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09575820/03/$23.50+0.00 # Institution of Chemical Engineers Trans IChemE, Vol 81, Part B, May 2003

OPTIMUM CONDITIONS FOR WASHING OF CRUDE OIL-CONTAMINATED SOIL WITH BIOSURFACTANT SOLUTIONS
K. URUM 1 , T. PEKDEMIR 1 and M. GOPUR2
1

Chemical Engineering, School of Engineering and Physical Sciences, HeriotWatt University, Edinburgh, UK 2 Chemical Engineering Department, University of Ataturk, Erzurum, Turkey

his paper presents the optimum conditions for washing Eko sk crude oil-contaminated soil with biosurfactant solutions using the Taguchi experimental design method. The optimum values obtained through experimental runs were used to predict crude oil removed at three con dent intervals (90, 95 and 99%). Results obtained through experimental runs and predicted crude oil removal were compared and used to access the robustness of the washing method. The biosurfactants tested were aescin, lecithin, rhamnolipid, saponin, tannin and a synthetic surfactant, sodium dodecyl sulphate. The experimental parameters and their four value levels investigated were: temperature (5, 20, 35 and 50 C); concentration of surfactant solutions (0.004, 0.02, 0.1 and 0.5%-mass); volume of surfactant solutions (5, 10, 15 and 20 ml); shaking speed (80, 120, 160 and 200 strokes=min) and washing time (5, 10, 15 and 20 min). Results showed that the optimum washing conditions for temperature and time were found to be 50 C and 10 min for all the surfactant solutions. The other parameters show optimum values at different point. However, SDS, rhamnolipid and saponin show an oil removal of greater than 79%. The washing method was found to be more stable at error of 1% for all the surfactant solutions except aescin and lecithin. Therefore, we suggest the applicability of this method in decontaminating crude oil-contaminated soil at the eld scale. Keywords: biosurfactants; crude oil removal; optimum conditions; predicted removal; contaminated-soil.

INTRODUCTION The use of surfactants in washing crude oil contaminated soil is a new area of application. Their use in subsurface systems dates back to 1963 when petroleum sulphonates were patented for widespread use in the enhanced oil recovery process (Pope and Wade, 1995). Nevertheless, their applications in environmental remediation have not yet fully explored. Over the past 20 years, many activities and much development have been carried out using similar chemical systems to the reduce risk posed by spilled and surface crude oil in the environment (American Petroleum Institute, 1979). This interest re ects the ineffectiveness of current available remediation methods to effectively restore a crude oil-contaminated soil to a low acceptable concentration standard (National Research Council, 1994). The soil-washing process has been used widely in the USA to remediate Superfund sites contaminated by petroleum hydrocarbon by-products (US Environmental Protection Agency, 1995). With this process, the washing solution extracts and separates the contaminants from the soil, thereby reducing the quantity of contaminant for further treatment. The physical characteristics of oil, such as density, temperature, surface and interfacial tension of oil=surfactant=soil system, will give an idea of the mechanisms behind the 203

separation and removal of oil from soil, without chemically destroying or modifying them. This will be possible because of the interfacial tension lowering ability of the surfactant in oilwater systems. Surfactants are amphiphilic molecules that have both hydrophobic and hydrophilic moieties. They have the potential to alter the properties of uid interfaces, and are the active ingredients found in soaps and detergents. Surfactants with biological-basedmaterials are known as biosurfactants.Biosurfactants have been recommended and classi ed for environmental applications because they are cost-effective and readily biodegradable with low or no environmental toxicity and are more effective than the synthetic surfactants (Maier and Soberon-Chavez, 2000; Lang and Wullbrandt, 1999). Surfactant applications in enhancing ex-situ soil-washing have been studied (Mulligan et al., 2001; Deshpande et al., 1999; Cheah et al., 1998). These studies indicated that the removal of oil using surfactant solutions occurs at concentrations above and below the surfactants critical micelle concentration (CMC). Thus, two mechanisms have been proposed for surfactant removal of oil from soil (Mulligan et al. 2001; Deshpande et al., 1999; Cheah et al., 1998). The mobilization mechanism occurs below the CMC due to the lowering of interfacial tensional between the oil and water, which further causes the reduction in capillary force that

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Table 1. Properties of soil samples. Soil texture (%) pH 7.43 Silt 6 Sand 72 Gravel 22

holds the oil and soil. Solubilization occurs at a concentration above the CMC, where surfactants cluster together, and start forming dynamic aggregates known as micelles. Previous studies have tested different surfactant solutions with anionic and non-ionic characteristics in removing automatic transmission uid (ATF) from shallow sandy aquifers (Abdul et al., 1990). Their results indicate that the effectiveness of surfactants in washing out ATF appear not to depend on ionic characteristics of the surfactant, because the surfactants that enhance greater oil removal from soil show identical properties such as low surface tension and soil dispersion, good detergency and solubilization. Even so, Deshpande et al. (1999) investigated batch scale studies on the selection of eight surfactants for washing three different soils that were contaminated with petroleum hydrocarbons. Their result indicated that, because of the low sorption of non-ionic surfactants on soil, both the ionic and non-ionic surfactants would have the same oil removal from soil. In addition, oil removal from soils using water only was about one to three fold lower than when certain surfactant solutions were applied. Also, surfactant enhancement of oil removal occured at concentrations greater than and less than the CMC, although certain surfactants were observed not to show any enhancement of oil removal at concentrations greater than CMC. Literature on crude oil contaminated soil washing using biosurfactant solutions is limited. This present work studied the removal of crude oil from soil using biosurfactants under given operating conditions by applying the Taguchi experimental design method. The biosurfactants tested were aescin, lecithin, rhamnolipid, saponin and tannin. Their performance will be compared at their optimum values with that of a synthetic-based surfactant (sodium dodecyl sulphate). The Taguchi method (Phadke, 1989; Ross, 1987; Taguchi, 1987, 1990; Peace Stuart, 1995) is not discussed in this paper, as it is not our main point of study. However, the advantages of using the Taguchi method are outlined brie y. The experimental plan provides an economical way of simultaneously studying the effects of many parameters on process mean and variance. The Taguchi method is a fractional factorial design that can show process variability and stability. Most importantly, values determined at optimum conditions in the laboratory are reproducible in industrial applications. MATERIALS AND METHODS Preparation of Contaminated Soil The soil sample used in this study was supplied by Williams Sinclair Horticulture Limited, UK. The soil was a horticultural grade, lime-free, washed, and graded quartzite grit sand with maximum nominal size of 5 mm. This soil was sieved with an Endecott test sieve shaker; soil particles up to 4 mm were allowed to pass through the sieve following the method given in Arora (1989). The properties of this soil is summarized in Table 1. A xed mass (2000 g) of the sieved soil was contaminated with the North Sea Eko sk crude oil blend (STATOIL, 1999) at 20 C. The contamination process was carried out using a horizontally positioned drum mixer (Grochopp & Co. 4060 Viesen 1) at 1400 rpm for about 1 h. This resulted in a contamination level of 54.4 mg oil per gram of soil.

Contaminated soils were stored in air-tight glass containers to prevent evaporation of the lighter components before washing commenced.

Washing Method The washing method was adopted based on a preliminary experiment carried out to determine the different parameters and their range of values that most affect surfactant=crude oil=soil system. The concentration levels were chosen based on the CMC of the surfactants concerned. Five grams of the contaminated soil were measured and introduced into 45 ml centrifuged test tubes. The test tube was positioned horizontally in a temperature-regulated water bath (Grant Instruments) and content shaken laterally following the experimental plan and conditions shown in Table 2 and the range of values presented in Table 3. At the end of each washing, the contents of the test tube were allowed to settle for 3 min. The settling time was chosen based on the soil particle sizes distribution described in Arora (1989). The washed solution was decanted from the test tube as the settling time was achieved. The washed soil was rinsed with 5 ml of distilled water at the same washing temperature. Then it was shook laterally for 3 min and the wastewater decanted. The wastewater was disposed of as the treatment process was not within the scope of this work. However it should be noted that the crude oil can be separated from the water and recycled. The rinsing of the soil in the test tube was carried out to remove the oil from the walls of the test tube as well as the remaining surfactant solution from the soil. This prevented the possible formation of an emulsion with
Table 2. L16 (45) Optimum condition investigation experimental plans. Experimental parameters and their levels Experiment numbers 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 A 1 1 1 1 2 2 2 2 3 3 3 3 4 4 4 4 B 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 C 1 2 3 4 2 1 4 3 3 4 1 2 4 3 2 1 D 1 2 3 4 3 4 1 2 4 3 2 1 2 1 4 3 E 1 2 3 4 4 3 2 1 2 1 4 3 3 4 1 2

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WASHING CRUDE OIL-CONTAMINATED SOIL

Table 3. Experimental parameter and levels. Levels Parameters (A) Washing temperature ( C) (B) Volume of surfactant solutions (ml) (C) Concentration surfactant solutions (%-mass) (D) Shaking speed (strokes min 1) (E) Washing time (min) Level 1 5 5 0.004
80 5

205

Level 2 20 10 0.02
120 10

Level 3 35 15 0.1
160 15

Level 4 50 20 0.5
200 20

the extracting solvent later when determining the remaining oil in the soil. Analysis of Oil in Soil The initial and remaining oil was extracted using n-hexane. Ten millilitres of n-hexane were added to the rinsed soil, shaken laterally for 5 min and the n-hexane crude oil extract was removed. This process was repeated four times, as the fourth n-hexanecrude oil extract gave the same absorbance reading as a pure n-hexane (zero absorbance). All the n-hexanecrude oil extract was collected into one volumetric ask and made upto 50 ml with n-hexane. A sample from the 50 ml extract was centrifuged for about 20 min at a speed of 3000 rpm. This was to separate any suspended particles and to prevent the interference of the absorbance measurement. Although n-hexane is a highly non-polar solvent, our choice of it was based on its low toxicity and its availability in comparison with other solvent listed in Sikdar and Irvine (1998). Also, different authors have used them in the extraction of petroleum products from soil (Zhang et al., 2000; Somasundaran et al., 1997). Absorbance of the centrifuged n-hexanecrude oil solution was measured at 400 nm using the HACH DR=2000 Spectrophotometer. The wavelength 400 nm was chosen based on investigations where a stock solution of n-hexanecrude oil mixture was absorbed and shows a highest absorbance at 400 nm. Concentration of crude oil at this absorbance was determined from the function obtained from the calibration curve of the stock solution of n-hexanecrude oil at 20 C given by: Thus, crude oil remaining in soil was determined and the percentage crude oil removed from the soil was calculated using the equation below: Oi Or Crude oil removed, (%) 100% (2) Oi
where w is the concentration of crude oil remaining in the soil (%-mass), g is the corresponding absorbance at 400 nm, Oi is the initial oil in the soil (g) before washing, and Or the oil remaining in the soil (g) after washing. This experiment was repeated twice. Repeatability and experimental error were found within the range 4 and 3%, respectively. Surfactants The selection of biosurfactants was based on their biological origin materials. The rhamnolipid (microbial) used was a blend of C26H48O9 and C32H58O13. It was composed of
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15% aqueous solution of biosurfactant with excellent wetting and emulsi cation properties, supplied by Jeneil Biosurfactants Company, USA. Sodium dodecyl sulphate, SDS, (C12H25NaO4S), with purity of 97%, was supplied by Fluka Company, Switzerland. Tannin (C76H52O46=1701.22 g), with purity of 92.5%, was supplied by Fisher Chemical, UK. However, saponin (plant; quillaja bark-based), aescin (C54H84O23=1101 g), and lecithin, with a purity of 10, 9095 and 19%, respectively, were supplied by Sigma Chemical Co., USA. All the surfactants were used as supplied without further puri cation. Surface Activity of Surfactants The surface activities of the surfactant (aescin, lecithin, rhamnolipid, saponin, sodium dodecyl sulphate and tannin) in aqueous solution were determined with a Du Nouy tensiometer (Torsion Balance: type OS) using a platinum ring method. Experimental Plan and Parameters The optimum condition for soil-washing was investigated using the Taguchi experimental design. The Orthogonal array was chosen to determine the experimental plan, L16 (45) as shown in Table 2. This plan is most suitable for the conditions being investigated with ve parameters and each with four levels (Phadke, 1989; Peace Stuart, 1995), as indicated in Table 3. In order to observe the effect of noise source during the washing process, each experiment was repeated twice under the same conditions at different times. The performance statistic was chosen as the optimization criterion, which was evaluated using the equation (Pignatiello, 1988): ( ) n 1X 1 Zb 10log (3) n n 1 Yi2
i

w 0:3858g (% - mass)

(1)

where Zb is the performance statistic, n the number of repetitions done for an experimental combination and Yi the performance value of the ith experiment. With the Taguchi method, the experiment corresponding to optimum working conditions might not have been done during the whole period of the experimental stage. In such cases the performance value corresponding to optimum working conditions can be predicted by utilizing the balanced characteristic of orthogonal array. For this purpose the additive model may be used (Phadke et al., 1983). Yi m Xi ei (4)

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where m is the overall mean of the performance value, Xi the xed effect of the parameter level combination used in the ith experiment and ei is the random error in the ith experiment. Since equation (4) is a point estimate, which is calculated by using experimental data in order to determine whether results of the con rmation experiments are meaningful or not, the con dence interval must be evaluated rst. The con dence interval at a chosen error level may be calculated by (Ross, 1987): 1=2 1m 1 Yi Fa:1:DFMSe (MSe) (5) N ni
where
1m 1 Fa:1:DFMSe (MSe) N ni

1=2

Ri

Figure 1. Crude oil removal vs surfactant solution concentration at 20 C, washed with 20 ml solutions for 20 min at 200 strokes min 1.

F is the value of the F table, a the error level, DFMSe the degree of freedom of mean square error (MSe), m the degree of freedom used in the prediction of Yi, N the number of total experiments, and ni the number of repetitions in the con rmation experiment. If experimental results are in percentages, before evaluating equations (4) and (5), transformation of the percentage values should be applied rst using the following equations. Values of interest are then later determined by carrying out reverse-transformation using the same equation (Taguchi, 1987): 1 1 O(db) 10log (6) P
where O(db) is the decibel value of percentage value subject to O transformation and P the percentage of the product obtained through experiment. The order of experiment was obtained by inserting parameter values into the columns of orthogonal array, L1645chosen as the experimental plan. The order of the experiments was made random in order to avoid noise source which had not been considered initially and could take place during an experiment and affect the result in a negative way. The validity of this study was checked by a con rmation experiment conducted at the optimum conditions. This value was compared with the predicted oil removal at the same conditions. RESULTS AND DISCUSSION Surface Activities of Surfactant Solutions The surface and interfacial tension lowering ability of the surfactant solutions was determined in waterair and crude oilwater interface. These studies conducted within
Table 4. Surface activities of surfactant solutions. CMC (%-mass)
0.1 0.4 0.02 0.1 0.2 0.008

the temperature of 17 4 C were repeated thrice and the average value presented with an error range of 0.003 N m1. Results are shown in Table 4, indicating the surfactant CMC and corresponding surface and interfacial tension. The interfacial tension-lowering ability of the surfactant solution indicates their tendency to remove oil from soil (Abdul et al., 1990). As the interfacial tension is lowered, the capillary force holding the crude oil and soil is reduced, which favours their separation. For instance, the surface tensions of waterair and crude oilwater systems were 71 and 25 mN m1. Rhamnolipid shows an interfacial tension of 4.5 mN m1 at the CMC. Thus, it has a greater tendency to remove crude oil from soil in comparison with aescin and SDS, which indicated an interfacial tension of about 7 mN m1 at CMC of 0.1 and 0.2%-mass, respectively. However, due to the effect of temperature on surfactant CMC at varying concentrations (Holmberg, 2002), we compared CMC values obtained in this study with those in the literature. SDS corresponded to values in Deshpande et al. (1999) and Holmberg (2002), aescin to Pekdemir et al. (1999), and saponin to Hong et al. (2002): therefore we assumed the other surfactants CMCs to be within range. Performance of Biosurfactant Solutions The performance of biosurfactant solutions and distilled water was rst tested in removing crude oil from the soil. As surfactant surface activities are best described in aqueous solutions, we tried to wash the contaminated soil at varying surfactant solution concentrations. It was observed that increasing solution concentration did not enhance the removal of crude oil using lecithin and tannin (Figure 1).
Table 5. Sorption of surfactant solutions on soil. Surfactants CMC (%-mass) 0.1 0.4 0.02 0.1 0.2 0.008 Supernatant CMC (%-mass) 0.4 0.9 0.08 0.4 0.3 0.02 Surfactant loss (%) 75.00 55.50 75.00 75.00 33.33 60.00

Surfactants
Aescin Lecithin Rhamnolipid Saponin SDS Tannin

Surface tension (mN m 1)

44 35 28 39 35 50

Interfacial tension (mN m 1)

7.00 5.00 4.50 6.00 7.00 4.50

Surfactants Aescin Lecithin Rhamnolipid Saponin SDS Tannin

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Figure 2. Effect of parameter on performance statistic. ( ) Aescin; ( ) lecithin; ( ) rhamnolipid; ( ) tannin; ( ) saponin; (

) SDS.

Their maximum crude oil removal occurred at 0.004%-mass solution, indicating a removal of 43 and 48% for lecithin and tannin, respectively. Although their interfacial tension were about 5.00 and 4.5 mN m1, which was comparable to that of
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rhamnolipid, this result then agreed with Abdul et al. (1990), that certain surfactants do not enhance the solubilization of oil in soil at concentrations greater than CMC. Maximum crude oil removal was obtained at concentrations below

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Table 6. Optimum conditions. Surfactant solutions
Aescin Lecithin Rhamnolipid Saponin SDS Tannin

Temperature ( C)
50 50 50 50 50 50

Concentration (%-mass)
0.004 0.004 0.5 0.004 0.5 0.004

Volume (cm3)
20 15 15 10 15 15

Speed (stroke min 1)

160 200 200 200 160 200

Time (min) 10 10 10 10 10 10

CMC, suggesting that the removal of crude oil was due to mobilization because of the reduction of interfacial tension. Meanwhile, results obtained using saponin and aescin also agree with Deshpande et al. (1999) and Abdul et al. (1990), indicting less crude oil removal after CMC. However, solubilization mechanisms were observed to be responsible for the removal of crude oil (about 90%) using SDS and rhamnolipid. Greater crude oil removal was observed as the concentration of the solution increased beyond the CMC values. Although SDS showed a better performance, considering the biological origin nature of rhamnolipid it may be assumed to be more effective because of its ready biodegradability characteristics and lower environmental toxicity. To ascertain the low removal of crude oil by some of the surfactant solutions, we studied their sorption on the soil. Following the method in Chu and Chan (2002), surfactant to soil ratio of 6:1 was shaken in a water bath at 20 C for 40 min. The supernatant was centrifuged for 1 h and the surface tension of the supernatant measured and the CMC determined with a Du Nouy tensiometer. The difference between the CMC of pure surface and that of the supernatant indicate the sorption or loss of surfactants in soil as summarized in Table 5. Results indicated that among the biosurfactants, lecithin and tannin showed minimum loss of surfactant solution to soil. Therefore, we conclude that the nature of these two biosurfactants attributed to their performances since distilled water washing (zero concentration) indicates crude oil removal of about 38.53%. Hence, this study was then limited to esh contaminated soil which was used within two weeks of contamination. Optimum Crude Oil Removal As this washing was carried out with the Taguchi method, crude oil removed by any parameter had an effect on the other parameter. Thus, the results of this study will be explained based on the Taguchi method. Since it is cumbersome to deduce an experimental plan as presented in Table 2 that resulted in the graphs in Figure 2ae, these gures will be explained by giving examples. For instance, Figure 2a investigated the variation of temperature with the performance statistics. To determine the experimental conditions of rhamnolipid at level 1 (that is, at 5 C) with the average performance statistics value of 26.34, from Table 2 the experiments with temperature level 1 are with experimental numbers 1, 2, 3 and 4. The performance statistics at this temperature are the averages of these four experiments. Experimental conditions for the second data point are experiments with experimental numbers 5, 6, 7 and 8 and so on. The performance statistics for each surfactant were plotted against the investigated parameters and the optimum

points were determined for each surfactant. The maximum point on the curve was chosen for each surfactant as the optimum point. In some cases, we chose lower level points when the performance statistics were within the same range of values. Hence, the optimum washing conditions determined are shown in Table 6. However, after evaluating equation (3), temperature was found to be the most in uential parameter for all biosurfactants except lecithin, which indicates solution concentration to be its most in uential parameter. However, the least in uential parameters were found to be washing time and volume of solutions. The order of the graphs in Figure 2 is according to the degree of the average in uence of parameters on crude oil removal from soil. This was determined by nding the range between the largest and the lowest value of crude oil removal for each surfactant solution after evaluating equation (3). Predicted Crude Oil Removal Considering the optimum conditions obtained from Figure 2, careful consideration of the experimental plan (Table 2) can explain that experiment corresponding to the optimum value may not have been carried out during the whole washing process. This is applicable for all the surfactant solutions except aescin, which corresponds to experiment number 16. With equations (4), (5) and (6), we predicted the crude oil would be removed at these optimum conditions at the following con dence limits: 90, 95 and 99%. The predicted crude oil removal was con rmed by carrying out a laboratory experiment twice at the optimum washing conditions shown in Table 6. The average result obtained from the laboratory-con rmed experiment is presented in the second column of Table 7. The value of the predicted crude oil removal shown in the third column of Table 7 can be obtained for any con dence intervals by inserting the value of Ri, that is, R90% 13.34, R95% 16.23 and R99% 22.45. For instance, Rhamnolipid predicted crude oil removal at 90% would be within the range 79.16105.84%. Figure 2 shows the predicted crude oil removal for the whole surfactants at the different
Table 7. Oil removal at optimum conditions. Crude oil removed (%) Surfactants Aescin Lecithin Rhamnolipid Saponin SDS Tannin Experiment 30.32152 9.645246 79.87805 80.73725 96.61863 32.92684 Predicted 4.4 3.3 92.5 92.9 94.9 45.8 Ri Ri Ri Ri Ri Ri

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WASHING CRUDE OIL-CONTAMINATED SOIL con dence intervals. The negative predicted crude oil removal for aescin and lecithin indicates that, over all the experimental runs, crude oil removal in some of the levels was zero. This may be due to their nature, discussed earlier, and also occurs using the Taguchi method as observed with 0.5%-mass lecithin solution, and during 5 min washing with aescin. Although aescin con rmatory experimental crude oil removal corresponds to the value of about 31% obtained during the experiment (experiment number 16 from Table 2), this removal is not within the range predicted for the three con dence intervals. This implies that the removal has a large variation and is not stable. For the other four surfactants, the con rmed experimental crude oil removed from soil was within the predicted limits, indicating process stability and robustness. The range of predicted crude oil removal at 1% error levels was greater than those of 5 and 10% error levels. Thus, with Taguchi experimental method higher process performance was obtained at low error levels indicating stability within the range of 1%. CONCLUSION The soil-washing study has been conducted to determine the optimum conditions for removing crude oil from a contaminated soil using various biosurfactant solutions. The Taguchi experimental design method was used to assess the robustness or stability and reproducibility of the experimental method for possible eld-scale applications. Results gained from these studies indicated that temperature and concentrations of surfactant solutions were the most in uential parameters. With the Taguchi method the removal of crude oil with rhamnolipid and saponin was observed to be about 80%. Owing to their low environmental toxicity and easily biodegradability they are preferable to SDS, , which shows more than 95% removal but is extremely toxic. The con rmatory experiment and the predicted crude oil removal showed that the washing method was stable for all the biosurfactant solutions expect aescin and lecithin, which showed predicted crude oil removal out of range. However, as error level increases from 1 to 10%, the stability of the washing method reduced. As certain surfactant solutions indicate less sorption in soil, and a lowering of surface and interfacial tension in aircrude oilwater systems, we suggest that a eld-scale study be undertaken to assess surfactant performance in the removal of crude oil from both weathered and nonweathered contaminated soils, although the cost analysis is not given. REFERENCES
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ADDRESS
Correspondence concerning this paper should be addressed to Mr K. Urum, Chemical Engineering, School of Engineering and Physical Sciences, HeriotWatt University, Edinburgh, EH14 4AS, UK. E-mail: k.urum@hw.ac.uk The manuscript was received 11 July 2002 and accepted for publication after revision 17 March 2003.

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