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Dissolution and removal of PAHs from a contaminated
soil using sun\ufb02ower oil
Zongqiang Gonga,b, Kassem Alefc, B.-M. Wilkec,*, Peijun Lia

aInstitute of Applied Ecology, Chinese Academy of Sciences, P.O. Box 417, Shenyang 110016, PR China
bGraduate School of Chinese Academy of Sciences, Beijing 100039, PR China
cInstitute of Ecology, Technical University Berlin, Franklinstrasse 29, D-10587 Berlin, Germany

Received 28 August 2003; received in revised form 25 June 2004; accepted 13 July 2004
Abstract

This study reports on the feasibility of remediation of polycyclic aromatic hydrocarbon (PAH) contaminated soils using sun\ufb02ower oil, an environmentally-friendly solvent. Batch experiments were performed to test the in\ufb02uence of oil/ soil ratio on the remediation of PAH contaminated soil, and to test the mass transfer behaviors of PAHs from soil to oil. An empirical model was employed to describe the kinetics of PAH dissolution and to predict equilibrium concen- trations of PAHs in oil. PAH containing oil was regenerated using active carbon. Results show that dissolution of PAHs from a Manufactured Gas Plant (MGP) soil at oil/soil ratios of one or two were almost the same. Nearly all PAHs (81\u2013100%) could be removed by sun\ufb02ower oil dissolution. Mass transfer coe\ufb03cients for low molecular PAHs namely \ufb02uoranthene, phenanthrene and anthracene were one or two orders of magnitude higher than those for high molecular PAHs with 4\u20136 rings. Ninety milliliters of PAH containing oil could be regenerated by 10 g active carbon in a batch reactor. Such a remediation procedure indicates that sun\ufb02ower oil is a promising agent for the removal of PAHs from MGP soils. However, further research is required before the method can be used for in situ remediation of contaminated sites.

\u00d32004 Elsevier Ltd. All rights reserved.
Keywords:Polycyclic aromatic hydrocarbons; Soil remediation; Vegetable oil; Mass transfer; Equilibrium partitioning
1. Introduction

Many laboratory and \ufb01eld studies have been carried out to date to achieve the cost-e\ufb00ective remediation of hydrophobic organic contaminants (HOCs) in soils

and sediments. Bioremediation by the use of living organisms, has been applied for the removal of organic contaminants, such as PCBs, PAHs, BTEX, TNT from soil (Wang et al., 1990; Macdonald and Rittmann,

1993; Bradley and Chapelle, 1995; Pagano et al., 1995; Tiehm et al., 1997; Daun et al., 1998; Bruns-Nagel et al., 1998; Rockne and Strand, 1998). Unfortunately,

even though bioremediation is one of the most cost- e\ufb00ective technologies, removals of HOCs, especially PAHs and PCBs with high molecular weights, were not e\ufb03cient as expected (May et al., 1997; Cornelissen

0045-6535/$ - see front matter\u00d3 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2004.07.035
*Corresponding author. Tel.: +49 30314 71193; fax: +49
30314 71431.
E-mail address:bmwilke@tu-berlin.de(B.-M. Wilke).
Chemosphere 58 (2005) 291\u2013298
www.elsevier.com/locate/chemosphere
et al., 1998). This was mainly due to their extremely low
solubility and slow desorption into the aqueous phase.

In recent years, many researchers have proposed some novel remediation measures to clean HOC con- taminated soils. The use of surfactants has been applied successfully for removal of soil-bound HOCs (West and

Harwell, 1992; Yeom et al., 1996). Because of political

and environmental reasons the use of surfactants and other chemical solvents has been prohibited in some countries (Dadkhah and Akgerman, 2002). Supercriti- cal \ufb02uid extraction (SFE) is also a technology that has been widely explored when cleaning organic con- taminated soils. CO2and water appear to be the most common \ufb02uids used for SFE (Schleussinger et al.,

1996; Lagadec et al., 2000). However, SFE necessitates

very special materials of construction in addition to the cost of high temperatures and pressures and cannot be used in situ.

With the aforesaid problems in mind, we are trying to \ufb01nd an environmentally-friendly solvent, which has additional advantages of being readily available, non- toxic and low in cost for the e\ufb03cient in situ remediation of Manufactured Gas Plant (MGP) sites heavily con- taminated with polycyclic aromatic hydrocarbons (PAHs). MGPs produced gas by cracking oil or coal and by releasing light hydrocarbons that were used for lighting and household needs. MGP sites exist com- monly in many countries. At MGPs that use coal, the primary residual carbon was pyrolyzed coal particles. At MGPs that use oil, a \ufb01ner organic carbon residue similar to lampblack soot was produced. In both cases, the primary organic pollutants of concern are PAHs (Hawthorne et al., 2002). Residual PAHs-containing material, either mixed in soils or sediments or occurring as a discrete phase, can also lead to the long-term desorption and dissolution of PAHs into groundwater (Haeseler et al., 1999). A number of chemical solvents have been explored to extract PAHs from contaminated soil aiming for soil remediation rather than analysis (Khodadoust et al., 2000; Rababah and Matsuzawa,

2002). The advantages of using vegetable oil as nontoxic,

inexpensive, and e\ufb00ective solvent for extraction of poly- chlorinated dibenzo-p-dioxins and dibenzofurans have been reported byIsosaari et al. (2001). The safety of \ufb01eld applications was also demonstrated in their report. To our knowledge, the possibility of using vegetable oil to remove PAHs from weathered MGP soils has not been investigated yet.

The objectives of this study were: (a) to determine dissolution of individual PAHs from a weathered MGP soil by the use of sun\ufb02ower oil; (b) to investigate the e\ufb00ects of PAH molecular weight and contact time on the transport and removal rates of PAHs; (c) to test the in\ufb02uence of oil/soil ratio on the removals of PAHs from soil; (d) to regenerate PAH containing oil for re- cycling purpose using activated carbon.

2. Materials and methods
2.1. Soil sample

A sandy soil (95.6% sand, 0.6% silt, 3.8% clay) was collected from a former MGP site historically contami- nated with PAHs. It was sieved to <2 mm to break soil clumps and to remove rocks and was then mechanically mixed to ensure homogeneity. The \ufb01eld moist soil was stored at 4\u00b0C for further experiments. The soil had a pH of 6.6 (measured in 0.01 M CaCl2) and an organic carbon content of 4.6%. It contained 5450 mg PAH kg

\u00c01soil. Concentrations of individual PAHs are given

inTable 1. Homogeneity of the soil was veri\ufb01ed by par- allel extraction. With exception of naphthalene standard deviations of PAH concentrations in the soil varied be- tween 2% and 11% (Table 1).

2.2. Solubilization of soil-bound PAHs using sun\ufb02ower oil

Extraction of PAHs from the MGP soil using sun- \ufb02ower oil was investigated in batch experiments. In our preliminary experiments we tested three di\ufb00erent oils, i.e., sun\ufb02ower oil, rape oil and soybean oil. Results showed that the three oils had the same extraction e\ufb03- ciency (Alef et al., 2003a). Sun\ufb02ower oil was chosen for further investigation because it was the cheapest one. To test mass transfer rates of PAHs from soil to sun\ufb02ower oil, 150 ml sun\ufb02ower oil was poured into a glass bottle, which contained 150 or 75 g MGP soil. The bottles were sealed and mechanically shaken at 200 rpm on an orbital shaker. After 5, 15, 50 min and 1, 3, 7 d, the soil suspensions were settled for 5 min and an aliquot of oil sample was withdrawn into a 4- ml vial for future analysis.

2.3. Modeling the dissolution kinetics of PAHs from
MGP soil

In order to describe the kinetics of PAHs dissolution, an empirical \ufb01rst order model was employed. This model can be used when dissolution (or desorption) arises out of equilibrium partitioning and mass transfer phenom- ena take place between two phases, one of which is a liq- uid phase and the other is a solid phase. The theoretical basis of this model is that at equilibrium, there is no net transfer between two phases and partition coe\ufb03cients can be used to represent the ratio of the concentration of the same chemical species in two phases. Relative con- centrations of PAHs between two distinct phases pro- vide an explicit measure of the propensity of PAHs to exist in each phase. In this study, the kinetics of PAH dissolution and equilibrium was plotted, and mass trans- fer theory was used to derive \ufb01rst-order mass transfer coe\ufb03cients and equilibrium oil phase concentration by \ufb01tting the data to

292
Z. Gong et al. / Chemosphere 58 (2005) 291\u2013298
C0\u00bc Ce\u00bd1 \u00c0exp\u00f0\u00c0kt\u00de\u008a

whereC0 is the PAH concentration of the oil phase at timet,k is the lumped mass transfer coe\ufb03cient,Ceis the equilibrium oil-phase concentration andt is the con- tact time with oil (Woolgar and Jones, 1999). Fitting of the data to the equation was achieved using a nonlinear curve \ufb01tting of software Sigma.

2.4. Feasibility of sun\ufb02ower oil regeneration

The feasibility of oil regeneration was investigated using activated carbon to adsorb PAHs from used oil by means of batch experiment in an Erlenmeyer \ufb02ask (250 ml nominal volume). A total of 90 ml used oil was poured into a 250-ml Erlenmeyer \ufb02ask, to which 10 or 20 g activated carbon was added, a \ufb02ask without activated carbon served as a control. The Erlenmeyer \ufb02asks were placed upright on the \ufb02at bed orbital shaker rotating at 150 rpm for 24 h. The suspensions were set- tled and oil samples were taken and \ufb01ltered through glass membrane for PAH analysis.

2.5. Methods for analyses of contaminated soil and oil
samples

PAHs in soil samples were extracted by a mechanical chemical extraction procedure proposed by VDLUFA. The method was most suitable for extraction of PAHs from highly contaminated soils (Song et al., 2002). Recovery rates varied between 43.1% for Naphthalene and 95% for Benzo(k)\ufb02uoranthene. Fifteen grams so- dium chloride, 100 ml deionized water, 200 ml acetone and 150 ml dichloromethane were added to 10 g soil in

a glass bottle. The bottle was sealed with Te\ufb02on screw cover, placed on the orbital shaker and shaken at 200 rpm over 16 h. After the separation of organic and water phases, an aliquot of organic phase was cleaned in a chromatography column \ufb01lled with 3 g deactivated aluminum oxide (deactivated by 15% water addition) and 5 g activated silica gel (70\u2013230 mesh, activated by oven-heating at 130\u00b0C for 16 h and cooled in a desicca- tor at least for 10 min before use) and 4 spoons of anhy- drous sodium sulphate. The chromatography column was eluted with 100 ml 4:1 hexane:dichloromethane (v:v). The eluate was concentrated by rotary evaporator and dried by a stream of nitrogen gas and \ufb01nally dis- solved in acetonitrile for HPLC analysis.

The oil sample was dissolved in petroleum ether and cleaned up in a chromatography column \ufb01lled with 10 g activated silica gel (activated under the same conditions as described above), and 4 spoons of anhydrous sodium sulphate. The chromatography column was eluted with 100 ml 2:1 toluene:petroleum ether (v:v). An aliquot of elution was taken and was then dried by nitrogen gas, and \ufb01nally dissolved in acetonitrile for HPLC analysis. The procedure was described byAlef et al. (2003b). Recovery rates varied between 82.5% for Napththalene and 105.6% for Fluoranthene. Standard deviations of three replicates were 3.5 mg kg\u00c01at a total concentra- tion of 2925 mg kg\u00c01.

2.6. HPLC analysis

PAH analysis was performed with an HPLC equipped with a gradient pump (KNAUER K1001), an autosampler (TSP AS100), and a reverse-phase

Table 1
PAH concentrations in the MGP soil
PAHs
Water solubility (mg/l)a
logKow
a
PAH in soil
Conc (mg/kg)
Sd(%)
Naphthalene
30
3.37
5.7
101.8
Acenaphthylene
3.47
4.33
175.8
2.7
Acenaphthene
3.93
4.07
550.4
3.7
Fluorene
1.98
4.18
291.7
2.9
Phenanthrene
1.29
4.46
1111.6
6.7
Anthracene
0.07
4.45
147.1
4.1
Fluoranthene
0.26
5.33
519.8
6.8
Pyrene
0.14
5.32
1312.4
2.8
Benz(a)anthracene
0.014
5.61
278.4
6.7
Chrysene
0.002
5.61
239.1
2.6
Benzo(b)\ufb02uoranthene
0.0012
6.57
117.3
5.1
Benzo(k)\ufb02uoranthene
0.0006
6.84
72.2
6.9
Benzo(a)pyrene
0.0038
6.04
301.9
2.4
Dibenz(ah)anthracene
0.0005
6.5
51.9
8.5
Benzo(ghi)perylene
0.00026
7.1
200
10.8
Indenopyrene
0.062
7.66
77.8
10.4
Sum of PAHs
5453.2
aAccording toTiehm et al. (1997) and Sim and Overcash (1983).
Z. Gong et al. / Chemosphere 58 (2005) 291\u2013298
293

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