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Characterization of Salt- and Surfactant-Containing Sandy Soil Extracts by Laser Light Methods Szilvia Joó1,2, Judit Tóth3, and Rita Földényi1*

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Characterization of Salt- and Surfactant-Containing Sandy Soil Extracts by Laser Light Methods Szilvia Joó1,2, Judit Tóth3, and Rita Földényi1* Int. Agrophys., 2015, 29, 291-298 doi: 10.1515/intag-2015-0034 Characterization of salt- and surfactant-containing sandy soil extracts by laser light methods Szilvia Joó1,2, Judit Tóth3, and Rita Földényi1* 1Department of Earth and Environmental Sciences, University of Pannonia, Egyetem str. 10, H-8200 Veszprém, Hungary 2Agricultural Institute, Centre for Agricultural Research, Hungarian Academy of Sciences, Brunszvik str. 2, H-2462 Martonvásár, Hungary 3Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar tudósok blv. 2, H-1117 Budapest, Hungary Received November 7, 2014; accepted June 15, 2015 A b s t r a c t. The aim of this work was to study how dif- and clay. There is no standard procedure for determination ferent salt and surfactant solutions influence the particle size of soil PSD by the LD method (Arriaga et al., 2006); distribution and colloidal stability of sandy soil extracts. Particle therefore, data are given in volume percentage. Commonly size distribution was investigated by the laser diffraction method. used methods for determination of PSD (pipette, aerometer Extracts were made from the soil – before and after removing etc.) are based on Stokes law and results are expressed in its organic content – with solutions of NaCl or CaCl2 and one cationic and two anionic surfactants. The surfactants influence the mass percentage. LD has the advantage that small samples particle size distribution of the soil. Due to the use of the NaCl can be analyzed accurately, which cannot be carried out by and surfactant mixtures after removal of organic content, the par- the pipette method (Cooper et al., 1984). The LD method is ticle sizes increased compared to the extract of the soil. Colloidal suitable to investigate also soil suspensions and soil extracts stability was investigated by the laser Doppler electrophoresis prepared by different methods (Ryżak and Bieganowski, method resulting in a zeta potential between -5.63 and -23.7 mV, 2010; 2011). Laser diffraction equipment can be used for showing that the extracts were rather instable. Static equilibrium experiments with sodium dodecyl sulphate on sandy soil resulted measurement of particle size in a rather wide range in an L-type of isotherm with three steps, indicating the formation (0.01-3000 mm), ie also in the colloid region. The stability of more surface layers. Comparison of the adsorption isotherm of colloidal solutions can be studied by measurement of and the measurements of particle size distribution demonstrated electrokinetic (zeta) potential. The alteration in zeta potential that the particle size changes comparably with the formation of is well in agreement with the alteration in physical stability. the different layers. The zeta potential of the equilibrated solution Minimum zeta potential greater than |60| mV and greater reached the region of instability and stability when the initial con- than |30| mV is required for excellent and good physical centration of sodium dodecyl sulphate was near its critical micelle concentration. stability, respectively (Malvern Instruments, 2007a). Freitas K e y w o r d s: adsorption, laser diffraction, particle size dis- and Müller (1998) have found that a potential around tribution, soil extract, surfactants |25| mV is just below the critical value; however, in principle, it can still be sufficient for a stable system in combination INTRODUCTION with the sterically stabilizing effect. Stability of solution The particle size distribution (also called grain size affects the sedimentation, adsorption, aggregation, and trans- distribution or texture) is one of the most important portation of contaminants in soils. Better stability means characteristics of soils. Currently, laser diffraction (LD) further transport. is increasingly used for particle size distribution (PSD) The soil solution is a colloidal system containing analysis of sediments and soils. The technique can be very inorganic (clay minerals) and organic (humic substances) precise and offers advantages of speed and cost over many constituents. Humic substances (HS) are special and impor- other methods when used to analyse mixtures of sand, silt, tant components of natural organic matter (NOM) present *Corresponding author e-mail: [email protected] © 2015 Institute of Agrophysics, Polish Academy of Sciences 292 S. JOÓ et al. in soil, water, and other geological deposits. Since HS these compounds disperse the organic matter content of soil molecules consist of an elongated hydrophobic portion and afterward create a stable colloidal solution (Czinkota with more anionic (carboxylate) groups, these compounds et al., 2002). have amphiphilic character and therefore they can be The soil texture and thus the shape of the PSD curve is considered as natural surfactants (Tombácz et al., 1988; a very important sign of other soil properties like hydraulic Wandruszka, 2000). This character makes them able to conductivity, adsorption capacity, etc. If the curve is gen- form micelles; however, the critical micelle concentration tly sloping, the hydraulic conductivity of the investigated (cmc) of humic acid was estimated to be as high as 10 g l-1 formation is lower; however, it is more compactable. If the (Tschapek and Wasowski, 1984). Humic substances are curve is steep, the soil contains a considerable amount of present in natural waters at lower concentration levels same-sized particles. This means higher hydraulic conduc- (5-100 mg l-1) when aggregates can be formed. These are tivity and less compactness. Smaller particles can achieve referred to as pseudomicelles having a hydrophobic interior longer distances than larger particles in the soil solution, and a more hydrophilic surface. The hydrophobic moiety in while they transport adsorbed contaminants. Even the the centre of these aggregates leads to enhanced dissolution presence of a small fraction of fine particles influences (‘solubilization’) of non-polar contaminants like PAH hydraulic conductivity of some porous formations and the (Földényi et al., 2013; Senesi, 1993; Wandruszka, 2000). possibility of contaminant transport. PSD data can be used This property of HS can be applied under controlled condi- for modelling of transport processes (Kovács et al., 2004). tions in remediation of contaminated sites (Nègre et al., Particle size distribution influences the specific surface area 2008) while under natural conditions the same process can of materials and hence the adsorption capacity of the adsor- lead to mobilization of pollutants (Földényi et al., 2013). bent (Bänninger et al., 2006). Our aim was to study how different salt and surfactant Adsorption is the most important process that plays a role solutions influence the particle size distribution and colloidal in the retention of pollutants in the bulk phase of soil. The stability of soil extracts (obtained after centrifugation and composition and properties of the soil solution (pH and the filtration). PSD is usually studied in the absence of soil nature of electrolytes) are important factors influencing the organic matter, but in this case, natural conditions cannot sorption of different ions and molecules by soil components be modelled. Sandy soil was chosen for our investigations (Barrow, 1993; Ertli et al., 2004). The adsorption of ions because it contains relatively high amounts of soluble affects the charge and electrokinetic potential of colloidal humic substances (mostly fulvic acids) at any pH values. particles, hence their dispersion-flocculation behaviour. The influence of the composition of any solution on This can have important consequences on soil structural sta- the PSD of soil extracts has not been studied by other bility, colloid mobility in soils, and groundwater aquifers, researchers yet; however, it can be very important due to as well as suspended sediment features in surface waters the alteration of various soil properties. Our investigations (Kretzschmar et al., 1993; McCarthy and Zachara, 1989). focused on the role of anionic and cationic surfactants Since processes of pollutant adsorption play a special (solutes) in the soil extracts. Three different surface-active role in the field of environmental research, there is an in- materials were selected: creasing demand for investigations of the effect of diffe- – sodium dodecyl sulphate (SDS), which is used most fre- rent chemicals in soil suspensions (Kovács et al., 2004) and quently as a detergent in cosmetics; extracts. Adsorption processes have determinative impor- – sodium diisopropyl naphthalenesulfonate (Supragil WP), tance for chemicals entering the environment. Materials a forming agent in pesticide formulations in agriculture; dissolved or suspended in groundwater can self-influence – and cetyl trimethyl ammonium bromide (CTAB, also the PSD of soil and the transport of chemicals (Haque and known as Cetrimide), an industrial forming agent. Freed, 1975; Wilson, 1991). Sodium dodecyl sulphate, which can be used also for The role of surface-active agents produced by the soil remediation (Khalladi et al., 2009), and Supragil WP chemical industry is to dissolve non- or barely water- represent the anionic, while CTAB is the cationic type of soluble materials as well as to form stable emulsion or surfactants. The structure of surfactants is shown in Fig. 1. extract; consequently, this type of compounds is likely PSDs of the extracts were investigated by the laser dif- to be very harmful to the environment.
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