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J. Ind. Eng. Chem., Vol. 13, No.

4, (2007) 650-656

Ultrasonic-Assisted Extraction to Release Heavy Metals from Contaminated Soil


Seon-Suk Hwang, Joon-Seok Park* , and Wan Namkoong**
Department of Environmental Engineering, College of Engineering, Konkuk University, Seoul 143-701, Korea *Department of Environmental Disaster Prevention Engineering, College of Engineering, Kangwon National University, Kangwon-do 245-711, Korea **Konkuk University Innovative Environmental Technology Center, Konkuk University, Seoul 143-701, Korea Received January 24, 2007; Accepted February 14, 2007

Abstract: The soil used in this research was obtained from a heavy metal-contaminated site near a Pb-smelting plant. For ultrasonic-assisted extraction, citrate and ethylenediaminetetraacetic acid (EDTA) were used as leaching solutions. When using 0.05 and 0.1 M citrates, the highest extraction efficiency was obtained at 30 W. For both citrate and EDTA, the efficiency increased with sonic time and showed the maximum at 12 min. At the same concentration (0.05 M), EDTA was better than citrate at extraction. Despite the short extraction time, the extraction efficiencies of metals with sonication were higher than those of soil washing for both 0.05 M citrate and 0.05 M EDTA. Extraction of metallic elements from contaminated soil could be enhanced with the aid of ultrasonic treatment. Keywords: ultrasonic-assisted extraction, contaminated soil, heavy metal

Introduction
1)

The deposition of metal-rich mine tailings, metal smelting, leather tanning, electroplating, emissions from gas exhausts, energy and fuel production, down-wash from power lines, intensive agriculture, and sludge dumping are the human activities that contaminate soil systems with the largest amounts of toxic metals [1,2]. The list of sites contaminated with toxic metals grows larger every year, presenting a serious health problem and a formidable danger to the environment. Determination of the exact forms of certain elements in natural systems is challenging and time-consuming because identifying the exact species usually requires sophisticated instrumental techniques [3]. Various sequential extraction methods have been widely used for the determination of metal behavior in environmental solid materials. One of the main limitations of sequential extraction procedures is that they are extremely timeconsuming. Extraction of metals from solid samples using ultrasonic treatment is both fast and efficient [4].

To whom all correspondence should be addressed. (e-mail: wan5155@kangwon.ac.kr)

Ultrasonic processing applies intense, high-frequency sound to liquids, producing intimate mixing and powerful chemical and physical reactions [1]. The process of cavitation is, in effect, cold boiling and results from the creation of chemical and physical reactions, such as those of surfactancy, which is why ultrasonic processing is a preferred extraction technique. Intensity is a measure of the energy available per unit volume of liquid and is directly related to amplitude. It is the intensity of cavitation that accelerates physical and chemical reactions, not the total power applied to the system. Therefore, parameters such as time, frequency, and volume of sample ought to be optimized. Soil washing technology has been applied to treat metal-contaminated sites. Soil washing systems offer the greatest promise for application to soils contaminated with a wide variety of heavy metal and organic contaminants [5]. In soil washing, sequential washing steps may be needed to enhance treatment efficiency, which is time-consuming and brings about an increase of reagent addition and wastewater generation. Sonication processes have been applied limitedly to pretreatment for metal analysis and pre-extraction of metals, including Cu, Pb, Ni, and Zn, in order to recover precious metals [6].

Ultrasonic-Assisted Extraction to Release Heavy Metals from Contaminated Soil Table 1. Experimental Conditions
Item Texture Sand (20.05 mm) (%) Silt (0.050.002 mm) (%) Clay (< 0.002 mm) (%) Moisture content (%) Field capacity (%) Volatile solids (%) pH Cation exchange capacity (meq/100 g) Contaminated soil Sandy loam 57.6 26.2 16.2 0.7 35 3.7 7.5 17.3

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The use of ultrasound power has been investigated to speed up sequential extraction methods because it has long been recognized that the cavitational effect created by ultrasound waves can break down the particle size, exposing a fresh surface and aggressively agitating the solution system [7]. When a suspension of solid particles is subjected to treatment with ultrasound, particle dispersion can take place, which, in turn, causes an increase in the surface area available for the reaction. When extraction applications of ultrasound are concerned, particle fragmentation can enhance the ability of the extractant to leach metals [3]. Ultrasonic-assisted extraction has not been studied for remediation of heavy metal-contaminated soil. Ultrasonic-assisted extraction could enhance the treatment efficiency and shorten the time required for washing contaminated soil. Therefore, in this study we estimated the possibility of using ultrasonic treatment for washing contaminated soil.

Figure 1. Laboratory apparatus used for ultrasonic extraction of heavy metals.

Experimental
Contaminated Soil The soil for this research was obtained from a heavy metal-contaminated site near a Pb-smelting plant in Goyang city, Kyungki-do. Soil near the plant, which had been operated for 30 years, was found to be highly contaminated with Pb and other heavy metals. After being sampled, the soil was air-dried and passed through a 2-mm sieve to remove large soil fractions, such as stone and gravel. Table 1 shows the characteristics of the soil. The texture of the soil was classified as a typical sandy loam (the portions of sand, silt, and clay in the soil were 57.6, 26.2, and 16.2 %, respectively). The cation exchange capacity (CEC) of the soil was 17.3 meq/100 g of dry soil, which was in the range of natural soils having CEC values of 10 to 30 meq/100 g [8]. Experimental Apparatus and Conditions A 3.0 g sample of soil was mixed with a leaching solution in a ratio of 1:10 (W/V). Citrate and ethyl-

enediaminetetraacetic acid (EDTA) were used as leaching solutions. In a previous study [9], it was shown that the extraction efficiency of citrate was lower than those of EDTA and HCl. The ultrasonic system for this research consisted of an ultrasonic generator, a piezoelectric transducer, and an acoustic horn, as shown in Figure 1. Ultrasonic irradiation at 20 kHz was carried out using an ultrasonic system from Mirae Ultrasonic Tech. Co., Korea. The generator could be controlled in a power range of 0100 W 2 (030 W/cm ). Sonication was performed with a horn of 2-cm diameter and 18-cm length. The bottom of the horn was immersed 0.5 cm beneath the surface of the sample solution. The experiment was carried out with the sonicated solutions open to the atmosphere. Ultrasonic power of 10 to 40 W was applied for up to 12 min. Analysis The initial concentration of heavy metals in the contaminated soil and the background soil were analyzed using the methods of Chlopecka [10] and Ure [11]. Hot acidic digestion was employed in soils with acids such as HNO3, HClO4, and HF. HNO3 (10 mL) was added to a Teflon beaker containing 1.0 g of soil; the beaker was heated until the solution was concentrated to a small volume, and then cooled to room temperature. After the addition of 5 mL of HNO3, 5 mL of HClO4, and 10 mL of HF, the solution was heated for 30 min with white fume generation. After the addition of HCl (1:1, V/V; 10 mL), the solution was heated for 10 min, and then cooled to room temperature. The final volume of the solution was adjusted to 100 mL with distilled water. Fractional concentration of heavy metals was also analyzed by sequential extraction schemes used in Tessier and coworkers research [12]. The determination of Pb, Cu, Zn, and Cd in the extracted solution was carried out using an Atomic Ab-

652

Seon-Suk Hwang, Joon-Seok Park, and Wan Namkoong

Table 2. Concentrations of Pb, Cu, Cd, and Zn for the Contaminated Soil and Background Soil
Item Exchangeable Carbonate Contaminated soil Reducible Oxidizable Residual Total Background soil Permission standard****
*

Pb (mg/kg) 366 (2.4)


* **

Cu (mg/kg) 0.31 (0.5) 4.30 (6.6) 10.96 (16.4) 12.27 (18.9) 37.44 (57.6) 653.7 24 50

Cd (mg/kg) 1.58 (9.9) 1.31 (8.2) 0.85 (5.3) 0.28 (1.7) 11.99 (74.9) 161.4 0.9 1.5

Zn (mg/kg) 1.33 (0.5) 18.62 (7.3) 100.46 (39.3) 37.22 (14.5) 98.38 (38.4) 25612 60 300

6082 (40.6) 2330 (15.5) 323 (2.2) 5899 (39.3) 15000993*** 60 400

Mean concentration of 15 samples. **( ) = % Portion relative to total concentration. ***Relative standard deviation. ****Soil Contamination Care Permission Standard for industrial region in Soil Environment Conservation Act.

sorption Spectrophotometer (Shimadzu AA-6501F, Japan) equipped with an acetylene-air flame. Hollow cathode lamps (Shimadzu) were used as a radiation source for all the studied elements. The instrumental parameters employed were a spectral bandwidth of 0.2 nm for Pb and Cd and 0.5 nm for Cu and Zn. The wavelengths were 217.0, 324.8, 213.9, and 228.8 nm for Pb, Cu, Zn, and Cd, respectively. Two-constant Rate Kinetic Model Zn adsorption or desorption processes have been based mainly on the study of equilibrium conditions using thermodynamic approaches [13]. The thermodynamic approach can predict only the final state of a soil system from an initial non-equilibrium state, while the analysis of the kinetics may yield important information concerning the nature of the reaction at a given time. Zinc desorption kinetics have been described by a two-constant rate equation by Kuo and Mikkelsen [14] as Qt = atb where Qt is the amount of Zn desorbed by EDTA (mg Zn/kg) after t (sec) period of extraction, a is the initial Zn desorption rate constant (mg Zn/kg/sec)b, b is the desorption rate coefficient (mg Zn/kg)-1, and t is the extraction time (sec). An increase in the value of a and a decrease in b probably indicates an increase in the rate of Zn desorption from the soils.

Results and Discussion


Initial Heavy Metal Concentrations in Contaminated Soil The mean concentrations of Pb, Cu, Cd, and Zn in the contaminated soil and in the background soil are summarized in Table 2. The concentrations of Pb, Cu, Cd,

and Zn in the contaminated soil were 15000, 65, 16, and 256 mg/kg, respectively. Pb was present at the highest concentration among all of the heavy metals. It is obvious that the plant affected the neighboring soil quality. The Pb concentration of the contaminated soil was 250 and 38 times higher than the 60 mg/kg of the background soil and the 400 mg/kg of the Soil Contamination Care Permission Standard for industrial region in Soil Environment Conservation Act, respectively. The distribution of heavy metals in the contaminated soil according to the chemical combined form is also presented in Table 2. The residual fraction in heavy metals was ca. 40 % for Pb and Zn, 60 % for Cu, and 75 % for Cd. The distributed characteristics of the exchangeable, carbonate, reducible, and oxidizable fractions in each metallic element were different. In the case of Pb, carbonate and reducible fractions were high relative to exchangeable and oxidizable fractions. In the case of Cd, exchangeable, carbonate, reducible, and oxidizable fractions were lower than 10 %. This situation may be due to the high residual fraction (ca. 75 %) of Cd. Ma and Rao reported that Cd was present mainly in residual fraction when the natural concentration was lower than 50 mg/kg [15]. The chemical combined fraction from sequential extraction analysis could be classified into two groups: non-detrital and detrital fractions [16]. Although these fractions (the five-step extraction scheme) are operational and caution is warranted in mechanistic interpretations, it is convenient to broadly consider two fraction categories. Non-detrital metals are displaceable without solid phase dissolution. Detrital metals are released into solution only if structural decomposition of minerals occurs. The nondetrital fraction includes the exchangeable, carbonate, and oxidizable fractions in metals and represent the portion of the soil metal that is potentially leachable and bioavailable. The reducible and residual metals will not be environmentally available under

Ultrasonic-Assisted Extraction to Release Heavy Metals from Contaminated Soil Table 3. Non-detrital and Detrital Fractions (%) of Pb, Cu, Cd, and Zn in the Contaminated Soil
Fraction Non-detrital Detrital Pb 45.2 54.8 Cu 26.0 74.0 Cd 19.8 80.2 Zn 22.3 77.7

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Figure 3. Effect of sonication time on extraction of metals with leaching solutions of 0.05 and 0.1 M citrate.

Figure 2. Effect of sonication power on extraction of metals.

normal conditions, and are termed detrital because their release requires solid phase dissolution. Therefore, it is more difficult to extract the detrital heavy metal fraction from contaminated soil relative to the non-detrital heavy metals. The non-detrital fraction of Pb was the highest (45.2 %) among the metals. Apart from the case of Pb, the non-detrital fractions of Cu, Cd, and Zn were below 20 % (Table 3). From this result, we predicted that Cu, Cd, and Zn could not be extracted simply. Effect of Sonication Power and Time on Extraction Efficiency The effect of the sonication power on the extraction of metals is provided in Figure 2. A low metal extraction efficiency was observed in 0.05 and 0.1 M citrate leaching solutions. Despite the concentration of Pb being the highest in this metal-contaminated soil, the extraction efficiency of Pb was the highest among the metals Pb, Cu, Cd, and Zn. As previous mentioned, this situation might

be due to the fact that the non-detrital fraction of Pb was the highest (45.2 %) among these metals. The extraction efficiency increased with an increase of the sonication power in 0.05 M citrate [Figure 2(a)]. The extraction efficiency at 40 W was 714 % higher than that at 10 W. The highest extraction efficiency was observed at 30 W for 0.1 M citrate [Figure 2(b)]. For both 0.05 and 0.1 M citrates, high extraction efficiency was mainly shown at 30 W. Figure 3 shows the effect of the sonication time on extraction of metals with leaching solutions of 0.05 and 0.1 M citrate. The sonication power was fixed at 25 W. The extraction efficiency increased slightly with the sonication time for 0.05 and 0.1 M citrates. However, a greater increase of the extraction efficiency was observed in 0.1 M citrate for Pb. When the sonication time was over 5 min in 0.05 and 0.1 M citrates, the extraction efficiency was ca. 10 % higher than those after 1 and 3 min. Pb was extracted the most among these metallic elements. For 0.01 and 0.05 M EDTA, the effect of the sonication time on the removal efficiency of metals is presented in Figure 4. The sonication power was fixed at 25 W. In this case, the extraction efficiency increased with the sonication time and was highest at 12 min. Visnen and coworkers reported that the optimum ultrasonic extraction time was 9 min for releasing metals [17].

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Seon-Suk Hwang, Joon-Seok Park, and Wan Namkoong

Figure 5. Removal efficiency of metals with 0.05 M citrate and 0.05 M EDTA after a 12-min sonication time.

Figure 4. Effect of sonication time on extraction of metals with leaching solutions of 0.01 and 0.05 M EDTA. Table 4. Kinetic Constant B Based on Two-constant Ratebased Model
0.05 M Citrate Item Pb Cu Cd Zn Sonication (min)-1 0.2553 0.1206 0.1066 0.2535 Soil washing (min)-1 0.1443 0.1079 0.0994 0.2211 0.05 M EDTA Sonication (min)-1 0.1010 0.1573 0.1170 0.3442 Soil washing (min)-1 0.1444 0.1449 0.1003 0.2247

Figure 6. Two-constant rate-based model for Pb in sonication and soil washing with 0.05 M citrate and 0.05 M EDTA.

At the same concentration of 0.05 M, the extraction efficiency of the metals for citrate was compared with that for EDTA (Figure 5). The extraction efficiencies of Pb, Cu, and Cd for EDTA were much higher than those of citrate, except for Zn. The extraction efficiency of Pb for EDTA was 2.5 times higher in comparison to that of citrate. Consequently, EDTA was better than citrate for metal extraction from contaminated soil. Two-constant Rate-based Kinetics The two-constant rate-based kinetics for Pb, Cu, Cd, and Zn, based on two-constant rate model, are provided in Figures 69 and Table 4. The concentrations of citrate and EDTA used were the same (0.05 M). The kinetics of ultrasonic treatment are presented with that of soil washing at the same concentration. Data for soil

washing were obtained from the previous research by Hwang and coworkers [9]. The kinetic model in this B research is given by C = At , where A is the extraction -1 efficiency (%), B is the desorption rate constant (min ), C is the extraction efficiency (%) at time t, and t is the extraction time (min). The model is linearly transformed to the following equation. Log C = Log A + BLog t Except of Pb, for sonication with 0.05 M EDTA, the two-constant rate-based kinetic model described the extraction reaction of metals with high correlation co2 efficients (R = 0.780.99). The kinetic constant for sonication was similar to, or slightly higher than, that for soil washing. In Pb with 0.05 M EDTA, the kinetic con-1 stant (0.144 min ) for soil washing was higher than that

Ultrasonic-Assisted Extraction to Release Heavy Metals from Contaminated Soil

655

Figure 7. Two-constant rate-based model for Cu in sonication and soil washing with 0.05 M citrate and 0.05 M EDTA.

Figure 9. Two-constant rate-based model for Zn in sonication and soil washing with 0.05 M citrate and 0.05 M EDTA.

min (log t = 2.556 min). This result indicates that the ultrasonic-assisted extraction could help to enhance the extraction of metals from contaminated soils and to shorten the extraction time greatly. Other researchers have reported that ultrasonic extraction could shorten extraction times during pretreatment for metal analysis [1,17,18].

Conclusions
The Pb, Cu, Cd, and Zn concentrations of the contaminated soil used in this research were 15000, 65, 16, and 256 mg/kg, respectively. The residual fraction in heavy metals was ca. 40 % for Pb and Zn, 60 % for Cu, and 75 % for Cd. The non-detrital fraction of Pb was the highest (45.2 %) among these metals, which indicates that Pb could be extracted more simply than the other metals. When using 0.05 and 0.1 M citrate, the highest extraction efficiency was obtained at 30 W. In both citrate and EDTA, the extraction efficiency increased with the sonication time; it was highest at 12 min. At the same concentration (0.05 M), extraction with EDTA showed higher efficiency than that with citrate. The two-constant rate-based kinetic model described the extraction reaction of metals with high correlation coefficients (R2 = 0.780.99). Despite the short extraction time, the extraction efficiencies of metals with sonication were higher than those with soil washing for both 0.05 M citrate and 0.05 M EDTA. Extraction of metallic elements from contaminated soil could be enhanced with the aid of ultrasonic treatment.

Figure 8. Two-constant rate-based model for Cd in sonication and soil washing with 0.05 M citrate and 0.05 M EDTA.

(0.101 min-1) for sonication (Table 4), which might be due to the fact that the non-detrital fraction of the contaminated soil was as high as 45.2 % and was extracted easily, even through soil washing with EDTA. Despite the short extraction time, extraction efficiencies of metals with sonication were higher than those of soil washing for both 0.05 M citrate and 0.05 M EDTA (Figures 69). For example, when the extraction time was 12 min (log t = 1.079 min), the values of log (Extraction Efficiency) of Pb for sonication and soil washing were 1.441 and 1.036, respectively (Figure 6). The value of log (Extraction Efficiency) for sonication at an extraction time of 12 min (log t = 1.079 min) was slightly higher than that (1.408) for soil washing for 360

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Seon-Suk Hwang, Joon-Seok Park, and Wan Namkoong

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