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Effect of Soil Chemical Properties on the Remediation of Phenanthrene-contaminated Soil by Electrokinetic-Fenton Process

Effect of Soil Chemical Properties on the Remediation of Phenanthrene-contaminated Soil by Electrokinetic-Fenton Process

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05/09/2014

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E\ufb00ect of soil chemical properties on the remediation
of phenanthrene-contaminated soil
by electrokinetic-Fenton process

Jung-Hwan Kima,*, Sang-Jae Hanb, Soo-Sam Kimb, Ji-Won Yangc
aEnvironment Energy Engineering (En3), 4th Floor, Dongcheon Building, 267-2 Nonhyun-Dong, Kangnam-Ku,
Seoul 135-010, South Korea
bDepartment of Civil and Environmental Engineering, Hanyang University, 1271 sa-1 dong, Aansan,
Kyunggi-do 425-791, South Korea
cNational Research Laboratory for Environmental Remediation, Department of Chemical and Biomolecular Engineering,
Korea Advanced Institute of Science and Technology (Kaist), 373-1 Geseong-dong, Yuseong-gu, Daejeon 305-701, South Korea
Received 14 February 2005; received in revised form 5 October 2005; accepted 5 October 2005
Available online 28 November 2005
Abstract

The electrokinetic-Fenton (EK-Fenton) remediation of soil contaminated with phenanthrene was studied. Two dif- ferent soils were chosen to investigate the e\ufb00ects of chemical properties, such as Fe oxide contents and acid soil bu\ufb00er capacity. The H2O2concentrations in pore water, the electrical potential distributions and the electrical currents were monitored to assess the electrochemical e\ufb00ect in relation to the soil properties. Hadong caly had high acid bu\ufb00er capac- ity, and thus the amount of electroosmotic \ufb02ow was lager in the experiment with Hadong clay than with EPK kaolin. The major mechanism of phenanthrene removal was a degradation in the experiment with EPK Kaolin, while it was a simple transport away from the system in experiment with Hadong clay. It was mainly because of the lower acid buf- fering capacity and better H2O2stability in case with EPK Kaolin than with Hadong clay.

\u00d32005 Published by Elsevier Ltd.
Keywords:Electrokinetic-Fenton process; HOCs; Fe oxide; Acid bu\ufb00er capacity
1. Introduction

Polycyclic aromatic hydrocarbons (PAHs) are organic contaminants commonly found in subsurface (Warman, 1985). These chemicals not only result in tox- icity, but also are carcinogens and endocrine disrupters (Sullivan and Krieger, 1992). Because of their low solu-

bilities and slow desorption rates, PAHs are di\ufb03cult to
be removed from subsurface environments.

Among various technologies employed for the reme- diation of soils contaminated with organic chemicals, Fenton process is one of the most widely used and stud- ied, in which hydroxyl radicals are produced by the reac- tion of hydrogen peroxide and ferrous ion. Hydroxyl radicals are non-speci\ufb01c oxidants that react with most organic contaminants at rates close to their theoretical limit, which is near the di\ufb00usion-controlled rate in water (109\u20131010M

\u00c01s
\u00c01) (Walling, 1975). However, they are
0045-6535/$ - see front matter\u00d3 2005 Published by Elsevier Ltd.
doi:10.1016/j.chemosphere.2005.10.008
*Corresponding author. Tel.: +82 2 540 3910; fax: +82 2 540
0935.
E-mail address:genkjh@wm.cau.ac.kr(J.-H. Kim).
Chemosphere 63 (2006) 1667\u20131676
www.elsevier.com/locate/chemosphere
e\ufb00ective only at low pH values, which require pH adjust-
ment during the remediation (Valentine and Wang,
1998).

Application of the modi\ufb01ed Fenton\u00d5s reagent has been e\ufb00ective in degrading contaminants and included the use of high concentrations of H2O2and iron oxides as catalysts (Tyre et al., 1991). Soil-bound contaminants are more resistant to oxidative attack during chemical treatments than contaminants in solution (Watts et al.,

1993; Watts and Dilly, 1996). The e\ufb00ects of sorption

on contaminant degradability can be minimized with high H2O2additions, which results in the generation of non-hydroxyl radical transient oxygen species, such as perhydroxyl radicals (HO

\u00c5
2), superoxide radical anions
(O\u00c5\u00c0
2) and hydroperoxide anion (HO\u00c02), which are capa-
ble of oxidizing sorbed contaminants (Watts and Stan-
ton, 1999). In the following equations, \u2013Fe3+and
\u2013Fe2+represent liganded iron or occupying sites at an
oxide surface:
H2O2\u00fe\u2013Fe2\u00fe !OH
\u00c5
\u00feOH\u00c0 \u00fe\u2013Fe3\u00fe
\u00f01\u00de
H2O2\u00feOH
\u00c5
!HO
\u00c5
2\u00feH2O
\u00f02\u00de
HO
\u00c52$O
\u00c5\u00c0
2\u00feH\u00fe;
pKa\u00bc 4:8
\u00f03\u00de
HO
\u00c52\u00fe\u2013Fe2\u00fe !HO\u00c02 \u00fe\u2013Fe3\u00fe
\u00f04\u00de
HO
\u00c52\u00feO
\u00c5\u00c0
2!HO\u00c02\u00feO2
\u00f05\u00de

However, the modi\ufb01ed Fenton method has di\ufb03culties in treating heterogeneous subsurface environments that contains clayey soil with low permeability. Electrokinetic remediation of soil possessing low permeability repre- sents a technology for both heavy metals and organics removal (Hamed et al., 1991; Acar et al., 1992). Recently, it has been demonstrated that the removal e\ufb03ciency can be improved by combined application of an electrical \ufb01eld and supplementary reagents for organic removal (Yang and Long, 1999; Reddy and Saichek, 2003). An

innovative remediation technique known as the electr- okinetically enhanced in situ Fenton oxidation method (Yang and Long, 1999) employs a high H2O2concentra- tions as the anode purging solution, which demonstrates a potential to treat contaminants sorbed onto soils pos- sessing low permeability. The H2O2introduced from the anode chamber is transferred toward the cathode by electroosmotic \ufb02ow, which is accompanied by the decomposition of contaminants on the mineral surface, where the anions (O

\u00c5\u00c0
2, HO\u00c02) may move towards the

anode due to electromigration (Fig. 1). The electrolysis of water produces hydrogen ions at the anode, which in turn generates an acid front, thus a\ufb00ects the contaminant remediation and H2O2stabilization, which may have direct in\ufb02uences from soil properties.

Thus the purpose of the present study is to examine the e\ufb00ect of soil chemical properties, such as bu\ufb00er capacity and iron contents, on the EK-Fenton process. A bench-scale experiments of the EK-Fenton process were conducted using two soils spiked with phenanthrene as the representative PAH and a low concentration acid (0.01 N H2SO4) as the anode purging solution for pH control. Electrical current, electrical potential distribu- tion and electroosmotic \ufb02ow, as well as the pH, were measured. The residual H2O2and phenanthrene concen- trations that existed in the soil at the end of each experi- ment were also detected.

2. Experimental
2.1. Materials

The soils selected for the present study were EPK (Edger\u00d5s Plastic Kaolin from Florida) kaolin and Hadong clay. EPK kaolin was purchased from the

Cathode
H2O2
Anode
Water flow
Hydrogen ion
Hydroxide ion
Ground level
H2O2 & H2O2 stabilizer Supply In-let
Soil
Anions
HO2
2
-
-
Organic contaminants
desorption, degradation and removal
of contaminants
Soil surface
Radical species
O
Fig. 1. Schematic diagram of the electrokinetic-Fenton process catalyzed by minerals in the subsurface.
1668
J.-H. Kim et al. / Chemosphere 63 (2006) 1667\u20131676

Feldspar Corporation and the Hadong clay was an actual soil in Hadong, Korea.Table 1 shows that the mineralogy, physical and chemical properties of these soils di\ufb00er signi\ufb01cantly. As seen in the table, the major mineral of EPK kaolin was kaolinite whereas the Hadong clay soil was largely composed of quartz, kaoli- nite and halloysite. The two soils had negligible amounts of organic carbon. The concentrations of extractable NO\u00c03and SO2\u00c0

4in the soil were determined by 0.01 M
HCl extraction, and the soluble Cl
\u00c0

concentration in the soil by de-ionized water, but the salts in the two soils were only in trace amount.

Table 2shows that the Fe, Mn and Ca concentration,

in di\ufb00erent forms, were determined by the sequential extraction procedure proposed by the Commission of the European Communities Bureau of (Tokaliog\u02d8 lu

et al., 2000). The two soils possessed much lesser amounts

of Mn, and the Fe concentration in the EPK kaolin was higher than that in Hadong clay, while the concentration of Ca indicated contrary tendency.

Phenanthrene was selected to be a representative
PAH compound, and has an aqueous solubility of
1.1 mg l
\u00c01and a logKow of 4.57 at 25\u00b0C (Schwarzen-
bach et al., 1993). The electrolyte was supplied from
the anode part and composed of 0.01 N H2SO4for pH
control and 7% H2O2for oxidation.
2.2. Electrokinetic reactor
The electrokinetic reactor was set up as shown in
Fig. 2. The reactor was divided into four parts: two elec-

trode chambers, an electrolyte reservoirs and a soil cell. The electrokinetic cell used for the tests was 8 cm in dia- meter and 20 cm long, and made of Plexiglas. Seven pas- sive electrodes were inserted into the soil cell and graphite electrodes of disk shape were placed in contact with the chambers. The electrodes were located at each end of the cell so that the electrolyte solution was only in contact with one face of each electrode. A \ufb01lter paper was placed at the end of the soil cell. Each electrolyte chamber occu- pied the space between a porous stone and an electrode. PVC valves were used to control the in\ufb02ow and out\ufb02ow of the solution. The inlet at the bottom of the anode cham- ber was connected to a reservoir containing 2000 ml of

Table 1
Chemical and physical characteristics of soils
Parameter
EPK kaolin
Hadong clay
Major mineral component (XRD)
Kaolinite
Quartz, kaolinite, halloysite
Speci\ufb01c gravity of solid particles (ASTM D 854)a
2.65
2.62
Composition (%) (ASTM D 422)a
Clay
97
55
Silt
3
23
Sand
0
22
Speci\ufb01c surface area (m2g\u00c01)
24.3
25.1
Organic carbon content (%) (Walkley and Black, 1934)
<0.1
<0.1
Cation exchange capacity (%) (US Soil Conservation Service, 1972)
5.5\u20136
10.1\u201310.6
Extractable salts concentration (mg kg
\u00c01)
SO2\u00c0
4(extracted with 0.01 M HCl)
42
13
NO\u00c03(extracted with 0.01 M HCl)
13
44
Cl
\u00c0
(soluble with de-ionized water)
ND
ND
CaO (%) (XRF)
0.18
2.16
Hydraulic conductivity (cm s\u00c01)
2\u00b7 10\u00c08
7\u00b7 10\u00c08
Initial soil pH (500%, water\u2013solid)
5.6
7
aASTM (1996).
Table 2
Distribution of di\ufb00erent iron, manganese and calcium fractions in soils
Fraction
EPK kaolin (mg kg\u00c01)
Hadong clayey soil (mg kg
\u00c01)
Fe
Mn
Ca
Fe
Mn
Ca
Exchangeable and bound to carbonates
69
2
1244
33
15
1249
Bound to Fe- and Mn-oxides
185
0.2
187
89
11
222
Bound to organic substances
44
0.2
64
51
1
319
Residual fraction
3866
7
712
2976
18
9857
Total
4163
10
2208
3147
45
11646
J.-H. Kim et al. / Chemosphere 63 (2006) 1667\u20131676
1669

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