A Research Note

Compositional Analysis of Powdered Cocoa Products by

Near Infrared Reflectance Spectroscopy
J. J. PERMANYER and M. L. PEREZ

ABSTRACT MATERLALS & METHODS

Near infrared reflectance (NIR) spectroscopy was used to measure
moisture, fat, and sucrose in powdered cocoa products. Spectra of a
series of known samples were recorded and multiple linear regression
techniques were used to relate the concentrations of each parameter
to reflectance measurements at selected wavelengths. Precision and
accuracy were estimated to evaluate the potential application of the
NIR spectroscopy in the quality control of powdered cocoa products.
Results showed that moisture, fat, and sucrose could be analyzed in
powdered cocoa products by near infrared reflectance spectroscopy
because good correlation coefficients and low standard errors were
achieved in prediction study.
INTRODUCTION
NEAR INFRARED REFLECTANCE (NIR) spectroscopy is
receiving widespread attention as a rapid method for deter-
mining the composition of many foods. It has been applied to
the rapid analysis of food and agricultural products including
cereals and cereal products, feedstuffs, forages, milk, meat,
seeds, legumes and confectionery (Giangiacomo et al., 1981;
Osborne, 1981, 1986; Baer et al., 1983; Suzuki et al., 1986).
Only a few studies, however, have been reported for the analy-
sis of cocoa products (Kaffka et al., 1982).
Powdered cocoa products added to milk are commonly con-
sumed for breakfast by children. They mostly consist of sugar
and cocoa powder. Therefore, the quality control for such
products focuses on their compositional analysis. To this end,
the traditional wet chemical methods are involved and time-
consuming.
The objective of this study was to investigate the use of NIR
spectroscopy as a rapid analytical method for determining
moisture, fat, and sucrose of the powdered cocoa products
which would aid their quality control.
SINCE THE NIR technique is based on the correlation of spectro-
scopic responsewith the constituent concentration, calibration of the
NIR instrument was carried out on a set of known samples in which
moisture, fat, and sucrosevaried. Fifty-six sampleswere directly taken
from production, and nine samples were specially formulated in the
pilot plant by mixing the raw materials (sugar and cocoa powder
containing lO-12% fat) in different ratios (Table 1). Another set of
10 different samples from production was used as a prediction set to
test the performance of the calibration equations.
The reference chemical methods were: for moisture and fat, the
official methods of the International Office of Cocoa, Chocolate and
Sugar Confectionery (IOCCC, 1952a, 1952b) and for sucrose, the
method from Boehringer Mannheim (1974).
For the NIR analysis, no sample preparation was required because
of the homogeneous particle size and the fineness of the product.
Samples were scanned from 1900 to 2320 nm using a single beam
NIR spectrophotometer with three tilting filters (Pacific Scientific,
Gardner Neotec Division, Model Compscan 3000). It had a baseline
correction to correct the sample curves for system response. The de-
tection system was based on lead sulfide detectors mounted at a 45
angle to the surface of the sample. The reflectance data were the
average of 32 scans per sample. For the development of calibration
equations a mathematical transformation of the raw optical data was
made to obtain the first and second derivative spectra (Fig. 1). Ref-
erence chemical values of the 65 samples were entered into the com-
puter and were correlated with the reflectance energies. Step-forward
linear least square regression yielded an equation of the form:
C = Ko + 5 Ki Li
i-l
where, C is the concentration of a given constituent in the product, p
is the number of terms in the equation, Ko and Ki are the calibration
constants, and Li, the mathematical transformation of the raw optical
data measured at the wavelength hi, i.e., first or second derivatives.
The performance of the NIR procedure was checked by calculating
the standard error of calibration (SEC):

SEC =
2 Vi- Y02
n-l
Authors Permanyer and Perez are with Analytical Research Lab-
oratory, Nutrexpa S. A., c/Lepanto, 410-414, 08025 Barcelona,
J
Spain. where, Yi is the reference chemical value, yi the NIR values, and n

Table 1 -Development and performance of N/R spectroscopy calibration equations for the analysis of powdered cocoa products
Calibration Prediction
Correlation Standard error Correlation Standard error
Range Calibration Wavelengths Mathematical coefficient of calibration Range coefficient of prediction
Parameter Ph.) constants (nm) treatment (r) (SEC) w.) (d (SW
Moisture 1.5 - 4.0 KO= 3.592 1 st derivative 0.978 0.157 1.6- 2.1 0.955 0.034
Kl = 1.306 1939
Fat 1.5 - 3.5 KO= 3.840 2nd derivative 0.987 0.100 2.1- 2.7 0.842 0.051
Kl= - 10.407 2296
K2= - 2.109 1959
Sucrose 51.5 - 81.5 KO= 69.726 Ist derivative 0.998 0.526 68.0-74.5 0.962 0.680
Kl= -6.505 2080
K2= 36.671 2785

768-JOURNAL OF FOOD SCIENCE-Volume 54, No. 3, 1989

 mations that gave the best fit. Results are summarizedin Table
1. Only two term equations were used becausethe addition of
other wavelength provided no improvement in calibration re-
sults.
High correlation coefficients and low standard errors of cal-
-19.16-
ibration indicated that the calibration equations were satisfac-
tory and that good prediction of unknown samples could be
achieved. This was demonstratedby results of the prediction
study (Table 1) ivhich contains multiple correlation coefficients
and standard errors of prediction.
No significant bias was found calculating the t-value for
each constituent by the equation,

t =&xii-NIR)
WAVELENGTH (nm)
ub
IWTI where n is the number of samples and ub =
l2.K
d/1/2 (olab* + ani?) and comparing with the Students t-
distribution values with n-l degrees of freedom and a two-
sided alternative hypothesis at 01= 0.05.
The precision of the NIR method was measuredby recording
ten spectral scanson the same sample and calculating the stan-
dard deviations of the prediction data for each constituent. The
coefficients of variation were 0.86% for moisture, 1.49% for
fat and 0.61% for sucrose.
Accuracy, comparedwith referencemethods, was measured
by comparing the root mean squareprediction error or standard
error of prediction (SEP) with the standarderror of calibration
(SEC) (Moen, 1976; Miner et al., 1978; Osborne and Fearn,
2816 2875 2116 2236 1986) and by the analysis of variance (ANOVA). The ANOVA
test showed no significant difference between the results ob-
WAVELENGTH (nm)
tained by NIR and by chemical analysis (p<O.O5), meaning
62 &Jl that the NIR method was as accurateas wet chemistry methods
16.46 for moisture, fat and sucroseof the powdered cocoa products
I examined.
lB.64 In summary, a NIR spectroscopymethod was developed to
provide a routine, fast and efficient method for determining
moisture, fat and sucrose in powdered cocoa products. Cali-
bration equationswere checkedfor precision and accuracyand
good prediction results were achieved. Therefore, the NIR
spectroscopy technique could be used in quality control of
powdered cocoa products, for moisture, fat, and sucrose.
-6.G
REFERENCES
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Fig. 1 -Near infrared spectra of powdered cocoa product: (a) Giangiacomo, R., Magee, J. B., Birth, G. S., and Dul!, G. G. 1981. Pre-
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MS received 6/20/88; revised 12128188; accepted 12/28/88.
THE COMPUTER PROGRAM determined the characteristic
wavelengths, calibration constants and mathematical transfor-

Volume 54, No. 3, 1989-JOURNAL OF FOOD SCIENCE-769