Use of Surfactants and Blends to Remove DDT from Contaminated Soils

L. E. Rios, M. David, J. Vazquez-Arenas and W. A. Anderson*

Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario, Canada, N2L 3G1

Removal of dichloro-diphenyl-trichloroethane (DDT) from soils using surfactant-enhanced solubilisation was studied both in batch and continuous ow arrangements to determine if there were advantages to using a combination of non-ionic (Tween and Brij) and anionic surfactants. It was observed that the presence of the anionic surfactant sodium dodecyl benzene sulphonate improved the DDT removal efciency, but had a potentially negative effect on ow rates in column leaching experiments at concentrations over 0.1%. The potential for re-use of the surfactant mixture was studied and demonstrated by removing DDT and its metabolites from the surfactant solution using activated carbon. Keywords: soil washing, soil remediation, hydrophobic contaminants, leaching, surfactant analysis

INTRODUCTION

rganochlorine pesticides have a high efcacy for pest control and for this reason, they have been used extensively in agriculture. However, their use introduced signicant environmental problems since many, such as dichlorodiphenyl-trichloroethane (DDT), are environmentally persistent and bioaccumulative, with the result that they can enter the food chain and cause ecological damage (Wang and Mulligan, 2004). Because of its low water solubility, DDT tends to remain adsorbed to soil particles in an immobile manner, and its resistance to biodegradation results in persistence in the soil environment for long periods of time, even though its use was discontinued in many countries several decades ago. Many jurisdictions have identied maximum permitted levels of DDT and its intermediates in soil for various uses, and this can pose problems for property owners who wish to sell or change the use of their contaminated land. For example, in Ontario the maximum permitted level of DDT in soil for industrial use and non-potable groundwater is 1.4 mg/kg (MOE, 2008). Therefore, it becomes necessary to identify and use techniques to clean the soil to a satisfactory level where historical contamination persists. Since many of the soils that are contaminated with DDT are in rural locations with lower land values, minimal cost remediation strategies are required. While thermal destruction has shown great efciency for DDT removal, these techniques are expensive. Bioremediation is generally considered an economical option for site remediation in general, but it has serious limitations in

this application due to the very low aqueous solubility of DDT and its relative resistance to biodegradation (Juhasz et al., 2003; Thomas and Gohil, 2011). The use of zero valent iron to dechlorinate DDT shows some promise but recalcitrant intermediate products such as DDD and DDE (dichlorodiphenyldichloroethane and dichlorodiphenyldichloroethylene, respectively) may result (Cao et al., 2010). The use of surfactants to remove hydrophobic contaminants from soil has been described at the laboratory, pilot and eld scale for a number of years (Mulligan et al., 2001), and a complex interaction between the contaminant, soil characteristics and surfactant properties has been identied (Zhou and Zhu, 2007). Many of these applications have been related to in situ ushing, but the same principles can also apply to ex situ leaching of contaminants from excavated soil. A wide variety of surfactants have been tested for soil washing with a number of hydrophobic contaminants, with variable results (Mulligan et al., 2001). Since three classes of surfactants are available (i.e. cationic, anionic and nonionic), a primary consideration has been to select from between these classes. Ying (2006) reports that the amount of surfactant

Author to whom correspondence may be addressed. E-mail address: wanderson@uwaterloo.ca Can. J. Chem. Eng. 9999:17, 2012 2011 Canadian Society for Chemical Engineering DOI 10.1002/cjce.21620 Published online in Wiley Online Library (wileyonlinelibrary.com).

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adsorption to soils and sediments generally follows the order cationic > non-ionic > anionic. Atay et al. (2002) found that two anionic surfactants were relatively irreversibly adsorbed to soil samples. Ahn et al. (2008) notes that non-ionic surfactants have lower critical micelle concentration (CMC) values and a lower tendency to occulate clay particles in the soil, compared to the other ionic surfactants. Cationic surfactants have been reported to enhance the adsorption of hydrophobic compounds onto the soil (Partt et al., 1995), and they tend to be toxic towards microorganisms (Volkering et al., 1998) and higher aquatic organisms (Ying, 2006) in the environment, so they are not generally used in soil remediation. Therefore, much of the literature has focused on the use of non-ionic surfactants, sometimes blended with anionic surfactants or organic solvents (Chu and Kwan, 2003). The use of surfactants specically for DDT removal has been reported by only a small number of researchers. Kile and Chiou (1989) noted that DDT water solubility was signicantly enhanced by non-ionic surfactants (Triton and Brij) at concentrations above and below the CMC. A similar effect was noted for DDT solubility enhancement by petroleum sulphonate surfactants (Kile and Chiou, 1990), which also contain emulsied mineral oils. Partt et al. (1995) extracted DDT from contaminated New Zealand soil, using Triton and polypropylene glycolethoxylate non-ionic surfactants. It was noted that most of the DDT was associated with the silt fraction of the soil, and 45% was removed using 2% surfactant solution in their laboratory experiments. Walters and Aitken (2001) used a non-ionic Brij surfactant and showed that DDT and its breakdown products (DDD and DDE) can be signicantly partitioned from the soil into the surfactant solution. Smith et al. (2004) used surfactants and other solvents such as propanol and ethanol (EtOH) to improve the removal of DDT from soil. The solvents (at concentrations up to 50%) were not very effective, but the surfactant concentrations used were quite low (100600 mg/L), which is well below the 12% typically reported in other publications, and possibly below the CMC for those surfactants. As an alternative to using solvents, Thangavadivel et al. (2011) tested the use of the anionic surfactant sodium dodecyl sulphate combined with heating and low frequency ultrasound, with efciencies ranging from 40% to 90%. In general, the reported results for surfactant enhanced washing of DDT from soils are quite variable, and mainly deal with single surfactants. In this work, it was hypothesised that combinations of two surfactants may be more effective for the leaching process, especially if non-ionic and anionic properties were combined. In addition, since surfactant costs are a major component of the overall economics of soil washing, it would be benecial if the DDT could be removed from the surfactant solution, allowing for recycle or reuse of the solution (Boussahel et al., 2009). Current approaches to reduce surfactant dosage are based on selective physical separation or chemical degradation of contaminants from surfactant solutions (Ahn et al., 2008), and in this work the selective adsorption of DDT by activated carbon was tested. Since surfactant losses by adsorption to soil (Laha et al., 2009) or activated carbon are of potential concern, methods for rapid measurement of surfactant concentration were also screened in this work.

MATERIALS AND METHODS

The sample material was obtained from a potentially contaminated site at 1 m below the ground surface with the intention of reducing the presence of decaying organic matter. In the labo-

ratory, the sample was dried and sieved with a USA #12 screen (1.7 mm) to remove large particles. Samples were stored at room temperature in clean 4 L paint can containers. Soil organic carbon levels were typically on the order of 1%. Hexane (purity >99.9%), EtOH (purity >99.9%), Tween 80 (purity >99%), Brij 35 (30% solution) and sodium dodecyl benzene sulphonate (SDBS, purity >99%) were purchased from SigmaAldrich Chemical Company (Oakville, Canada). For the soil in these experiments, preliminary analyses showed that DDT concentrations were very low (<1 mg/kg), and this soil was considered to be clean, relative to the concentrations that would be used in subsequent experiments. Therefore, for each test soil samples were prepared with 25 mg/kg of DDT using the following procedure. First, 5 mL of a 50 mg/L DDT solution in hexane was thoroughly mixed with 10 g of soil. The solvent was then allowed to evaporate completely overnight to yield soil with a concentration of 25 mg/kg of DDT, since DDT has a very low volatility. Where necessary, larger soil samples were prepared using similar ratios. The soil pH was measured and found to be approximately 8.1. Chemical oxygen demand (COD) of surfactant solutions was measured as a surrogate analysis of the total concentration of surfactants in the aqueous washing uids before and after leaching. Hach Test N tubes were used (01500 mg/L range) together with a Hach DR/2000 spectrophotometer (Hach Company, Loveland, CO). Dilutions of 1/20 of the surfactant solution were used to keep the concentration within the appropriate test range. The COD contributed by the DDT is negligible compared to the surfactant concentrations, such that the majority of COD is attributed to surfactant. Blank experiments with water and surfactant solutions contacted with soil did not indicate any signicant interference by leached soil organics. A soil leaching batch experiment was conducted by putting 10 g of the contaminated soil into a vial to which 25 mL of surfactant solution was added. The contents were mixed on a roto-torque device at 60 rpm for 24 h and then left to settle for 1 h. Then 10 mL of hexane was added to 10 mL of leachate and mixed for 30 more minutes and left to settle for another hour. Five millilitres of the resulting emulsion at the top of the vial was put into a closed vial to which 2 mL of EtOH was added to break the emulsion. The contents were shaken gently for 10 s and allowed to settle for 1 min. One microlitre from the top organic phase was removed for gas chromatographic (GC) analysis. A soil leaching column experiment was prepared by placing glass wool at the bottom of a column (2.5 cm 30 cm), and adding the contaminated soil with moderate compaction. Glass wool was put on the top of the soil and then 250 mL of surfactant solution was introduced at the top. Aliquots of leachate from the bottom of the column were collected and extracted into hexane for GC analysis following the previously described method. Analysis for DDT and its related compounds DDD and DDE were completed using GC. The samples (1 L) were injected into a GC (HP5890; Agilent Technologies, Santa Clara, CA) equipped with an electron-capture detector (GC-ECD), and an RTX-5 (Restek Corp., Bellefonte, PA) quartz capillary column with an inner diameter of 0.53 mm, a lm thickness of 0.50 m and a length of 30 m. The oven temperature started at 140 C and was increased to 280 C at 10 C/min with a nal hold time of 2 min. Injector and detector temperatures were kept constant at 240 and 290 C, respectively. For calibration, standard solutions of DDT, DDE and DDD (analytical standard grade, SigmaAldrich Chemical Co.) were prepared in hexane at ve different concentrations ranging from 0 to 200 mg/L.

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RESULTS AND DISCUSION Surfactant Selection

Selection of surfactants was developed by a review of the available literature. According to Keller and Rickabaugh (1992), longer alkyl chain compounds display lower CMCs and so are potentially most effective. According to Mulligan et al. (2001), the optimal features for a surfactant in this application are: low adsorption to soil, low surface tension, low CMC, low toxicity, effective at concentrations under 3%, soluble at environmental temperatures and relatively biodegradable. Based on this and considerations of environmental impact, expected performance, safety and cost, the non-ionic surfactants Tween 80 and Brij 35 were selected. SDBS was also selected to elucidate how an anionic surfactant may affect the leaching performance.

Subsequently, a COD method was tested using a Hach TestN-Tube reagent kit (01500 mg/L range). This method is fairly rapid (about 2 h for a batch of samples) and can be performed in remote locations with portable equipment. Standards and samples were diluted 1/20 to keep the results within the acceptable range for the test method, which would also further dilute interfering compounds, if any. Comparison of Tween 80 standards and samples from column washing did not indicate any significant interference from soil compounds, and so it was concluded that the COD method is an adequate quick analysis for surfactant solutions. In other words, COD could be used as a surrogate indicator to analyse the changes in surfactant concentration during and after soil washing processes. COD values for the Tween 80 standards were found to follow the correlation COD (1/20 dilution) = 23.0 + 951.4 (Tween concentration %) with a correlation coefcient (R2 ) of 0.96.

Surfactant Analysis Methods

For eld applications, in order to adequately assess the need for adding surfactant to make-up for losses via soil adsorption, a rapid method is needed to measure the concentration of the surfactant in leachates draining from the soil. This would be especially important for eld applications of a washing process where quick feedback on the surfactant concentration in the wash stream would be desirable. Several rapid surfactant analysis methods were tested using Tween 80. An initial attempt was made to measure the Tween 80 concentration with UV spectrophotometry. While pure standard solutions yielded UV absorbance peaks that could be used to quantify the surfactant, the presence of soil components extracted with the Tween 80 caused signicant interference so that the approach was abandoned. A CTAS method (cobalt thiocyanate active substances) was selected based on literature reports where it was applied to wastewater and industrial applications (Boyer et al., 1977; Holt et al., 1998). In this method, cobalt thiocyanate (a blue compound) is allowed to interact and bind with the non-ionic surfactant molecules (Tween 80) to form a tetrathiocyanatocobaltate(II) complex that is transferred to a nonaqueous phase (dichloromethane) and measured using visible spectrophotometry. The cation associated with this complex is usually ammonium ion (Schmitt, 2001). Two different applications of the method were attempted: (1) the aqueous surfactant was mixed with cobalt thiocyanate and then extracted into dichloromethane; and (2) the surfactant was extracted into dichloromethane rst (in an attempt to eliminate interfering soil compounds) and then complexed with cobalt thiocyanate in the organic phase in a slower process. Four standard solutions of Tween 80 were prepared for calibration purposes for analysis of the leachate samples from soil washing experiments, as well as water-only blanks. After comparing the standard solutions with the leachates from soil washing experiments, it was concluded that the two CTAS methods, while straightforward and rapid, were too non-specic for the non-ionic surfactant. Other soil components in the leachate were apparently complexing with the cobalt thiocyanate, leading to impossibly high readings in comparison to the water-only blanks (results not shown). Therefore, it appears that the surfactant leaches hydrophobic compounds from the soil that interact with the CTAS reagent in addition to the surfactant itself. The conclusion is that the CTAS method does not appear to be a useful analytical method for monitoring surfactant concentrations in the soil washing solutions.

Surfactant Sorption to Soil

Efcacy of a soil washing process depends in-part on minimising the loss of surfactant via adsorption on the soil, since any lost surfactant must eventually be replenished to maintain the enhanced solubility of DDT in the aqueous solution. Therefore, several tests were performed to quantify these losses for one of the non-ionic surfactants (Tween 80), as characterised by COD change. Previous studies suggest that losses might be in the range of 5 mg surfactant/g soil (Ahn et al., 2008), but it was thought to be likely that this loss is highly variable and dependent on the nature of the specic soil. Approximately two pore volumes (as measured using a water saturation method) of a 1% Tween 80 solution were passed through a column (approximately 2 cm diameter by 15 cm high) lled with a soil sample. This was repeated at total of six times in series (not recirculated), followed by six rinses with similar volumes of tap water. The concentration of surfactant in each wash was determined by the COD method, and the results are shown in Figure 1. Figure 1 indicates that approximately 25% of the surfactant (as measured by COD) was adsorbed during the rst two-surfactant washes (Surf 1 and 2, compared to the 1% standard value), but subsequent washes approached the same value of COD as the

Figure 1. Apparent adsorption and desorption of Tween 80 during column washing and rinsing.

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Figure 2. COD remaining in the aqueous phase after a xed amount of Tween 80 surfactant solution was contacted with varying amounts of soil. Figure 3. Batch extraction experimental results, showing the amount of DDT recovered in hexane extracts of the leachate (ng/ L), when 25 mL of each surfactant solution was contacted with 10 g of soil containing 25 mg/kg DDT.

initial surfactant solution. Furthermore, the rst rinse with tap water (Rinse 1) appeared to desorb a signicant amount of surfactant, while subsequent rinses had very little effect. This result was repeated a second time (Run 2), which showed similar trends with a fresh sample of the same soil. Even when adsorption occurs, the surfactant concentration in the solution leaving the column was above 5000 mg/L, which is well above the CMC reported for Tween 80 of approximately 25 mg/L (Franzetti et al., 2006). Therefore, it would still be expected that signicant amounts of DDT could be solubilised although a portion of the surfactant was lost through adsorption. In a second adsorption test, a xed volume of 1% Tween 80 was contacted with varying amounts of soil, and the COD was analysed after approximately 4 h of contact, with the results shown in Figure 2. Figure 2 indicates that it requires about 5 L of 1% Tween 80 surfactant solution to completely overcome the adsorption losses to 1 kg of soil, such that the remaining solution contains a signicant amount of surfactant. Lower levels, such as 1 L/kg, are likely satisfactory since the adsorption does not deplete the surfactant concentration to a value below its CMC. At high values of applied surfactant (about 3100 L/kg), the adsorption of surfactant is approximately 5 mg/g soil, which agrees well with Ahn et al. (2008). However, at low levels (<3 L/kg), the adsorption apparently increases to between 15 and 80 mg/g, with the adsorption increasing as the amount applied decreases. This result does not t with typical adsorption theory, and suggests that there is another unknown phenomenon occurring, especially when the surfactant/soil ratio is very low.

surfactant decreased the partitioning losses of a non-ionic surfactant in soil washing, resulting in better removal efciencies, but in Figure 3 the 2% Brij 35 + 0.5% SDBS solution showed only a very minor improvement at best. A ternary system comprised of 2% Brij 35 + 0.5% SDBS + 0.5% EtOH showed the best removal efciency of the blends tested. Adding a co-solvent such as EtOH to the surfactant solution can also reduce the adsorption of surfactant to the soil particles and increase the efciency of contaminant removal from soil (Ganeshalingam et al., 1994), and it was observed that EtOH concentrations of 2% enhanced extraction more than a 1% concentration. The use of EtOH was tested for interest, although in practice it raises problems with potential air emissions due to evaporation and with worker safety due to ammability. Since the improvement in contaminant removal was modest, the use of EtOH was not pursued further.

Leaching Column Soil Washing

Chandler et al. (1997) have shown that leachability depends on a number of physical parameters such as homogeneity, particle size, porosity, permeability of the solid phase inuencing the ow rate and contact time between solution and solid, temperature, pH, redox condition, total organic carbon content, chemical reaction kinetics, chemical speciation of contaminants and complexation with other contaminants. Considering that a blend of Brij 35 and SDBS nominally gave the best removal results for the least amount of surfactant during the batch experiments, this combination was tested further in the larger scale column washing, and compared to Tween 80 performance. These results are shown in Table 1, where the DDT removal efciency and time required for 100 mL of leachate ow through the column are listed. It was noted that the combination of 2% Brij 35 + 1% SDBS yielded the highest removal (99.7%), but the time required was also very high (1170 min). Since the kinetics of the process can have an impact on overall cost, the rates of removal of DDT were determined and are also shown in Table 1. Based on this, the solutions containing 1% SDBS are seen to have low DDT removal rates, but if the SDBS concentration is reduced to 0.1% SDBS or eliminated altogether, the time is also reduced so that the removed rate becomes much better. As determined

DDT Removal in Batch Soil Washing

The performance of various surfactants and blends was tested in batch mixing experiments, as previously described, and the results are shown in Figure 3. It was observed that 2% Brij 35 alone achieved a good efciency for DDT removal, while 2% Tween 80 only removed about one half as much under the same conditions. The lower performance of Tween 80 is possibly due to the presence of a sorbitan carbon group and longer carbon branches, which can reduce the ability of the surfactant micellar core to dissolve organics (Jafvert et al., 1994). In addition, this behaviour may be attributed to the potentially strong interaction of Tween 80 with the soil (Karagunduz et al., 2007). Some literature (Paria, 2007) has suggested that the presence of anionic

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Table 1. DDT removal in leaching column experiments with 100 mL of leachate produced. DDT removal was calculated by mass balance from analysis of the leachate and the known initial concentration in the soil DDT removal (%) 99.7 83.1 76.7 56.3 44.0 39.2 36.3 29.7 Time (min) 1170 100 86 118 70 840 165 60 Leaching rate (ng/min) 0.039 0.382 0.410 0.219 0.289 0.021 0.101 0.228

Solution 2% Brij 35 + 1% SDBS 2% Brij 35 + 0.1% SDBS 2% Brij 35 2% Tween 80 1% Brij 35 0.1% Brij 35 +1% SDBS 1% Tween 80 0.5% Brij 35

in the batch experiments, 1% and 2% Tween 80 solutions yielded moderate removals, and the rates in the leaching columns were not signicantly better than for Brij 35. The effect of SDBS on owrate through the column is likely due to its anionic nature, which has been known to disperse and suspend clay particulates in soil (Ahn et al., 2008), and this behaviour was observed in sample vials prepared during this work. Suspension and dispersal of clay particles may cause blockage of ow channels in the leaching columns and therefore reduce ow rates. In any soil washing process that relies on gravity drainage, this will be a signicant problem. Since soil heterogeneity and experimental reproducibility are common concerns in soil washing research, the reproducibility was tested in six replicates of two sets of leaching column experiments, by collecting the rst 100 mL of leachate and carrying out hexane extraction as described above. The replicates resulted in 35.0 1.6 mg/L (SD) and 38.7 2.6 mg/L DDT in the hexaneextracted leachate for 2% Brij 35 with and without 0.1% SDBS, respectively. It can therefore be seen that the surfactant solutions are reasonably consistent in their removal of DDT from these given soil samples in the rst 100 mL of leachate production. Finally, additional quantities of leachate were recovered over time from the leaching columns for the 2% Brij 35 solutions (with and without 0.1% SDBS), and the results are shown in Table 2. After each leaching process with 400 mL of leachate, the soil contains <1 mg/kg DDT, corresponding to approximately 2.7 L of leachate required per kg of contaminated soil to reach this level. The rate of removal of DDT from the soil during the leaching process is shown in Figure 4, where it can be observed that the process follows an apparent rst order decay curve for the surfactant leaching process, with a decay rate constant of 0.01048/min. A very similar curve (not shown) with a rate constant of 0.01418/min was obtained for surfactant containing 0.1% SDBS. Since the rate constants are not signicantly different, it

Figure 4. Estimated remaining amounts of DDT in the soil as a function of contact time in leaching columns using 2% Brij solutions.

appears that the presence of low levels of SDBS had no signicant effect under the tested conditions.

Recovery of Surfactant for Re-Use

For economic reasons it would be desirable to re-use the surfactants rather than simply dispose of the mixture after one use. One of the possible ways to do this is to use activated carbon to selectively remove the more hydrophobic DDT from the surfactant solutions. Ahn et al. (2008) used activated carbon to remove the hydrophobic polyaromatic phenanthrene from a Triton X-100 non-ionic surfactant solution. Therefore, it was hypothesised that a similar approach might be successful in removing DDT and its related breakdown products from the surfactants used here. To simulate the passage of surfactant solution through an activated carbon adsorption drum, such as might be used in the eld, 25 mL of fresh contaminated surfactant solution was passed repeatedly through a column containing 5 g of SigmaAldrich activated carbon. DDT, DDD and DDE concentrations were measured after each pass, and the results are shown in Figure 5. This indicates that activated carbon is capable of adsorbing the hydrophobic contaminants, although the extent of removal from the surfactant solution was only about 50%. The shape of the curves in Figure 5 suggests that the adsorption capacity for the carbon was overwhelmed for this volume and concentration of uid. In addition, the concentrations in the rst pass are higher than expected, and the curve does not follow a sigmoidal shape that might be expected for adsorption. This indicates either some type of adsorption interference by the surfactants. Based on these preliminary results, it was estimated that the adsorption capacity

Table 2. Mass Balances and contact times for a surfactant solutions passing through a leaching column 2% Brij 35 Volume (mL) 100 200 300 400 Time (min) 86 91 101 131 DDT recovered (%) 60.3 23.6 9.7 4.5 DDT in soil (mg/kg) 9.9 4.0 1.6 0.5 Time (min) 71 81 82 107 2% Brij 35 + 0.1% SDBS DDT Recovered (%) 65.5 20.9 8.0 4.0 DDT in soil (mg/kg) 8.6 3.4 1.4 0.4

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pursued further during this work. Initially, 500 mL of contaminated surfactant solution was applied to the column in this work. After the sixth pass, approximately 305 mL of solution remained, due to sampling losses for analysis and liquid remaining in the pore volumes of the carbon. In this experiment, the adsorption capacity was found to be approximately 3 mg/g for each of the contaminants (for a total of approximately 9 mg/g). This is much higher than the capacity estimated in the rst experiment. One suggestion is that the adsorption is strongly kinetically controlled, due to the presence of the surfactants at concentrations that are much higher than the contaminants, on a relative basis. In repeating the ow through fresh carbon beds, there is additional time and fresh surface available to achieve much higher loadings. This suggests that the kinetics of adsorption should be investigated in more detail for this system.

CONCLUSIONS
Figure 5. Change in contaminant concentration in the efuent from an activated carbon adsorption column (5 g), using 1% Brij 35 + 0.1% SDBS aqueous solution, 25 mL per pass.

of this carbon is in the range of 0.250.3 mg/g for each of the three contaminants, or approximately 0.85 mg/g for the total of DDT and its relatives. To obtain a better understanding of the process, the adsorption experiment was repeated, but in this case a fresh amount of activated carbon (4 g) was used for each pass, and an larger initial volume of 500 mL of surfactant solution was used so that a signicant volume could be captured and re-used for each pass. This experiment was done to simulate the adsorption process as if a series of clean adsorption canisters were to be used in the eld, and to determine more accurately when breakthrough might occur. These results are shown in Figure 6. Figure 6 indicates that relatively low values of contaminant concentration can be achieved when fresh activated carbon was used with each pass through the column. It is uncertain why the concentration appeared to increase for DDT and DDE in the rst pass or two. This may have been due to a sampling and analysis artifact related to carbon nes in the samples being extracted for GC analysis. This apparent increase was noted in some other preliminary experiments, but since the focus of the work was on the low concentration endpoint shown in Figure 6, the reasons were not

The non-ionic surfactants performed reasonably well for remediation of DDT in the soils used in this work. The Brij 35 surfactant was found to be the most effective and is recommended for continued work in this area. The use of EtOH as a co-solvent in conjunction with the surfactant solution can signicantly increase the capacity for DDT extraction or clean-up of contaminated soil. However, the risks of volatilisation and ammability of the cosolvent would have to be addressed for eld applications and may not be acceptable for environmental and safety reasons. The presence of SDBS in the surfactant solution at concentrations much higher than 0.1% causes signicant ow problems in a soil column, likely because of clay dispersion that blocked pores and slowed the ow signicantly. While the presence of an anionic surfactant might prove benecial for DDT removal, its potential benet may be limited due to this concern. However, if a mixing system was to be used instead (such as an agitated tank), the negative impact of SDBS on ow would not be important and it could be used at higher concentrations. Recovery of DDT and its related compounds DDE and DDD on activated carbon appears to be feasible, although the interferance by the surfactants is signicant and may limit the overall effectiveness. The economics of surfactant clean-up and recovery using activated carbon need to be investigated further.

ACKNOWLEDGEMENTS
We specially thank Dr. Carol Moralejo for assistance in the laboratory, with data interpretation and proof reading. This work was supported by industrial partners through a collaboration with Prof. E. McBean of the University of Guelph.

REFERENCES
Ahn, C. K., Y. M. Kim, S. H. Woo and J. M. Park, Soil Washing Using Various Nonionic Surfactants and Their Recovery by Selective Adsorption With Activated Carbon, J. Haz. Mater. 154, 153160 (2008). Atay, N. Z., O. Yenigun and M. Asutay, Sorption of Anionic Surfactants SDS, AOT and Cationic Surfactant Hyamine 1622 on Natural Soils, Water Air Soil Pollut 136, 5568 (2002). Boussahel, R., H. Irinislimane, D. Harik and K. M. Moussaoui, Adsorption, Kinetics, and Equilibrium Studies on Removal of 4,4-DDT from Aqueous Solutions Using Low-Cost Adsorbents, Chem. Eng. Commun. 196, 15471558 (2009).

Figure 6. Change in contaminant concentration in a 1% Brij 35 + 0.1% SDBS solution passed through beds of 4 g of activated carbon. The carbon was replaced with fresh carbon after each pass.

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Manuscript received July 12, 2011; revised manuscript received September 22, 2011; accepted for publication October 7, 2011.

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