Abstract
Specific surface area (SSA) of soil is an intrinsic property governing many geotechnical and geoenvironmental engineering properties. SSA can be physically divided into two categories: external or particle surface area, and internal or intracrystalline surface area. Although both of them are well known to play different roles in physical, chemical, and biological processes, few methods have been developed to quantitatively distinguish between them. Using a recent theoretical advancement of an augmented Brunauer–Emmett–Teller (BET) adsorption equation for soil, the writers develop a procedure based on measured water adsorption isotherms to quantify the external and internal SSAs. Extensive adsorption isotherms of water, ethylene glycol monomethyl ether, and nitrogen of a variety of silty and clayey soils are used to validate the procedure. Practical implications of SSA are also provided by linking the importance of the internal SSA to swelling behavior, and the importance of the external SSA to adsorption of nonpolar materials. The demonstrated procedure to quantify external and internal SSAs should provide a pressing and powerful method to understand physical, chemical, and biological processes in soils.
Get full access to this article
View all available purchase options and get full access to this article.
Data Availability Statement
Data used in this work are available from the corresponding author by request.
Acknowledgments
This research was sponsored by National Science Foundation Grant Nos. CMMI-1363315 and CMMI-1561764.
References
Akin, I. D. 2014. Clay surface properties by water vapor sorption methods. Madison, WI: Univ. of Wisconsin–Madison.
Akin, I. D., and W. J. Likos. 2014. “Specific surface area of clay using water vapor and EGME sorption methods.” Geotech. Test. J. 37 (6): 1016–1027. https://doi.org/10.1520/GTJ20140064.
Akin, I. D., and W. J. Likos. 2016. “Single-point and multi-point water-sorption methods for specific surface areas of clay.” Geotech. Test. J. 39 (2): 291–300. https://doi.org/10.1520/GTJ20150117.
Akin, I. D., and W. J. Likos. 2017. “Evaluation of isotherm models for water vapor sorption behavior of expansive clays.” J. Perform. Constr. Facil. 31 (1): D4016001. https://doi.org/10.1061/(ASCE)CF.1943-5509.0000899.
Anandarajah, A., and N. Lu. 1991. “Numerical study of double-layer repulsion between non-parallel clay particles of finite length.” Int. J. Numer. Anal. Methods Geomech. 15 (10): 683–703. https://doi.org/10.1002/nag.1610151002.
Arthur, E., M. Tuller, P. Moldrup, A. C. Resurreccion, M. S. Meding, K. Kawamoto, T. Komatsu, and L. W. de Jonge. 2013. “Soil specific surface area and non-singularity of soil–water retention at low saturations.” Soil Sci. Soc. Am. J. 77 (1): 43. https://doi.org/10.2136/sssaj2012.0262.
ASTM. 2010. Standard test methods for liquid limit, plastic limit, and plasticity index of soils. ASTM D4318. West Conshohocken, PA: ASTM.
Aylmore, L. A. G. 1970. “Surface area of homoionic illite and montmorillonite clay minerals as measured by the sorption of nitrogen and carbon dioxide.” Clays Clay Miner. 18 (2): 91–96. https://doi.org/10.1346/CCMN.1970.0180204.
Brunauer, S., P. H. Emmett, and E. Teller. 1938. “Adsorption of gases in multimolecular layers.” J. Am. Chem. Soc. 60 (2): 309–319. https://doi.org/10.1021/ja01269a023.
Chen, F. H. 1975. Foundations on expansive soils. Amsterdam, Netherlands: Elsevier.
De Wit, C. T., and P. L. Arens. 1950. “Moisture content and density of some clay minerals and some remarks on the hydration pattern of clay.” In 4th Int. Congress of Soil Science Transactions, 59–62. Groningen, Netherlands: Hoitesema Brothers.
Dolinar, B., M. Mišič, and L. Trauner. 2007. “Correlation between surface area and Atterberg limits of fine-grained soils.” Clays Clay Miner. 55 (5): 519–523. https://doi.org/10.1346/CCMN.2007.0550506.
Freundlich, H., and E. Mäkelt. 1909. “Über den absoluten Nullpunkt des Potentials.” Z. Elektrochem. Angew. Phys. Chem. 15 (6): 161–165.
Heister, K. 2014. “The measurement of the specific surface area of soils by gas and polar liquid adsorption methods-limitations and potentials.” Geoderma 216 (Mar): 75–87. https://doi.org/10.1016/j.geoderma.2013.10.015.
Hensen, E. J. M., and B. Smit. 2002. “Why clays swell.” J. Phys. Chem. B 106 (49): 12664–12667. https://doi.org/10.1021/jp0264883.
Israelachvili, J. N. 2011. Intermolecular and surface forces. San Diego: Academic Press.
Khorshidi, M., N. Lu, I. D. Akin, and W. J. Likos. 2017. “Intrinsic relationship between specific surface area and soil water retention.” J. Geotech. Geoenviron. Eng. 143 (1): 04016078. https://doi.org/10.1061/(ASCE)GT.1943-5606.0001572.
Khorshidi, M., N. Lu, and A. Khorshidi. 2016. “Intrinsic relationship between matric potential and cation hydration.” Vadose Zone J. 15 (11): 04015032. https://doi.org/10.2136/vzj2016.01.0001.
Laird, D. A. 1996. “Model for crystalline swelling of 2:1 phyllosilicates.” Clays Clay Miner. 44 (4): 553–559. https://doi.org/10.1346/CCMN.1996.0440415.
Laird, D. A. 1999. “Layer charge influences on the hydration of expandable 2: 1 phyllosilicates.” Clays Clay Miner. 47 (5): 630–636. https://doi.org/10.1346/CCMN.1999.0470509.
Langmuir, I. 1918. “The adsorption of gases on plane surfaces of glass, mica and platinum.” J. Am. Chem. Soc. 40 (9): 1361–1403. https://doi.org/10.1021/ja02242a004.
Leão, T. P., and M. Tuller. 2014. “Relating soil specific surface area, water film thickness, and water vapor adsorption.” Water Resour. Res. 50 (10): 7873–7885. https://doi.org/10.1002/2013WR014941.
Likos, W., N. Lu, and W. Wenszel. 2011. “Performance of a dynamic dew point method for moisture isotherms of clays.” Geotech. Test. J. 34 (4): 373–382. https://doi.org/10.1520/GTJ102901.
Likos, W. J. 2008. “Vapor adsorption index for expansive soil classification.” J. Geotech. Geoenviron. Eng. 134 (7): 1005–1009. https://doi.org/10.1061/(ASCE)1090-0241(2008)134:7(1005).
Likos, W. J., and A. Wayllace. 2010. “Porosity evolution of free and confined bentonites during interlayer hydration.” Clays Clay Miner. 58 (3): 399–414. https://doi.org/10.1346/CCMN.2010.0580310.
Lu, N. 2016. “Generalized soil water retention equation for adsorption and capillarity.” J. Geotech. Geoenviron. Eng. 142 (10): 04016051. https://doi.org/10.1061/(ASCE)GT.1943-5606.0001524.
Lu, N., and Y. Dong. 2017. “Correlation between soil-shrinkage curve and water-retention characteristics.” J. Geotech. Geoenviron. Eng. 143 (9): 04017054. https://doi.org/10.1061/(ASCE)GT.1943-5606.0001741.
Lu, N., and M. Khorshidi. 2015. “Mechanisms for soil–water retention and hysteresis at high suction range.” J. Geotech. Geoenviron. Eng. 141 (8): 04015032. https://doi.org/10.1061/(ASCE)GT.1943-5606.0001325.
Lu, N., and W. J. Likos. 2004. Unsaturated soil mechanics. New York: Wiley.
Lu, N., and C. Zhang. 2019. “Soil sorptive potential: Concept, theory, and verification.” J. Geotech. Geoenviron. Eng. 145 (4): 04019006. https://doi.org/10.1061/(ASCE)GT.1943-5606.0002025.
Mackenzie, R. C. 1958. “Density of water sorbed on montmorillonite.” Nature 181 (4605): 334. https://doi.org/10.1038/181334a0.
Marcus, Y. 1991. “Thermodynamics of solvation of ions. Part 5—Gibbs free energy of hydration at 298.15 K.” J. Chem. Soc., Faraday Trans. 87 (18): 2995–2999. https://doi.org/10.1039/FT9918702995.
Martin, R. T. 1960. “Adsorbed water on clay: A review.” Clays Clay Miner. 9 (1): 28–70. https://doi.org/10.1346/CCMN.1960.0090104.
McKeen, R. G. 1992. “A model for predicting expansive soil behavior.” In Proc., 7th Int. Conf. on Expansive Soils, 1–6. Reston, VA: ASCE.
Mitchell, J. K., and K. Soga. 2005. Fundamentals of soil behavior. New York: Wiley.
Mooney, R. W., A. G. Keenan, and L. A. Wood. 1952a. “Adsorption of water vapor by montmorillonite. I. Heat of desorption and application of bet theory.” J. Am. Chem. Soc. 74 (6): 1367–1371. https://doi.org/10.1021/ja01126a001.
Mooney, R. W., A. G. Keenan, and L. A. Wood. 1952b. “Adsorption of water vapor by montmorillonite. II. Effect of exchangeable ions and lattice swelling as measured by X-ray diffraction.” J. Am. Chem. Soc. 74 (6): 1371–1374. https://doi.org/10.1021/ja01126a002.
Newman, A. C. D. 1983. “The specific surface of soils determined by water sorption.” J. Soil Sci. 34 (1): 23–32. https://doi.org/10.1111/j.1365-2389.1983.tb00809.x.
Norrish, K. 1954. “The swelling of montmorillonite.” Discuss. Faraday Soc. 18: 120. https://doi.org/10.1039/df9541800120.
Pomonis, P. J., D. E. Petrakis, A. K. Ladavos, K. M. Kolonia, G. S. Armatas, S. D. Sklari, P. C. Dragani, A. Zarlaha, V. N. Stathopoulos, and A. T. Sdoukos. 2004. “A novel method for estimating the -values of the BET equation in the whole range using a Scatchard-type treatment of it.” Microporous Mesoporous Mater. 69 (1–2): 97–107. https://doi.org/10.1016/j.micromeso.2004.01.009.
Puri, B. R., and K. Murari. 1964. “Studies in surface area measurements of soils: 2. Surface area from a single point on the water isotherm.” Soil Sci. 97 (5): 341–343. https://doi.org/10.1097/00010694-196405000-00008.
Quirk, J. P. 1955. “Significance of surface areas calculated from water vapor sorption isotherms by use of the BET equation.” Soil Sci. 80 (6): 423–430. https://doi.org/10.1097/00010694-195512000-00001.
Quirk, J. P., and R. S. Murray. 1999. “Appraisal of the ethylene glycol monoethyl ether method for measuring hydratable surface area of clays and soils.” Soil Sci. Soc. Am. J. 63 (4): 839–849. https://doi.org/10.2136/sssaj1999.634839x.
Ravikovitch, P. I., B. W. Bogan, and A. V. Neimark. 2005. “Nitrogen and carbon dioxide adsorption by soils.” Environ. Sci. Technol. 39 (13): 4990–4995. https://doi.org/10.1021/es048307b.
Salles, F., O. Bildstein, J.-M. M. Douillard, M. Jullien, and H. Van Damme. 2007. “Determination of the driving force for the hydration of the swelling clays from computation of the hydration energy of the interlayer cations and the clay layer.” J. Phys. Chem. C 111 (35): 13170–13176. https://doi.org/10.1021/jp0719762.
Santamarina, J. C., K. A. Klein, Y. H. Wang, and E. Prencke. 2002. “Specific surface: Determination and relevance.” Can. Geotech. J. 39 (1): 233–241. https://doi.org/10.1139/t01-077.
Sposito, G., and R. Prost. 1982. “Structure of water adsorbed on smectites.” Chem. Rev. 82 (6): 553–573. https://doi.org/10.1021/cr00052a001.
Tokunaga, T. K., and J. Wan. 1997. “Water film flow along fracture surfaces of porous rock.” Water Resour. Res. 33 (6): 1287–1295. https://doi.org/10.1029/97WR00473.
Tuller, M., and D. Or. 2005. “Water films and scaling of soil characteristic curves at low water contents.” Water Resour. Res. 41 (9): 1–6. https://doi.org/10.1029/2005WR004142.
Tunega, D., M. H. Gerzabek, and H. Lischka. 2004. “Ab initio molecular dynamics study of a monomolecular water layer on octahedral and tetrahedral kaolinite surfaces.” J. Phys. Chem. B 108 (19): 5930–5936. https://doi.org/10.1021/jp037121g.
Wang, J., A. G. Kalinichev, and R. J. Kirkpatrick. 2006. “Effects of substrate structure and composition on the structure, dynamics, and energetics of water at mineral surfaces: A molecular dynamics modeling study.” Geochim. Cosmochim. Acta 70 (3): 562–582. https://doi.org/10.1016/j.gca.2005.10.006.
Woodruff, W. F., and A. Revil. 2011. “CEC-normalized clay-water sorption isotherm.” Water Resour. Res. 47 (11): 1–15. https://doi.org/10.1029/2011WR010919.
Yukselen, Y., and A. Kaya. 2006. “Comparison of methods for determining specific surface area of soils.” J. Geotech. Geoenviron. Eng. 132 (7): 931–936. https://doi.org/10.1061/(ASCE)1090-0241(2006)132:7(931).
Zhang, C., Y. Dong, and Z. Liu. 2017. “Lowest matric potential in quartz: Metadynamics evidence.” Geophys. Res. Lett. 44 (4): 1706–1713. https://doi.org/10.1002/2016GL071928.
Zhang, C., and N. Lu. Forthcoming. “Unified effective stress equation for soil.” J. Eng. Mech.
Zhang, C., and N. Lu. 2018a. “Measuring soil–water density by helium pycnometer.” J. Geotech. Geoenviron. Eng. 144 (9): 02818002. https://doi.org/10.1061/(ASCE)GT.1943-5606.0001929.
Zhang, C., and N. Lu. 2018b. “What is the range of soil water density? Critical reviews with a unified model.” Rev. Geophys. 56 (3): 532–562. https://doi.org/10.1029/2018RG000597.
Zhang, C., and N. Lu. 2019a. “Augmented Brunauer–Emmett–Teller equation for water adsorption on soils.” Vadose Zone J. 18 (1): 1–12. https://doi.org/10.2136/vzj2019.01.0011.
Zhang, C., and N. Lu. 2019b. “Soil sorptive potential: Its determination and predicting soil water density.” J. Geotech. Geoenviron. Eng. 145 (4): 04019006. https://doi.org/10.1061/(ASCE)GT.1943-5606.0002188.
Zhang, C., and N. Lu. 2019d. “Unitary definition of matric suction.” J. Geotech. Geoenviron. Eng. 145 (2): 02818004. https://doi.org/10.1061/(ASCE)GT.1943-5606.0002004.
Information & Authors
Information
Published In
Journal of Geotechnical and Geoenvironmental Engineering
Volume 146 • Issue 2 • February 2020
Copyright
©2019 American Society of Civil Engineers.
History
Received: Mar 6, 2019
Accepted: Aug 27, 2019
Published online: Nov 26, 2019
Published in print: Feb 1, 2020
Discussion open until: Apr 26, 2020
Authors
Metrics & Citations
Metrics
Citations
Download citation
If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.