This document presents a research project on the synthesis and characterization of a magnetite-magnesium sulfate-sodium dodecyl sulfate-clay composite for remediating crude oil polluted soil. The research involved sampling polluted soil, synthesizing the composite and its constituents, characterizing the materials, using the composite to treat the soil, and analyzing the effectiveness of treatment. Results showed the composite has a porous structure and is effective at decreasing concentrations of petroleum pollutants like BTEX and PAHs in the soil over time, with degradation increasing with higher composite concentrations. The composite performed better than its individual constituents, indicating it is a promising material for crude oil soil remediation.

1. SYNTHESIS AND CHARACTERIZATION OF MAGNETITE-MAGNESIUM
SULPHATE-SODIUM DODECYL SULPHATE - CLAY FOR REMEDIATION OF
CRUDE OIL POLLUTED SOIL
PRESENTED
BY
NKIN, GIFT KIISI
PG:2020/00731
SUPERVISORS:
DR. J. L KONNE and DR. O. M AKINFOLARIN
1
JUNE, 2023

2. OUTLINE
 INTRODUCTION
 AIM AND OBJECTIVES
 JUSTIFICATION OF STUDY
 LITERATURE REVIEW
 METHODOLOGY
 RESULTS AND DISCUSSION
 CONTRIBUTIONS TO KNOWLEDGE
 CONCLUSION
 REFERENCES
2
DEPARTMENT OF CHEMISTRY, RIVERS STATE
UNIVERSITY

3.  Dr. J. L. Konne and Dr. O. M. Akinfolarin: Supervisors
 Prof. N. Boisa and all the lecturers in the Department of Chemistry: Head of Department and
staff.
Mr. D. Bekee, Mr. Emmanuel Dornubari Iyor and Mr. Chinedu Enyindah: Technologist
Mr. Sunday Nwaagor, Mr. Nkin Bariyaradum Lincoln, Mrs. Nkin Doris Akunna: Parents, siblings
and friends.
God almighty: For his protection, good health, and enablement to execute this research.
DEPARTMENT OF CHEMISTRY 3
ACKNOWLEDGEMENT

4. INTRODUCTION
 Crude oil exploitation in Nigeria has triggered prodigious damage to the ecosystem, most
especially in the Niger-Delta Region (Kadafa, 2012).
 Soil pollution caused by the petroleum industries occur as a result of accidents involving oil
drilling, transportation and storage (Wang et al., 2017).
 Common soil pollutants associated with petroleum industries include; Total Petroleum
Hydrocarbons(TPHs), Polycyclic Aromatic Hydrocarbons(PAHs), Benzene, Toluene, Ethylbenze
and Zylene(BTEX) amongst others (Constantin et al., 2018).
 Crude oil polluted soil is dangerous to human health, flora and fauna (Esin et al., 2011).
Therefore, for the normal functioning of ecological and biological system in the region of oil
production, there is a need for efficient remediation and utilization (Esin et al., 2011).
4
DEPARTMENT OF CHEMISTRY

5.  Crude oil polluted soil can be remediated using different technologies but the
application of composite is one of the effective and current remediation technologies.
 It offers advantages such as, faster transformation kinetics, larger surface area for
adsorption, better penetration and most importantly, possibility of in-situ treatment
(Xiaoming et al., 2021).
5
INTRODUCTION CONT’D

6. AIM AND OBJECTIVES
AIM
To Synthesize Magnetite -Magnesium sulphate –Sodium dodecyl sulphate-Clay for remediation of Crude
Oil polluted Soil.
OBJECTIVES
Sampling, air drying, sieving and apportioning of crude oil polluted soil for treatments.
Synthesis of each constituents of the composite(Fe3O4, MgSO4.7H2O, SDS-Clay).
Characterization of each constituents and the composite using XRD, XRF, FTIR and SEM for the
composite only.
Remediation of the crude oil polluted soil using the composite and the constituents.
Monitoring the level of remediation by testing for parameters such as Total Petroleum
Hydrocarbons(TPHs), Polycyclic Aromatic Hydrocarbons(PAHs) and Benzene, Toluene, Ethylbenzene and
Xylene(BTEX) on the crude oil polluted soil control experiment and the treated samples.
DEPARTMENT OF CHEMISTRY 6

7. JUSTIFICATION OF STUDY
Crude oil pollution has become a major problem in the environment. It is dangerous to
human health, fueling climate change, poisoning soil dwelling organisms amongst others.
However, physical and chemical approaches for its remediation are in use but most of
these methods are less-effective, costly and non-environmental friendly.
The application of Magnetite-magnesium sulphate-sodium dodecyl sulphate clay
composite that is ecofriendly, though not yet been reported in the available literature will
be investigated in crude oil remediation in this research work.
DEPARTMENT OF CHEMISTRY 7

8. REVIEW STUDIES
8
TITLE FINDINDS STRENGHTS LIMITATIONS RECOMMENDATIONS REFERENCES
Surfactants
treatment of
crude oil
contaminated
soil
The surfactants were found to
have considerable potential
in removing crude oil from
different contaminated soils.
The removal of crude oil with
either rhamnolipid or SDS was
within the repeatability range
of ± 6%.
The most
influential
parameters on
oil removal were
surfactant
concentration
and washing
temperature.
Low crude oil
removal was
achieved.
The study
recommended that, two
or more materials
should be combined
with surfactants so as
to achieve high level of
crude oil removal.
Kingsley et
al., 2004.
Application of
Biochar in the
remediation
of
contaminated
soil with high
concentration
of lead and
zinc.
The results showed that after
56 days curing, the biochar
treated soil had a neutral PH
and EC value and higher soil
fertility compared with the PC
treated
soil.
It was observed
that the biochar
was more
effective than
Portland cement
(PC) on heavy
metal
immobilization
The period
of curing was
just 56 days.
Extension of curing
period was
recommended
Xiaoming
zhao et al.,
2021.

9. DEPARTMENT OF CHEMISTRY 9
TITLE FINDINDS STRENGHTS LIMITATIONS RECOMMENDATION REFERENCES
Nanomaterial
s for
remediation
of petroleum
contaminated
soils & water.
The report suggested that
the use of nanocomposites
materials presents Interesting
alternative to the existing
remediation technologies.
A wide treatable
range of
contaminants and
faster
transformation
kinetics
Repeated
applications
may be needed
The study
Recommended that
more research should
be conducted on
nanocomposite
material in
remediation
Jude,
2017.
Bentonite
composite: a
potential
immobilizing
agent of
heavy
metals in soil
The results showed that the
desorption percentage of
metals from the composite
treated soil was significantly
lower than the untreated
contaminated soil. The finding
indicated that immobilization
of heavy metals in soils could
be achieved by the chitosan
bentonite, which would
potentially be an inexpensive
and sustainable
environmental
remediation technology
The study
demonstrated
the usefulness
of biopolymer
composite in
removing
metals from
aqueous
solutions by
adsorption
mechanism.
Kumararaja,
2018.
REVIEW STUDIES CONT’D

10. METHODOLOGY
10

11. B
11
Filtration of Magnitite Recrystalization of MgSO4 Filtration of SDS clay
Remediation of crude oil polluted soil
Air drying of crude oil
polluted soil
Characterization of Composite and constituents.
A Thermoscientific Diffractometer

12. RESULTS
12
A B
C D
Fig 1: Surface morphologies of Magnetite-magnesium sulphate-sodium dodecyl sulphate clay composite
(A) 50 µm (B) 80µm (C) 100 µm (D) 200 µm
A B
D
C

15. 15
FIG 10: XRF OF THE ELEMENTAL COMPOSITION OF MAGNETITE-MAGNISIUM SULPHATE-SODIUM DODECYL SULPHATE CLAY
COMPOSITE
XRF OF SDS CLAY XRF OF MAGNITITE
MAGNETITE-MAGNISIUM SULPHATE-SODIUM DODECYL SULPHATE CLAY
COMPOSITE
XRF OF MAGNISUM SULPHATE

16. 16
TABLE 1: ELEMENTAL COMPOSITION OF MAGNETITE-MAGNISIUM SULPHATE-SODIUM DODECYL
SULPHATE CLAY COMPOSITE WITH CORRESPONDING CONCENTRATIONS
ELEMENTAL COMPOSITION % CONCENTRATION
Fe2O3 18.428%
SiO2 13.168%
SO3 12.827%
MgO 10.74%
Al2O3 4.612%
MnO 1.1209%
TiO2 0.3345%
P2O2 0.2653%
K2O 0.1241%
ZrO2 0.02139%
V3O5 0.0156
ZnO 0.01479
As2O3 0.0076%
Cr2O3 0.00388
CuO 0.00125%
EU2O3 0.000066%

17. FIG 11: BTEX CONCENTRATIONS WITH VARYING PERCENTAGES OF COMPOSITE IN 7 DAYS
REMEDIATION
17
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0% 2% 4% 6% 8% 10%
BTEX
CONCENTRATION
(PPM)
VARYING PERCENTAGES OF COMPOSITE
Benzene
Toluene
Ethylbenzene
O-Xylene
P-Xylene

18. 18
FIG 12: PAHs CONCENTRATIONS WITH VARYING PERCENTAGES OF COMPOSITE IN 7 DAYS
REMEDIATION
0
0.5
1
1.5
2
2.5
3
0% 2% 4% 6% 8% 10%
PAHs
Concentration
(PPM)
Varying Percentages of Composite
Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene
Fluoranthene Pyrene Benzo[a]anthracene Chrysene Benzo[b]fluoranthene Benzo[k]fluoranthene

19. 19
FIG 13: PAHs CONCENTRATIONS WITH VARYING PERCENTAGES OF COMPOSITE IN 14 DAYS
REMEDIATION
0
0.5
1
1.5
2
2.5
3
0% 2% 4% 6% 8% 10%
PAHs
Concentration
(ppm)
Varying Percentages of Composite
Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene
Fluoranthene Pyrene Benz[a]anthracene Chrysene Benzo[b]fluoranthene Benzo[k]fluoranthene

20. DEPARTMENT OF CHEMISTRY 20
FIGURE 14: % EFFICIENCY OF PAHs DEGRADATION IN 7 & 14 DAYS
0
37.46
68.8
78
86 87
0
81
91 92
97 99
0
20
40
60
80
100
120
0% 2% 4% 6% 8% 10%
Percentage
Efficiency
of
Degradation
Varying Percentages of Composite
PAHs 7 DAYS PAHs 14 DAYS

21. DEPARTMENT OF CHEMISTRY 21
FIGURE 15: % EFFICIENCY OF TPHs DEGRADATION IN 7 AND 14 DAYS REMEDIATION
0
12
19
24
29
35
0
86 88 90 91 92
0
10
20
30
40
50
60
70
80
90
100
0% 2% 4% 6% 8% 10%
Percentage
Efficiency
of
Degradation
Varying Percentages of Composite
TPHs 7 DAYS TPHs 14 DAYS

22. DEPARTMENT OF CHEMISTRY 22
0
5
10
15
20
25
30
35
40
10% MAGNESIUM SULPHATE 10% MAGNETITE 10% SDS CLAY
TPHs
CONCENTRATION
(PPM)
10% OF CONSTITUENTS OF COMPOSITE
7 DAYS 14 DAYS
FIGURE 16: EFFECT OF INDIVIDUAL CONSTITUENTS OF THE COMPOSITE ON TPHs
CONCENTRATION IN 7 AND 14 DAYS REMEDIATION

23. DEPARTMENT OF CHEMISTRY 23
0
1
2
3
4
5
6
10% MAGNETITE 10% SDS CLAY 10% MAGNESIUM SULPHATE
PAHs
CONCENTRATION
(PPM)
7 DAYS 14 DAYS
FIGURE 17: EFFECT OF INDIVIDUAL CONSTITUENTS OF THE COMPOSITE ON PAHs
CONCENTRATION IN 7 AND 14 DAYS REMEDIATION
10% OF CONSTITUENTS OF COMPOSITE

24. DEPARTMENT OF CHEMISTRY 24
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
10% SDS CLAY 10% MAGNETITE 10% MAGNESIUM SUILPHATE
BTEX
CONCENTRATION
(PPM)
7 DAYS 14 DAYS
FIGURE 18: EFFECT OF INDIVIDUAL CONSTITUENTS OF THE COMPOSITE ON BTEX
CONCENTRATION IN 7 AND 14 DAYS REMEDIATION
10% OF CONSTITUENTS OF COMPOSITE

25. DEPARTMENT OF CHEMISTRY 25
FIGURE 19: COMPARISON OF EFFICIENCY OF DEGRADATION OF TPHs, BTEX AND PAHs USING
10% COMPOSITE AND 10% MAGNESIUM SULPHATE, MAGNETITE AND SDS CLAY IN 7 DAYS
37.45
0.02 0.19
20.62
0.13 1.1
35.11
0.15 1.29
17.71
0.11 0.88
57.8
0.29
1.4
0
10
20
30
40
50
60
70
TPHs BTEX PAHs
EFFICIENCY
OF
DEGRADATION
10 % COMPOSITE 10% MAGNESIUM SULPHATE 10% MAGNETITE
10% SDS CLAY 0%(CONTROL)

26. DEPARTMENT OF CHEMISTRY 26
FIGURE 20: COMPARISON OF EFFICIENCY OF DEGRADATION OF TPHs, BTEX AND PAHs
USING 10% COMPOSITE AND 10% MAGNESIUM SULPHATE, MAGNETITE AND SDS CLAY IN
14 DAYS
4.92
0 0.014
17.86
0.11 0.59
32.72
0.12 0.6
15.78
0.04 0.77
57.8
0.29 1.4
0
10
20
30
40
50
60
70
TPHs BTEX PAHs
10 % COMPOSITE 10% MAGNESIUM SULPHATE 10% MAGNETITE
10% SDS CLAY 0% (CONTROL)
EFFICIENCY
OF
DEGRADATION

27. CONCLUSION
 Sampling and preparation of Crude oil polluted soil was successfully done using standard method recommended by the U.S EPA 2016.
 Constituents of the composite were successfully synthesized by standard methods which include Co-precipitation, recrystallization and
calcination.
 Characterization results showed surface morphology of the composite as apparently porous, platy and irregular sized polycrystallites,
elemental composition indicated iron, silica and magnesium oxide peaks as the most prominent, XRD showed crystalline and amorphous
phases denoted by sharp and broad peaks with elevated background and functional groups present were Si-O-Si, SO4
2-, C=O, Fe-OH being
the most prominents.
 The results of remediation showed decrease in the concentration of BTEX, PAHs and TPHs as the concentration of composite increases from
2% to 10%. This could be linked to catalytic effect of the composite which caused sigificant decrease in the concentration of the recalcitrant
TPH from 57.8 to 4.92 ppm which is approximately 92% of degradation in 14 days.
 The efficiency of degradation of BTEX, TPHs, and PAHs increases with increase in the concentration of the composite with respect to time.
DEPARTMENT OF CHEMISTRY 27

28. CONTRIBUTION TO KNOWLEDGE AND RECOMMENDATION
The research showcased a novel eco-friendly composite for the
degradation of BTEX, TPHs and PAHs by Ex-situ remediation of crude oil
polluted soil.
RECOMMENDATION
Use of SDS clay is recommended for remediation of crude oil polluted soil.
Supposing that, the composite is used in Ex-situ remediation, the duration of
remediation and concentration should exceed 14 days and 1g(one gram)
respectively.
DEPARTMENT OF CHEMISTRY 28

29. REFERENCES
Ahmad, A., Zabihollah, Y., Reza, A., Zohre, P.(2022). Measurement of BTEX(Benzene, Toluene, Ethylbenzene and Xylene) Concentration at
gas station .Environmental Health Engineering and Management Journal, 9(1), 23-31.
Ajanta, S., & Dayakar, P. (2007). Identification of Microfabric of Kaolinite Clay Mineral Using X-ray Diffraction Technique. Journal of Geo-
technical and Geological Engineering, 25(6), 603-616.
Buchel, H. K., Dietmar, W. (2000). Industrial inorganic chemistry. John Wiley & Son publishers, Second Edition. ISBN-978-3527-6133-5.
Constantin, S., Diana, M.C., Irina, A.l., & Adrian, A.B. (2018). Decontamination of Petroleum contaminated soils using the Electrochemical
Technique: Remediation Defree and Energy consumption. Scientific Reports,8(1), 32-72.
Damilola, A.K., Asaolu, S.S., Adefemi, S., Ibigbami, O.A., Akinsola, A.F., Marcus, A., Popoola, O.K. (2021). Surfactant Enhancement of Clay
Properties for Heavy Metals Adsorption. Indonesian Journal of Chemistry, 21(4), 825-841.
Dell’Anno, G., Treiber, J. W.G., Partridge, I. K. (2016). Manufacturing of composite parts reinforced through - thickness by tufting. ISSN
073-5845.
Dunia, K.M. (2013). Determinationn of Microstructure Properties of Magnesium sulphate (MgSO4) Thin Film. Material Science Research
Journal of Social Science and Management. ISSN: 2251-1571.
Esin, E.E, & Ayten, K. (2011). Bioremediation of crude oil polluted soils. Asian Journal of Biotechnology, 3(3), 206-213.
Jude, N.C. (2017). Nanomaterials for remediation of petroleum contaminated soils and water. Umudike Journal of Engineering and
Technology, 3(2), 23-29.
Konne, J.L., Obomanu, F.G., Kordah, M.(2019). Application of Caladium-Clay Composite as Oil Spill Treatment Agent in Soil from Bodo Oil
Spill Site. Nigeria Journal of Chemical Research, 24(2), 67-76.
Kumararaja, P., Manjaiah, K.M., Datta, S.C., Ahammed, S. (2018). Bentonite Composite: A potential immobilizing agent of heavy metal in
soil, 25(7), 3985-3999.
Kadafa, A. A. (2012). Environmental impacts of oil exploration and exploitation in the Niger Delta of Nigeria. Global Journal of Science
Frontier Research Environment and Earth Sciences, 12(3), 2249-4626.
29

30. REFRENCES CONT’D
Kingsley, U., & Mehmet, C. (2004). surfactants treatment of crude oil contaminated soil. Journal of colloid and interface Science,
276(2), 456-643.
Kumari, P. (2019). Magnetite Nanoparticules for Environmental Remediation. LAP-Lambert Academic Publisher. ISBN-
6200501289.
Odochian, L. (2010). Study of the nature of the crystallization water in some magnesium hydrates by thermal methods. Journal of
Thermal Analysis and Calorimetry, 45(6), 1437-1448.
Paria, S. (2008). Surfactant – enhanced remediation of organic contaminated soil and water. Advances in colloid and interface
science, 138(1), 24-58.
Rosen, M. J., KujappAu, J.T. (2012) Surfactants and interfacial Phenomena. John Wiley & Sons Publishers Fourth Edition ISBN-
978-1-118-22902-6.
Sharma, p., Kumar, R., Chauhan, S., Singh, D., & Chauhan, M.S. (2014). Facile Growth and Characterization of Alpha-Fe2O3
Nanoparticles for Photocatalytic Degradation of Methyl Orange. Journal of Nanoscience and Nanotechnology,14(6), 6153-6157.
Waterman, P. J. (2007). The life of composite materials. desktop Engineering magazine, 41(10), 66-192.
U.S. EPA. (2016). In situ Treatment Technologies for contaminated soil; Engineering Forum issue paper EPA 542/F – 061016.
Wang, S., Yan, X., Lin, Z., Jishi, Z., Namkha, N., & Wei, L. (2017). The harm of petroleum – polluted soil and its remediation
research. AIP Conference Proceedings, 1864(1), 020222.
Xiaoming, Z., Binbin, Y., Yuan, L., Dongqi, T., & Dongdong, L. (2021). Application of Biochar in the Remediation of contaminated
Soil with High concentration of lead and Zinc. Advances in Civil Engineering, 21(5), 1-7.
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31. THANK YOU
FOR
LISTENING.
31