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LWT 38 (2005) 821–828


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Multivariate determination of free fatty acids and moisture in fish oils


by partial least-squares regression and near-infrared spectroscopy
D. Cozzolinoa,, I. Murraya, A. Chreeb, J.R. Scaifec
a
Animal Biology Division, Scottish Agricultural College, Ferguson Building, Craibstone State, Aberdeen AB21 9YA, Scotland, UK
b
United Fish Products Ltd., Tullos, Aberdeen AB12 3AY, Scotland, UK
c
Department of Agriculture, University of Aberdeen, MacRobert Building, Aberdeen, AB12 5UA, Scotland, UK
Received 27 May 2004; received in revised form 6 October 2004; accepted 26 October 2004

Abstract

The oxidative and hydrolytic degradation of lipids in fish oil was monitored using partial least-squares (PLS) regression and near-
infrared reflectance (NIR) spectroscopy. One hundred and sixty (n ¼ 160) fish oil samples from a fishmeal factory were scanned in
transflectance by an NIR monochromator instrument (1100–2500 nm). Calibration models were performed for free fatty acids
(FFA), moisture (M), peroxide value (PV) and anisidine value (AV). Coefficients of determination in calibration (R2) and standard
errors of cross validation (SECV) were 0.96 (SECV: 0.59) and 0.94 (SECV: 0.03) for FFA and M in g/kg, respectively. The accuracy
of the NIR calibration models were tested using a validation set, yielding coefficients of correlation (r) and standard errors of
prediction (SEP) of 0.98 (SEP: 0.50) and 0.80 (SEP: 0.05) for FFA and M in g/kg, respectively. Poor accuracy (R2o0.80) was
obtained for the NIR calibration models developed for PV and AV. The paper demonstrates that fish oil hydrolytic degradation of
lipids, which seriously affect oil use and storage under industrial conditions, can be successfully monitored using PLS regression and
NIR spectroscopy by the fishmeal industry.
r 2004 Swiss Society of Food Science and Technology. Published by Elsevier Ltd. All rights reserved.

Keywords: Near-infrared spectroscopy; NIR; Fish oil; Free fatty acids; Lipid oxidation; Moisture; Peroxides; Partial least squares

1. Introduction acids (PUFA), consequently, fish and fish oils are highly
susceptible to the development of oxidative rancidity,
A chemical reaction that usually takes place at unpleasant odours, off-flavours and taints (Borquez,
ambient temperatures between atmospheric oxygen Kolle, Wolf, & SpieX, 1997; Chantachum, Benjakul, &
and an organic compound is generally referred to as Sriwirat, 2000). The formation of lipid hydroperoxides
autoxidation (Hamilton, 1989; Hamilton, Kalu, Prisk, as the primary intermediates in the oxidative degrada-
Padley, & Pierce, 1997). The majority of foods that are tion of unsaturated lipids has been studied for many
subject to autoxidation are composed of unsaturated years (Chan & Coxon, 1987; Hamilton, 1989; Borquez
compounds (Chan, 1987; Hamilton, 1989; Hamilton et al., 1997). In addition to unpalatability, peroxidation
et al., 1997). Fish oil contains about 20 percent of their of fats and oils may give rise to toxic levels of certain
total fatty acids as long-chain polyunsaturated fatty products such as aldehydes, hydroperoxides and ep-
oxides which detracts from their important nutritional
Corresponding author. Actual address: Department of Chemis-
value as a source of essential n-6 and n-3 PUFA and
energy (Chan, 1987; Chan & Coxon, 1987; Borquez
try—NIR group, The Australian Wine Research Institute, Waite
Campus, Urrbrae, P.O. Box 197, Glen Osmond, Adelaide 5064, South
et al., 1997; Chantachum et al., 2000). Many features
Australia. Tel.: +61 8 8303 6600; fax: +61 8 8303 6601. affect the onset and development of rancidity (oxidative
E-mail address: daniel.cozzolino@awri.com.au (D. Cozzolino). and hydrolytic degradation of lipids), including the

0023-6438/$30.00 r 2004 Swiss Society of Food Science and Technology. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.lwt.2004.10.007
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degree of unsaturation of the oil, the type and & De Boer, 1988; Church, 1991). The nutritional
concentrations of antioxidants, pro-oxidants, moisture importance of fish oils lies partly in its high energy
content, oxygen availability, temperature and degree of content of 37 MJ/kg, which is more than twice the
exposure to light (Chan, 1987; Coxon, Rigby, Chan, energy value of carbohydrate foods. Nutritionally, fish
Lund, & George, 1987; Chan & Coxon, 1987; Robards, oils also supply fat soluble vitamins A, D and E and
Kerr, & Patsalides, 1988; Borquez et al., 1997; Chanta- sources of n-6 and n-3 PUFA, as docosahexanoic acid
chum et al., 2000). Several chemical and physical (C22, n-6), arachidonic acid (C20:4, n-6) and eicosapentae-
techniques applied alone or together have been used to noic acid (C20:5, n-3) (Pike & Tatterson, 1980; Miller &
determine the degree of oxidation and hydrolytic De Boer, 1988; Church, 1991). Although fish oil is not
degradation of lipids in edible oils. considered the most important product for the fishmeal
The determination of free fatty acids (FFA), peroxide industry, its use in the feed manufacturing industry and
value (PV), anisidine value (AV), TOTOX (2PV+AV), for human consumption demands rigorous quality
thiobarbituric acid test (TBARS) are examples of the control to meet the specifications set by the consumers.
chemical techniques used to analyse fats and edible oils The combination of both NIR spectroscopy and multi-
(Robards et al., 1988; Borquez et al., 1997; Iñon, variate techniques provide a powerful tool for monitor-
Garrigues, Garrigues, Molina, & de la Guardia, 2003). ing a variety of processes and is arousing increasing
However, such chemical and physical techniques are interest for quality control purposes in the food industry
slow (e.g. require accurate weighting of the sample, (Blanco & Pages, 2002; Larrechi & Callao, 2003).
dissolution in solvents and titration with standardized This paper reports the use of partial least-squares
solutions) and are expensive when used for monitoring (PLS) regression and NIR spectroscopy to monitoring
industrial processes (Iñon et al., 2003). both oxidation and hydrolytic degradation of lipids in
Near-infrared (NIR) spectroscopy has many applica- fish in oil, which seriously affects both end use and
tions in the food industry and is of particular use in the storage of this byproduct in the fishmeal industry.
quality control of raw materials and food products
(Osborne, Fearn, & Hindle, 1993). Several references in
the use of NIR spectroscopy to analyse animal fats and 2. Materials and methods
vegetable oils were found in the literature, but none of
these related to fish oil. One of the earliest reports on the 2.1. Samples and chemical analysis
use of the NIR region to analyse oils was related to the
analysis of fatty acid composition (Holman & Edmond- One hundred and sixty samples (n ¼ 160) of fish oil
son, 1956), the analysis of patterns of fatty acids in both were obtained from United Fish Products (UFP, Tullos,
fats and oils (Sato, Kawano, & Iwamoto, 1990; Sato, Aberdeen, Scotland) between March 1997 and July
Kawano, & Iwamoto, 1991; Boot & Speek, 1994), the 1997. The samples were the byproduct of the manu-
prediction of lipid oxidation in edible oils (Takamura, facture of fishmeal. The oil was obtained by centrifuga-
Hyakumoto, Endo, Matoba, & Nishiike, 1995a; Taka- tion from the press water, which results from cooking
mura, Hyakumoto, & Matoba, 1995b), the use of optic and pressing the raw fish material (Cozzolino, 1998;
probes to analyse oxidation in frying fats (Bünin–Pfaue Cozzolino, Chree, Murray, & Scaife, 2002). Fish oil
& Kehraus, 2001) and the determination of hydrogen samples had different chemical composition due to both
peroxides (Kangming, Van de Voort, & Ismail, 1997; differences in species and seasonality of the fish used to
Pimenta et al., 2003). The use of both NIR spectroscopy produce the fishmeal and stored in different tanks in the
and chemometrics (e.g. principal component analysis factory (Cozzolino, 1998; Cozzolino et al., 2002). FFA,
and discriminant techniques) were used as a tool to peroxide value (PV), anisidine value (AV) and moisture
authenticate oil samples (Chen & Chen, 1994; Bewig, (M) were analysed following standard methods de-
Clarke, Roberts, & Unklesbay, 1994; Wesley, Barnes, & scribed elsewhere (AOAC, 1990). For operational
McGill, 1995; Blanco & Pages, 2002; Downey, McIn- reasons the samples had been analysed progressively at
tyre, & Davies, 2002). More recently the use of Fourier- the material was produced. Consequently reference
transformed NIR spectroscopy (FT-NIR) was explored analyses were not conducted as the same time of
as a rapid method to determine FFA in fats and oils scanning. Delay time between sampling and scanning
(Ismail, van de Voort, Emo, & Sedman, 1993), both was 5 days minimum. During this period the samples
iodine value and saponification number of edible oils were stored at room temperature (20 1C) in dark
(Li, van de Voort, Sedman, & Ismail, 1999) and conditions.
determination of hydroperoxides in high-erucic-acid
rapeseed oil (Dong, Ma, van de Voort, & Ismail, 1997). 2.2. NIR analysis
Fish oil is produced during the processing of fishmeal,
and under these conditions is considered a byproduct Samples were scanned in reflectance mode (transflec-
for the fishmeal industry (Pike & Tatterson, 1980; Miller tance) (1100–2500 nm) in a monochromator instrument
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NIRSystems 5000 (Silver Spring, MD, USA). The set, and evaluated by the standard error of prediction
samples were placed in a cam lock circular cell (50 mm (SEP), the coefficient of regression (r), the slope and bias
diameter) and presented as an oil film of 0.1 mm (Martens & Naes, 1989; Naes et al., 2002).
path length. This cell is fitted with a circular quartz
window and an aluminium backing plate (NIRSystems,
Silver Spring, MD, USA) (Sample cup Part number 3. Results and discussion
NIRS-IH-0345).
Both diagnostics and spectra were manipulated using 3.1. Fish oil NIR spectra
the Infrasoft International (ISI) software (version 3.01,
ISI, Port Matilda, PA, USA). Reflectance (R) data were Fig. 1 shows the NIR mean spectrum of fish oils.
stored as log 1/R, at 2 nm intervals to collect a total of Absorption bands were observed at 1208 nm related to
700 data points. Samples were scanned at room CH stretch second overtone, a small absorption band at
temperature (between 18 and 22 1C) and were not 1400 nm related to OH stretch first overtone, at 1720
rotated. Between samples, the sample cell was washed and 1760 nm related to CH stretch first overtone
with detergent using warm water, rinsed with distilled (Murray, 1986; Miller, 2001). At 2144 nm related to
water at room temperature and dried using paper tissue. CQC and C–H stretch combination tone of cis
unsaturated fatty acids, and two absorption bands at
2.3. Data analysis 2308 and 2348 nm are related with CH combinations
and deformation tones (Holman & Edmondson, 1956;
Spectra were exported from the ISI software in NSAS Murray, 1986; Miller, 2001). The CH stretch absorption
format for chemometric analysis to The Unscrambler
software (version 7.5, CAMO ASA, Norway). Principal
Component Analysis (PCA) was performed before PLS
regression calibration models were developed. PCA was
used to derive the first 20 principal components from the
spectral data. These were used in further analysis to
examine the relevant and interpretable structure in the
data as well as outlier detection (Martens & Naes, 1989;
Naes, Isaksson, Fearn, & Davies, 2002). Calibration
models between chemical data and NIR spectra were
developed using PLS regression with cross validation.
The optimum number of terms in the PLS calibration
models were determined by cross validation and defined
by the PRESS function (predicted error sum of squares)
in order to avoid overfitting of the models (Naes et al.,
2002). Cross validation estimates the prediction error by
splitting the calibration samples into groups (four in this Fig. 1. NIR mean spectrum (line) and standard deviation (dotted line)
case). One group was reserved for validation and the of fish oil samples.
remaining groups were used for calibration. The process
was repeated until all groups had been used for
validation once (Martens & Naes, 1989; Naes et al.,
2002).
Second derivative of the spectra was used as a
mathematical treatment to correct the baseline effects
and separate overlapping peaks when PCA was devel-
oped (Hruschka, 1992; The Unscrambler Manual,
1998). Second derivative was performed using Savitz-
ky–Golay derivation and smoothing (20 point and
second-order filtering operation). Both calibration and
validation models were developed using raw spectra.
The data set was split randomly into a training
(n ¼ 80) and a validation set (n ¼ 80). Statistics
calculated included the coefficient of determination in
calibration (R2) and the standard error in cross
validation (SECV). The prediction accuracy of the Fig. 2. Second derivative of the mean NIR spectrum (line) and
NIR calibration models was tested using the validation standard deviation (dotted line) of fish oil samples.
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bands of terminal double bonds and cis unsaturation meal and consequently the fish oil (Cozzolino, 1998;
around 2100 nm are characteristic of oil (Murray, 1986). Cozzolino et al., 2002).
The second derivative of the mean spectrum allows To investigate the basis for the observed spectral
identification of smaller absorption bands (Fig. 2). The discrimination between the sampling periods, the PCA
second derivative shows absorption bands at 1410 nm loadings were analysed (see Fig. 4). Highest and positive
related with OH first overtone, at 1832 nm with CH loadings in PC1 were found at 1716 and 1760 nm related
stretch first overtone of carbonyl compounds and at with CH2 overtones, at 2140 nm and 2310 and 2350 nm
1928 nm related with OH stretching first overtone and related to C–H and CQC tones (Murray, 1986;
OH deformation combination of hydroxyl groups Takamura et al., 1995a,b). These spectral regions are
(Holman & Edmondson, 1956; Murray, 1986; Miller, characteristic of fatty acids in different oil types
2001). The highest standard deviations are observed (Murray, 1986). PC2 explains 1 percent of the variation.
around 1700 nm and between 2200 and 2300 nm, related Negative loadings in PC2 were found at 1912 nm related
with several classes of oxygenated compounds (Murray,
1986). Those wavelength regions are mainly related
with oxidation and hydrolytic degradation of lipids in
fish oil (Holman & Edmondson, 1956; Murray, 1986,
Takamura et al., 1995a,b; Miller, 2001).

3.2. PCA analysis

PCA was performed on the whole spectra


(1100–2500 nm) to examine outlier samples as well as
qualitative differences between the different sampling
periods. Fig. 3 shows the PCA scores (PC1 vs. PC2)
after baseline correction (Savitzky–Golay derivation).
The first two PC’s account for more than 99% of the
variation in the spectra. PC1 explained 98 percent of
the total variance between the samples, and the shape of
the loading is identical to the whole spectra. Three
groups were observed corresponding with different
sampling periods. Those differences could be explained Fig. 4. Loadings for the first two PCs of fish oil samples (PC1 ¼ line;
due to different fish species used to make the fish- PC2 dotted line).

Fig. 3. Principal component scores plot for the first two PCs of fish oil samples.
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to O–H first overtone (water) and at 2174 nm related standard error of prediction (SEP) was calculated
with C–H tones (Murray, 1986; Miller, 2001). (Fearn, 2002). This relationship shows how good the
calibration and prediction will work for analytical
3.3. NIR calibration and prediction

Table 1 shows the descriptive statistics (mean,


standard deviation and range) of the chemical para-
meters evaluated in the fish oil samples. A wide spread in
the chemical parameters was observed due to the
different tanks and fish species used (sampling periods).
Table 2 shows the NIR calibration statistics for FFA
and M in the fish oil samples analysed. The R2 values
were 0.96 (SECV: 0.59) and 0.94 (SECV: 0.03) for FFA
and M in g/kg, respectively. The number of PLS
regression factors used to develop the calibration models
were 7 and 11 for FFA and M, respectively. Figs. 5 and
6 plot the chemical reference data against the NIR
predicted values in the independent validation set. These
plots illustrate the relationship between the chemical
data and the NIR calibration models as well as the
presence of outlier samples, which represent atypical Fig. 5. NIR predicted values against measured data for FFA in fish oil
samples included in the population. Such atypical samples (g/kg).
samples arise from variations in the raw material
depending on fish species, seasonality or source, or
more usually due to oxidized samples rejected from
production (Cozzolino, 1998; Cozzolino et al., 2002).
Table 2 shows the performance of the NIR calibration
models using a validation set. The ratio between the
standard deviation of the population (SD) and the

Table 1
Descriptive statistics (mean, standard deviation and range) of chemical
composition of fish oil samples (n ¼ 160)

Mean SD Min. Max.

FFA (g/kg) 4.1 4.0 1.6 19.4


M (g/kg) 0.23 0.11 0.07 0.8
PV (mEq/kg) 5.2 2.8 0.12 16.0
AV(na) 12.3 6.5 0.01 27.3

FFA: free fatty acids, M: moisture, PV: peroxide value, AV: anisidine
value, SD: standard deviation, Min.: minimum, Max.: maximum, na: Fig. 6. NIR predicted values against measured data for moisture (M)
not applicable. in fish oil samples (g/kg).

Table 2
Near infrared calibration and validation statistics for free fatty acids, moisture, peroxide and anisidine values in fish oil samples (calibration, n ¼ 80;
validation n ¼ 80)

Calibration Validation

n SECV R2 r SEP Slope SD/SEP PLS factors

FFA (g/kg) 80 0.59 0.96 0.98 0.5 0.98 8.0 7


M (g/kg) 74 0.03 0.94 0.80 0.05 0.80 2.2 11
PV (mEq/kg) 80 2.2 0.60 0.40 3.9 0.33 0.7
AV 71 5.76 0.93 0.77 6.2 0.96 1.0

FFA: free fatty acids; M: moisture; PV: peroxide value; AV: anisidine value; SD: standard deviation; R2: coefficient of determination in calibration;
SECV: standard error of cross validation; n: number of samples left in calibration, SEP: standard error of prediction, r: coefficient of correlation
(validation set).
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purposes. A SD/SEP value greater than 5 is considered practice such oils need to be recognized and segregated
good for quality control and a value greater than 3 is to maintain high standards in the oil produced by the
considered useful for screening (Williams, 2001; Fearn, industry. The determination of acidity (FFA) in oils is of
2002). For FFA, the NIR calibration statistics are particular interest. From the industrial point of view, the
considered excellent (SD/SEP48) and intermediate for FFA content is one of the most important factors
screening purposes for M (SD/SEP42). determining the quality and economic value of edible
The prediction of FFA shows a bimodal distribution oils in particular fish oil. FFA are more likely to be
in both the calibration and validation sets (see Fig. 5). proned to oxidation than triglycerides, so their presence
This bimodal distribution could be related to the in oils increases the possibility of developing oxidative
inclusion of oils from a particular storage tank in the and hydrolytic degradation of lipids (Hamilton, 1989;
calibration set. It is well known, from the literature Iñon et al., 2003). Although, NIR spectroscopy with
regarding FFA determination that FFA varies among multivariate analysis is very attractive for industry in
sample composition depending on the different insa- both the laboratory and the process quality control, the
turation index, cis/trans ratio of unsaturated fatty acids, challenge remains to ensure that the calibration models
which could be considered a source of variation to the are suitable for the measurement being taken (Blanco &
NIR spectra (Ismail et al., 1993; Li et al., 1999; Iñon et Pages, 2002; Larrechi & Callao, 2003). This involves
al., 2003). Thus, it is important to include those sources ensuring that the analytical system is consistent and that
of variation in NIR calibration models, in order to have the samples are of the same type as when the system was
a real representation of the variability in the industrial set up (Larrechi & Callao, 2003).
process.
The tank referred to above was used to collect and
store fish oils that are considered unsatisfactory on 4. Conclusions
grounds of being of poor quality unsuitable for use and
hence rejected from production. Inclusion of this poorer This work demonstrates the use of PLS regression and
quality oil in the calibration model is controversial to be NIR spectroscopy is a simple and easy technique that
use in blends as an ingredient for human food but it can be used to monitor hydrolytic and oxidative changes
improved the NIR calibration models by extending the during production and storage of fish oil. NIR spectro-
range of oxidized samples. The high R2 in calibration scopy allows the segregation of fish oil into quality
and a small SECV indicated that lipid hydrolysis and bands or blending to meet specifications continuously
moisture can be reliably predicted by NIR spectroscopy. during production. The operational measurements such
The NIR calibration models for both AV and PV seem as FFA and M were adequately determined by NIR
to be less stable (see Table 2). Some features explain the spectroscopy. This may be used to improve speed of
poorer performance for the PV calibrations including reporting results and assist in decision-making processes
the species of fish used to produce the fishmeal, the of management with greater efficiency. However, NIR
seasonality of the fish, and modifications in the steps of spectroscopy cannot completely replace all reference
the manufacturing process during the period of sam- analytical methods for oil quality, especially for PV and
pling. Although most of the samples did not suffer big AV, and it is important to maintain the skills in
changes in the PV their inclusion in both calibration and reference analysis by the lab staff. The industry would
validation sets affected positively the performance of the like to get more specific chemical information on the
NIR models due to the changes in the storage conditions nutritional qualities of the oil (fatty acid profiles,
and in physical characteristics. These samples were not oxidative stability, and vitamin potency) and physical
strictly considered as outliers because they represent the measurements (viscosity and density) which still requires
real variation in the industrial conditions and a different periodical monitoring. The use of NIR spectroscopy
calibration strategy needs to be adopted for manage- together with multivariate techniques (PLS regression)
ment purposes (e.g. build a separate calibration for alleviates lab staff time from routine quality control
those samples). The calibrations for PV was limited by analysis and allows more effort to be re-directed
the changes in the oxidative state of the samples from towards the establishment of more sophisticated tech-
the time that the reference analysis was take to the time niques to obtain chemical information on fish oil
when the NIR spectrum was recorded. For the predic- quality, which may in future be determined by NIR
tion of AV, different problems arose. The chemical spectroscopy.
reference analysis determined zero values, indicating
negligible decomposition or degradation of the perox-
ides. Such zero values were included in the calibration. Acknowledgements
Consequently, the NIR models predicted some negative
values in the independent validation set, which clearly The authors thank UFP Tullos (Aberdeen, Scotland)
invalidates the use of NIR for this parameter. In for supplying the samples and Ms. K. Kreshow for the
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D. Cozzolino et al. / LWT 38 (2005) 821–828 827

chemical analysis of the fish oil samples. Suggestions Fearn, T. (2002). Assessing calibrations: SEP, RPD, RER and R2. NIR
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