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ABSTRACT: In this paper, we analyzed the crude oils of ve dierent regions of Iran to identify their sources of geographical origin. The
Fourier transform infrared (FTIR) spectra of samples were analyzed by chemometrics methods to make discrimination between the dierent
crude oil sources. Infrared (IR) spectroscopy in conjunction with chemometrics techniques allows for online monitoring in real time, which
can be of considerable use in the petroleum industry. Principal component analysis (PCA) and extended canonical variates analysis (ECVA),
as unsupervised and supervised classication methods, respectively, were employed. The PCA scores made a relative discrimination between
the dierent crude oil sources; however, the degree of classication was not satisfactory. Instead, more accurate classication results were
achieved by ECVA. The results show that the spectral region 13501490 cm1 possessed much better performances for classication by
ECVA. This spectral region, which is attributed to the SO, aromatic CC, and methylene CC vibrations, suggests that the dierence
between crude oils of these geographical origins is primarily attributed to the dierence in sulfoxide and aromatic compounds. The ECVA
technique was found as a promising classication model and has shown good classication power for crude oil sources.
1. INTRODUCTION
Identication of the source of the geographical origin of crude
oils and their products is of high importance for not only their
fractions in the environment but also forensic and quality control
studies. Making classication models to distinguish crude oils and
the petrochemical products of dierent geographical origin is of
great importance in arson investigations, spills of crude oil, and
geochemical and reservoir management studies.13 However,
because these materials possess a complex matrix, aliating a
crude oil sample to its native geographical origin is not simple.
Hyphenation of infrared (IR) spectroscopy with chemometrics methods makes it a fast and reliable analytical
technique, which has found widespread applications in
pharmaceutical4 and industrial57 elds, disease detections,8,9
monitoring of chemical and biotechnological processes,10
bacterial identication,11 and also the petroleum industry.1215
The above-mentioned examples show the quantitative analytical
aspects of IR spectroscopy (as a non-destructive measurement)
besides its extensive qualitative applications for structural
elucidations of chemical compounds. IR spectroscopy benets the
advantage of studying samples in any state, including (solutions and
thin lms) solids (powders, lms, and bers), pastes, and gases.1618
Because of the importance of the classication of crude oil
and products in petroleum, some papers have been devoted to
this problem.12,14,1923 However, according to the best of our
knowledge, source identication of Iranian oil using IR
spectroscopy and chemometrics data analyses has not yet
been reported. As holder of 10% of the worlds proven oil
reserves and 15% of its gas, Iran is the second largest exporter
of the Organization of the Petroleum Exporting Countries
(OPEC) and, by producing 132.5 billion barrels, is the fourth
oil producer of the world.24
In this work, we made discrimination models for the crude
oil samples collected from ve dierent regions of Iran, using
IR spectroscopy analyzed with multivariate classication methods.
2014 American Chemical Society
2. EXPERIMENTAL SECTION
2.1. Data Set. In this study, 100 samples of crude oil collected
from ve dierent regions of Iran (belonging to Aghajari, Ahvaz,
Maroon, Rage Sed, and Ramshir regions) and 20 samples for each
region, were investigated. All regions are located in the Khozestan
state. The oil samples were collected directly from the top of the oil
well after exhausting gases and before entering the transport section.
Information about samples and classes is given in Table 1. To ensure
number of samples
1
2
3
4
5
total
Aghajari
Ahvaz
Maroon
Rage Sed
Ramshir
20
20
20
20
20
100
Article
into training (70 samples; 14 samples from each region) and test
(30 samples; 6 samples from each region) sets.
2.2. IR Spectra Measurement. The IR spectra were acquired with
a Shimadzu 8000 series FTIR spectrometer with a deuterated,
1
L-alanine-doped triglycine sulfate (DLATGS) detector set to 16 cm
optical resolution, and 15 scans were averaged. Liquid lms of oils were
used for spectral measurements. A liquid demountable IR cell with NaCl
windows with a spectral path length of 30 m (equipped with a Teon
spacer) was used throughout. About 5.0 L aliquots of oil samples were
transferred into the cell, and their FTIR spectra were acquired after 2 min,
at room temperature (23 25 C). The cell was cleaned by toluene
solvent and then dried for further uses. Each spectrum was recorded
3 times, and the average spectrum was reported for each sample.
2.3. Software and Data Analysis. Data analyses were run in a
MATLAB (Mathwork, Inc., version 8) environment. The MATLAB
Statistics Toolbox and the ECVA Toolbox, version 2.02, developed by
the Technology and Quality Research Group at Kopenhagen
University (available at http://www.models.life.ku.dk) were used.
The transmittance IR spectra of the studied samples were digitized
in absorbance units in the form of a data matrix D of size (100 nw),
where nw is the number of absorbance readings per spectrum. Autoscaling
to unit variance and zero mean was used as data preprocessing.
Spectral data were rst analyzed by principal component analysis
(PCA), employing a singular value decomposition (SVD) function of
MATLAB. Then, ECVA as a supervised classication method was
applied on the data. Cross-validation was used to optimize the ECVA
model, e.g., determination of the optimum number of PLS models,
which is used as inner part of ECVA for discrimination analysis. To
judge the overall prediction ability of the model, six samples from each
group were randomly selected as the prediction set. These samples did
not contribute in the model development.
Figure 1. Example of crude oil FTIR spectra: (a) Aghajari, (b) Ahvaz,
(c) Maroon, (d) Rage Sed, and (e) Ramshir.
Article
from the spectral data matrix, and hence, they are not essentially
correlated with discriminate variables.25 On the other hand, the
principal factors obtained by supervised classication methods,
such as discriminate partial least squares (DPLS), are calculated
using the information included in both spectral data and classes of
samples.26 However, DPLS does not oer good results for real
data sets, and in some instances, overtting is observed.27
Canonical variates analysis (CVA)28 is another supervised method
that cannot be applied to highly collinear spectroscopic data.
ECVA is an extension of CVA and proposed by Norgaard et al. to
overcome limitations of CVA.27 Using PLS in the inner part of
ECVA allows for the analysis of collinear data.
Therefore, in the next data analysis step, we used ECVA for
its growing applications and its promising results.25,2931 The
model renement procedure used 5-fold cross-validation to select
the number of PLS factors. From the plot of misclassication error
as a function of the number of PLS factors (see Figure S1 of the
Supporting Information), 11 factors were selected as the optimum
factors. At this number of factors, cross-validation error is in its
minimum value and closer to the calibration error.
In this study, ve classes of samples were investigated, and hence,
the ECVA solution is a four-dimentional model (one unit less than
the number of classes). The values of canonical variates calculated
for each sample in all four directions are depicted in Figure 4.
EV
PV
CPV
1
2
3
4
5
6
7
8
9
10
420.9
16.14
0.7750
0.1278
0.0188
0.0090
0.0055
0.0040
0.0028
0.00176
96.1
3.69
0.18
0.03
0
0
0
0
0
0
96.1
99.78
99.96
99.99
99.99
100
100
100
100
100
Article
4. CONCLUDING REMARKS
The FTIR spectra of crude oil samples in ve states of
Khozestan, Iran, were analyzed by chemometrics methods to
make discrimination between the dierent crude oil sources.
PCA of the IR spectral data does not represent any discrimination
between the sources of crude oil compounds. However, high
discrimination was obtained by ECVA, so that all crude oil
compounds used in this study were correctly assigned to their
native sources. In comparison to analysis of the whole spectral
region, using selected spectral regions (12811475 cm1) resulted
in models of better classication results.
ASSOCIATED CONTENT
* Supporting Information
S
Article
(31) Hansen, C. L.; van den Berg, F.; Rasmussen, M. A.; Engelsen, S.
B.; Holroyd, S. Chemom. Intell. Lab. Syst. 2010, 104, 243248.
(32) Shakirullah, M.; Ahmad, W.; Ahmad, I.; Ishaqand, M.; Khan, M.
I. J. Chil. Chem. Soc. 2012, 57, 13751380.
AUTHOR INFORMATION
Corresponding Author
REFERENCES
(1) Tan, B.; Hardy, J. K.; Snavely, R. E. Anal. Chim. Acta 2000, 422,
3746.
(2) Lavine, B. K.; Ritter, J.; Moores, A. J.; Wilson, M.; Faruque, A.;
Mayfield, H. T. Anal. Chem. 2000, 72, 423431.
(3) Peters, K. E.; Fowler, M. G. Org. Geochem. 2002, 33, 536.
(4) Sekulic, S.; Ward, H. W.; Brannegan, D.; Stanley, E.; Evans, C.;
Sciavolino, S.; Hailey, P.; Aldridge, P. Anal. Chem. 1996, 68, 509513.
(5) Blanco, M.; Coello, J.; Eustaquio, A.; Iturriaga, H.; Maspoch, S.
Anal. Chim. Acta 1999, 392, 237246.
(6) Ozaki, Y.; Cho, R.; Ikegaya, K.; Muraishi, S.; Kawauchi, K. Appl.
Spectrosc. 1992, 46, 15031507.
(7) Blanco, M.; Coello, J.; Garcia Fraga, J. M.; Iturriaga, H.; Maspoch,
S. Analyst 1999, 122, 7780.
(8) Backhaus, J.; Mueller, R.; Formanski, N.; Szlama, N.; Meerpohl,
H.; Eidt, M.; Bugert, P. Vib. Spectrosc. 2010, 46, 173177.
(9) Kondepati, V. R.; Keese, M.; Mueller, R.; Manegold, B. C.;
Backhaus, J. Vib. Spectrosc. 2007, 44, 236242.
(10) Huber, W.; Bubendorf, A.; Grieder, A.; Obrecht, D. Anal. Chim.
Acta 1999, 393, 213221.
(11) Marcott, C.; Dowrey, A. E.; Poppel, J. V.; Noda, I. Vib. Spectrosc.
2004, 36, 221225.
(12) Balabina, R. M.; Safievab, R. Z.; Lomakinac, E. I. Anal. Chim.
Acta 2010, 671, 2735.
(13) Midttun, .; Kvalheim, O. M. Fuel 2001, 80, 717730.
(14) Balabin, R. M.; Safieva, R. Z. Fuel 2008, 87, 10961101.
(15) Peinder, P. d.; Visser, T.; Petrauskas, D. D.; Salvatori, F.;
Singelenberg, F.; Soulimani, F.; Weckhuysen, B. M. Appl. Spectrosc.
2008, 62, 414422.
(16) Crowther, M. W. J. Chem. Educ. 2008, 85, 15501555.
(17) Stuart, B. H.; George, B.; Mc Intyre, P. Modern Infrared
Spectroscopy; John Wiley and Sons, Ltd.: Hoboken, NJ, 1996.
(18) Mullins, O. C.; Daigle, T.; Crowell, Ch.; Groenzin, H.; Joshi, N.
B. Appl. Spectrosc. 2001, 55, 197201.
(19) Brudzewski, K.; Kesik, A.; Kolodziejczyk, K.; Zborowska, U.;
Ulaczyk, J. Fuel 2006, 85, 553558.
(20) Zhang, Q. K.; Dai, L. K. Control Instrum. Chem. Ind. 2005, 32,
5359.
(21) Pasadakis, N.; Kardamakis, A.; Sfakianak, P. Fuels 2007, 21,
34063409.
(22) Clark, H. A.; Jurs, P. C. Anal. Chem. 1979, 51, 616623.
(23) Peinder, P. D. Characterization and classication of crude oils
using a combination of spectroscopy and chemometrics, Ph.D. Thesis,
Utrecht University, Utrecht, Netherlands, 2009; http://igiturarchive.
library.uu.nl/dissertations/2010-0113-200208/UUindex.html.
(24) U.S. Energy Information Administration (EIA). Iran; EIA:
Washington, D.C., 2012; www.eia.gov/countries/country-data.
cfm?ps=IR (accessed July 31, 2012).
(25) Mobaraki, N.; Hemmateenejad, B. Chemom. Intell. Lab. Syst.
2011, 109, 171177.
(26) Barker, M.; Rayen, W. J. Chemometrics 2003, 17, 166173.
(27) Nrgaard, L.; Bro, R.; Westad, F.; Engelsen, J. Chemometrics
2006, 20, 42535.
(28) Russell, E. I.; Chiang, L. H.; Braatz, R. D. Chemom. Intell. Lab.
Syst. 2000, 51, 8193.
(29) Winning, H.; Viereck, N.; Salomonsen, T.; Larsen, J.; Engelsen,
S. B. Carbohydr. Res. 2009, 344, 18331841.
(30) Nrgaard, L.; Soletormos, G.; Harrit, N.; Albrechtsen, M.;
Olsen, O.; Nielsen, D.; Kampmann, K.; Bro, R. J. Chemometrics 2007,
21, 451458.
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