
Yu, A.A., Stone, P.R., Norville, J.E., Vaughn, M., Pacsial, E.J., Bruce, B.D., Baldo, M., Raymo, F.M. & Stellacci, F. (2006 a). A simple atomic force microscopy method for the visualization of polar and non-polar parts in thin organic films. J Exp Nanosc 1(1), 6373.Google Scholar
Yu, A.A., Stone, P.R., Norville, J.E., Vaughn, M., Pascal, E.J., Bruce, B.D., Baldo, M., Raymo, F.M. & Stellacci, F. (2006 b). A simple atomic force microscopy method for the visualization of polar and non-polar parts in thin organic films. J Exp Nan 1(1), 6373.Google Scholar