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Journal of the Chinese Institute of Engineers, Vol. 28, No. 2, pp.

375-379 (2005)


Short Paper


Jiunn-Fwu Lee*, Ming-Hung Hsu, Chung-Kung Lee, Huan-Ping Chao, and Bai-Her Chen

The effects of surface area, soil organic matter (SOM) content, and cation exchange capacity (CEC) of natural soils and clays on the adsorption capacity of cationic, anionic, and nonionic surfactants in water-solid systems were investigated based on the adsorption isotherm analysis. The sorption capacity for a cationic surfactant was proportional to the CEC of the solids. For both anionic and nonionic surfactants, the sorption capacity was related to the soil mineral fraction. However, other soil properties probably affect the practical sorption. The investigated soil properties were treated case by case. Key Words: soil properties, surfactants, adsorption capacity, adsorption model.

I. INTRODUCTION A better understanding of surfactant adsorption by clays and soils is of great importance due to the wide spread use of these compounds in household and industrial activities. For subsaturated organic contaminants in a soil-water-surfactant system, the surfactants enable the micelle to greatly promote the apparent aqueous solubility of relatively insoluble solutes. As such, it has potential as a means of removing pollutants from soil during a remediation treatment process. However, surfactants in a soilwater system are also considered to have potential to be adsorbed by soils to increase contaminant partitioning in the soils (Lee et al. , 2000). Thus, prior to using surfactants for subsaturated contaminant remediation in soil, it is prudent to establish the relation between the soil properties and the surfactant adsorption characteristics, as a guide to proper surfactant selection and the best concentration for maximum performance. For this, in addition to the
*Corresponding author. (Tel: 886-3-4227151-34658; Fax: 8863-4226742; Email: J. F. Lee, M. H. Hsu, H. P. Chao, and B. H. Chen are with the Graduate Institute of Environmental Engineering, National Central University, Chungli, Taiwan 320, R.O.C. C. K. Lee is with the Department of Environmental Engineering, Van-Nung Institute of Technology, Chungli, Taiwan 320, R.O.C.

quantitative adsorption measurement, and endeavoring to theoretically describe the adsorption isotherms, numerous instrumental methods have been used to characterize the adsorption process, the formation of bonds, the structure of interfacial layers, overall dispersion, and organocomplex properties (Goloub et al. , 1996). The experimental data basis for surfactant sorption by soils and clays is quite extensive. It was found that there are some internal factors, such as the length and nature of the surfactant polar chain and the nature of the solid surface that must be taken into account. In this study, various natural clays and soils were used. The effects of their properties on the adsorption of cationic, anionic, and nonionic surfactants were examined to give a more comprehensive description of the adsorption profile of surfactants in soils and clays. These adsorbents offer a wide range of physicochemical properties. We think that this is an ideal platform from which to critically examine the relationships between the clay and soil characteristics and their adsorption capacity for the surfactants. II. EXPERIMENTS 1. Natural Solids Six agricultural soils and two natural clays


Journal of the Chinese Institute of Engineers, Vol. 28, No. 2 (2005)

Table 1 Properties of the studied solid samples Solid (Abbreviation) Kuaikuan bottom soil (KKB) Kuaikuan top soil (KKT) Shamou Mountain soil (SM) Chinsing Mountain soil (CS) Li Mountain soil (LM) Hsiushui soil (HS) Ca-montmorillonite (Ca-Mon) Na-kaolinite (Na-Kao) Sand (%) 10 14 46 68 28 6 Silt (%) 56 54 46 22 44 68 Clay (%) 34 32 8 10 28 26 99 99 BET (m 2/g) 4.73 13.28 57.23 10.14 15.35 2.10 80.79 11.52 Pore volume Pore size SOM CEC (cm 3/g) (nm) (%) (meq/100g) 0.018 0.034 0.079 0.019 0.041 0.008 0.146 0.056 13.61 9.88 5.18 8.00 10.42 14.09 6.97 17.05 20.0 5.6 27.3 14.8 0.5 3.9 0.03 0.02 41.9 19.5 53.9 19.8 6.8 9.9 120.2 2.3

Table 2 Properties of the studied surfactants: MW=molecular weight, CMC=critical micelle concentration, and WL=UV absorption wave length Surfactant DB DBS TX-100 MW 414 349 624 CMC (mol/m 3) 1.77 1.50 0.21 WL (nm) 268.4 260.8 274.8

lengths (see Table 2). The specific excess amount was calculated, using the relation Q = V C / m , where V is the volume of the liquid phase, m is the mass of the solid, and C is computed as the difference between the initial and final UV readings. III. RESULTS AND DISCUSSION The most frequently exhibited adsorption isotherms of surfactants in soils and clays are three types: the Langmuir (L-type); the S-shape (S-type) and the two plateaus shape (LS-type). According to the Freundlich equation, the adsorptive amount of the surfactants relative to equilbrium concentration in the liquid phase is expressed as,
x = KC 1/n Q=m

(Ca-montmorillonite and Na-kaolinite) were selected for the sorption experiments. All of the soil samples were collected from Taiwan. The Ca-montmorillonite and Na-kaolinite samples were purchased from the University of Missouri-Columbia, Source Clay Minerals Repository. The properties of the above adsorbents are given in Table 1. 2. Surfactants The cationic, anionic, and nonionic surfactants used were domiphen bromide (DB or D+ Br), sodium dodecylbenzene sulfonate (DBS or DB Na + ), and octylphenol polyethoxylate with an average ethylene oxide chain length of n =9.5 (TX-100). All of these compounds were of analytical grade or better and were used as received. Some of the properties of the surfactants used are listed in Table 2. 3. Adsorption Measurements A few grams of solid were placed in a 25 ml tube containing the surfactant water solutions of known concentrations. Equilibrium was reached by shaking for 24 h with a reciprocating shaker at 25 C. The solution and solid phases were separated using a high-speed centrifuge (Sorvall Co., Model RC-5C) at 8000 rpm for 25 min. A 15-ml aliquot of the supernatant was removed and analyzed using the UV wave


Here n>1, n=1, and n<1 represent the L-type, the linear-type and the S-type, respectively. In addition, a two-step adsorption model (LS types) has been proposed (Zhu and Gu, 1991). In the first step the surfactants are adsorbed as individual ions or molecules (depending on the type of surfactant involved) in the first layer of the solid surface, through electrostatic attraction (this is only present in the case of cationic surfactants) and/or specific attraction (i.e., van der Waals or hydrogen bonding between hydrophilic groups in the surfactants and the mineral surface). In the second step, the adsorbed surfactant molecules, on the adsorbent, through association, or hydrophobic interactions between the hydrocarbon chains of the surfactants, increase dramatically. Although the two-step adsorption model may provide a theoretical basis for the mechanism of surfactants adsorbed into soils and clays, the adsorption capacity of surfactants for solids correlated with the properties of the adsorbent, the surfactant characteristics, and the solutions properties and should be discussed further. In this study, three types of the surfactants, and eight solids were used to evaluate the

J. F. Lee et al.: Effect of Soil Properties on Surfactant Adsorption


20 20

DB uptake, Q (mol102/kg)

15 KKT (n=9.2, K=0.15) SM (n=10.7, K=0.16) CS (n=14.7, K=0.16) LM (n=7.1, K=0.06) HS (n=8.3, K=0.10) Na-Kao (n=2.4, K=0.04)

DB uptake, Q (mol101/kg)

15 KKB (n=11.0, K=0.28) Ca-Mon (n=9.2, K=2.38) 10


CMC 0 0 2 4 6 8 10 12 14 16 Equilibrium DB concntration, X (mol/m3) 0 0 2

CMC 4 6 8 10 12 14

Equilibrium DB concntration, X (mol/m3)

Fig. 1 The DB sorption isotherms of the selected natural solids, n and K are noted in Eq. (1)

adsorption characteristics of the surfactants on the basis of their respective isotherm types. The solids with striking differences in the physicochemical properties, relative to the surfactant adsorption, were selected to describe the adsorption mechanisms. 1. Cationic Surfactants As shown in Fig. 1, all of the exhibited adsorption isotherms are L-type and the maximum adsorption capacity is ordered as follows: Ca-Mon>KKB> SM>KKT CS>HS>LM>Na-Kao, which is generally consistent with the order of the CEC values, except for the KKB and SM sequences (see Table 1). Electrostatic interaction and hydrophobic bonding are important driving forces for cationic surfactant adsorption (Xu and Boyd, 1995). In our results, the adsorption isotherms of the DB only reach a plateau in the given concentration range, indicating the absence of two-step adsorption when the aqueous DB concentration reaches the CMC. It is well known that the CEC plays a key role in the adsorption of cationic surfactants by solids. Since both the mineral surfaces and the SOM have a number of exchangeable cation sites, the overall DB adsorption is weakly related to the surface area or the SOM. However, in some cases, another factor must also be taken into consideration. For example, although SM has a larger CEC than KKB, the saturation capacity of KKB is larger than that of SM. The reason may be ascribed to the small SM pore size, which may inhibit some of the DB from entering the pores and thus prevent adsorption by the pores. The

DB, therefore, remains primarily on the external surface of the substrate. 2. Anionic Surfactants The DBS adsorption isotherms for the five solids are presented in Fig. 2. The shapes of the surfactant adsorption isotherms for the selected solids can be basically divided into two types: the S-shape (Stype) and the two plateaus shape (LS-type). The adsorption capacity of the examined soils and clays is in the following order: Ca-Mon>SM>KKB>NaKao>CS. In general, anionic surfactants are composed of highly polar and non-polar functional groups. Hence, hydrogen bonding, adsorption by the polarization of electrons, adsorption by dispersion forces, and hydrophobic bonding (partitioning), may all be operative mechanisms. The isotherms were S- types representing low affinity of DBS to the soils under low surfactant concentration. This is because soils in aqueous solutions often contain negative charges on the surface to produce repulsion with anionic surfactants. The LS-type isotherms may be explained with the above-mentioned two-step adsorption model. For Ca-Mon and SM, this higher surface area is a dominant factor, which leads to higher adsorptive amounts. Another probably influential factor is the organic matter content. The KKB with the high SOM, onto which DBS can partition, indicates the relatively higher adsorptive amounts with respect to its low surface area. Thus, the anionic surfactants adsorbing on natural soils theoretically increase as the SOM increases, regardless of the surface area. However,


Journal of the Chinese Institute of Engineers, Vol. 28, No. 2 (2005)

40 KKB (left Y axis, n=0.3, K=0.006) SM (left Y axis, n=1.8, K=0.013) CS (left Y axis, n=0.7, K=0.001) Ca-Mon (right Y axis, n=0.7, K=0.014) Na-Kao (left Y axis, n=1.4, K=0.004)

120 100 80 60 40

DBS uptake, Q (mol103/kg)



10 20 0 0 0 3 4 5 6

1 CMC 2

Equilibrium DBS concntration, X (mol/m3) Fig. 2 The DBS sorption isotherms of the selected natural solids n and K are noted in Eq. (1)



TX-100 uptake, Q (mol103/kg)

TX-100 uptake, Q (mol102/kg)


KKB (n=4.1, K=0.046) KKT (n=4.4, K=0.023) Ca-Mon (n=1.7, K=0.22)


SM (n=4.3, K=0.007) CS (n=2.3, K=0.012) LM (n=6.8, K=0.010) Na-Kao (n=1.6, K=0.005) CMC

0 0.0 0.6 1.2 1.8 2.4 3.0 Equilibrium TX-100 concntration, X (mol/m3)

0 0.0

CMC 0.6 1.2 1.8 2.4 3.0 3.6

Equilibrium TX-100 concntration, X (mol/m3)

Fig. 3 The TX-100 sorption isotherms of the selected natural solids n and K are noted in Eq. (1)

an unknown SOM ingredient may complicate the partitioning behavior of the surfactants to produce a disparate result. We thus suggest that the influential factors on anionic surfactant adsorption have the following order: surface area >SOM>other factors. 3. Non-Ionic Surfactants The TX-100 adsorption isotherms for seven natural solids are shown in Fig. 3. Ca-Mon exhibited the highest uptake, and the others, following order, are KKB, KKT, CS/LM, SM, and Na-Kao. The TX100 uptake reached a plateau when the concentration X was 1- 2 times the nominal CMC in pure water.

All of the adsorption isotherms are L type, appearing to take place more by adsorption than by partitioning. For Ca-Mon, LM, and Na-Kao, the adsorption capacity is closely related to the solid surface area. However, the effects of the SOM content are beyond the surface area for TX-100 uptake on KKB and KKT. One of the possible reasons is that the surface area difference between KKB and KKT is small and the van der Waals force between TX-100 and SOM is more than that between TX-100 and soil mineral matter. Since both SM and CS have comparable SOMs and surface areas, the TX-100 uptake involves adsorption of the mineral matter, and partitioning or

DBS uptake, Q (mol103/kg)

J. F. Lee et al.: Effect of Soil Properties on Surfactant Adsorption


adsorption onto the SOM. This indicates that the overall TX-100 adsorption is not only related to the surface area but also weakly related to the SOM. Both the SOM and the surface area for SM are the highest, but its saturation capacity is lower than most above soils, indicating that another factor must be taken into consideration. Although the TX-100 adsorption capacity was not closely related to the SOM, which is in contrast to the findings of Haigh (1996), this result should be limited at the specific SOM range. It can be concluded that the nonionic surfactant sorption is proportional to the soil mineral matter content unless the soil has a fairly high organic matter content. IV. CONCLUSIONS Form this study, it can be concluded that cationic surfactants tended to be strongly adsorbed to soils and clays via the electrostatic interactions and thus the DB adsorption capacities were directly proportional to the CEC values of the examined solids. The possible sorption mechanism for the anionic surfactant is the adsorption by van der Waals force or hydrogen bonding and partitioning into the SOM. The adsorption of nonionic surfactants usually showed a correlation with the soil mineral properties, but the relatively higher SOM soils may produce divergent results. NOMENCLATURE C equilbrium concentration of solutes in the solution mol/m 3 the difference between the initial and final surfactant concentration mol/m 3 equilibrium constant

m n Q V X x

mass of the solid adsorbent kg experimental constant adsorption amount mol/kg adsorbent volume of the liquid phase m 3 equilibrium surfactant concentration mol/m 3 solute amount on the soils or clays mol REFERENCES

Goloub, T. P., Koopal, L. K., Bijsterbosch, B. H., and Sidorova, M. P., 1996, Adsorption of Cationic Surfactants on Silica Surface Charge Effects, Langmuir , Vol. 12, No. 13, pp. 3188-3194. Haigh, S. D., 1996, A Review of the Interaction of Surfactants with Organic Contaminants in Soil, Science of The Total Environment , Vol. 185, No. 1-3, pp. 161-170. Lee, J. F., Liao, P. M., Kuo, C. C., Yang, H. T., and Chiou, C. T., 2000, Influence of a Nonionic Surfactant (Triton X-100) on Contaminant Distribution between Water and Several Soil Solids, Journal of Colloid and Interface Science , Vol. 229, No. 2, pp. 445-452. Xu, S., and Boyd, S. A., 1995, Alternative Model for Cationic Surfactant Adsorption by Layer Silicates, Environmental Science & Technology, Vol. 29, No. 12, pp. 3022-3028. Zhu, B. Y., and Gu, T., 1991, Surfactant Adsorption at Solid-Liquid Interfaces, Advances in Colloid and Interface Science , Vol. 37, Nos. 1-2, pp. 132. Manuscript Received: Feb. 09, 2004 Revision Received: Jun. 18, 2004 and Accepted: Jul. 09, 2004