Accepted Manuscript

Decontamination of petroleum-contaminated soil via pyrolysis under carbon dioxide

atmosphere

Youkwan Kim, Jeong-Ik Oh, Sang Soo Lee, Kyun Ho Lee, Jechan Lee, Eilhann E.
Kwon

PII: S0959-6526(19)32580-6
DOI: https://doi.org/10.1016/j.jclepro.2019.117724
Article Number: 117724
Reference: JCLP 117724

To appear in: Journal of Cleaner Production

Received Date: 1 April 2019

Revised Date: 13 July 2019
Accepted Date: 20 July 2019

Please cite this article as: Kim Y, Oh J-I, Lee SS, Lee KH, Lee J, Kwon EE, Decontamination of
petroleum-contaminated soil via pyrolysis under carbon dioxide atmosphere, Journal of Cleaner
Production (2019), doi: https://doi.org/10.1016/j.jclepro.2019.117724.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
 ACCEPTED MANUSCRIPT

Decontamination of Petroleum-contaminated Soil via Pyrolysis under

Carbon Dioxide Atmosphere

Youkwan Kima,1, Jeong-Ik Ohb,1, Sang Soo Leec, Kyun Ho Leed, Jechan Leee,*, Eilhann E. Kwona,*

PT
a

RI
Department of Energy and Environment, Sejong University, Seoul 05006, Republic of Korea
b
Advanced Technology Department, Land & Housing Institute, Daejeon 34047, Republic of Korea

SC
c
Department of Environmental Engineering, Yonsei University, Wonju 26493, Republic of Korea
d
Department of Aerospace Engineering, Sejong University, Seoul 05006, Republic of Korea

U
e
Department of Environmental and Safety Engineering, Ajou University, Suwon 16499, Republic of Korea
AN
Abstract
M

Accidental leakage and/or spillage of crude oil contaminates soil occurring during petroleum

extraction, which can have harmful effects both on the environment and human beings. Therefore,
D

petroleum-contaminated soil needs to be effectively decontaminated. As a study of thermal remediation of

TE

petroleum-contaminated soil, a real soil sample contaminated with petroleum was pyrolyzed at different
EP

pyrolysis conditions. In particular, carbon dioxide (CO2) was used as the pyrolysis medium for effective

thermal remediation of the petroleum-contaminated soil. At temperatures above 620 °C, pyrolytic gas
C

evolution patterns obtained in CO2 condition were distinguishable from those obtained in N2 condition;
AC

the generation of carbon monoxide (CO) was observed. The formation of CO at temperatures higher than

620 °C might be a clue about the role of CO2 in pyrolysis of the petroleum-contaminated soil in that CO2

helps form CO via reactions between CO2 and volatile species evolved from the petroleum hydrocarbons

deposited on the soil during the pyrolysis. For further investigating the effect of CO2 on the pyrolysis,

1
These authors are co-first authors because they contributed equally to this work.
*
Corresponding authors: Jechan Lee (jlee83@ajou.ac.kr); Eilhann E. Kwon (ekwon74@sejong.ac.kr)
 ACCEPTED MANUSCRIPT

two-stage pyrolysis of the petroleum-contaminated soil was conducted. The CO evolution also occurred

in the CO2 condition during the two-stage pyrolysis at >210 °C. The different compositions of pyrolytic

oil obtained from the pyrolysis in N2 and CO2 were identified in that the formation of polycyclic aromatic

hydrocarbons was restricted by the consuming the source of carbon. The pyrolysis operated under CO2

PT
atmosphere would be an effective decontamination method to treat petroleum-contaminated soil.

RI
Keywords: soil remediation; decontamination; petroleum; pyrolysis; CO2 utilization

SC
1. Introduction

U
Soil can be contaminated with petroleum hydrocarbons by oil spillage and/or leakage from industrial
AN
activities (Abbasian et al., 2016). The spilling petroleum substances increase the amount of organic

carbon and decrease the phosphorus availability (Ogboghodo et al., 2004). The petroleum hydrocarbons
M

spilled on the ground also coat surface of the soil, making it impermeable (Osuji and Nwoye, 2007). The

impermeable coating on the soil surface leads not only to poor water circulation in the soil but also to
D

impaired gas exchange between air and the soil, which makes the soil anaerobic (Streche et al., 2018). In
TE

the anaerobic soil, the number of bacteria and their metabolic activity decrease, and plant roots are

suffocated, thereby leading to ecological imbalances (Streche et al., 2014). Petroleum hydrocarbons such
EP

as BTEX (benzene, toluene, ethylbenzene, and xylene) contaminating soil can also pollute groundwater,

which have harmful effects on human health (Yang et al., 2005). In addition, some volatile hydrocarbons
C
AC

can evaporate and be released into the atmosphere (Shi et al., 2015). Hence, remediation of the petroleum-

contaminated soil is a critical issue in the field of environmental protection in organizational financial

aspects (Streche et al., 2018).

Even though different methods to treat petroleum-contaminated soil exist (e.g., extraction (Ávila-

Chávez and Trejo, 2010), washing (Li et al., 2016), thermal desorption (Lee et al., 1998), and chemical

oxidation (Lu et al., 2010)), most of the methods used expensive reagents that can remain in the soil.
 ACCEPTED MANUSCRIPT

Toxic pollutants (e.g., polycyclic aromatic hydrocarbons (PAHs)) possibly contained in the petroleum-

contaminated soil are merely transferred, thereby requiring post-treatments (Li et al., 2018). In addition,

some petroleum hydrocarbons (e.g., heavy oil) have high viscosity (Liu and Fan, 2002), low volatility

(Bennett et al., 2019), and low bioavailability and biodegradability (Cai et al., 2016) which also make the

PT
removal of the contaminants from the contaminated soil more difficult. Therefore, the development of

effective petroleum-contaminated soil remediation technique is highly necessary.

RI
Thermal treatment methods are known to be effective at remediating soils contaminated with organic

compounds, including incineration (Bucala et al., 1994), thermal desorption (Falciglia et al., 2011), and

SC
pyrolysis (Li et al., 2018; Vidonish et al., 2016). Among these methods, pyrolysis has received increasing

U
attention because it is a proven technology to remove highly toxic persistent organic species (Li et al.,
AN
2018; Vidonish et al., 2016). For example, Li et al. pyrolyzed a simulated petroleum-contaminated soil at

500 °C for 30 min to remove total petroleum hydrocarbons (TPH) from the soil with a residual TPH of
M

<0.4 mg g−1 (Li et al., 2018). Vidonish et al. reported that the fertility of an artificial petroleum-

contaminated soil can be enhanced after pyrolysis treatment at 420 °C for 3 h (Vidonish et al., 2016).
D

However, soils collected from the field where petroleum is spilled are more difficult to remediate than
TE

simulated petroleum-contaminated soils because recalcitrant fraction and strong bonding of hydrocarbons

are dominant in the real petroleum-contaminated soils (Khan et al., 2018; Trindade et al., 2005). In
EP

addition, the pyrolysis of petroleum-contaminated soils previously reported was conducted for long

retention time which may lead to high energy consumption. Therefore, it is imperative to develop a
C
AC

pyrolysis treatment method of real petroleum-contaminated soil with a high thermal efficiency.

Pyrolysis is to transform carbonaceous substances to useful products under deliberate oxygen-free

conditions. The products can be combustible pyrolytic gases (e.g., carbon monoxide (CO), hydrogen (H2),

and methane (CH4)), liquid oil (e.g., bio-oil), and solid char (Lee et al., 2019). However, pyrolysis is an

endothermic process, thereby being energy-intensive (Cheung et al., 2011; Kim et al., 2019). It has been

demonstrated that pyrolysis operated in carbon dioxide (CO2) environment is more effective to recover
 ACCEPTED MANUSCRIPT

energy from complicated carbonaceous feedstocks than pyrolysis operated in typical inert condition (i.e.,

nitrogen (N2)), which can make pyrolysis less energy-intensive (i.e., high thermal efficiency) (Kwon et al.,

2019). Considering that petroleum contains large hydrocarbons (Brown et al., 2017), the carbons

contained in petroleum-contaminated soil might be recovered as fuels.

PT
In this regard, we hypothesized that the pyrolysis under a CO2 condition is effective to decontaminate

petroleum-contaminated soil simultaneously with recovering energy from the carbonaceous contaminant.

RI
The aim of this work was to prove the feasibility of remediation of petroleum-contaminated soil via

pyrolysis operated in CO2. The petroleum-contaminated soil was pyrolyzed under different conditions to

SC
study the effects of pyrolysis conditions on the soil decontamination by characterizing pyrolytic products.

U
AN
2. Materials and methods

2.1. Materials and chemicals

M

Petroleum-contaminated soil was collected from the field where petroleum spilled in Kuwait. The N2

and CO2 gases was purchased from AirTech Korea. Dichloromethane (≥99.8%) for the extraction of
D

petroleum from the contaminated soil was purchased from Sigma-Aldrich.

TE

2.2. Thermogravimetric analysis of petroleum-contaminated soil

EP

Thermogravimetric analysis (TGA) of the petroleum-contaminated soil was conducted using a

Netzsch STA 449 F5 Jupiter TG analyzer. The loading of the petroleum-contaminated soil was 10 (±0.02)
C
AC

mg. Mass flow controllers (MFCs) were equipped with the TGA unit, which maintained the flow rate of

N2 or CO2 (used as a purge gas) as 70 mL min−1. Prior to a TGA experiment, a blank experiment without

loading a sample was performed to exclude buoyancy effects from density variations of purge gas during

the TGA test. The TGA tests of the petroleum-contaminated soil were conducted from 25 to 900 °C at a

heating rate of 10 °C min−1.

 ACCEPTED MANUSCRIPT

2.3. Pyrolysis of petroleum-contaminated soil

In this study, one-stage pyrolysis and two-stage pyrolysis were conducted separately. Figure 1a

schematically described the one-stage pyrolysis reactor setup. A 0.6 m-long quartz tube (inner diameter:

22 mm and outer diameter: 25 mm) was employed as a tubular reactor. Ultra-Torr vacuum fittings (SS-4-

PT
UT-6-600, Swagelok) were employed to connect inlet (feeding N2 or CO2 gas) and outlet (product

samples). The 0.6 m-long quartz tube was placed in a tubular furnace (FT-830, DAIHAN Scientific)

RI
equipped with a temperature controller, inside which a thermocouple was located to monitor the increase

in pyrolysis temperature (ramping rate: 10 °C min−1). For an experiment using the one-stage setup, the

SC
petroleum-contaminated soil of 1 g was used (loaded in a combustion boat and the sample-loaded boat

U
was put in the center of the furnace). AN
Figure 1b schematically described the one-stage pyrolysis reactor setup. A 1.2 m-long quartz tube

(inner diameter: 22 mm and outer diameter: 25 mm) was employed as a tubular reactor. Ultra-Torr
M

vacuum fittings which were same as used for the one-stage setup were used to connect inlet and outlet.

For the two-stage setup, two tubular furnaces were put in series (the 1.2 m-long quartz tube placed inside
D

the two furnaces in succession), which allowed to make two different heating zones. The first heating
TE

zone was a temperature-ramping zone with a ramping rate of 10 °C min−1. The second heating zone was

maintained at 680 °C for an isothermal zone. Two thermocouples were located inside the quartz tube to
EP

monitor temperatures in the two zones. For an experiment using the two-stage setup, the petroleum-

contaminated soil of 1 g was used (loaded in a combustion boat and the sample-loaded boat was put in the
C
AC

center of the first furnace).

For both reactor setup, the stream from the reactor outlet was passed through three condensers

maintained at −20 °C using a chiller to condense organic species (i.e., liquid pyrolytic products). The non-

condensable gases (i.e., gaseous pyrolytic products) were then either vented or analyzed using a micro-gas

chromatography (GC). The N2 or CO2 gas was fed into the tube during pyrolysis using separate Brooks

Instrument 5850E MFCs (gas flow rate: 500 mL min−1).

 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M

Figure 1. Scheme of the (a) one-stage and (b) two-stage pyrolysis reactor setup used in this study
D

2.4. Product analysis

TE

Gaseous pyrolytic products were identified and quantified by a micro-GC (3000A, INFICON)

equipped with a thermal conductivity detector. Gaseous effluent from the reactor outlet at ambient
EP

temperature was injected into the micro-GC to monitor gaseous products. A molecular sieve (10 m × 0.32
C

mm × 30 µm) was used to separate chemical species contained in the effluent. The column oven
AC

temperature was set to 80 °C for 3 min (run time). The sample inlet and injector temperatures were set to

100 °C. A standard gas mixture composed of H2 (19.97 mol.%), N2 (19.99 mol.%), CH4 (20 mol.%), CO

(20.02 mol.%), and CO2 (20.02 mol%), purchased from RIGAS, was used to calibrate the micro-GC.

Liquid pyrolytic products were analyzed qualitatively by a GC/mass spectrometry (MS) (Agilent

7890B/ALMSCO). The product was separated by an Agilent HP-5MS column (60 m × 0.25 mm × 0.25

µm). Prior to each analysis, the sample was diluted 50-fold by dichloromethane. The column oven
 ACCEPTED MANUSCRIPT

temperature was changed with retention time: the initial temperature was set to 50 °C for 4 min. The

temperature was then increased to 300 °C with a ramping rate of 4 °C min−1. The temperature was held at

300 °C for 15 min. Total analysis time for a sample was 81.5min. The flow rates of gases for the detector

were 25 mL min−1 for N2, 30 mL min−1 for H2, and 400 mL min−1 for air. The sample injection volume

PT
was 1 µL. Detected peaks were matched with the GC/MS database (NIST/Wiley library).

RI
3. Results and discussion

To check the composition of the petroleum contained in the soil sample, we first extracted the

SC
petroleum from the contaminated soil, and the petroleum extract was analyzed using GC/MS. Figure 2

U
shows the result of the GC/MS analysis. As shown in Figure 2, the petroleum extract was largely
AN
composed of large hydrocarbons ranging from C18 to C25.
M
D
TE
C EP
AC

Figure 2. The GC/MS chromatogram obtained from analysis of the petroleum extract from the petroleum-
contaminated soil

Figure 3 presents the results of TGA of the petroleum-contaminated soil in N2, CO2, and air from 20

to 900 °C at a heating rate of 10 °C min−1. The TGA experiments were conducted to characterize thermal
 ACCEPTED MANUSCRIPT

decomposition patterns of the soil. As shown in Figure 3a and b, ~85 wt.% of the soil was remained after

the thermal decomposition of the petroleum-contaminated soil in N2 and CO2. To further confirm this, the

TGA of the soil was conducted in air condition by removing all combustible species contained in the

sample (Figure 3c). Despite the combustion of the petroleum-contaminated soil, the residual mass was

PT
~85 wt.% that is consistent with those in N2 and CO2. This indicates that the petroleum-contaminated soil

used in this study contains inorganic species (e.g., minerals in soil) as ~85 wt.%, and pyrolysis in N2 and

RI
CO2 can remove all organic carbon substances from the soil.

As presented in Figure 3a and b, the effect of CO2 on thermal decomposition of the soil was not

SC
distinguishable at <620 °C. However, at temperatures above 620 °C, the thermal decomposition rate

U
(expressed as DTG curve) under CO2 atmosphere was faster than that under N2 atmosphere. This was not
AN
likely due to the Boudouard reaction because it is initiated above at least 710 °C (Cho et al., 2015).

Considering that the range of temperature from 620 to 710 °C gave off volatile matters (Kwon et al.,
M

2019), the presence of CO2 in the thermal degradation of the petroleum-contaminated soil allowed the

emission of the volatile species to be enhanced. At temperatures higher than 710 °C, an additional mass
D

loss was seen in the thermal degradation of the soil contaminated with petroleum in CO2. The additional
TE

mass loss was due to the Boudouard reaction. Note that the Boudouard reaction is thermodynamically

favorable at temperatures higher than 710 °C (Kwon et al., 2013).

C EP
AC
 ACCEPTED MANUSCRIPT

PT
RI
SC
Figure 3. Thermogravimetric analysis of the petroleum-contaminated soil in N2, CO2, or air condition at a

U
ramping rate of 10 °C min−1 (dotted line: change in residual mass; solid line: differential thermogram
AN
(DTG) curve)

As shown in the TGA results, the existence of CO2 affects the rate of thermal decomposition of
M

organic carbons contained in the petroleum-contaminated soil. We then conducted pyrolysis of the soil in
D

a tubular reactor where a 1-g loading of the soil to monitor the change of pyrolytic gas production as a
TE

function of pyrolysis temperature, as shown in Figure 4.

Both in N2 and in CO2, the generation of H2 was increased with an increase in temperature because
EP

thermal cracking of hydrocarbon species releases H2 via dehydrogenation. The CH4 evolution was

initiated at lower temperatures than the H2 evolution. The CH4 was formed via random bond scissions of
C

the hydrocarbons existing in the petroleum-contaminated soil.

AC

However, the gas evolutions from pyrolysis of the petroleum-contaminated soil in N2 and CO2 were

distinguishable in an aspect of the CO evolution. While no CO generation was seen under the N2

atmosphere, the formation of CO was observed at >620 °C in the CO2 environment (0.04 to 0.06 mole %).

The formation of CO for pyrolysis in CO2 was not attributed from the Boudouard reaction, as discussed

above. It was reported that CO2 serves as an effective carbon scavenger during pyrolysis (Lee et al.,
 ACCEPTED MANUSCRIPT

2017b). This may be because CO2 plays a role in consuming carbons like a carbon scavenger, which is

important in that the use of CO2 helps thermally break down large hydrocarbons into CO (i.e., ease of

decontamination of petroleum-contaminated soil).

PT
RI
U SC
AN
M

Figure 4. Concentrations of pyrolytic gases composed of H2, CH4, and CO produced from the petroleum-
D

contaminated soil via pyrolysis of in N2 or CO2 conducted using the one-stage pyrolysis setup (Figure 1a)
TE

As shown in Figure 4, the formation of CO was only occurring in the presence of CO2. However, the

effectiveness of CO2 was hard to be figured out because volatilization of the major constituents (C18 to
EP

C25) in the petroleum contaminating the soil (Figure 2) was almost completed at <500 °C. For the further
C

study on the mechanistic role of CO2, two-step pyrolysis of the petroleum-contaminated soil in N2 or CO2
AC

environment was conducted. The isothermal temperature of 680 °C was chosen to exclude any effect of

the Boudouard reaction. The concentrations of pyrolytic gases were monitored, as presented in Figure 5.

The overall evolution of H2 and CH4 from the N2 and CO2 environments were similar, consistent with the

results shown in Figure 4. The CO evolution was observed only in the CO2 environment. The formation

of CO in the presence of CO2 was likely ascribed to reactions between CO2 and volatile species generated

during the pyrolysis (Choi et al., 2018). The generation of CO was observed at >210 °C in Figure 5
 ACCEPTED MANUSCRIPT

because the reactions between the volatile species and CO2 were initiated at the isothermal zone (680 °C).

The pyrolysis of petroleum-contaminated soil suggested that employing CO2 may help convert the

petroleum deposited on the soil into light gaseous product such as CO, meaning that the use of CO2

allows to relatively easily remove the petroleum hydrocarbons from the contaminated soil as a form of

PT
CO.

RI
U SC
AN
M
D
TE

Figure 5. Concentrations of pyrolytic gases composed of H2, CH4, and CO produced from the petroleum-
contaminated soil via pyrolysis of in N2 or CO2 conducted using the two-stage pyrolysis setup (Figure 1b).
EP

Note that the change in temperature shown in x-axis was made at the first stage of the setup.
C

For further investigation into the role of CO2 in pyrolysis of the petroleum-contaminated soil, the
AC

pyrolytic oils obtained from the two-stage pyrolysis under N2 and CO2 conditions were analyzed by

GC/MS. The integrated GC/MS peak areas are compared, as presented in Figure S1 and Table 1.

Compositions of the pyrolytic oils obtained from pyrolysis of the petroleum-contaminated soil in the two

different atmospheres (N2 and CO2) were clearly different. Considering the fact that the concentration of

each chemical species in pyrolytic oil is linearly proportional to the peak area, the formation of chemical

species shown in Figure S1 and Table 1 was affected by CO2.

 ACCEPTED MANUSCRIPT

As shown in Table 1, long-chain hydrocarbons such as pentacosane, hexacosane, and heptacosane

were observed in pyrolytic liquid produced via the pyrolysis of the petroleum-contaminated soil in N2. No

such hydrocarbons existed in the liquid product in CO2. This observation along with the experimental

results shown in Figure 5 may indicate that the heavy hydrocarbons (molecular weight: >350 g mol−1) are

PT
cleaved to light gases such as CO under the CO2 atmosphere during the pyrolysis.

The liquid pyrolytic products produced both in N2 and CO2 contained a variety of polycyclic

RI
hydrocarbons (including PAHs). As seen in Table 1, the use of CO2 in the pyrolysis of the petroleum-

contaminated soil led to the formation of polycyclic hydrocarbons and PAHs having relatively low

SC
molecular weights (e.g., indene, naphthalene, and methylnaphthalenes). Except the relatively light

U
polycyclic hydrocarbons and PAHs, the GC/MS peak areas of the polycyclic chemical species in liquid
AN
pyrolytic products obtained in N2 and CO2 were decreased in the presence of CO2. Among the PAHs, 3-

Methylphenanthrene and fluorene were most decreased PAHs (bigger than −30% difference in the
M

GC/MS peak area) for the pyrolysis under the CO2 atmosphere. This phenomenon could be because CO2

impedes the formation of PAHs. In other words, CO2 may block the gas phase addition reaction that
D

enables to form PAHs via cyclization (Lee et al., 2017a). PAHs are toxic and carcinogenic, thereby being
TE

harmful to human health and atmospheric, aquatic, and soil environments (Manzetti, 2013). Therefore, the

emission of PAHs during pyrolysis into the atmosphere can cause a second pollution, the pyrolysis
EP

operated under CO2 condition would be highly preferable.

C
AC

Table 1. Comparison of chemical species in pyrolytic oil obtained from pyrolysis of the petroleum-
contaminated soil in N2 and CO2

GC/MS peak area

Compound % Difference
N2 CO2
Pentacosane 245271 N/D -
Hydrocarbons Hexacosane 648594 N/D -
Heptacosane 316303 N/D -
Polycyclic Indene 722624 2085639 188.6
 ACCEPTED MANUSCRIPT

hydrocarbons Benzo[b]thiophene 614490 867705 41.2

Dibenzothiophene 696216 546841 −21.5
Biphenyl 1773352 1636259 −7.7
Biphenylene 383494 327567 −14.6
Naphthalene 31776164 43750012 37.7
1-Methylnaphthalene 2803457 3267557 16.6

PT
2-Methylnaphthalene 1256148 1477439 17.6
2-Ethylnaphthalene 2826230 2742521 −3.0

RI
1-Phenylnaphthalene 898377 728207 −18.9
Acenaphthene 242248 221013 −8.8

SC
Acenaphthalene 12998556 12804387 −1.5
Anthracene 5428270 4710813 −13.2

U
2-Methylanthracene 382664 313449 −18.1
9-Ehtylanthracene 322697 255595 −20.8
AN
Benzo[a]anthracene 2579293 2233317 −13.4
Phenanthrene 17330820 14819386 −14.5
M

3-Methylphenanthrene 354424 244072 −31.1

4H-
Polycyclic aromatic 1313030 1166297 −11.2
Cyclopenta[def]phenanthrene
D

hydrocarbons
(PAHs) Benzo[c]phenanthrene 704945 559300 −20.7
TE

Pyrene 18597270 16141159 −13.2

3,4-
1005045 856467 −14.8
Dihydrocyclopenta(cd)pyrene
EP

Benzo[a]pyrene 2735144 2239893 −18.1

Indeno[1,2,3,4]pyrene 869654 783483 −9.9
Fluorene 7795988 4736336 −39.2
C

7H-Benzo[b]fluorene 564979 485173 −14.1

AC

Benzo[ghi]perylene 1637910 1333586 −18.6

Chrysene 2437597 2124393 −12.8
Benzo[ghi]fluoranthene 1072670 1065159 −0.7
Benzo[b]fluoranthene 1903958 1668623 −12.4
Benzo[k]fluoranthene 777042 706640 −9.1
Benzo[e]fluoranthene 416862 392470 −5.9
Benzo[j]fluoranthene 1266153 1098246 −13.3
 ACCEPTED MANUSCRIPT

4. Conclusions

In this study, it was recommended pyrolysis under CO2 atmosphere to decontaminate the soil polluted

by petroleum hydrocarbons which are harmful to the environment and human beings as well as to

PT
maximize energy recovery from the soil and to prevent the formation of PAHs during the soil remediation.

To remediate petroleum-contaminated soil, CO2 was employed as a pyrolysis medium in that CO2 played

RI
a role in making the transformation of petroleum hydrocarbons deposited on the soil to CO during the

pyrolysis easy. A discernable observation under CO2 environment was the CO evolution at >620 °C. For

SC
instance, no CO was formed under N2 atmosphere at all temperatures tested, but 0.04~0.06 mole % CO

U
was formed under CO2 atmosphere when using a one-stage pyrolysis setup. For a two-stage pyrolysis
AN
setup, the effect of CO2 on the evolution of CO was more discernible (~0.5 mole % CO was formed). This

observation provided a key clue about the effect of CO2 on pyrolysis of the petroleum-contaminated soil
M

since CO2 may help convert petroleum hydrocarbons into CO. The pyrolytic oil compositions obtained

from the different atmospheres (N2 and CO2) were different because the formation of PAHs was restricted
D

by the converting hydrocarbons to CO in the existence of CO2 during pyrolysis of the petroleum-
TE

contaminated soil. For example, a relative amount of methylphenanthrene and fluorene contained in the

pyrolytic liquid obtained in CO2 environment was 31.1% and 39.2% less than that obtained in N2
EP

environment, respectively. Future works should involve techno-economic analysis of the pyrolysis

process for industrial adoption of the thermal treatment of petroleum-contaminated soil using CO2 and
C
AC

management of the treated soil to further improve the soil fertility.

Acknowledgements

This study was supported by Korea Institute of Geoscience and Mineral Resources (KIGAM) Basic

Research Project (No. 19-3413).

 ACCEPTED MANUSCRIPT

References

Abbasian, F., Lockington, R., Megharaj, M., Naidu, R., 2016. The biodiversity changes in the microbial
population of soils contaminated with crude oil. Current Microbiology 72, 663-670.

Ávila-Chávez, M.A., Trejo, A., 2010. Remediation of soils contaminated with total petroleum
hydrocarbons and polycyclic aromatic hydrocarbons: Extraction with supercritical ethane. Industrial &
Engineering Chemistry Research 49, 3342-3348.

PT
Bennett, B., Jiang, C., Larter, S.R., 2019. Deterioration of oil quality during sample storage: Are stored
reservoir core samples a viable resource for oil viscosity determination? Fuel 245, 115-121.

RI
Brown, D.M., Bonte, M., Gill, R., Dawick, J., Boogaard, P.J., 2017. Heavy hydrocarbon fate and transport
in the environment. Quarterly Journal of Engineering Geology and Hydrogeology 50, 333-346.

SC
Bucala, V., Saito, H., Howard, J.B., Peters, W.A., 1994. Thermal treatment of fuel oil-contaminated soils
under rapid heating conditions. Environmental Science & Technology 28, 1801-1807.

Cai, B., Ma, J., Yan, G., Dai, X., Li, M., Guo, S., 2016. Comparison of phytoremediation,

U
bioaugmentation and natural attenuation for remediating saline soil contaminated by heavy crude oil.
Biochemical Engineering Journal 112, 170-177.
AN
Cheung, K.-Y., Lee, K.-L., Lam, K.-L., Chan, T.-Y., Lee, C.-W., Hui, C.-W., 2011. Operation strategy for
multi-stage pyrolysis. Journal of Analytical and Applied Pyrolysis 91, 165-182.
M

Cho, D.-W., Cho, S.-H., Song, H., Kwon, E.E., 2015. Carbon dioxide assisted sustainability enhancement
of pyrolysis of waste biomass: A case study with spent coffee ground. Bioresource Technology 189, 1-6.
D

Choi, D., Kim, H., Lee, S.S., Nam, I.-H., Lee, J., Kim, K.-H., Kwon, E.E., 2018. Enhanced accessibility
of carbon in pyrolysis of brown coal using carbon dioxide. Journal of CO2 Utilization 27, 433-440.
TE

Falciglia, P.P., Giustra, M.G., Vagliasindi, F.G.A., 2011. Low-temperature thermal desorption of diesel
polluted soil: Influence of temperature and soil texture on contaminant removal kinetics. Journal of
Hazardous Materials 185, 392-400.
EP

Khan, M.A.I., Biswas, B., Smith, E., Naidu, R., Megharaj, M., 2018. Toxicity assessment of fresh and
weathered petroleum hydrocarbons in contaminated soil- a review. Chemosphere 212, 755-767.
C

Kim, S., Tsang, Y.F., Kwon, E.E., Lin, K.-Y.A., Lee, J., 2019. Recently developed methods to enhance
stability of heterogeneous catalysts for conversion of biomass-derived feedstocks. Korean Journal of
AC

Chemical Engineering 36, 1-11.

Kwon, E.E., Jeon, E.-C., Castaldi, M.J., Jeon, Y.J., 2013. Effect of carbon dioxide on the thermal
degradation of lignocellulosic biomass. Environmental Science & Technology 47, 10541-10547.

Kwon, E.E., Kim, S., Lee, J., 2019. Pyrolysis of waste feedstocks in CO2 for effective energy recovery
and waste treatment. Journal of CO2 Utilization 31, 173-180.

Lee, J., Choi, D., Tsang, Y.F., Oh, J.-I., Kwon, E.E., 2017a. Employing CO2 as reaction medium for in-
situ suppression of the formation of benzene derivatives and polycyclic aromatic hydrocarbons during
pyrolysis of simulated municipal solid waste. Environmental Pollution 224, 476-483.
 ACCEPTED MANUSCRIPT

Lee, J., Lee, T., Ok, Y.S., Oh, J.-I., Kwon, E.E., 2017b. Using CO2 to mitigate evolution of harmful
chemical compounds during thermal degradation of printed circuit boards. Journal of CO2 Utilization 20,
66-72.

Lee, J., Sarmah, A.K., Kwon, E.E., 2019. Production and Formation of Biochar, in: Ok, Y.S., Tsang,
D.C.W., Bolan, N., Novak, J.M. (Eds.), Biochar from Biomass and Waste. Elsevier, pp. 3-18.

Lee, J.K., Park, D., Kim, B.-U., Dong, J.-I., Lee, S., 1998. Remediation of petroleum-contaminated soils
by fluidized thermal desorption. Waste Management 18, 503-507.

PT
Li, D.-C., Xu, W.-F., Mu, Y., Yu, H.-Q., Jiang, H., Crittenden, J.C., 2018. Remediation of petroleum-
contaminated soil and simultaneous recovery of oil by fast pyrolysis. Environmental Science &

RI
Technology 52, 5330-5338.

Li, G., Guo, S., Hu, J., 2016. The influence of clay minerals and surfactants on hydrocarbon removal

SC
during the washing of petroleum-contaminated soil. Chemical Engineering Journal 286, 191-197.

Liu, Y., Fan, H., 2002. The effect of hydrogen donor additive on the viscosity of heavy oil during steam
stimulation. Energy & Fuels 16, 842-846.

U
Lu, M., Zhang, Z., Qiao, W., Guan, Y., Xiao, M., Peng, C., 2010. Removal of residual contaminants in
AN
petroleum-contaminated soil by Fenton-like oxidation. Journal of Hazardous Materials 179, 604-611.

Manzetti, S., 2013. Polycyclic aromatic hydrocarbons in the environment: Environmental fate and
transformation. Polycyclic Aromatic Compounds 33, 311-330.
M

Ogboghodo, I.A., Iruaga, E.K., Osemwota, I.O., Chokor, J.U., 2004. An assessment of the effects of crude
oil pollution on soil properties, germination and growth of maize (Zea Mays) using two crude types –
D

Forcados Light and Escravos Light. Environmental Monitoring and Assessment 96, 143-152.

Osuji, L.C., Nwoye, I., 2007. An appraisal of the impact of petroleum hydrocarbons on soil fertility: the
TE

Owaza experience. African Journal of Agricultural Research 2, 318-324.

Shi, Y., Xu, S., Xu, L., Cai, Y., 2015. Distribution, elimination, and rearrangement of cyclic volatile
EP

methylsiloxanes in oil-contaminated soil of the Shengli Oilfield, China. Environmental Science &
Technology 49, 11527-11535.

Streche, C., Badea, A., Istrate, I.A., Cocârţă, D.M., Apostol, T., 2014. Experimental research regarding
C

the application of electro-flushing method on diesel contaminated soils. Present Environment and
Sustainable Development 8, 37-44.
AC

Streche, C., Cocârţă, D.M., Istrate, I.-A., Badea, A.A., 2018. Decontamination of petroleum-contaminated
soils using the electrochemical technique: Remediation degree and energy consumption. Scientific
Reports 8, 3272.

Trindade, P.V.O., Sobral, L.G., Rizzo, A.C.L., Leite, S.G.F., Soriano, A.U., 2005. Bioremediation of a
weathered and a recently oil-contaminated soils from Brazil: a comparison study. Chemosphere 58, 515-
522.
 ACCEPTED MANUSCRIPT

Vidonish, J.E., Zygourakis, K., Masiello, C.A., Gao, X., Mathieu, J., Alvarez, P.J.J., 2016. Pyrolytic
treatment and fertility enhancement of soils contaminated with heavy hydrocarbons. Environmental
Science & Technology 50, 2498-2506.

Yang, X., Beckmann, D., Fiorenza, S., Niedermeier, C., 2005. Field study of pulsed air sparging for
remediation of petroleum hydrocarbon contaminated soil and groundwater. Environmental Science &
Technology 39, 7279-7286.

PT
RI
U SC
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

Highlights

· Enhanced production of CO via using CO2 in pyrolysis of petroleum-contaminated

soil

· Enhanced thermal cracking of volatile species caused by CO2 in the pyrolysis

· Two-stage pyrolyzer to provide a precise observation in effect of CO2 on the

PT
pyrolysis

· Pyrolysis in CO2 would be an effective remediation of petroleum-contaminated soil.

RI
U SC
AN
M
D
TE
C EP
AC