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606)
Solar Photocatalytic Process Design for Decontamination of Crude Oil
Contaminated Soil
S.K. Samdarshi and Bhaskar J. Nath
Department of Energy, Tezpur University, Tezpur-784028, Assam, India.
E-mail drsksamdarshi@rediffmail.com

Abstract:
The photocatalytic decontamination of soil contaminated by crude oil has been investigated in the
presence of Titanium dioxide (TiO2) photocatalyst; TiO2 modified with Ca(OH)2 and a mixture of TiO2 with
activated carbon.
The experiments were performed under natural condition in months of November and December using
solar radiation. The method of preparation of soil samples and photocatalyst samples are presented. The
degradation of oil contaminant has been studied by taking FTIR spectra of the samples. From IR-spectra
the reaction rate constant is determined. Some control parameters have been considered out of
operational and meteorological parameters to carry out orthogonal array experiment required for process
optimization, which gives much reduced variance for the experiment with optimum setting of control
parameters. Analysis of variance and analysis of mean has been used to determine the interaction
between the parameters considered. Signal-to-Noise (S/N) ratio has been identified as the objective
function to optimize the process of decontamination of crude oil contaminated soil.
For the optimization of degradation process of crude oil, four parameters have been selected such as
catalyst type, concentration of oil, time of exposure and catalyst loading. Here we have found that the
catalyst type and catalyst loading are most critical parameters for soil decontamination.
Thus the present work provides method and options to decontaminate soil and to optimize the process of
decontamination. This method scores over conventional method in terms of high efficiency, shorter time
requirement, lower cost, without any secondary pollution to the environment.

1. Introduction:
Currently increasing ecological problems, connected with the presence of oil derivatives in the soil, are
observed especially in Assam oil field in India. These oil derivatives are quite dangerous for the growth of
plants. The impact of oil-contaminated soil on vegetation is both physical and chemical[10, 12]. Also, the
half life of non-volatile component of oil is quite high in contaminated soil. Moreover, due to the
migrational characteristics of these oil derivatives, removing oil pollutants from soil and prevention of
spreading is a tedious job. The conventional methods currently used for the removal of oil derivatives
(such as: combustion, extraction, phytoremediation, bioremediation) are not perfect. Their disadvantages
are: low efficiency, long time process, secondary pollution of environment and high costs [1, 11].
Therefore, it is a necessity to look for a new method for removing oil from soil, which does not have the
drawbacks of and is better than the conventional methods.
Heterogeneous photocatalysis has been successfully tested as an emerging technology for the
decontamination of industrial effluents. The mechanism of this process has been described in detail
elsewhere [5, 13]. It has been mentioned that the active centers on TiO2 semiconductor particles need to
be photo-activated by means of the UV-radiation to give h+/e- couples [6, 7]. Here we are using TiO2 as a
semiconductor photocatalyst and solar energy as an activator of the process of pollutants degradation.
Titanium dioxide can be used as pure or with various additives. In the present study pure TiO2 as well as
modified TiO2 has been used. The presence of Ca(OH)2 with the photocatalyst can change the pH [17],
which is an important factor for photocatalytic degradation. It not only modifies the surface charge in the
catalyst, but also determines the predominant species of the substrate, controlling the mechanism of
adsorption, thus potentially affecting the kinetics of degradation. The addition of activated carbon (AC)

with TiO2 changes some of physico-chemical properties of TiO2 [3]. The two main advantages of mixing
AC are homogeneous TiO2 particle distribution on the AC surface and consequent enhancement in
catalyst ability to absorb light in the visible spectra [3].

2. Experimental:

Preparation of Photocatalyst: Titanium dioxide (Qualigens, particle size 60-65nm, surface area 60m2/g,
100% anatase) is used as photocatalyst in the present investigation. The addition of lime, Ca(OH)2 is
accomplished by simple mixing of a correct amount of reagent (0.5 g) to 1g of TiO2 .The photocatalyst
with AC is obtained by mixing TiO2 with AC at 13% (w/w) proportion in an aqueous suspension under
continuously stirred condition for one hour. This is followed by the filtration of the mixture. The composite
is denoted as 13%-AC-TiO2. This composite catalyst acquires a blue colour.
Preparation of soil sample: Sandy soil (pH 5.5, Organic carbon 0.03%, Nitrogen 37.33kg/ha,
Phosphorous 2.20kg/ha, Potassium 103.49kg/ha, Sand 80.78%, Silt 9.24%, Clay 9.98%, Water holding
capacity29.11%)collected from Dhemaji (Assam) is used for the photocatalytic degradation experiments.
The crude (NR-6), collected from Numalighar refinery, Assam is used as a pollutant. The experiments are
carried out on a laboratory scale, where 15g of soil and 1g of catalyst is taken as standard. The samples
are prepared in Petri-dishes of diameter 7.5 cm. All samples are accurately mixed.
The ratio of amount of oil and soil has been used to represent the actual contaminated soil. For this,
separation of oil from actual contaminated soil is done and measured (oil extracted using petroleum ether
as a solvent). It is found that, the values of the ratio are similar to those used by Hamerski et.al [8]. Five
samples are made with TiO2 as photocatalyst, where pollutant amount is taken as 1.0ml, 1.5ml, 2.0ml,
2.5ml, and 3.0ml. The soil (15g) and catalyst (1g) are in standard amounts. The same is done for
Ca(OH)2 modified TiO2 and 13%-AC-TiO2 catalyst. These samples are denoted as catalytic samples.
Samples are prepared as references for calibration of oil content in the soil sample. For this, four samples
are prepared with pollutant amount 0.5ml, 1ml, 1.5ml, and 2.5ml respectively and standard amount of soil
and catalyst. Similarly calibration plots are generated using 13%-AC-TiO2 and Ca(OH)2 modified TiO2 for
different level of pollutant. These samples are denoted as reference samples. Lastly two samples are
prepared without adding any catalyst taking same amount of soil (15 g) and pollutant (1.5 ml) in order to
compare the results of oil decomposition carried out by solar heating or any other environmental factor.
These two samples are denoted as blank samples.
Experimental procedure and conditions: The experiments are conducted in good weathered conditions
especially in identical sunny days. The solar radiation is measured by using a Pyranometer. The average
solar radiation for the months of November and December is 540 w/m2 and the temperature is 2450C.
Care is taken to conduct the experiment within 2 hours of solar noon. The measured mean hourly
humidity level is 50-60% and the moisture content of the soil is 0.0713%. The catalytic samples and one
blank sample are exposed to sunlight. The duration of exposure of the samples amounted to 10, 20, 30 h.
After every 1 h we accurately mixed the samples. Again after every 10 h, 4 g of each sample is removed
and kept in separate glass bottles with lid and placed in the dark. The reference samples and another
blank sample are not exposed to solar radiation and are kept in glass bottles and placed in the dark of the
laboratory to see the possibility of any degradation by non-photocatalytic means.
The quantitative analysis of the oil contents is conducted using IR-studies of the soil samples. The IR
analysis was performed using a Nicolet (Madison, USA) FTIR Impact 410 spectrometer, using KBr
pellets.

3. Results, analysis and discussion:

Even though crude oils are a continuum of tens of thousands of different hydrocarbon molecules, the
proportions of the elements in crude oils vary over fairly narrow limits. Nevertheless, a wide variation in
properties is found from the lightest crude oils to the highly asphaltenic crudes. Due to the complex
composition of crude oils, characterization by the individual molecular types is not possible, and
elemental analysis is unattractive because it gives only limited information about the constitution of

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petroleum due to the constancy of elemental composition. Instead, hydrocarbon group type analysis is
commonly employed [2].
FTIR studies in the region between 4000 and 1300 cm-1 have been performed in order to determine
possible changes in the oil concentration [8]. Fig. 1(a) shows the FTIR spectra of pure soil (without any
catalyst and pollutant) and the unexposed blank sample.
100

%T

%T

100

(a)
.. Unexposed soil
Unexposed soil + oil

1300

0
4000
100

%T

Wave number (cm-1)

%T

0
4000
100

(b)
---, for soil + oil (30h exposed)
, for soil + oil (unexposed)

0
4000

Wave number (cm-1)

c
b
a

(c)
---, for soil + oil + TiO2 (unexposed)
, for soil + oil + TiO2 (30h exposed)

1300

(d)
a, for soil + oil + TiO2 (30h exposed)
b, for soil + oil + 13% AC-TiO2 (30h
exposed)
c, for soil + oil + Ca(OH)2
exposed)

+ TiO2 (30h

0
Wave number (cm-1)
4000
1300
Fig. 1: IR spectra of soil samples

Wave number (cm-1)

1300

It can be seen that peaks at wave number 2919cm-1, 2853cm-1, 1462cm-1 show the presence of
hydrocarbon in the soil sample, which has also been seen to be present in chemical testing as shown in
table. 1. These peaks basically correspond to the absorption bands of hydrocarbons. The corresponding
functional groups of these peaks are given in table-1.
Table. 1: Peaks corresponds to hydrocarbons

Wave number
Groups

2921cm-1
-CH3, -CH2-,

2852cm-1
-CH2-

1461cm-1
-CH3, -CH2-

-C-H
Though a crude oil contains a wide range of compounds, we concentrated our study on the abovementioned peaks.
Fig. 1(b) shows the IR spectra of unexposed and 30 h exposed blank samples. Here it can be seen that,
there is no change in the intensity of hydrocarbon peaks. This indicates that no oil decomposition occurs
due to solar thermal effect or any other environmental factor. The spectra of soil sample (15 g soil + 1.5
ml oil + 1 g TiO2 catalyst) for exposing time 30 h is presented in fig. 1(c). Very promising results have
been obtained. The intensity of the hydrocarbon peaks is gradually decreasing with increasing time of
exposure. This indicates disappearance of some functional groups implying oil decomposition during the
photocatalytic reaction. The comparative IR results for the three types of catalysts are presented in fig.
1(d). Here it can be seen that for Ca(OH)2 modified TiO2 and 13%-AC-TiO2 show a considerably higher

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degree of decomposition than pure TiO2 . The best degree of decomposition is obtained in the case of the
catalyst 13%-AC-TiO2. Studying the spectra of the reference samples, quantitative analysis of the oil
decomposition has been carried out.
Reaction rate: Fig. 2(a) shows the results obtained for the degradation of the target functional groups
when the oil amount is 0.10ml/gm of soil using 1g (6.6% by weight) of pure TiO2 catalyst and exposed to
sunlight for 10, 20 and 30 h [8]. The kinetics of the disappearance of groups is presented in fig. 2(b),
where final amount of the respective functional groups are calculated from the calibration plot. According
to a great number researchers the influence of the initial concentration of the pollutant on the photo
degradation rate of most organic compounds is described by a pseudo first order kinetics, which is
rationalized in terms of Langmuir-Hinshelwood model [7] from which we can calculate the apparent
reaction rate constant kapp can be calculated using equation-(1) .
dC

= k app C
dt
(1)
Where, C is the bulk solute concentration, t represents time and kapp is the apparent reaction rate
constant. A linear expression (fig. 2( c )) can be conveniently obtained by plotting the exposing time vs.
ln(Ci/Cf). From this plot, we can calculate the reaction rate constant. The calculated reaction rate constant
for 2921cm-1is 0.00097min-1,for 2852cm-1 is 0.00069min-1 and for 1461cm-1 is 0.00091min-1. Here It is
seen that the degradation of functional groups corresponding to 2852cm-1 is slower than the other two
peaks. Therefore reaction rate for 2852cm-1 reflects the limiting rate of reaction under these types of
experimental conditions. This gives us an extra insight into the correctness of our measurement because
the rate of degradation of single functional group at 2852cm-1 is lower than that of the combination of
functional groups at 2921cm-1 and 1461cm-1.

Effect of catalyst type: When the oil contamination in the soil was fixed at 1.5ml (in 15g soil), changes in
the catalyst type keeping the amount costant at 6.6 %( w/w) has a significant effect in the rate of oil
degradation, as presented in fig. 2(d). The fig. 2(d) clearly shows that adding 13%-AC-TiO2 does
significantly increases the photo catalytic degradation of oil when compared to that with pure TiO2.
However this may not be the optimum value for oil contaminated soil and it will need additional
observations [3]. As discussed above, mixing TiO2 with AC has shown changes in the catalyst color and
probably provides enough catalyst surface area to promote maximum rates of oil degradation [3].
The point of zero charge (pzc) of TiO2 is at pH 6.8 [4, 6]. The TiO2 surface is positively charged in acid
media (pH< 6.8) whereas it is negatively charged under alkaline condition (pH> 6.8). the influence of
Ca(OH)2 in the photocatalytic degradation of crude is as a pH controller [8, 9]. The addition of Ca(OH)2 is
done to bring the pH to more alkaline, that can modify the surface charge density as well as the
photodegradation process. Fig. 2(d) shows that the use of Ca(OH)2 modified TiO2 does not significantly
alter the photocatalytic degradation of oil compared to pure TiO2.
Parameters selection for optimization of degradation of crude oil contaminated in soil: The nature
of oil degradation contaminated in soil is influenced by a number of parameters such as Catalyst type,
radiation intensity, time of exposure, catalyst loading, oxidant loading, concentration of contaminant, pH
of solution, temperature etc [4, 7]. This demands a quantitative understanding of various parameters that
affect the output of oil degradation, which in turn reflects the need of optimization of various experimental
parameters involved. Taguchi robust designing approach [14, 15] is a multipleparameter optimization
procedure found to be useful in identifying and optimizing the dominant parameters, which control outputs
of a process, with a minimum number of experiments [18].
Four practically controllable parameters were selected for experimentation (Table. 2). All parameters are
having three levels.

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Table. 2: Parameters & their levels:

Parameters
A. Catalyst type
B. Time
C. Catalyst loading
D. Concentration of contaminant

Level 1
TiO2
10hr
3.33%(w/w)
0.06ml/gm

Level 2
13%AC TiO2
20hr
6.66%(w/w)
0.13ml/gm

Level 3
TiO2 with Ca(OH)2
30hr
10%(w/w)
0.2ml/gm

Absorbance (a.u.)

L-9 orthogonal matrix (Table. 3) for the oil degradation is made from the different parameters levels. The
soils samples are prepared for each experiment and are IR-analyzed. Degradation rate is determined with
the help of corresponding calibration plot as discussed above. Here we are taking the lowest degradation
rate which corresponds to 2852cm-1.

Fig. 2(b): Kinetics of disappearance of oil

Cf/Ci

ln (Ci/Cf)

Fig. 2(a): Degradation results obtained from the IR-spectra

Fig. 2(c): Time Vs. ln(Ci/Cf) plot

Fig. 2(d): Influence of catalyst type on oil degradation
Table. 3: L-9 Orthogonal Array with reaction rate and S/N ratio

Ex. No.

Reaction rate(min-1)

S/N ratio

1
2
3
4
5
6
7
8

TiO2
TiO2
TiO2
13%AC TiO2
13%AC TiO2
13%AC TiO2
TiO2 with Ca(OH)2
TiO2 with Ca(OH)2

10
20
30
10
20
30
10
20

3.33%
6.66%
10.00%
6.66%
10.00%
3.33%
10.00%
3.33%

0.06
0.13
0.20
0.20
0.06
0.13
0.13
0.20

0.00038
0.00044
0.00041
0.00063
0.00059
0.00053
0.00049
0.00043

-68.40
-67.13
-67.74
-64.01
-64.58
-65.51
-66.19
-67.33

TiO2 with Ca(OH)2

30

6.66%

0.06

0.00040

-67.95

Calculation of S/N ratios & Taguchi plot: The S/N ratio [14,15] is calculated by using the larger-thebetter type of objective function. The result of the S/N ratio is given in table. 3. S/N ratio vs. different
control factors are plotted to get the best result (fig. 3). Fig. 3 suggests that catalyst type 13%-AC-TiO2
with exposing time10 h, catalyst loading 10%(w/w) and initial contaminant concentration 0.13ml/gm would
be the best choice to get better degradation. Sum of squares (SoS) and factor effects were obtained

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employing corresponding equations [14, 15]. The contributions of each parameter level towards the S/N
ratio (mi) as obtained from ANOM is displayed (table. 4) along with it.
As seen in the response diagram, degradation of oil primarily depends upon Catalyst type. The parameter
effect for this is 81.4%. This can be explained with the help of effective surface area and particle size of
the photo catalyst on degradation. From the catalysis point of view, a higher surface area is an advantage
in terms of a greater concentration of active sites per square meter, and hence generally leads to a higher
reactivity [16]. In our experiment we have found that 13%-AC-TiO2 is the best supporting catalyst
compared to the others. Thus all experiments involving 13%- AC-TiO2 have yielded better degradation
rate. A possible explanation for this observation is the difference in the particle size, active surface and its
ability to absorb at higher wavelength region area [3]. In case of 13%-AC-TiO2, the inner support of AC
provides higher active surface area on degradation. Again we have found that pure TiO2 is the least
supporting catalyst on degradation of oil. A possible explanation for this is that, during the degradation
reaction the TiO2 surface may undergo coagulation processes that can hamper the light incidence on
these active centers and consequently reduce its catalytic activity [8, 17].

S/N ration

Mean S/N ratio

Fig-3: Plot of S/N ratio vs. different control factors.

Table. 4: Summary of parameters effects for the degradation of oil

parameters
A. Catalyst type

B. Time
C. Catalyst
loading
D. Concentration
of contaminant

Levels

Mi(dB)

SOS

SOS/DOF

Parameters
effect (%)

TiO2
13%AC TiO2
TiO2 with
Ca(OH)2
10h
20h
30h
3.33%
6.66%
10%
0.06ml/gm
0.13ml/gm
0.2ml/gm

67.76
64.70
67.16

15.78

7.88

81.47

1.2978

0.6489

6.70

1.4046

0.7023

7.26

0.8808

0.4404

4.55

66.2
66.35
67.07
67.08
66.34
66.17
66.98
66.28
66.36

We now focus on the effect of catalyst loading on the oil degradation. Here both 6.66% and 10% are
found to be supporting the degradation. The 10% of catalyst loading is the better one than the other. This
is because as the amount of catalyst is increased, the number of photons absorbed and the number of oil
molecules adsorbed are increased owing to an increase in the number of catalyst particles [13, 5]. The
density of particles in the area of illumination also increases and so that the rate is enhanced. Since
3.33% of catalyst is the least supporting level, hence experiments involving 3.33% catalyst give lower
degradation rate.

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Other two parameters (Time and concentration of contaminant) display parameters effect 6.7% and
4.55% respectively. Among these two, time has the great influence on oil degradation. It has been seen
that for the 10 h the degradation rate is better compared to the other two levels. A possible explanation
for this observation is that, for first 10 h the catalyst is more active and it provides higher surface area,
after that its catalytic activity is reduced by the coagulation of the catalyst particle [3, 8]. It may also be
due to the adsorption of the reaction products on active sites.
It has been found that both the oil concentrations of 0.13ml/gm and 0.2ml/gm have produced the best
results in terms of oil degradation suggesting high oil concentration logically enhances the probability of
collision between organic matter and oxidizing species, leading to an increase in the degradation rate [6,
7, 8].

4. Conclusion:
It has been demonstrated that the combination of photocatalyst with solar light can destroy crude oil
contaminated in soil. The degradation is fast in case of 13%-AC-TiO2 catalyst. As expected, photocatalyst
particle size and its active surface area is an important parameter to control the degradation despite the
fact that the destruction was fast for first 10h and mixing is an important criterion for proper degradation.
Taguchi optimizations on the degradation of crude oil have been presented. Relative effects of four
parameters in determining the output of degradation and their optimum levels are quantitatively obtained
by performing analysis of variance and analysis of mean, respectively. All parameters are found to be
contributing to the degradation of oil, while catalyst type is found to be dominant parameter for
degradation of oil-contaminated soil.
Compared to other conventional method for oil degradation contaminated in soil, this method would be
expected management procedure for in situ remediation.

Acknowledgement:
The help provided by Dr. N. S. Islam, Head, Department of Chemical Sciences. Tezpur University and Mr.
B. Gohain, in making the characterization facilities available is gratefully acknowledged.

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